JP2002069319A - Resin composition having gas barrier property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier resin composition excellent in gas barrier properties, especially the barrier properties against oxygen gas, having an oxygen-absorbing function, and further having good low-smelling properties, and to provide a molded article such as a packaging material and container, excellent in the gas barrier properties, transparency, and oxygen-absorbing properties, and useful for packaging products which are easily deteriorated by oxygen, such as foods medicaments and cosmetics. SOLUTION: This resin gas barrier composition comprises (A) a gas barrier resin having an oxygen permeability rate of <=500 ml.20 μm/m2.day.atm (20 deg.C, 65%RH), (B) a thermoplastic resin having carbon-carbon double bonds, (C) a transition metal salt, and (D) a deodorant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a gas barrier property, a moisture proof property, and a fragrance retention property which are used for products which are sensitive to oxygen and are easily deteriorated, especially for packaging materials and containers for foods, beverages, pharmaceuticals, cosmetics and the like. The present invention relates to a resin composition having excellent flavor barrier properties and low odor, and further having an oxygen absorbing ability. Further, the present invention relates to a molded article using such a composition, which is excellent in appearance, particularly transparency, such as a packaging material, a container, and the like for foods, beverages, pharmaceuticals, cosmetics, and the like.

[0002]

2. Description of the Related Art Gas barrier resins such as ethylene-
Resins such as vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH), polyamide, polyvinyl chloride, and polyacrylonitrile can be melt-molded and have excellent oxygen or carbon dioxide gas barrier properties. Widely used for sheets, bottles, containers and the like. Multilayer plastic packaging materials laminated with layers of thermoplastic resins with excellent moisture resistance and mechanical properties, especially polyolefin resins, are used as containers with excellent oxygen barrier properties in the form of bags, bottles, cups, pouches, etc. It is widely used in various fields such as cosmetics, medicinal chemicals, toiletries and the like.

[0003] Packaging materials using such gas barrier resins are excellent in barrier properties against oxygen and carbon dioxide gas, but are not suitable for metal materials used for canning and the like and glass used for bottles and the like. As described above, the permeability to gas such as oxygen is not always close to zero, and the gas permeates a non-negligible amount of gas. In particular, in packaging materials for food applications, there is a concern that the quality may deteriorate due to oxidation of the contents when stored for a long period of time. Further, when packaging contents that are easily oxidized, it is also desired to prevent deterioration of the contents by scavenging oxygen mixed into the packaging container together with the contents when the contents are packed or filled. Therefore, it has been proposed to mix an oxygen scavenger with a gas barrier resin to give the gas barrier resin an oxygen scavenging function.

[0004] As a method for imparting an oxygen absorbing function (scavenging function) to a gas barrier resin, the following method has been proposed: EVOH is oxidized by adding an oxidation catalyst such as a transition metal to EVOH. A method of causing oxygen to be permeated to react with the EVOH, thereby imparting an oxygen absorbing function to the EVOH (Japanese Patent Laid-Open Publication No.
No. 211444); By adding an oxidation catalyst such as a transition metal to polyvinyl chloride, the polyvinyl chloride is easily oxidized, and the oxygen to be permeated is reacted with the polyvinyl chloride. A method of imparting an oxygen-absorbing function to a product (JP-A-4-45144);
EVO using a resin composition comprising a polyolefin and an oxidation catalyst
A method of obtaining a resin composition having an oxygen absorbing function by dispersing in oxygen H and reacting oxygen to be permeated with polyolefin in EVOH (Japanese Patent Laid-Open No. 05-15)
No. 6095); and a method of obtaining a resin composition having an oxygen absorbing function by blending EVOH, a polyolefin and an oxidation catalyst, and reacting oxygen to be permeated with the polyolefin and EVOH (Japanese Patent Application Laid-Open No. 05-2005).
170980).

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

[0006]

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

[0007]

Means for Solving the Problems The first gas barrier resin composition of the present invention has an oxygen permeation rate of 500 ml · 20 μm.
gas barrier resin (A) having m / m ² · day · atm (20 ° C., 65% RH) or less, thermoplastic resin (B) having a carbon-carbon double bond, transition metal salt (C) and deodorant ( D).

[0008] In a preferred embodiment, the composition has an oxygen absorption rate of 0.01 ml / m ² · day or more.

Further, the second gas barrier resin composition of the present invention has an oxygen transmission rate of 500 ml · 20 μm / m ² ···
It contains a gas-barrier resin (A) of a day.atm (20 ° C., 65% RH) or less, a thermoplastic resin (B) having a carbon-carbon double bond, and a deodorant (D), and has an oxygen absorption rate of 0%. 0.01 ml / m ² · day or more.

