JP2001072873A - Thermoplastic resin composition and multilayer container using the composition - Google Patents

Abstract

(57) [Problem] To provide a thermoplastic resin composition having an excellent oxygen absorption function, which can be used in many fields including packaging materials for beverages, foods, pharmaceuticals, cosmetics, and the like. SOLUTION: The thermoplastic resin composition contains a thermoplastic resin (A), multilayer polymer particles (B) and a transition metal salt (C). The multilayer polymer particles (B) have at least one oxygen absorbing layer, and the oxygen absorbing layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component. The transition metal salt (C) is contained at a ratio of 1 to 5000 ppm in terms of a metal element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition having oxygen absorbability. The present invention further relates to a resin composition having excellent gas barrier properties against oxygen, carbon dioxide gas and the like, moisture-proof properties, fragrance retention properties, and flavor barrier properties in addition to oxygen absorption properties. The present invention further relates to a multilayered structure using such a composition, which is a structure having good appearance, particularly transparency, such as a packaging container for beverages, foods, pharmaceuticals, cosmetics, and the like.

[0002]

2. Description of the Related Art Gas-barrier resins such as ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) are generally melt-moldable and have excellent oxygen or carbon dioxide gas barrier properties. , Sheets, bottles, containers and the like. Multilayer plastic packaging materials such as these resins and thermoplastic resins with excellent moisture resistance and mechanical properties, especially polyolefin resins, provide oxygen barrier properties in the form of bags, bottles, cups, pouches, etc. As an excellent container, it is widely used in various fields such as food, cosmetics, medicinal chemicals, and toiletries.

[0003] Packaging materials using such resins are excellent in barrier properties against oxygen, carbon dioxide gas and the like. However, such materials as metal materials used for canning and glass used for bottling are used. , The permeability to gases such as oxygen is not infinitely close to zero, but permeates non-negligible amounts of gas. In particular, in the case of packaging materials for food applications, there is a concern that the quality may deteriorate due to oxidation of the contents when stored for a long time.

[0004] When protecting the contents of a package such as food, especially the contents that are easily oxidized, from oxygen and the like, in addition to using the means of cutting off oxygen and carbon dioxide as described above, it is also possible to protect the contents during packaging. It is desired to prevent deterioration of the contents by absorbing oxygen mixed into the packaging container together with the contents at the time of filling. Therefore, it has been proposed to enclose an oxygen absorbent or mix the oxygen absorbent into a resin of the packaging material to give the resin an oxygen absorbing function.

[0005] For example, the following method has been proposed as a method for imparting an oxygen absorbing function to EVOH as a packaging material: By adding an oxidation catalyst such as a transition metal to EVOH, the EVOH is oxidized. A method of allowing oxygen to be permeated to react with the EVOH, thereby imparting an oxygen absorbing function to the EVOH (Japanese Patent Application Laid-Open No. HEI 0-1990).
No. 4-211444); a resin composition having an oxygen absorbing function is obtained by dispersing a resin composition comprising a polyolefin and an oxidation catalyst in EVOH and reacting oxygen to be permeated with the polyolefin in EVOH. Method (JP-A-05-156095); and EV
A method in which OH, a polyolefin, and an oxidation catalyst are blended, and oxygen to be permeated is reacted with the polyolefin and EVOH to obtain a resin composition having an oxygen absorbing function (Japanese Patent Application Laid-Open No. 05-170980).

However, the above-mentioned methods have a problem that the oxygen absorbing function is not sufficient and the transparency is not sufficient because a large amount of an oxidation catalyst is added. The methods (1) and (2) have a problem that the transparency is significantly impaired by adding a polyolefin to the EVOH resin.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems. The object of the present invention is to provide a variety of fields including packaging materials for beverages, foods, pharmaceuticals, cosmetics and the like. An object of the present invention is to provide a thermoplastic resin composition having an excellent oxygen absorbing function that can be used. Another object of the present invention is to provide a resin composition having excellent gas barrier properties, particularly excellent barrier properties against oxygen gas, in addition to the above-described excellent oxygen absorption function. Still another object of the present invention is to provide a resin composition having good transparency in addition to the above-mentioned excellent oxygen absorbing function and gas barrier function. Still another object of the present invention is to provide a multilayer structure, for example, a multilayer container using the composition.

[0008]

The first thermoplastic resin composition of the present invention comprises a thermoplastic resin (A), polymer particles having a multilayer structure (B), and a transition metal salt (C). The structural polymer particles (B) have at least one oxygen absorbing layer, the oxygen absorbing layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component, and
In this composition, the transition metal salt (C) is 1 to 1 in terms of a metal element.
It is contained at a rate of 5000 ppm.

The second thermoplastic resin of the present invention contains a thermoplastic resin (A) and a multilayer polymer particle (B),
The multilayer polymer particles (B) have at least one oxygen absorbing layer, the oxygen absorbing layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component, and The oxygen absorption rate of the composition is 0.01 ml / m ²
-It is day or more.

In a preferred embodiment, the thermoplastic resin composition of the present invention comprises the thermoplastic resin (A) in an amount of 10 to 9%.
It contains 9.9% by weight and the multilayer polymer particles (B) in a proportion of 0.1 to 90% by weight.

In a preferred embodiment, the thermoplastic resin (A) is a polyvinyl alcohol resin (A1),
It is at least one selected from the group consisting of a polyamide resin (A2) and a polyester resin (A3).

In a preferred embodiment, the diene-based polymer (B1) is a polymer containing only a conjugated diene-based monomer as a polymerization component, or a vinyl copolymerizable with a conjugated diene-based monomer and another copolymerizable vinyl. It is at least one kind of a polymer having a polymerization monomer as a polymerization component.

[0013] In a preferred embodiment, the transition metal salt (C) is at least one selected from iron salts, nickel salts, copper salts, manganese salts, and cobalt salts.

In a preferred embodiment, the thermoplastic resin (A) is a polyvinyl alcohol resin (A1), and the polyvinyl alcohol resin (A1) has an ethylene content of 3 to 60 mol%, It is an ethylene-vinyl alcohol copolymer having a degree of 90% or more.

In a preferred embodiment, the polymer constituting the multilayer polymer particles (B) contains a carbon-carbon double bond at a rate of 0.0001 eq / g or more.

In a preferred embodiment, the difference in the refractive index between the thermoplastic resin (A) and the multilayer polymer particles (B) is 0.01 or less.

In a preferred embodiment, the multilayer polymer particles (B) are dispersed in a matrix of the thermoplastic resin (A).

[0018] The third thermoplastic resin of the present invention contains polymer particles (B) having a multilayer structure and a transition metal salt (C).
In this composition, the multilayer structure polymer particles (B) have at least two thermoplastic resin layers, and one of the two layers contains a conjugated diene monomer as a polymerization component. An oxygen-absorbing layer made of a resin containing a diene-based polymer (B1), wherein the diene-based polymer (B1) includes the conjugated diene-based monomer as a copolymer component to constitute the oxygen-absorbing layer. The other layer does not substantially contain the diene-based polymer (B1), and the layer has a multilayer structure of polymer particles (e.g., 10 mol% or more based on the total amount of the resin). The outermost layer of B) is formed. The composition contains a transition metal salt (C) at a rate of 1 to 5000 ppm in terms of a metal element.

The present invention includes a multilayer structure and a multilayer container including a layer made of the above-mentioned thermoplastic resin composition.

The present invention also includes a multilayer film including a layer made of the above thermoplastic resin composition and having a total thickness of 300 μm or less, and a multilayer container formed by molding the multilayer film.

The present invention also includes a multilayer container having a layer made of the thermoplastic resin composition and a layer made of thermoplastic polyester.

[0022]

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

The type of the thermoplastic resin (A) contained in the resin composition of the present invention is not particularly limited. For example, polyvinyl alcohol resin, polyamide resin, polyester resin, polyolefin resin, polystyrene resin, polyvinyl chloride resin, acrylic resin, polyvinylidene chloride resin, polyacetal resin, polycarbonate resin, polyurethane resin And the like.
The thermoplastic resin used in the present invention includes a thermoplastic elastomer. Among these, polyvinyl alcohol resin (A1), polyamide resin (A2), and polyester resin (A3) are preferable. Since these have excellent gas barrier properties, using such a resin provides a good gas barrier function in addition to the oxygen absorbing function.

The above polyvinyl alcohol-based resin (A1)
Is obtained by saponifying a homopolymer of vinyl ester or a copolymer of vinyl ester and another monomer (particularly, a copolymer of vinyl ester and ethylene) using an alkali catalyst or the like.

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

The above polyvinyl alcohol resin (A1)
The degree of saponification of the vinyl ester component is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more. If the saponification degree is less than 90 mol%,
The gas barrier properties under high humidity may be reduced. Also, ethylene-vinyl alcohol copolymer (EVOH)
In the case of, the thermal stability deteriorates and gel
Bubbles are likely to occur.

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

As the polyvinyl alcohol-based resin (A1) used in the present invention, ethylene-vinyl alcohol copolymer (EVOH) is preferred because it can be melt-molded and has good gas barrier properties under high humidity. is there.

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

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

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

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

Further, a polyvinyl alcohol-based resin (A
1) In particular, EVOH may contain a small amount of another monomer as a copolymer component as long as the object of the present invention is not impaired. Examples of the monomer that can be a copolymerization component include α such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
-Olefins; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, and salts thereof;
Partial or complete esters, their amides, their anhydrides; nitriles such as acrylonitrile and methacrylonitrile; vinylsilane-based compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; No.