[0010] In a preferred embodiment, the thermoplastic resin (B) has a carbon-carbon double bond of 0.0001 eq.
/ G or more.

In a preferred embodiment, the thermoplastic resin (B) is a copolymer of an aromatic vinyl compound and a diene compound.

In a preferred embodiment, the thermoplastic resin (B) has the structural formula (I):

[0013]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and 1 to 10 carbon atoms. alkyl group, a substituted aryl group, an unsubstituted aryl group, -COOR _4, -OCOR _5, a cyano group or a halogen atom,, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl Group, an alkylaryl group, or an alkoxy group], and has a number average molecular weight of 100
The range is from 0 to 500,000.

In a preferred embodiment, the gas barrier resin (A) has a refractive index of 1.50 to 1.56.

In a preferred embodiment, the gas barrier resin (A) is at least one selected from the group consisting of a polyvinyl alcohol-based resin, polyamide, polyvinyl chloride, and polyacrylonitrile.

In a preferred embodiment, the gas barrier resin (A) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.

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. This transition metal salt (C) is contained in the composition in an amount of 1 to 1 in terms of a metal element.
It is contained at a rate of 5000 ppm.

In a preferred embodiment, the deodorant (D)
Has a particle size of 0.5 to 10 μm.

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

In a preferred embodiment, the gas barrier resin (A) contains 60 to 9 in the resin composition of the present invention.
9.8% by weight, the thermoplastic resin (B) is 30 to 0.1%
% By weight, and 10 to 0.1% by weight of a deodorant (D).

In a preferred embodiment, in the resin composition of the present invention, particles made of the thermoplastic resin (B) are dispersed in a matrix of the gas barrier resin (A).

The present invention includes a molded article, a multilayer structure, and a multilayer container comprising the above-mentioned gas barrier resin composition.

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

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

The present invention also includes a cap provided with a gasket comprising the above-mentioned gas barrier resin composition.

[0027]

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

The type of the gas barrier resin (A) contained in the resin composition of the present invention is not particularly limited. Any of resins having good gas barrier properties can be used. Such a resin has an oxygen transmission rate of 50
0ml ・ 20μm / m ²・ day ・ atm (20 ℃ 、 6
5% RH) or less is used. This is 20
When measured in an environment at a temperature of 65 ° C. and a relative humidity of 65%, the volume of oxygen permeating through a film having an area of 1 m ² and a thickness of 20 μm per day is 500 ml or less in the presence of a pressure difference of 1 atm. Means that. Oxygen transmission rate is 500ml
If it exceeds 20 μm / m ² · day · atm, the gas barrier performance will not be sufficiently exhibited. In order to obtain good gas barrier properties, the gas barrier resin (A) preferably has a low oxygen permeation rate. Preferably, 100ml ・ 20μ
m / m ² · day · atm or less, more preferably 20 ml · 20 μm / m ² · day · atm or less, and still more preferably 5 ml · 20 μm / m ² · da.
y · atm or less.

By blending such a gas barrier resin (A) and a thermoplastic resin (B) having a carbon-carbon double bond as described later, the resin (B) can be used in addition to the gas barrier effect of the resin (A). Thereby exhibiting an oxygen scavenging effect, and as a result, a resin composition having extremely high gas barrier properties can be obtained.

The gas barrier resin (A) used in the present invention preferably has a refractive index of 1.50 to 1.56.
When the ratio deviates from this range, the difference between the refractive index of the gas barrier resin (A) and the refractive index of the thermoplastic resin (B) increases, as described later, and the transparency of the obtained resin or resin composition decreases. There is a fear. In general, since the refractive index of the thermoplastic resin (B) having oxygen absorption is often in the above range, the thermoplastic resin (B) and the gas barrier resin (A)
It is easy to reduce the difference in the refractive index of the resin composition, and as a result, a resin composition having good transparency can be obtained.
In the above range, the refractive index of the gas barrier resin (A) is more preferably 1.51 or more, and still more preferably 1.52 or more. Further, it is preferably 1.55 or less in the above range, and more preferably 1.54 or less.

The type of the gas barrier resin (A) is not particularly limited. As described above, the oxygen transmission rate is 500 ml
Examples of the gas barrier resin (A) satisfying the condition of not more than 20 μm / m ² · day · atm and having a refractive index of 1.50 to 1.56 include polyvinyl alcohol resin (A1) and polyamide. Typical resins include (A2), polyvinyl chloride (A3), and polyacrylonitrile (A4), but are not limited to these resins.

Among the gas barrier resins (A), the polyvinyl alcohol resin (A1) is a homopolymer of vinyl ester or a copolymer of vinyl ester and another monomer (particularly, a copolymer of vinyl ester and ethylene). Copolymer)
Is obtained by saponification 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 degree of saponification of the vinyl ester component of the polyvinyl alcohol resin is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more.
% Or more. If the saponification degree is less than 90 mol%, the gas barrier properties under high humidity may be reduced. Further, in the case of an ethylene-vinyl alcohol copolymer (EVOH), the thermal stability is deteriorated, and the resulting molded article is liable to generate gels and bumps.

When the polyvinyl alcohol-based resin is composed of a blend of two or more kinds of polyvinyl alcohol-based resins having different degrees of saponification, the average value calculated from the 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, EVOH is preferred among the above-mentioned gas-barrier resins, since melt-molding is possible and gas barrier properties under high humidity are good.

The ethylene content of EVOH is preferably from 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.

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

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

However, when two types of EVOH are blended, it is 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. Also,
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, nitriles, amides, anhydrides; vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidones.

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

Further, when a boron compound is added to EVOH, the melt viscosity of EVOH is improved, and this is effective in that a homogeneous co-extrusion or co-injection molded product can be obtained. Here, examples of the boron compound include boric acids, borate esters, borates, borohydrides, and the like.
Specifically, as boric acids, orthoboric acid (hereinafter, referred to as
Abbreviated as boric acid), metaboric acid, tetraboric acid and the like, boric acid esters such as triethyl borate and trimethyl borate, and boric acid salts of the above-mentioned various boric acids. Metal salts, alkaline earth metal salts, borax and the like. Of these compounds, orthoboric acid 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.

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

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

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

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

The kind of the polyamide resin (A2) which is the gas barrier resin (A) is not particularly limited. For example, polycaproamide (nylon-6), polyundecaneamide (nylon-11), polylauryl lactam (nylon-12), polyhexamethylene adipamide (nylon-
6,6), polyhexamethylene sebacamide (nylon-
6,12) and other aliphatic polyamide homopolymers; caprolactam / laurolactam copolymer (nylon-6 / 1
2), caprolactam / aminoundecanoic acid copolymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylene adipamide copolymer (nylon-6)
/ 6,6), caprolactam / hexamethylene adipamide / hexamethylene sebacamide copolymer (nylon-6
/ 6,6 / 6,12) and other aliphatic polyamide copolymers;
Aromatic polyamides such as polymethaxylylene adipamide (MX-nylon) and hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (nylon-6T / 6I) can be mentioned. These polyamide resins can be used alone or in combination of two or more.

Among these polyamide resins, polycaproamide (nylon-6) or polyhexamethylene adipamide (nylon-6,6) is preferred from the viewpoint of gas barrier properties.

Examples of the polyvinyl chloride resin (A3) used in the present invention include homopolymers of vinyl chloride or vinylidene chloride, and copolymers with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers and the like.

The polyacrylonitrile resin (A4) used in the present invention includes, in addition to acrylonitrile homopolymers, copolymers with acrylates and the like.

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

In the present invention, a thermoplastic resin (B) having a carbon-carbon double bond is used. Since the thermoplastic resin (B) has a carbon-carbon double bond in its molecule, it can efficiently react with oxygen and obtain an oxygen scavenging function (oxygen absorbing function). The carbon-carbon double bond includes a conjugated double bond but does not include a multiple bond contained in an aromatic ring.

This carbon-carbon double bond is preferably
It is contained in the thermoplastic resin (B) at a rate of 0.0001 eq / g or more. This double bond is more preferably
0.0005 eq / g or more, more preferably 0.00
It is contained at a rate of 1 eq / g or more, most preferably 0.002 eq / g or more. When the content of the carbon-carbon double bond is less than 0.0001 eq / g, the oxygen absorption rate may not be sufficient, and the oxygen scavenging effect of the composition of the present invention may not be sufficiently improved.

The molecular weight of the thermoplastic resin (B) is preferably from 1,000 to 300,000. Further, in consideration of the moldability and workability of the resin composition, the mechanical properties of the molded article obtained therefrom, and the dispersibility of the resin composition in the gas barrier resin (A), etc., more preferably 10,000 to 25,000.
0, most preferably in the range of 40,000 to 200,000.