When EVOH contains 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymer component, the consistency of the melt viscosity with the base resin at the time of coextrusion molding or coinjection molding is improved. Improved and homogeneous moldings can be produced. Here, as the vinylsilane-based compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy)
Silane, 3-methacryloyloxypropyltrimethoxysilane and the like. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

Furthermore, even when a boron compound is added to EVOH, the consistency of the melt viscosity with the base resin and the thermal stability during co-extrusion molding or co-injection molding are improved, and long-term operation is possible. It is effective in that a homogeneous co-extrusion or co-injection molded product can be obtained even in some cases. Here, examples of the boron compound include boric acids, borate esters, borates, borohydrides, and the like. Specifically, boric acids include boric acid, orthoboric acid, metaboric acid, tetraboric acid, and the like.Boric esters include triethyl borate, trimethyl borate, and the like. And alkali metal salts, alkaline earth metal salts, and borax of various boric acids. Borate Among these compounds, orthoboric acid, NaBH ₄ is preferred.

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

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

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

With respect to EVOH, a phosphorus compound is 2 to 200 ppm in terms of phosphorus element, more preferably 3 to 150 pp.
m, optimally at a ratio of 5 to 100 ppm. If the phosphorus concentration in the EVOH is less than 2 ppm or more than 200 ppm, problems may occur in melt moldability and thermal stability. In particular, when melt molding is performed for a long time, gel-like bumps and coloring are likely to occur.

The type of the phosphorus compound added to the EVOH is not particularly limited. Various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. The phosphate may be contained in any form of primary phosphate, secondary phosphate and tertiary phosphate, and the cationic species of the phosphate is not particularly limited. As phosphates, alkali metal salts,
Alkaline earth metal salts and the like. Especially, it is preferable to add a phosphorus compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

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

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

The type of the polyamide resin (A2) is not particularly limited. For example, the following polyamide resins are used: polycaprolactam (nylon-6), poly-ω-
Aminoheptanoic acid (nylon-7), poly-ω-aminononanoic acid (nylon-9), polyundecaneamide (nylon-11), polylaurolactam (nylon-1)
2), polyethylene adipamide (nylon-2, 6),
Polytetramethylene adipamide (nylon-4, 6),
Polyhexamethylene adipamide (nylon-6,6),
Polyhexamethylene sebacamide (nylon-6,1
0), polyhexamethylene dodecamide (nylon-6,
12), polyoctamethylene adipamide (nylon 8,
6), polydecamethylene adipamide (nylon-10,
6), polydodecamethylene sebacamide (nylon-1
2,10), caprolactam / laurolactam copolymer (nylon-6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylene adipamide copolymer (nylon -6
/ 6,6), laurolactam / hexamethylene adipamide copolymer (nylon-12 / 6,6), hexamethylene adipamide / hexamethylene sebacamide copolymer (nylon-6,6 / 6,10), ethylene adipamide / hexamethylene adipamide copolymer (nylon-2,6 /
6,6), caprolactam / hexamethylene adipamide / hexamethylene sebacamide copolymer (nylon-6 /
6,6 / 6,10), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, and hexamethylene isophthalamide / hexamethylene terephthalamide copolymer. These polyamide resins can be used alone or in combination of two or more.

The type of the polyester resin (A3) is not particularly limited. Polyester resins include poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene terephthalate / ethylene isophthalate), and poly (ethylene terephthalate / cyclohexane dimethylene terephthalate). Further, to these polymers, ethylene glycol, butylene glycol, cyclohexane dimethanol, neopentyl glycol,
Diols such as pentanediol; or isophthalic acid, benzophenone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl methane dicarboxylic acid, propylene bis (phenyl carboxylic acid), diphenyl oxide dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipine Copolyesters containing dicarboxylic acids such as acids, pimelic acid, suberic acid, azelaic acid, sebacic acid, and diethylsuccinic acid can also be used.

The multi-layer polymer particles (B) contained in the thermoplastic resin composition of the present invention are particles having a multi-layer structure (two or more layers) mainly composed of a thermoplastic resin. At least one layer. This oxygen absorption layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component. Diene polymer (B1)
Has an oxygen absorbing function as described later. The multilayer polymer particles (B) have a layer structure called a core / shell,
In other words, even if the inner layer / outer layer structure in which the inner layer is covered by the outer layer is generally formed and the inner layer is
It may be composed of layers or more. Here, the layer includes a core portion of the multilayer structure particle (this core portion is referred to as a core layer). The inner layer and the outer layer are relative terms. For example, in the case of a three-layered multi-layer particle composed of a core layer, an intermediate layer, and an outermost layer, the intermediate layer is an outer layer with respect to the core layer, and an outer layer with respect to the outermost layer. It is the inner layer.

The multilayer polymer particles (B) usually contain a hard layer in addition to the oxygen absorbing layer. The hard layer is a resin layer having a higher hardness than the oxygen absorbing layer, and is provided for the purpose of maintaining the shape of the particles and improving the handling properties.

When the polymer particles of the multilayer structure of the present invention have a two-layer structure, they usually have an oxygen absorbing layer (core layer) / hard layer (outermost layer) structure. Core layer) / oxygen absorbing layer (intermediate layer) / hard layer (outermost layer), oxygen absorbing layer (core layer) / hard layer (intermediate layer) / hard layer (outermost layer) or oxygen absorbing layer (core layer) / oxygen It is a structure of an absorption layer (intermediate layer) / hard layer (outermost layer). In the case of a four-layer structure, for example, an oxygen absorbing layer (core layer) / hard layer (intermediate layer)
/ Oxygen absorbing layer (intermediate layer) / hard layer (outermost layer). In a multilayer polymer particle having a layer structure of three or more layers, the polymer particle may have two or more oxygen absorbing layers.

In the multilayer polymer particles (B), an oxygen-absorbing layer and a hard layer are provided for the purpose of imparting flexibility to the particles to improve mechanical properties such as impact resistance, or to improve weather resistance. In addition to the layer, a rubber layer can be provided at an arbitrary site. Further, the oxygen absorbing layer or the hard layer itself can be modified to have rubber elasticity as long as the oxygen absorbing function is not practically impaired (all will be described later).

The above-mentioned various multilayer structures may be, for example, embodiments in which the inner layer is partially surrounded by the outer layer. further,
Embodiments in which microvoids (including microvoids, voids, cavities) are present (having at least one) in any one or more layers of the multilayer polymer particles, and such embodiments. In addition, embodiments including one or more passages in which the voids are connected to the space outside the particles are also included.

The outermost layer of the multi-layer polymer particles of the present invention comprises:
As described later, it is desirable that the layer is substantially free of the diene polymer (B1).

The “particles” used in the present specification have properties generally possessed by polymer particles used in polymer chemistry. An overview of such polymer particles is described, for example, in the following literature: New Development of Fine Particle Polymers as Functional Materials (Toray Research Center); State-of-the-art Technology of Ultrafine Particle Polymers (CMC, 1991); Particle design (Industry Research Council, 198
7).

The structure of the multilayer polymer particles is not limited to the above, and can be variously modified.

The diene polymer (B1) used in the oxygen absorbing layer is a polymer containing a conjugated diene monomer as a polymerization component. Such a polymer is a polymer containing only a conjugated diene monomer as a polymerization component, and a polymer containing a conjugated diene monomer and another copolymerizable vinyl monomer as a polymerization component. At least one of them.

Since such a compound has a reactive double bond in the molecule, it can react with oxygen.
Thereby, it has an oxygen absorbing function.

The conjugated diene monomer includes butadiene and isoprene. As a polymer containing only such a monomer as a polymerization component, polybutadiene, polyisoprene, butadiene-isoprene copolymer, and the like are preferable.

Examples of the vinyl monomer contained in the polymer containing a conjugated diene monomer and another copolymerizable vinyl monomer as a polymerization component include (meth) acrylic acid ester and aromatic vinyl. And acrylonitrile. Among these (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate , Decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, isobornyl (meth) acrylate, etc. There is. Examples of the aromatic vinyl compound include styrene and α-methylstyrene. The term “(meth) acrylate” refers to a general term for “acrylate” and “methacrylate”.

Specific examples of the polymer containing a conjugated diene monomer and another copolymerizable vinyl monomer as polymerization components include styrene-butadiene copolymer, styrene-isoprene copolymer and acrylonitrile. -Butadiene copolymer, acrylonitrile-isoprene copolymer, acrylate-butadiene copolymer, acrylate-isoprene copolymer and the like, and these are preferably used.

By using a polymer containing a conjugated diene monomer and another copolymerizable vinyl monomer as a polymerization component, the thermoplastic resin (A) can be used as the diene polymer (B1). It is easy to control the difference in refractive index between the polymer particles (B) and the multilayer polymer particles (B). Further, the control of the reaction time when preparing the polymer layer of the particles is facilitated. For example, as the thermoplastic resin (A), a polyvinyl alcohol-based resin (A
When 1) is used, a polymer containing styrene as a copolymer component is preferred from the viewpoint of controlling the difference in refractive index from the resin, and an acrylate ester is preferred from the viewpoint of shortening the polymerization reaction time. Is preferred as a copolymer containing Styrene-butadiene-acrylate copolymer and styrene-isoprene-acrylate copolymer are particularly preferred from the viewpoints of both controlling the refractive index difference and shortening the polymerization reaction time.

From the viewpoint of obtaining a sufficient oxygen absorbing function, the conjugated diene-based monomer contained as a polymerization component in the diene-based polymer (B1) is 10% based on the weight of the polymer in the entire oxygen-absorbing layer. % By weight, preferably at least 20% by weight, more preferably at least 30% by weight. The upper limit of the content of the conjugated diene-based monomer as a polymerization component is not particularly limited.
%. That is, the oxygen absorption layer may be composed of only a polymer containing only the conjugated diene monomer as a polymerization component. However, in consideration of reducing the difference in the refractive index between the thermoplastic resin (A) and the multilayer polymer particles (B), and controlling the reaction time when preparing the polymer layer, the conjugated diene-based monomer may be used. The body is preferably present in a proportion of up to 90% by weight, more preferably up to 80% by weight. Therefore, the content of the conjugated diene-based monomer contained as a polymerization component in the polymer is preferably 10 to 90% by weight based on the weight of the entire oxygen absorbing layer.