If the molecular weight of the thermoplastic resin (B) is less than 1,000, the dispersibility in the gas barrier resin (A) is reduced, and the transparency, gas barrier properties and oxygen scavenging performance may be reduced. Even when the molecular weight exceeds 300,000, dispersibility in the gas barrier resin (A) is reduced, and transparency and
The gas barrier property and oxygen scavenging performance may be reduced, and the processability of the resin composition may be deteriorated.

The carbon-carbon double bond of the thermoplastic resin (B) is generally derived from a diene compound, but is not limited thereto. Examples of the diene compound used in the synthesis of the thermoplastic resin (B) used in the present invention include:
Isoprene, butadiene, 2-ethylbutadiene, 2-
Butyl-butadiene and the like. As the diene compound, only one component may be used, or two components may be used simultaneously, and there is no particular limitation.

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

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

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

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

Suitable thermoplastic resins (B) include, for example, resins having at least one unit represented by the following structural formula (I) and having a number average molecular weight in the range of 1,000 to 500,000:

[0066]

Embedded image

[Wherein, R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and 1 to 10 carbon atoms. alkyl group, a substituted aryl group, an unsubstituted aryl group, -COOR _4, -OCOR _5, a cyano group or a halogen atom,, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl Group, an alkylaryl group, or an alkoxy group] In the definition of the structural formula (I), the number of carbon atoms of the aryl group is preferably 6 to 10, and the number of carbon atoms of the alkylaryl group is Preferably it is 7-11, and the number of carbon atoms of an alkoxy group is preferably 1-10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, examples of the aryl group include a phenyl group, examples of the alkylaryl group include a benzyl group, examples of the alkoxy group include a methoxy group and ethoxy group. Examples of the group in which the group is a halogen atom include a chlorine atom.

The structural formula (I) of the thermoplastic resin (B)
Has an alkyl group having 1 to 3 carbon atoms as R ₁ (especially when it has a structural unit obtained by polymerizing isoprene, 2-ethylbutadiene, and 2-butylbutadiene);
The thermoplastic resin (B) is easily oxidized and is preferred as an oxygen-absorbing resin. Among them, a structural unit obtained by polymerizing isoprene as a structural unit represented by the structural formula (I) with the thermoplastic resin (B) (that is, R ₁ in the structural formula (I))
Contains a methyl group and R ₂ and R ₃ are hydrogen atoms), since the double bond (vinyl bond) of this structural unit effectively reacts with oxygen, and especially the thermoplastic resin (B) is oxidized. Easy to absorb and excellent in oxygen absorption. Further, isoprene is easily available and easily polymerizes with other monomers, so that isoprene is also suitable from the viewpoint of the cost of synthesizing the thermoplastic resin (B).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the case where an oxidation catalyst composed of a transition metal salt (C) is added at the time of melt-blending in order to promote oxidation, the thermoplastic resin (B) contains a certain amount of an antioxidant. However, a resin composition having good oxygen absorbing ability can be obtained. In such a case, the content of the antioxidant is preferably 0.01 to 1% by weight, and 0.02% by weight.
~ 0.5 wt% is more preferred. This antioxidant may be added to the thermoplastic resin (B) in advance, as described above, or each component of the resin composition of the present invention is mixed in the same manner as other general additives described below. May be added sometimes.

[0085] The resin composition of the present invention preferably contains a transition metal salt (C). The transition metal salt (C) is preferably 1 to 5000 ppm, preferably 5 to 1000 ppm, more preferably 10 to 500 ppm in terms of a metal element.
pm. Thereby, the oxygen oxidation reaction of the thermoplastic resin (B) can be promoted. For example, the thermoplastic resin (B) can efficiently react with oxygen present inside the packaging material obtained from the composition of the present invention and oxygen which is going to permeate the packaging material. As a result, the oxygen barrier properties and the oxygen scavenging action of the resin composition of the present invention are improved. However, when the content of the transition metal salt (C) exceeds 5,000 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 a gel substance 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,
Vanadium and ruthenium include, but are not limited to. Preferred among these metals are iron, nickel, copper, manganese and cobalt, more preferably manganese and cobalt, and even more preferably cobalt.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Further, as other deodorants, a composition in which a metal compound such as a composition comprising a zinc compound and a polycarboxylic acid is stabilized, a bioenzyme model compound such as an iron (II) -phthalocyanine derivative, a drill, Magnesium silicate clay minerals such as holly, mokusei, tsuwabuki, butterbur, lilac, sapwood, chestnut, alder, etc. Activated humic acid, activated alumina,
Activated carbon can also be used. Also, a porous adsorbent such as a porous microcapsule powder can be used.

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

The particle size of the deodorant (D) used in the present invention is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and still more preferably 1 to 5 μm. Particularly preferably, it is 1 to 4 μm. When the particle diameter of the deodorant (D) exceeds 10 μm, the odor barrier properties and the transparency become insufficient. A method for producing such a deodorant having a small particle size is not particularly limited, but a method in which a commercially available deodorant is subjected to a pulverizing treatment is exemplified as a suitable method. When the deodorant (D) is a porous adsorbent such as a porous microcapsule powder, the adsorbent having the above particle size can be obtained by preparing the adsorbent by a sol-gel method. it can.

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

When the present invention has a multilayer structure such as a multilayer container, the deodorant is contained in the multilayer structure in various forms. As described later, it can be contained in a layer made of the resin composition or a layer other than this layer. In the multilayer structure of the present invention, when an adhesive resin layer is provided between the composition layer and another thermoplastic resin layer, a deodorant can be contained in the adhesive resin layer. The deodorant may be blended in only one of these layers or, if necessary, in two or more layers. The content of the deodorant is 0.1% by weight or more, preferably 0.2 to 50% by weight, more preferably 0.5 to 10% by weight based on the total weight of the layer (such as a resin layer) to be mixed.

The composition of the present invention may contain a thermoplastic resin (E) other than the gas barrier resin (A) and the thermoplastic resin (B) to the extent that the effects of the present invention are not impaired. Examples of the thermoplastic resin (E) include, but are not limited to, the following resins: ethylene homopolymer and ethylene copolymer (copolymer of ethylene and the following monomers: propylene, 1-butene) Α-olefins such as isobutene, 4-methyl-1-pentene, 1-hexene and 1-octene; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride; Esters, their nitriles, their amides, their anhydrides; vinyl carboxylate esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate, and vinyl arachidonate A vinylsilane compound such as vinyltrimethoxysilane; Sulfonic acid or its salts; alkylthiols; vinyl pyrrolidones and the like),
Propylene homopolymers and propylene copolymers (copolymers of propylene and the following monomers: α-olefins such as ethylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; itaconic acid, Unsaturated carboxylic acids such as methacrylic acid, acrylic acid and maleic anhydride, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl Carboxylic acid vinyl esters such as octanoate, vinyl dodecanoate, vinyl stearate and vinyl arachidonate; vinyl silane compounds such as vinyl trimethoxy silane; unsaturated sulfonic acids or salts thereof; alkyl thiols; vinyl pyrrolidones ), Poly 4-me Rupenten -1, polyolefins such as polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyethylene naphthalate; polystyrene, polycarbonate, polyacrylate and the like. The selection of the thermoplastic resin (E) depends on the structure and use of the molded article to be produced. Such selection factors are well known in structure and use,
Thereby, the thermoplastic resin (E) is selected.

When a composition containing the thermoplastic resin (E) is produced, it is preferable to consider the miscibility of the thermoplastic resin (E) with the gas barrier resin (A) and the thermoplastic resin (B). . Due to the miscibility of these resins, gas barrier properties, transparency, cleanliness, effectiveness as an oxygen scavenger,
Mechanical properties, product texture, etc. may be affected.

In the gas barrier resin composition of the present invention, preferably, the content of the gas barrier resin is 60 to 99.9% by weight, the content of the thermoplastic resin (B) is 30 to 0.1% by weight, and the deodorant (D). Is contained in a ratio of 10 to 0.1% by weight. The transition metal salt is 1 to 10000 ppm, preferably 1 ppm.
It is contained at a rate of ５5000 ppm. The preferred range of the content of the thermoplastic resin (B) in the resin composition is from 1 to
20% by weight, and a more preferred range is 2 to 15% by weight. A more preferable range of the content ratio of the gas barrier resin (A) is 80 to 99% by weight, and a more preferable range is 8 to 99% by weight.
5 to 98% by weight. The preferred range of the content of the deodorant (D) is 8 to 0.3% by weight, and the more preferred range is 5 to 0.3% by weight.
To 0.5% by weight.

When the content ratio of the gas barrier resin (A) is 70
When the amount is less than the weight percentage, transparency and gas barrier properties such as oxygen gas or carbon dioxide gas in a molded article such as a multilayer container using the resin composition may be reduced. 9 content
If it exceeds 9.9% by weight, the content of the thermoplastic resin (B) is reduced, so that the oxygen absorption rate is reduced, and the oxygen gas barrier property and the oxygen scavenging property tend to be reduced.