As the polymer constituting the hard layer in the multilayer polymer particles (B), a polymer having a glass transition temperature (Tg) higher than 25 ° C. is used, and the type thereof is not particularly limited. The hard layer is preferably provided as the outermost layer. By using the multilayer polymer particles (B) having a hard layer as the outermost layer, the handling properties of the particles and the dispersibility when melt-kneaded with the thermoplastic resin (A) are improved. Common polymerizable monomers that can be used to form the hard layer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate,
Methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and isobornyl methacrylate Styrene, α
-Aromatic vinyl compounds such as methylstyrene; acrylonitrile; Among these, it is preferable to form a hard layer by using methyl methacrylate or styrene alone, or to form a hard layer by combining one or more of the above monomers with one of them as a main component.

As the polymer constituting the rubber layer, olefin rubbers such as ethylene-propylene copolymer;
An acrylic rubber such as a polyacrylic ester; an organopolysiloxane; a thermoplastic elastomer; an ethylene ionomer copolymer; and the like, among which an acrylic rubber composed of a polyacrylic ester is particularly preferable. Examples of the acrylate that can form the acrylic rubber include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate. . Among these, butyl acrylate or 2-ethylhexyl acrylate is preferred. This rubber layer can be provided at an arbitrary site in the multilayer polymer particles (B).

Further, as described above, it is also possible to modify the oxygen absorbing layer itself to have rubber elasticity as long as the oxygen absorbing function is not practically impaired. More specifically, the oxygen-absorbing layer has a crosslinked molecular chain structure for exhibiting rubber elasticity, and / or the molecular chain in the oxygen-absorbing layer and the molecular chain in the layer adjacent thereto are chemically bonded. It is also preferred that they are grafted. For that purpose, for example, in the polymerization of a monomer for forming an oxygen absorbing layer, it is desirable to use a small amount of a polyfunctional polymerizable monomer in combination as a crosslinking agent or a grafting agent. The polyfunctional polymerizable monomer is a radical polymerizable monomer having two or more carbon-carbon double bonds in the molecule, for example, unsaturated monomers such as acrylic acid, methacrylic acid, and cinnamic acid. A carboxylic acid;
Esters with unsaturated alcohols such as allyl alcohol and methallyl alcohol or glycols such as ethylene glycol and butanediol; esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and maleic acid with the above-mentioned unsaturated alcohols. Included. Specific examples of the polyfunctional polymerizable monomer include allyl acrylate, methallyl acrylate, allyl methacrylate, methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, and terephthalic acid. Examples include diallyl, diallyl isophthalate, divinylbenzene, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate. The term "di (meth) acrylate" means a general term for "diacrylate" and "dimethacrylate".

The polyfunctional polymerizable monomers can be used alone or in combination of two or more. Among these, butanediol diacrylate, hexanediol diacrylate, allyl methacrylate and the like are preferably used. However, when a polyfunctional polymerizable monomer is used, if the amount is too large, the performance of the multilayer structure polymer particles as a rubber decreases. As a result, the impact resistance and oxygen absorption of the obtained thermoplastic resin composition are reduced. The amount of the polyfunctional polymerizable monomer is preferably 10% by weight or less based on the entire polymerizable monomer forming the oxygen absorbing layer. When a polymerizable monomer containing a conjugated diene-based compound as a main component is used, it itself functions as a cross-linking point or a graft point. Also, an oxygen absorbing layer having rubber elasticity is formed.

The proportion of the oxygen-absorbing layer in the multilayer polymer particles (B) is not particularly limited, but is preferably in the range of 20 to 95% by weight.
More preferably, it is in the range of 50 to 90% by weight. If the amount of the polymer portion forming the oxygen absorbing layer is too small, the oxygen absorbing ability of the resin composition of the present invention may be insufficient.

It is preferable that the outermost layer of the multilayer polymer particles (B) does not substantially contain the diene polymer (B1). This is because the multilayer polymer particles (B) have excellent handling properties and dispersibility of the particles when melt-kneaded with the thermoplastic resin (A). Specifically, the content of the diene polymer (B1) is preferably 5 mol% or less.
The outermost layer is preferably a hard layer.

The whole resin constituting the multilayer polymer particles (B) contains carbon-based carbon based on the weight of the whole resin.
It is preferable to contain a carbon double bond at a rate of 0.0001 eq / g or more. This carbon-carbon double bond may be derived from the diene polymer (B1). When the content of the carbon-carbon double bond is less than 0.0001 eq / g, the oxygen absorption rate may not be sufficient, and the oxygen absorbing effect of the composition of the present invention may be insufficient. From the viewpoint of obtaining a sufficient oxygen absorbing effect, the content of the carbon-carbon double bond is more preferably 0.0005 eq / g or more,
More preferably, it is 0.001 eq / g or more.

The term "carbon-carbon double bond" as used herein refers to a double bond of an aliphatic compound and an aromatic ring side chain, including a conjugated double bond but not a multiple bond contained in an aromatic ring. .

The multi-layer polymer particles (B) may contain an antioxidant in some cases. Examples of antioxidants include 2,5-di-t-butylhydroquinone,
2,6-di-t-butyl-p-cresol, 4,4′-
Thiobis- (6-t-butylphenol), 2,2′-
Methylene-bis- (4-methyl-6-t-butylphenol), octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate,
4,4′-thiobis- (6-t-butylphenol),
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, pentaerythritol tetrakis (3-laurylthiopropionate) and the like can be mentioned.

The optimum amount of the antioxidant is determined in consideration of the type and content of the components in the thermoplastic resin composition, the purpose of use, storage conditions and the like. In general, when a large amount of an antioxidant is contained, oxygen which is to pass through the resin composition and the diene polymer (B) in the multilayer polymer particles (B) are used.
The reaction with 1) is hindered. Therefore, the oxygen absorbing function of the composition of the present invention may not be sufficiently exhibited. On the other hand, when the antioxidant is not contained or its content is too small, the reaction with oxygen proceeds during the storage or melt processing of the thermoplastic resin composition, and the oxygen absorption performance decreases during actual use. May have been done.

When the multi-layered polymer particles (B) are stored in an inert gas atmosphere, or when a resin composition is produced by melt-blending at a relatively low temperature or in a state sealed with nitrogen, an antioxidant is used. May be small.

When the resin composition of the present invention contains an oxidation catalyst comprising a transition metal salt (C) as described later, the multilayer polymer particles (B) contain a certain amount of an antioxidant. However, a resin composition having good oxygen absorbing ability can be obtained. In such a case, the content of the antioxidant is preferably 0.01 to 1% by weight, and 0.05 to 0.5% by weight.
% Is more preferred. As described above, the antioxidant may be added at the time of preparing the multilayer polymer particles (B), or may be added at the time of mixing each component of the resin composition.

The method for producing the multilayer polymer particles (B) is not particularly limited. For example, using a normal emulsion polymerization method,
Spherical multilayer polymer particles (B) can be easily obtained. For example, when obtaining particles having a two-layer structure having an oxygen absorbing layer as a core layer and a hard layer as an outermost layer,
First, emulsion polymerization is performed using a monomer capable of forming an oxygen-absorbing layer, and then, a monomer capable of forming a hard layer is charged into a reaction system and emulsion polymerization is performed to obtain the desired 2
Particles having a layer structure are obtained. In the emulsion polymerization method, a chain transfer agent such as octyl mercaptan and lauryl mercaptan can be used as necessary according to a known means. After the emulsion polymerization, the multi-layered polymer particles (B) can be separated and obtained from the polymer latex according to a known method, for example, by coagulation and drying.

The average particle size of the multilayer polymer particles (B) is not particularly limited, but is preferably in the range of 0.02 to 2 μm, and more preferably in the range of 0.05 to 1.0 μm. Is more preferred. If the average particle diameter is too small, the production cost of the multilayer polymer particles (B) increases. Conversely, if it is too large, the transparency of the resin composition of the present invention may be lost.

The form of the multilayer polymer particles (B) to be produced is not particularly limited. For example, the resin composition may be in the form of pellets fused to each other at the outermost layer, or may be in the form of powder or granules. In any case, the resin composition of the present invention can be used.

The refractive index of the multilayer polymer particles (B) is preferably not more than 0.01 from the thermoplastic resin (A) from the viewpoint of transparency of the resin composition. . Thermoplastic resin (A) and multi-layer polymer particles (B)
If the difference in the refractive index from the resin composition exceeds 0.01, the transparency of the resin composition of the present invention may be poor. In order to obtain good transparency, the difference in refractive index between the thermoplastic resin (A) and the multilayer polymer particles (B) is preferably 0.007 or less, and more preferably 0.005 or less. More preferred. Here, the refractive index of the multilayer structure polymer particles (B) refers to the refractive index of the unstretched film having a thickness of 20 μm obtained by press-molding the multilayer structure polymer particles (B) at a mold temperature of 210 ° C. Refers to the measured value.

The multilayer polymer particles (B) themselves are also preferably excellent in transparency. The multilayer polymer particles (B) were press-molded at a mold temperature of 210 ° C., and the obtained unstretched film having a thickness of 20 μm had an internal haze value of 1
It is preferably 0% or less.

The content of the thermoplastic resin (A) and the multilayer polymer particles (B) in the resin composition of the present invention is not particularly limited.
99.9% by weight, 0.1 to 0.1% by weight of the multilayer polymer particles (B)
It is contained in a proportion of 90% by weight. Preferably, the thermoplastic resin (A) is in a proportion of 70 to 99% by weight, the multilayer polymer particles (B) in a proportion of 1 to 30% by weight, more preferably the thermoplastic resin (A) is in a proportion of 80 to 98% by weight, Multilayer polymer particles (B) are contained at a ratio of 2 to 20% by weight. When the content of the multilayer polymer particles (B) is less than 0.1% by weight, the oxygen absorbing function may not be sufficiently exhibited. When a gas-barrier resin such as EVOH is used as the thermoplastic resin (A) for the purpose of gas-barrier properties, if the amount of the gas-barrier resin is small, the resin composition as a whole is inferior in gas-barrier properties.