When the amount of the deodorant (D) is less than 0.1% by weight, a sufficient deodorizing function cannot be obtained. Further, when the amount of the deodorant (D) exceeds 10% by weight, the deodorants (D) tend to agglomerate in the gas barrier resin composition, and sufficient transparency may not be obtained. .

In the resin composition of the present invention, the particles composed of the thermoplastic resin (B) are composed of a resin other than the resin (B) (a gas barrier resin (A) and, if necessary, a thermoplastic resin (E)) and It is recommended that the composition be dispersed in a matrix containing various additives described below, if necessary. For example, the resin composition of the present invention comprises a gas barrier resin (A)
In the case of using a thermoplastic resin (B), it is recommended that particles of the thermoplastic resin (B) be dispersed in a matrix of the gas barrier resin (A). Various molded articles made of the composition in such a state have good transparency, gas barrier properties and oxygen scavenging properties. At this time, the dispersed particle diameter of the particles made of the thermoplastic resin (B) is preferably 10 μm or less. When the dispersed particle size exceeds 10 μm, the thermoplastic resin (B) and the thermoplastic resin (B)
In some cases, the area of the interface with other resins becomes smaller, the oxygen gas barrier properties decrease, and the oxygen scavenging performance may decrease. In light of oxygen scavenging properties, gas barrier properties, and transparency of molded articles such as a multilayer container using the resin composition, the dispersed thermoplastic resin (B) particles have an average particle diameter of preferably 5 μm or less, more preferably 2 μm. The following are more preferred.

In the resin composition of the present invention, when the difference between the refractive indices of the gas barrier resin (A) and the thermoplastic resin (B) is 0.01 or less, a molded article obtained from this composition is used. Good transparency. Thermoplastic resin (E) described below
Is preferable, the difference between the refractive indices of the gas barrier resin (A), the thermoplastic resin (B) and the thermoplastic resin (E) is preferably 0.01. The difference in refractive index is 0.
When it exceeds 01, the molded article obtained from the resin composition tends to be slightly opaque. In order to obtain good transparency, the difference in the refractive index is preferably 0.007 or less, more preferably 0.005 or less. As a gas barrier resin (A) having a difference in refractive index from the thermoplastic resin (B) of 0.01 or less, polyvinyl alcohol,
Preferred are, but not limited to, vinyl alcohol resins such as poly (ethylene vinyl alcohol), polyamide, polyvinyl chloride, polyacrylonitrile, and the like.

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

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

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

Further, when the resin composition contains a metal salt of a higher aliphatic carboxylic acid, gels and fish eyes which occur over time can be prevented, and the long-term operation stability is further improved. be able to.

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

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

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

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

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

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

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

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

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

The gas barrier resin composition of the present invention has various excellent properties. The second resin composition of the present invention comprises:
As described above, the oxygen absorption rate is 0.01 ml / m ²
-It is day or more. Further, the first resin composition of the present invention preferably has an oxygen absorption rate of 0.01 ml / m ² · day or more. Oxygen absorption rate is 0.05ml / m ²
day or more, more preferably 0.1 ml / m
More preferably, it is not less than ² · day. When the oxygen absorption rate is less than 0.01 ml / m ² · day, the molded article such as a multilayer container molded using the resin composition of the present invention does not have sufficient oxygen barrier properties and has an oxygen scavenging effect. Is often not enough.

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

The preferred melt flow rate (MFR) in the resin composition of the present invention (210 ° C., under a load of 2160 g, based on JIS K7210) is from 0.1 to 100 g.
/ 10 min, more preferably 0.5 to 50 g / 10 min, even more preferably 1 to 30 g / 10 min. When the melt flow rate of the resin composition of the present invention is out of the range of 0.1 to 100 g / 10 minutes, workability at the time of performing melt molding often deteriorates.

The gas barrier resin composition or resin of the present invention is formed into various molded products depending on the purpose.

The method of mixing and molding each component of the resin composition of the present invention is not particularly limited. The order of mixing the components is not particularly limited. For example, when a molded article is prepared by mixing a gas barrier resin (A), a thermoplastic resin (B), a transition metal salt (C), and a deodorant (D), these components may be mixed at the same time. Good, after producing a blend of thermoplastic resin (B) and transition metal salt (C),
The deodorant (D) may be further mixed with the gas barrier resin (A).

The components of these compositions may be melt-blended and formed into pellets and then subjected to molding, or may be dry-blended and directly subjected to molding.