The resin composition of the present invention preferably contains a transition metal salt (C). When the transition metal salt (C) is contained, its content is 1 to 50 in terms of a metal element.
00 ppm, preferably 5 to 1000 ppm, more preferably 10 to 500 ppm.

Thus, the oxygen oxidation reaction of the diene polymer (B1) in the multilayer polymer particles (B) can be promoted. For example, the diene polymer (B1) can efficiently react with oxygen present inside the packaging material obtained from the composition of the present invention and oxygen that is going to permeate the packaging material. As a result, the oxygen absorbing effect of the resin composition of the present invention is improved. However, when the content of the transition metal salt (C) exceeds 5000 ppm in terms of a metal element, the thermal stability of the resin composition of the present invention is reduced, and generation of decomposition gas and generation of gel and butter become remarkable. . From such a viewpoint, the content of the transition metal salt (C) is preferably in the above range.

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

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

The first thermoplastic resin composition of the present invention contains the above-mentioned thermoplastic resin (A), multilayer polymer particles (B) and transition metal salt (C).

The second thermoplastic resin composition of the present invention contains the thermoplastic resin (A) and the multilayer polymer particles (B), and has an oxygen absorption rate of 0.01 ml / m ² · day or more. It has the feature of.

The third thermoplastic resin composition of the present invention contains a multilayer structure polymer particle (B) and a transition metal salt (C), and the multilayer structure polymer particle (B) has a specific constitution described below. Having.

In any of the above resin compositions, various additives can be blended as required. Examples of such additives include antioxidants, plasticizers, heat stabilizers, ultraviolet absorbers, antistatic agents, lubricants, coloring agents, fillers, drying agents and other high molecular compounds, These can be blended as long as the effects of the present invention are not inhibited.

Further, one or more other high molecular compounds may be blended to such an extent that the effects of the present invention are not impaired.

The resin composition of the present invention may contain one or two of a hydrotalcite compound and a metal salt of a higher aliphatic carboxylic acid (for example, calcium stearate, magnesium stearate, etc.) in order to improve the melt stability and the like. The above can be added to such an extent that the effects of the present invention are not inhibited. When these are used, it is preferable to add 0.01 to 1% by weight to the resin composition.

When a hydrotalcite compound is added to the resin composition of the present invention, it is possible to prevent the formation of gels and fish eyes in a layer made of the resin composition.
Long-term operation stability can be further improved.

When a metal salt of a higher aliphatic carboxylic acid is added to the resin composition, the generation of gels and fish eyes can be prevented, and the long-term operation stability can be further improved.

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

In the resin composition of the present invention, for example, the first and second compositions, the multilayer structure polymer particles (B) and, if necessary, the particles of the transition metal salt (C) are formed of a thermoplastic resin (C). A), particularly preferably dispersed in a matrix of a thermoplastic resin having gas barrier properties.
Such a resin composition and a molded article such as a multilayer container using the resin composition have good oxygen absorption and transparency. When a thermoplastic resin having gas barrier properties is used, the gas barrier properties and oxygen absorbency of the molded product are extremely good. The dispersion state of the multilayer polymer particles (B) in the resin composition of the present invention is not necessarily limited. A state in which individual particles are uniformly dispersed in a completely independent form, a state in which a plurality of particles are uniformly dispersed in the form of agglomerated particles, and these states coexist. Any of the states may be used. However, the dispersed particle size (the particle size of a single particle or an aggregate composed of a plurality of particles) of the multilayer polymer particles (B) is preferably 10 μm or less. When the dispersed particle size exceeds 10 μm, the area of the interface between the thermoplastic resin (A) and the multilayer polymer particles (B) becomes small, and the oxygen absorption performance is reduced. The average particle size of the multilayer polymer particles (B) dispersed in the matrix of the thermoplastic resin (A) is preferably 5 μm or less, more preferably 2 μm or less. It is particularly preferable that particles having a particle diameter in the range of 0.03 to 1 μm are uniformly dispersed in the thermoplastic resin phase.

As described above, the third thermoplastic resin composition of the present invention contains the polymer particles (B) having a multilayer structure and the transition metal salt (C), and the polymer particles (B) have a multilayer structure. It has a specific configuration. One of the at least two thermoplastic resin layers contained in the multilayer polymer particles (B) includes:
An oxygen absorbing layer (layer containing a diene polymer (B1) containing a conjugated diene monomer as a polymerization component). The oxygen absorbing layer contains a copolymer component of the conjugated diene-based monomer at a ratio of 10 mol% or more. The other layer is a layer forming the outermost layer, and this layer does not substantially contain the diene-based polymer (B1). Here, “substantially not containing the diene polymer (B1)” means that the content of the diene polymer (B1) is 5 mol% or less.

As described above, the outermost layer is composed of the diene polymer (B
1) Since it is a layer which does not substantially contain, usually a hard layer,
The handling properties of the particles are good. Such a composition is prepared by, for example, mixing only the multi-layered polymer particles (B) and the transition metal salt (C) and melt-molding the mixture, and the outermost layers of the multi-layered polymer particles (B) are connected to each other. Various molded articles can be obtained. Such a molded product is suitably used, for example, for film applications. This composition can further contain a thermoplastic resin (A).

The oxygen absorption rate of the second composition of the present invention.
Is 0.01 ml / m²・ Day or more, other
Even in the composition, the oxygen absorption rate is 0.01 ml / m²
-It is preferable that it is day or more. Oxygen in resin composition
Absorption rate is 0.05ml / m ²・ Being more than day
Is more preferable, and 0.1 ml / m²-It is more than day
Is more preferred. Oxygen absorption rate is 0.01ml / m
²If less than day, use the resin composition of the present invention.
Of the oxygen absorption effect of molded articles such as multilayer containers
There is a possibility that it will be troublesome.

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

Suitable melt flow rate (MFR) of the resin composition of the present invention (210 ° C., 2160 g load, JI
0.1 to 100 g / 10m based on SK7210)
in. , More preferably 0.5 to 50 g / 10 min. ,
More preferably, 1 to 30 g / 10 min. It is. The resin composition of the present invention has a melt flow rate of 0.1 to 100.
g / 10 min. If the ratio is out of the range, workability at the time of performing melt molding may be deteriorated.

The thermoplastic resin composition of the present invention is formed into various molded products according to the purpose. For example, as described below,
A multilayer structure including a layer composed of the thermoplastic resin composition,
For example, a multilayer film and a multilayer container are manufactured. The multilayer container is suitably manufactured, for example, by molding the multilayer film.

The method of mixing and molding each component of the thermoplastic resin composition of the present invention is not particularly limited. The order of mixing the components is not particularly limited.

For example, when a molded article is produced by blending the three components of the thermoplastic resin resin (A), the multilayer polymer particles (B) and the transition metal salt (C), the blending order is not particularly limited. . The thermoplastic resin (A), the multilayer structure polymer particles (B) and the transition metal salt (C) may be mixed simultaneously, or after mixing the multilayer structure polymer particles (B) and the transition metal salt (C). It may be mixed with the thermoplastic resin (A). Further, a thermoplastic resin (A) and a transition metal salt (C)
May be mixed with the multilayer structure polymer particles (B), or the thermoplastic resin (A) and the multilayer structure polymer particles (B) may be mixed and then mixed with the transition metal salt (C). Good. Further, a mixture obtained by mixing the thermoplastic resin (A) and the multilayer structure polymer particles (B) with the thermoplastic resin (A)
And a mixture obtained by mixing the transition metal salt (C).

As means for mixing the components of the resin composition of the present invention, a ribbon blender, a high-speed mixer,
Examples thereof include a co-kneader, a mixing roll, an extruder, and an intensive mixer.

Each component of the resin composition of the present invention can be dry-blended and directly used for melt molding. More preferably, for example, the mixture is kneaded with a Banbury mixer, a single screw or twin screw extruder, pelletized, and then subjected to melt molding. From the viewpoint of preventing the oxidation of the multilayer polymer particles (B) from proceeding during the blending operation, it is preferable to extrude at a low temperature by sealing the hopper port with nitrogen. It is preferable to use an extruder having a high kneading function and to make the dispersion state fine and uniform in terms of improving oxygen absorption performance and transparency and preventing generation and mixing of gels and butter.

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

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

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

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

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

The resin composition of the present invention can be formed into films, sheets, containers and other packaging materials using various molding methods.

For example, it can be formed into a film, sheet, pipe or the like by melt extrusion molding, into a container shape by injection molding, or into a bottle-like hollow container by hollow molding. As the hollow molding, there are extrusion hollow molding in which a parison is formed by extrusion molding and blow molding to form the preform, and injection hollow molding in which a preform is formed by injection molding and blown to form the preform.

In the present invention, the molded article obtained by the above molding may be a single layer, but it is often used as a laminate (multilayer structure) with a layer composed of other various resins. It is more preferable because the function can be provided. When the resin composition of the present invention is used in a single layer, the oxygen absorbability may be reduced due to the contents or the moisture of the outside air, and the mechanical strength may not be sufficient. To compensate for this, it is preferable to laminate a layer having a water vapor barrier property or a layer having high mechanical strength on the side where much moisture exists.

In the present invention, by covering the outside of the resin composition layer with another resin layer, the rate of intrusion of oxygen from the outside can be suppressed, and the oxygen absorbing function of the resin composition is maintained for a long time. From the viewpoint that it can be maintained, it is preferable to adopt a multilayer structure.

When the innermost layer of the container is a resin composition, the oxygen absorbing function in the container may be quickly exhibited and effective.

As a specific layer configuration of the multilayer structure, X / Y, X / Y, when a layer made of another resin is an X layer, a resin composition layer is a Y layer, and an adhesive resin layer is a Z layer. / X, X / Z /
Y, X / Z / Y / Z / X, X / Y / X / Y / X, X / Z
Although layer configurations such as / Y / Z / X / Z / Y / Z / X and the like are exemplified, it is not limited to the above-mentioned example without any problem to appropriately add other layers to these. When a plurality of layers made of another resin are provided, they may be of different types or the same. Further, a collected resin layer made of scrap such as trim generated during molding may be separately provided, or the collected resin may be blended with a layer made of another resin. Although there is no particular limitation on the thickness configuration of the multilayer structure, the thickness ratio of the resin composition layer to the total thickness is preferably 2 to 20% in consideration of moldability and cost.

As a material of another resin layer to be laminated with the resin composition of the present invention, a thermoplastic resin is preferable from the viewpoint of processability and the like. Such thermoplastic resins are not particularly limited, but polyolefins such as ethylene homopolymer and ethylene copolymer, propylene homopolymer and propylene copolymer, poly-4-methylpentene-1, polybutene-1; polyethylene terephthalate, polybutylene Polyesters such as terephthalate and polyethylene naphthalate; poly ε-caprolactam,
Polyamides such as polyhexamethylene adipamide and polymethaxylylene adipamide; polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylate and the like.
Such a thermoplastic resin layer may be unstretched or may be uniaxially or biaxially stretched or rolled.

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

In the present invention, an adhesive resin can be used for bonding the resin composition layer of the present invention to another resin layer. The adhesive resin is not particularly limited as long as it can bond the respective layers, but polyurethane-based, polyester-based one-pack or two-pack curable adhesives, carboxylic acid-modified polyolefin resins and the like are preferably used. . Carboxylic acid-modified polyolefin resins include unsaturated carboxylic acids or their anhydrides (such as maleic anhydride).
Or a graft copolymer obtained by grafting an unsaturated carboxylic acid or an anhydride thereof to an olefin-based polymer or copolymer.

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

Examples of the method for obtaining the multilayer structure include an extrusion lamination method, a dry lamination method, a co-injection molding method and a co-extrusion molding method, and are not particularly limited.
Examples of the coextrusion molding method include a coextrusion laminating method, a coextrusion sheet molding method, a coextrusion inflation molding method, and a coextrusion blow molding method.

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

The transparency of the resin composition of the present invention can be improved by appropriately selecting the types of the resins constituting the thermoplastic resin (A) and the multilayer polymer particles (B) in consideration of the refractive index. Is good. Therefore, by selecting a resin having excellent transparency as another resin to be laminated, a packaging container in which the contents are easily visible can be obtained. To obtain a multilayer structure having excellent transparency, the internal haze is 10% or less,
More preferably, it is 5% or less, more preferably 3% or less.

Molded articles such as containers using the resin composition of the present invention, especially multilayer structures are used for various applications. Among them, the superiority of using the resin composition of the present invention, which is excellent in oxygen absorption and extremely excellent in gas barrier property by appropriately selecting the thermoplastic resin (A), is used in various packaging containers. It is greatly demonstrated when In particular, it is suitable as a packaging container for foods, pharmaceuticals, agricultural chemicals, etc., whose quality is likely to deteriorate due to the presence of oxygen.

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

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

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

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

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

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

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

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

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

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

The multilayer film thus obtained is processed into a bag shape, and can be used as a packaging container for filling contents. Since it is flexible and simple, and is excellent in transparency and oxygen absorption, it is extremely useful for packaging of contents that are easily degraded by the presence of oxygen, particularly foods and the like.

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

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

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

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

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

The polyester resin used in the multilayer container of the present invention comprising a layer comprising the above-mentioned thermoplastic resin composition and a thermoplastic polyester layer includes aromatic dicarboxylic acids or their condensation esters formed from diols and diols. Coalescing is used. In particular, to achieve the object of the present invention, a polyester resin containing an ethylene terephthalate component as a main component is preferable. In the polyester resin used in the present invention, the total ratio (mol%) of terephthalic acid units and ethylene glycol units is generally 70 mol% or more with respect to the total mol number of all structural units constituting the polyester. Is more preferable, and it is more preferable that it is 90 mol% or more. The total proportion of terephthalic acid units and ethylene glycol units in the polyester is 7
When the content is less than 0 mol%, the obtained polyester becomes amorphous, so that when heat-filled (hot-filled) into a stretching container, shrinkage is large, heat resistance is inferior, and strength is reduced. Furthermore, during solid phase polymerization performed to reduce the amount of oligomers contained in the resin, sticking due to softening of the resin is likely to occur, and production becomes difficult.

The polyester resin may contain a bifunctional compound unit other than a terephthalic acid unit and an ethylene glycol unit, if necessary, as long as the processability, strength, heat resistance and the like are not significantly impaired. The ratio (mol%) is preferably 30 mol% or less, more preferably 20 mol% or less, and more preferably 10 mol% or less, based on the total mol number of all the structural units constituting the polyester. More preferably, there is.

Preferred bifunctional compound units which can be contained are at least one unit selected from dicarboxylic acid units, diol units and hydroxycarboxylic acid units.
Species of bifunctional compound units. These may be any of aliphatic bifunctional compound units, alicyclic bifunctional compound units, and aromatic bifunctional compound units.

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

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

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

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

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

In particular, isophthalic acid has the advantage that, when the obtained copolymerized polyester is used, the production conditions under which good products can be obtained are wide, and as a result, the reject rate is low. Further, it is preferable from the viewpoint that whitening of a molded article due to suppression of the crystallization rate can be prevented.

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

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

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

When a polycondensation catalyst is used in the production of the polyester resin, those usually used in the production of polyester can be used. For example, antimony compounds such as antimony trioxide; germanium dioxide, germanium tetraethoxy And titanium compounds such as germanium tetra-n-butoxide; titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium; di-n-butyltin dilaurate and di-n-butyl Examples thereof include tin compounds such as tin oxide and dibutyltin diacetate. These catalyst compounds may be used alone or in combination of two or more. Among these polymerization catalysts, a germanium compound is preferable from the viewpoint that the obtained polyester has good color tone, and an antimony compound is preferable from the viewpoint of catalyst cost. As the germanium compound, germanium dioxide is particularly preferable, and as the antimony compound, antimony trioxide is particularly preferable. The polycondensation catalyst is used in an amount of 0.002 to 100 parts by weight of dicarboxylic acid.
It is preferable to add 0.8 parts by weight.

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

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

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

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

The method for manufacturing such a container is not particularly limited, but it is preferable to use a co-injection blow molding method from the viewpoint of productivity and the like. In the co-injection blow molding method, a container precursor (parison) having a multilayer structure is usually subjected to a single mold clamping operation in a single mold using a molding machine having two injection cylinders, and the molten polyester resin (parison) is melted. PES) and the oxygen-absorbing resin composition of the present invention can be obtained by alternately injecting from the respective injection cylinders at different timings, simultaneously injecting them from concentric nozzles, or by using both of them in combination. For example, (1) PES for the inner and outer layers is first injected, and then the resin composition to be the intermediate layer is injected simultaneously with the inner and outer layers to obtain PES / resin composition /
A method for producing a three-layer container of PES; or (2) first injecting PES for the inner and outer layers, then injecting the resin composition simultaneously with the inner and outer layers, and simultaneously or subsequently, PES to be the central layer At the same time as the above layers, and P
A method of making a container having a five-layer structure of ES / resin composition / PES / resin composition / PES;
A bottomed parison completely encapsulated in the S layer is obtained. These methods are general methods for producing a bottomed parison,
There is no particular limitation on equipment. In the above-described layer structure, an adhesive resin layer may be provided between the PES layer and the resin composition layer, if necessary.

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

In the above-mentioned molding, the thermoplastic resin composition of the present invention is preferably injected in a temperature range of 170 to 250 ° C., more preferably in a temperature range of 180 to 240 ° C. It is more preferred to inject within the temperature range of ~ 230 ° C.

When the injection temperature of the resin composition is lower than 170 ° C., the resin composition pellets are not sufficiently melted, so that an unmelted substance (fish eye) is mixed into the molded product, resulting in poor appearance. Further, in extreme cases, the screw torque increases and causes a failure of the molding machine. On the other hand, when the injection temperature of the resin composition exceeds 250 ° C., oxidation of the diene polymer (B1) in the multilayer polymer particles (B) proceeds. As a result, the oxygen absorbing ability of the resin composition decreases,
It is easy to cause a decrease in oxygen absorption. At the same time, the appearance of the molded article may be poor due to coloring or gelling, or the fluidity may be non-uniform or impaired due to decomposed gas or gelling, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to generation of a gel. In order to suppress the progress of oxidation during melting,
It is also preferred to seal the feed hopper with nitrogen.

The resin composition may be supplied to a molding machine in the form of pellets in which the thermoplastic resin (A), the multilayer polymer particles (B) and, if necessary, the transition metal salt (C) are melt-blended. Alternatively, the dry-blended material may be supplied to a molding machine.

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

If the temperature of the hot runner portion is lower than 220 ° C., crystallization of PES proceeds, and the PES solidifies in the hot runner portion, making molding difficult. on the other hand,
When the temperature of the hot runner portion exceeds 300 ° C., oxidation of the multilayer polymer particles (B) proceeds, and the oxygen absorbing ability of the resin composition is reduced, which tends to cause a decrease in the oxygen absorbing property. At the same time, the appearance of the molded article may be poor due to coloring or gelling, or the fluidity may be non-uniform due to the decomposition gas or gelling, or the fluidity may be impaired, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gel.