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

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

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

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

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

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

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

In the present invention, the molded article obtained by the above-mentioned molding may be a single layer, but if it is used as a laminate with a layer composed of other various resins, multi-function can be imparted. Is more preferable. When the resin composition of the present invention is used in a single layer, the oxygen barrier properties may be reduced due to moisture in the contents or 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.

[0143] Of the containers having a multilayer structure, the embodiment in which the innermost layer of the container is formed of the resin composition of the present invention is preferable from the viewpoint that the oxygen scavenging function in the container is promptly exhibited.

As a specific layer constitution of the multilayer structure, a layer composed of a resin other than the thermoplastic resin (B), metal, paper, woven fabric or non-woven fabric, etc. may be a layer A, a thermoplastic resin (B) or a thermoplastic resin (B). A resin composition layer containing a plastic resin (B) as a B layer,
When the adhesive resin layer is a C layer, A / B, A / B / A, A
/ C / B, A / C / B / C / A, A / B / A / B / A,
Layer configurations such as A / C / B / C / A / C / B / C / A are exemplified, however, it is not limited to adding the other layers to these layers at all, and limited to the above examples. is not. When a plurality of layers made of another resin are provided, they may be of different types or the same. Further, a layer using a collected resin made of scrap such as trim generated at the time of molding may be separately provided, or the collected resin may be blended with a layer made of another resin. Although there is no particular limitation on the thickness configuration of the multilayer structure, the thickness ratio of the B layer to the total layer thickness is preferably 2 to 20% in consideration of moldability, cost, and the like.

As a material for forming a resin layer to be laminated on a molded article of the gas barrier resin composition of the present invention, a thermoplastic resin is preferable from the viewpoint of processability and the like. Such thermoplastic resins include, but are not limited to, the following resins: ethylene homopolymers and ethylene copolymers (copolymers of ethylene and the following monomers: propylene, 1-butene, isobutene) , 4-methyl-1-pentene, 1-hexene, 1-octene and the like
-Olefins; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, and salts thereof;
Its partial or complete esters, its nitriles, its amides, its anhydrides; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate,
Carboxylic acid vinyl esters such as vinyl dodecanoate, vinyl stearate, and vinyl arachidonate; vinyl silane compounds such as vinyl trimethoxy silane; unsaturated sulfonic acids or salts thereof; alkyl thiols; vinyl pyrrolidones, etc.), propylene homo Polymers and propylene copolymers (copolymers of propylene with the following monomers: ethylene, 1-butene, isobutene, 4
Α-olefins such as -methyl-1-pentene, 1-hexene and 1-octene; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride, salts thereof, partial and complete esters thereof, and nitriles thereof Carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate and vinyl arachidonate; vinyl trimethoxy Vinylsilane compounds such as silane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidones, etc.), polyolefins such as poly-4-methylpentene-1 and polybutene-1; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphate Polyesters such as rate; poly ε- caprolactam, polyhexamethylene adipamide, polyamide such as poly-m-xylylene adipamide; polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonates, polyacrylates and the like. The layer laminated by such a thermoplastic resin may be unstretched or may be uniaxially or biaxially stretched or rolled.

[0146] Among these thermoplastic resins, polyolefins are preferable because they are excellent in moisture resistance, mechanical properties, economy, heat sealability and the like. Further, since the polyester has good transparency and excellent mechanical properties, the usefulness of laminating with the resin composition of the present invention having good transparency is great.

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

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

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

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

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

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

Molded articles such as containers using the resin composition of the present invention, particularly multilayer structures are used for various purposes. Among them, the superiority of using the resin composition of the present invention, which is extremely excellent in gas barrier properties and excellent in oxygen scavenging properties, is greatly exerted when used as various packaging containers.
In particular, it is suitable as a packaging container for foods, pharmaceuticals, agricultural chemicals, etc., whose quality is likely to deteriorate due to the presence of oxygen. Further, the resin composition of the present invention is suitable for use as a packing (gasket) for a container, particularly as a gasket for a cap of a container. A cap provided with such a gasket has excellent gas barrier properties and oxygen scavenging properties.

Further, since the resin composition of the present invention can have good transparency by appropriately selecting a resin, it is also suitable for use as a packaging container in which the contents are easily visible. Among such packaging containers, the performance required for transparency is strict, and the use of the resin composition of the present invention is highly useful.
There are various embodiments. That is, one includes a layer made of the resin composition of the present invention, and the total layer thickness is 300 μm.
The following is a container composed of a multilayer film, and the other is a multilayer container composed of a layer composed of the resin composition of the present invention and a thermoplastic polyester layer. Hereinafter, these embodiments will be sequentially described.