In order to obtain good resistance to delamination (resistance to delamination) and transparency of a multilayer container obtained by stretch-blowing the bottomed parison, the PES of the parison and the thermoplastic resin should be used during the injection molding. It is important to suppress crystallization of (A) as much as possible. Thereby, uniform stretchability can be obtained, and a molded article excellent in delamination resistance, transparency, and shape can be obtained. In order to suppress the crystallization of the parison PES and the thermoplastic resin (A), the mold temperature is preferably set in the range of 0 ° C to 70 ° C, and preferably 5 ° C to 50 ° C.
C. More preferably, it is in the range of 10 ° C., and even more preferably in the range of 10 to 30 ° C. If the mold temperature is less than 0 ° C., the appearance of the parison is impaired by the condensation of the mold,
Good molded products cannot be obtained. On the other hand, when the mold temperature exceeds 70 ° C., the crystallization of the PES of the parison and the thermoplastic resin (A) proceeds, so that uniform stretchability cannot be obtained, and the delamination resistance of a molded product obtained by stretch blow molding. In addition, it becomes difficult to obtain a molded article shaped into an intended shape. Furthermore, crystallization of PES impairs transparency.

As for the thickness of the parison, the total thickness is 2 to 2.
5 mm, thermoplastic resin composition layer is 10 to 500 μm in total
m is preferred.

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

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

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

In this manner, a multilayer container comprising a layer made of the thermoplastic resin composition of the present invention and a thermoplastic polyester layer is obtained. This container can be manufactured to have good transparency and gas barrier properties,
And it is extremely excellent in oxygen absorption. Therefore, it is useful for packaging of contents that are easily degraded due to the presence of oxygen, for example, foods, pharmaceuticals, and the like. In particular, it is extremely useful as a container for beverages such as beer. Further, a container made of a multilayer film having a total thickness of 300 μm or less or a multilayer container laminated with a thermoplastic polyester layer is prepared as a container having gas barrier properties and oxygen absorbing properties and having excellent transparency. It is possible to use the resin composition of the present invention.

[0167]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited thereto. In this example, analysis and evaluation were performed as follows.

(1) Polyvinyl alcohol resin (A
Ethylene content and degree of saponification of 1): The ethylene content and degree of saponification of the polyvinyl alcohol-based resin (A1) were measured by 1H-NMR (nuclear magnetic resonance) spectrum using deuterated dimethyl sulfoxide as a solvent (Japan). (Measured by "JNM-GX-500" manufactured by Denshi Co., Ltd.).

(2) Carbon of the multilayer polymer particles (B)
Carbon double bond content: The carbon-carbon double bond content of the multilayer polymer particles (B) is determined by 1H-NMR (nuclear magnetic resonance) spectrum ("JNM" manufactured by JEOL Ltd.) measured using heavy chloroform as a solvent. -GX-500 type "). Here, the content of the carbon-carbon double bond is obtained by calculating the number of moles (eq / g) of the double bond contained in 1 g of the multilayer structure polymer particle (B).

(3) Content of each structural unit in polyester: The content of each structural unit in polyester is as follows:
It was calculated from the 1H-NMR (nuclear magnetic resonance) spectrum of the polyester measured using deuterated trifluoroacetic acid as a solvent (measured by "JNM-GX-500" manufactured by JEOL Ltd.).

(4) Polyvinyl alcohol-based resin (A
Phosphate radical content in 1): phosphate radical content was obtained as a phosphate ion (PO 4 ^_3-) content in accordance with the following method. 10 g of a dried polyvinyl alcohol-based resin (A1) as a sample was charged into 50 ml of a 0.01 N hydrochloric acid aqueous solution, and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to obtain a phosphate ion content. The column is CIS manufactured by Yokogawa Electric Corporation.
-A23 was used, and the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium bicarbonate. In the determination, a calibration curve prepared with a phosphoric acid aqueous solution was used.

(5) Polyvinyl alcohol resin (A
Content of Na, K, and Mg ions in 1): 10 g of a dry chip to be used as a sample is 50 m of a 0.01 N hydrochloric acid aqueous solution
and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring is quantitatively analyzed using ion chromatography,
The amounts of a ion, K ion and Mg ion were quantified.
The chromatography column is manufactured by Yokogawa Electric Corporation.
The eluent was an aqueous solution containing 5.0 mM tartaric acid and 1.0 mM 2,6-pyridinedicarboxylic acid using CS-C25. In the determination, a calibration curve prepared with an aqueous solution of sodium chloride, potassium chloride and magnesium chloride was used. From the amounts of the Na ions, K ions and Mg ions thus obtained, the amounts of the alkali metal salt and the alkaline earth metal salt in the dry chip were obtained in terms of the metal element.

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

(7) Glass transition temperature and melting point of polyester: A sample film layer (sample) was cut from the polyester layer of the body of the multilayer container, and was subjected to differential thermal analysis (DSC) according to JIS K7121 as follows. A measurement was made. Using a differential scanning calorimeter (DSC) RDC220 / SSC5200H type manufactured by Seiko Electronic Industry Co., Ltd.
After keeping the sample at a temperature of 280 ° C. for 5 minutes,
After the temperature was raised to 30 ° C. under the condition of 00 ° C./min, and the temperature was further maintained for 5 minutes, the measurement was performed at the rate of temperature increase of 10 ° C./min. However, indium and lead were used for temperature calibration. Further, the glass transition point in the present invention refers to the midpoint glass transition temperature (Tmg) in the JIS, and the melting point in the present invention refers to the melting peak temperature (Tpm) in the JIS.

(8) Melt flow rate: Measured using a melt indexer L244 (manufactured by Takara Kogyo Co., Ltd.). Specifically, a resin chip to be measured was placed with an inner diameter of 9.5.
5 mm, filled into a 162 mm long cylinder, 210
C. and then weigh 2160 with respect to the molten resin.
g, a uniform load was applied by a plunger having a diameter of 9.48 mm, and the resin was extruded from an orifice having a diameter of 2.1 mm provided at the center of the cylinder.
Was measured, and this was defined as a melt flow rate.

(9) Refractive index of resin: thermoplastic resin (A)
Alternatively, the multilayer polymer particles (B) were press-molded to obtain a non-stretched film having a thickness of 20 μm. Using the obtained film, an Abbe refractometer (4T type manufactured by Atago Co., Ltd.,
The refractive index was measured using a SL-Na-1 lamp manufactured by Toshiba Corporation.

(10) Haze value (cloudiness value): The multilayer structure polymer particles (B) or the resin composition was press-molded to a thickness of 2
A 0 μm unstretched film was obtained. Using the obtained film, according to ASTM D1003-61, the internal haze value was measured using a Poick integrating sphere type light transmittance / total light reflectance meter (“HR-100” manufactured by Murakami Color Research Laboratory). It was measured. In addition, a multilayer film was measured in the same manner.

Further, with respect to the multilayer bottle, the internal haze value was measured at each of the four locations obtained by dividing the center of the bottle body into four on the circumference, and the average value was taken to determine the haze value (cloudiness value) of the bottle. did.

(11) Oxygen absorption rate of resin composition: A film was extruded using the resin composition, and the thickness was 20 μm.
Was obtained. Obtained single layer film 0.9m
² (0.2 mx 4.5 m; surface area 1.8 m ² ) was wound into a roll 5 hours after the film formation, and the temperature was 20 ° C, 65%
The flask was placed in a 375 ml Erlenmeyer flask filled with RH air. The air in the Erlenmeyer flask contains oxygen and nitrogen in a ratio of 21:79 (volume ratio). The mouth of the Erlenmeyer flask was sealed with a multilayer sheet containing an aluminum layer using an epoxy resin, and then left at 20 ° C. Enclosure 4
After 8 hours, 96 hours, and 192 hours, the air inside was sampled with a syringe, and the oxygen concentration of this air was measured using gas chromatography. The pores vacated in the multilayer sheet at the time of measurement were closed each time using an epoxy resin. The measurement was obtained by calculating the amount of decrease in oxygen (oxygen absorption amount) from the volume ratio of oxygen and nitrogen obtained by gas chromatography. The oxygen absorption rate (ml / m ² · day) of the resin composition was calculated by dividing the amount of oxygen reduction in 6 days from 2 days to 8 days by the number of days and the surface area.

(12) Oxygen Permeation Amount of Multilayer Container: The obtained bottle was kept in a nitrogen atmosphere under the nitrogen
0 ° C-65% RH, 20 ° C-100% RH inside the bottle
After adjusting the temperature and humidity, the oxygen permeation amount measurement device (OX-TRAN-10 / 50A manufactured by Modern Control Co., Ltd.)
Oxygen permeation amount per container 10 days after molding (ml /
container / day / atm) was measured.

(Synthesis Example 1) Multilayered polymer particles (B-
Preparation Example of a) 200 parts by weight of distilled water in an autoclave, 4.0 parts by weight of sodium oleate as an emulsifier, 0.267 of Rongalite (formaldehyde sodium sulfoxylate)
Parts by weight, disodium ethylenediaminetetraacetate 0.13
Parts by weight and 0.008 parts by weight of ferrous sulfate heptahydrate were charged, and the temperature was raised to 50 ° C. with stirring while replacing the atmosphere with nitrogen. After 30 minutes, 33.1 parts by weight of styrene and 7.4 parts of butyl acrylate were used as monomers for forming a core layer.
Parts by weight and 29.5 parts by weight of butadiene were added, and stirring was continued for another 30 minutes while maintaining this temperature. Then, at the same temperature, 0.1 part by weight of cumene hydroperoxide was added to start the first polymerization. Four hours later, gas chromatography confirmed that all the monomers had been consumed. Thus, a polymer latex was obtained.

Next, the obtained polymer latex was transferred to a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel under a nitrogen atmosphere, and heated to 70 ° C. Further, after adding 0.1 part by weight of potassium peroxodisulphide, methyl methacrylate as a monomer for forming the outermost layer is added.
A mixture of 5 parts by weight and 1.5 parts by weight of methyl acrylate was dropped from the dropping funnel over 2 hours. After dropping,
The reaction was continued with stirring at 70 ° C. for another 30 minutes, and the second polymerization was terminated after confirming that all the monomers had been consumed by gas chromatography. The particles (multilayer polymer particles (B
-A) The particle diameter of the laser particle size analysis system PAR
It was measured by a dynamic light scattering method using -III (Otsuka Electronics Co., Ltd.). As a result, the particle diameter of the particles (Ba) was 0.1
It was 5 μm.

The obtained latex was cooled to −20 ° C. for 24 hours to aggregate the particles.
The resultant was washed three times with hot water at 50 ° C., and further dried under reduced pressure at 50 ° C. for 2 days to obtain multilayer polymer particles (Ba). The obtained multilayer polymer particles (Ba) had, as a core layer, an oxygen absorbing layer composed of 47.3% by weight of styrene, 10.5% by weight of butyl acrylate, and 42.2% by weight of butadiene. The particles had a core-shell type two-layer structure having a hard layer composed of 95% by weight of methyl acrylate and 5% by weight of methyl acrylate as the outermost layer. The content of butadiene (contained as a copolymer component in the diene-based polymer) in the multilayer polymer particles (B) was 29.5% by weight of the whole particles (B).

The obtained multilayer polymer particles (Ba) were subjected to press molding at a mold temperature of 210 ° C. to give a thickness of 20 μm.
Was obtained. When the refractive index and the haze value (cloudiness value) of the obtained film were measured, each was 1.5.
31 and 0.9%. The content of the carbon-carbon double bond in the obtained multilayer polymer particles (Ba) was 0.005 eq / g.

Example 1 As a polyvinyl alcohol resin (A1), an ethylene content of 32 mol%, a saponification degree of 99.5%, and a melt flow rate (210 ° C.-2160)
(g load) EVOH was prepared at 8.4 g / 10 min. The E
When the phosphate group content and the Na, K, and Mg ion contents of VOH were measured, they were 100 ppm and 20 pp, respectively.
m, 60 ppm and 20 ppm. In addition, the EVO
The measured refractive index of H was 1.533.

95 parts by weight of the EVOH, 5 parts by weight of the multilayer polymer particles (Ba) prepared according to Synthesis Example 1, and cobalt stearate (I) as the transition metal salt (C)
I) 0.2121 parts by weight (0.02 as a cobalt atom)
00 parts by weight), and a 30 mmφ twin screw extruder (Nippon Steel Works TEX-30SS-30CRW-).
2V) at 210 ° C. and a screw rotation speed of 300 rpm
m, and extruded under the conditions of an extruded resin amount of 25 kg / hour and pelletized. This was dried under reduced pressure at 30 ° C. for 16 hours to obtain resin composition pellets. The resin composition has a melt flow rate (210 ° C.-2160 g load) of 9.5 g / 1.
It was 0 minutes. Observation of the fracture surface of the pellet by an electron microscope revealed that the multilayer polymer particles (Ba) were dispersed in a matrix composed of EVOH in a particle shape of about 1 μm.

Using the above resin composition pellets, press molding was performed at a mold temperature of 210 ° C. to form a film having a thickness of 20 μm. The internal haze and oxygen absorption of the obtained single-layer film were measured.

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

Thermoplastic polyester resin: Prepared using germanium dioxide as a polymerization catalyst. When the content of each structural unit of the polyester resin was determined by NMR measurement, the content of the terephthalic acid unit, ethylene glycol unit, and diethylene glycol unit in the polyester resin was 50.0 mol% and 48.9, respectively.
Mol%, 1.1 mol%. The intrinsic viscosity, melting point, and glass transition temperature are 0.83 dl / g, 252 ° C., 8
It was 0 ° C.

In the production of multilayer bottles, Nissei ASB
Co-Injection Stretch Blow Molding Machine (ASB-50HT Model 750)
ml, 2 pieces), and the PES side injection machine temperature 290
° C, resin composition side injection machine temperature 220 ° C, hot runner block part 260 ° C where PES and resin composition merge,
Injection mold core temperature 15 ° C, injection mold cavity temperature 1
Co-injection molding at 5 ° C, PES / resin composition / PES
Was formed in two and three layers.

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

The haze of the body of the obtained bottle and the oxygen permeation amount of the bottle were measured.

The results of the above test are shown in Table 1. Table 1 also shows the results of Examples 2 to 4 and Comparative Example 1 described below.

(Example 2) Cobalt (II) stearate
Of 0.1060 parts by weight (as cobalt atom 0.0
100 parts by weight), except that it was changed to 100 parts by weight.

(Example 3) The same as Example 1 except that the amount of EVOH was changed to 90 parts by weight and the amount of the multilayer polymer particles was changed to 10 parts by weight.

Example 4 In this example, the ethylene content was 44 mol%, the saponification degree was 99.5%, and the melt flow rate (210 ° C.-2160 g load) was 13.0 g / 1.
0 min, phosphate content 75 ppm, Na ion content 7
EVOH having 5 ppm, a K ion content of 30 ppm, a Mg ion content of 20 ppm, and a refractive index of 1.528 was used. Except that 95 parts by weight of this EVOH, 5 parts by weight of the same multilayer polymer particles as used in Example 1, and 0.2121 parts by weight of cobalt (II) stearate (0.0200 parts by weight as a cobalt atom) were used. Is Example 1
A composition and a bottle were manufactured and evaluated in the same manner as described above.

Comparative Example 1 The same E as used in Example 1 was used.
Using a VOH resin alone, press molding was performed at a mold temperature of 210 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of the obtained single-layer film was measured,
0.7%. When the oxygen absorption rate of this EVOH film was measured in the same manner as the oxygen absorption rate of the resin composition in the example, it was 0.000 ml / m ² · day.

Next, this EVOH resin and Example 1
Using the same thermoplastic polyester resin as in Example 1, co-injection blow molding was performed in the same manner as in Example 1, and two types and three layers of multi-layer co-injection blow molding in which the average thickness at the trunk portion was 200 μm for the inner layer PES, 20 μm for the intermediate layer EVOH, and 70 μm for the outer layer PES. Got a bottle.

The haze of the body of the bottle and the oxygen permeation amount of the bottle were measured using the obtained bottle, and found to be 2.4% and 0.02 cc / container, respectively.
r.day.atm.

[0200]

[Table 1]

(Synthesis Example 2) Multilayered polymer particles (B-
Preparation Example of b) 16 parts by weight of styrene, 13.5 parts by weight of butyl acrylate, and 40.5 parts by weight of butadiene as monomers for forming the core layer, and as monomers for forming the outermost layer 10 parts by weight of styrene, methyl methacrylate 19
The same procedure as in Synthesis Example 1 was performed to obtain a multilayer polymer particle (multilayer polymer particle (Bb)) using 1 part by weight of methyl acrylate and 1 part by weight of methyl acrylate. The particle size of the particles is 0.13μ
m.

The obtained multilayer polymer particles (Bb)
Is 22.9% by weight of styrene and 19.
It has a core layer (oxygen absorbing layer) composed of 2% by weight and 57.9% by weight of butadiene, and a core layer composed of 33.3% by weight of styrene, 63.4% by weight of methyl methacrylate and 3.3% by weight of methyl acrylate. The particles had a core-shell type two-layer structure having an outer layer (hard layer). The content of butadiene (contained as a copolymer component in the diene-based polymer) in the multilayer polymer particles (Bb) is determined by the particle (B-b).
b) 40.5% by weight of the whole.

The obtained multilayer polymer particles (Bb) were subjected to press molding at a mold temperature of 210 ° C. to give a thickness of 20 μm.
Was obtained. When the refractive index and the haze value (cloudiness value) of the obtained film were measured, each was 1.5.
25 and 0.8%. Further, the content of the carbon-carbon double bond in the obtained multilayer polymer particles (Bb) was 0.007 eq / g.

(Synthesis Example 3) Multilayer structured polymer particles (B-
Production example of c) Styrene 54.1 as a monomer for forming the core layer
Parts by weight and 24.7 parts by weight of butadiene, and 16.2 parts by weight of styrene, 4.7 parts by weight of methyl methacrylate and 0.3 parts by weight of methyl acrylate as monomers for forming the outermost layer. In the same manner as in Example 1, multilayer polymer particles (multilayer polymer particles (Bc)) were obtained. The particle size of the particles was 0.11 μm.

The obtained multilayer polymer particles (Bc)
Is 68.7% by weight of styrene and 31.3 of butadiene.
Core shell having a core layer (oxygen absorbing layer) consisting of 76.4% by weight of styrene, 22.2% by weight of methyl methacrylate, and 1.4% by weight of methyl acrylate (hard layer). The particles had a two-layer structure.
The content of butadiene (contained as a copolymer component in the diene polymer) in the multilayer polymer particles (Bc) was 24.7% by weight of the whole particles (Bc). Was.

The obtained multilayer polymer particles (Bc) were subjected to press molding at a mold temperature of 210 ° C. to give a thickness of 20 μm.
Was obtained. When the refractive index and the haze value (cloudiness value) of the obtained film were measured, each was 1.5.
70 and 0.9%. Moreover, the content of the carbon-carbon double bond in the obtained multilayer polymer particles (Bc) was 0.0045 eq / g.

Example 5 In this example, nylon 6 (Ube Industries, 1024f) was used as the polyamide resin.
dx41, IV value = 3.68). The measured refractive index of this nylon 6 was 1.525.

95 parts by weight of the nylon 6, 5 parts by weight of the multilayer polymer particles (Bb) prepared according to Synthesis Example 2, and 0.2121 parts by weight of cobalt (II) stearate as the transition metal salt (C) ( 0.1 as a cobalt atom.
0200 parts by weight) and a 30 mmφ twin screw extruder (TEX-30SS-30CR, Japan Steel Works, Ltd.)
W-2V) at 240 ° C. and a screw rotation speed of 300
The mixture was extruded and pelletized under the conditions of rpm and an extruded resin amount of 25 kg / hour. This was dried at 80 ° C. under reduced pressure for 10 hours to obtain a resin composition pellet. Observation of the fracture surface of the pellet with an electron microscope revealed that the multilayer structure polymer particles (Bb) were dispersed in a matrix composed of nylon 6 in a particle shape of about 1 μm.

Using the above resin composition pellets, film extrusion was performed at an extrusion temperature of 240 ° C.
A μm monolayer film was prepared. The internal haze of the obtained film was measured. Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

The results of the above test are shown in Table 2. Table 2 also shows the results of Examples 6 and 7 and Comparative Examples 2 to 4 described below.

Example 6 In this example, polyethylene terephthalate (Kuraray, KS750RC, IV value = 0.74) was used as the polyester resin.
The measured refractive index of the polyethylene terephthalate was 1.575.

95 parts by weight of the above polyethylene terephthalate, 5 parts by weight of multilayer polymer particles (Bc) prepared according to Synthesis Example 3, and 0.2121 parts by weight of cobalt (II) stearate as a transition metal salt (0% by weight of cobalt atom) 0.0200 parts by weight) and dry-blended
mφ twin screw extruder (Nippon Steel Works TEX-30SS-)
Using 30 CRW-2V), the mixture was extruded at 270 ° C. under the conditions of a screw rotation speed of 300 rpm and an extruded resin amount of 25 kg / hour, and pelletized. This was dried at 80 ° C. under reduced pressure for 10 hours to obtain a resin composition pellet. Observation of the fracture surface of the pellet with an electron microscope revealed that the multilayer structure polymer particles (Bc) were dispersed in a matrix of polyethylene terephthalate in a particle shape of about 1 μm.

Next, using the resin composition pellets, a film was extruded at an extrusion temperature of 270 ° C. to obtain a film having a thickness of 20 μm. The internal haze of the obtained single-layer film was measured. Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

(Comparative Example 2) The same nylon 6 used in Example 5 was used alone, and extrusion molding was performed at an extrusion temperature of 240 ° C to obtain a single-layer film having a thickness of 20 µm. At this time, the internal haze of the obtained film was measured. Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

(Comparative Example 3) The same polyethylene terephthalate as used in Example 6 was used singly and at an extrusion temperature of 27.
Extrusion was performed at 0 ° C. to obtain a single-layer film having a thickness of 20 μm. The internal haze of the obtained film was measured.
Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

(Synthesis Example 4) Multilayer structured polymer particles (B-
Production Example of d) 16 parts by weight of styrene, 13.5 parts by weight of butyl acrylate, and 40.5 parts by weight of butadiene as monomers for forming the core layer, and as monomers for forming the outermost layer 10 parts by weight of styrene, methyl methacrylate 1
Using 8.9 parts by weight, 1 part by weight of methyl acrylate and 0.1 part by weight of octyl mercaptan, multilayer polymer particles (multilayer polymer particles (B-
d)) was obtained. The particle size of the particles was 0.12 μm.

The obtained multilayer polymer particles (Bd)
Is 22.9% by weight of styrene and 19.
It has a core layer (oxygen absorbing layer) composed of 2% by weight and 57.9% by weight of butadiene, 33.4% by weight of styrene, 63.0% by weight of methyl methacrylate, 3.3% by weight of methyl acrylate and 3.3% by weight of octyl mercaptan 0.3% by weight
Having a core-shell type two-layer structure having an outermost layer (hard layer) composed of The content of butadiene (contained as a copolymer component in the diene polymer) in the multilayer polymer particles (Bd) was 40.40% of the total number of the particles (Bd).
It was 5% by weight.

The obtained multilayer polymer particles (Bd) were subjected to press molding at a mold temperature of 210 ° C. to give a thickness of 20 μm.
Was obtained. When the refractive index and the haze value (cloudiness value) of the obtained film were measured, each was 1.5.
25 and 0.5%. Further, the content of carbon-carbon double bonds in the obtained multilayer polymer particles (Bd) was 0.007 eq / g.

(Example 7) 100 parts by weight of the multilayer polymer particles (Bd) prepared according to Synthesis Example 4 and 0.2121 parts by weight of cobalt (II) stearate (0.0200 parts by weight as a cobalt atom) were added. Dry blend, 3
0mmΦ twin screw extruder (Nippon Steel Works TEX-30S)
Using S-30CRW-2V), pellets were extruded at 220 ° C. under the conditions of a screw rotation speed of 300 rpm and an extruded resin amount of 25 kg / hour. This was dried at 80 ° C. under reduced pressure for 10 hours to obtain a resin composition pellet.

The above resin composition pellets were used at an extrusion temperature of 2
Film extrusion was performed at 20 ° C. to prepare a single-layer film. The internal haze of this film was measured. Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

(Comparative Example 4) The multilayer polymer particles (Bd) prepared according to Synthesis Example 4 were used alone at an extrusion temperature of 2
The film was extruded at 20 ° C. to obtain a single-layer film having a thickness of 20 μm. The internal haze of the obtained film was measured. Further, the oxygen absorption amount of the film was measured, and the oxygen absorption rate was calculated.

[0222]

[Table 2]

[0223]

As described above, according to the present invention, there is provided a thermoplastic resin composition having an excellent oxygen absorption function, which can be used in many fields including packaging materials for beverages, foods, pharmaceuticals, cosmetics, and the like. Is done. By selecting a gas barrier resin as the thermoplastic resin contained in the composition, a resin composition having excellent gas barrier properties, particularly excellent oxygen gas barrier properties, in addition to the excellent oxygen absorption function described above, can be obtained. Further, by selecting an appropriate resin, a resin composition having good transparency is provided. A multilayer structure using the above composition, for example, a multilayer film or a multilayer container, is useful for packaging contents that are susceptible to deterioration due to the presence of oxygen, for example, foods, pharmaceuticals, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 23/26 C08L 29/04 C 29/04 47/00 47/00 67/00 67/00 77/00 77/00 B65D 1/00 B (72) Inventor Hiroyuki 1621 Sazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Toshiaki Sato 1621 Sakurazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (72) Invention Takashi Yamashita 41 Miyukigaoka, Tsukuba, Ibaraki Prefecture Kuraray Co., Ltd. (72) Inventor Yoshiki Mukao 41 Miyukigaoka, Tsukuba, Ibaraki Prefecture Kuraray Co., Ltd.

Claims (16)

[Claims] 1. A thermoplastic resin composition containing a thermoplastic resin (A), multilayer polymer particles (B), and a transition metal salt (C), wherein the multilayer polymer particles (B) contain oxygen. It has at least one absorption layer, the oxygen absorption layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component, and the transition metal salt (C) is converted to a metal element. A thermoplastic resin composition containing 1 to 5000 ppm. 2. A thermoplastic resin composition comprising a thermoplastic resin (A) and multilayer polymer particles (B),
The multilayer polymer particles (B) have at least one oxygen absorbing layer, the oxygen absorbing layer contains a diene polymer (B1) containing a conjugated diene monomer as a polymerization component, and The composition has an oxygen absorption rate of 0.01 ml / m ²
-A thermoplastic resin composition having a value of day or more. 3. The method according to claim 1, wherein the thermoplastic resin (A) is 10 to 99.
3. The resin composition according to claim 1, wherein the resin composition contains 9% by weight and the multilayer polymer particles (B) in a ratio of 0.1 to 90% by weight. 4. 4. The thermoplastic resin (A) is a polyvinyl alcohol resin (A1) or a polyamide resin (A).
The resin composition according to any one of claims 1 to 3, wherein the resin composition is at least one selected from the group consisting of 2) and a polyester resin (A3). 5. The diene polymer (B1) is a polymer containing only a conjugated diene monomer as a polymerization component, and a conjugated diene monomer and another copolymerizable vinyl monomer. Is a polymer having at least one polymer as a polymerization component,
The resin composition according to claim 1. 6. The method according to claim 1, wherein the transition metal salt (C) is at least one selected from an iron salt, a nickel salt, a copper salt, a manganese salt, and a cobalt salt. The resin composition as described in the above. 7. The thermoplastic resin (A) is a polyvinyl alcohol resin (A1), and the polyvinyl alcohol resin (A1) has an ethylene content of 3 to 60 mol% and a saponification degree of 90% or more. The resin composition according to any one of claims 1 to 6, which is an ethylene-vinyl alcohol copolymer. 8. The polymer constituting the multilayer polymer particles (B) has a carbon-carbon double bond of 0.0001 eq /
The resin composition according to any one of claims 1 to 7, which is contained in a proportion of at least g. 9. The resin composition according to claim 1, wherein a difference in refractive index between the thermoplastic resin (A) and the multilayer polymer particles (B) is 0.01 or less. 10. The resin composition according to claim 1, wherein the multilayer polymer particles (B) are dispersed in a matrix of the thermoplastic resin (A). 11. A thermoplastic resin composition containing multilayer polymer particles (B) and a transition metal salt (C), wherein said multilayer polymer particles (B) have at least two thermoplastic resin layers. One of the two layers is an oxygen absorbing layer made of a resin containing a diene polymer (B1) containing a conjugated diene monomer as a polymerization component; In the coalescence (B1), the conjugated diene-based monomer is contained as a copolymer component in an amount of 10 mol% or more based on the total amount of the resin constituting the oxygen absorbing layer. However, the layer does not substantially contain the diene polymer (B1), the layer forms the outermost layer of the multilayer polymer particles (B), and the transition metal salt (C) is 1 to 1 in terms of a metal element. 5000pp
m. A thermoplastic resin composition contained at a ratio of m. 12. A multilayer structure comprising a layer made of the thermoplastic resin composition according to any one of claims 1 to 11. 13. A multilayer container comprising a layer comprising the resin composition according to claim 1. 14. A multilayer film comprising a layer made of the resin composition according to claim 1 and having a total layer thickness of 300 μm or less. 15. A multilayer container formed by molding the multilayer film according to claim 14. 16. A multilayer container having a layer made of the resin composition according to any one of claims 1 to 11 and a layer made of thermoplastic polyester.