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

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

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

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

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

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

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

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

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

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

The form of the multilayer container composed of the layer composed of the resin composition of the present invention and the thermoplastic polyester layer is not particularly limited, and examples thereof include a bag-shaped container, a cup-shaped 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.

[0167] Blow-molded bottles made of thermoplastic polyester resin are now widely used as beverage containers. In such applications, it is necessary to prevent deterioration of the contents, and it is required that the beverage as the contents be sufficiently visible to consumers. In addition, when packaging contents such as beer that is extremely susceptible to flavor deterioration due to oxygen, it is desired to have extremely high gas barrier properties and oxygen scavenging performance. Is not easy.

The multilayer blow bottle composed of the layer composed of the resin composition of the present invention and the thermoplastic polyester layer is extremely excellent in the ability to maintain the quality of the contents while maintaining the 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 a gas-barrier resin composition and a thermoplastic polyester layer includes aromatic dicarboxylic acids or their condensation esters containing alkyl esters and diols as main components. 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, generally, the total ratio (mol%) of terephthalic acid units and ethylene glycol units is based on the total mol number of all structural units constituting the polyester.
It is preferably at least 70 mol%, more preferably at least 90 mol%. If the total proportion of terephthalic acid units and ethylene glycol units in the polyester is less than 70 mol%, the resulting polyester will be non-crystalline, so that when it is heated and filled (hot-filled) in a stretching container, the shrinkage is large and the heat resistance is poor. In addition, the strength also decreases.
Furthermore, during solid phase polymerization performed to reduce the amount of oligomers contained in the resin, sticking due to softening of the resin is likely to occur, and production becomes difficult.

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

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

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

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

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

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

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

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

The 1,4-cyclohexanedimethanol unit or 1,4-cyclohexanedicarboxylic acid is preferred also from the viewpoint that molded articles obtained therefrom have excellent drop strength.

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

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

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

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

Therefore, when using polyethylene terephthalate which does not contain a copolymer component other than diethylene glycol as a by-product, the crystallization speed is higher than when using polyethylene terephthalate modified in small amounts with other copolymer components. 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 above-mentioned multilayer containers having a thermoplastic polyester layer will be described.

The method for producing such a container is not particularly limited, but it is preferable to use the 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 resin composition of the present invention can be obtained by alternately injecting the resin composition at different timings from the respective injection cylinders, simultaneously injecting the concentric nozzles, or using both of them in combination. For example, (1) PES for inner and outer layers first
And then injecting the resin composition to be the intermediate layer simultaneously with the inner and outer layers to produce a container having a three-layer structure of PES / resin composition / PES; or (2) P for the inner and outer layers first.
ES is injected, and then the resin composition is injected simultaneously with the inner and outer layers, and then simultaneously or thereafter, the PES serving as the central layer is injected simultaneously with each of the above layers, and PES / resin composition / PES / resin composition / PES The inner layer is obtained by a general method of a bottomed parison completely enclosed in a PES layer, and is not particularly limited in terms of equipment. In the above-mentioned layer structure, an adhesive resin layer may be provided between the PES layer and the resin composition layer, if necessary.

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

The resin composition of the present invention is preferably injected within a temperature range of 170 to 250 ° C.,
More preferably in the temperature range of 190-2.
More preferably, the injection is performed within a temperature range of 30 ° 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 product (fish eye) is mixed into the molded product, resulting in poor appearance. Further, in extreme cases, the screw torque increases and causes a failure of the molding machine. On the other hand, when the injection temperature of the resin composition exceeds 250 ° C., the oxidation of the thermoplastic resin (B) proceeds, and the oxygen absorbing ability of the resin composition decreases, causing a decrease in gas barrier properties and oxygen scavenging properties. Cheap. At the same time, the appearance of the molded article may be poor due to coloring or gelling, or the fluidity may be non-uniform or impaired due to decomposed gas or gelling, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gel. In order to suppress the progress of oxidation during melting, it is also preferable to seal the raw material supply hopper with nitrogen.

The resin composition of the present invention is previously melt-blended with a gas barrier resin (A), a thermoplastic resin (B), a deodorant (D), and, if necessary, a transition metal salt (C) to form pellets. May be supplied to a molding machine. Alternatively, the dry-blended materials may be supplied to a molding machine.

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

When the temperature of the hot runner portion is lower than 220 ° C., crystallization of PES occurs, and the PES is solidified in the hot runner portion.
On the other hand, when the temperature of the hot runner portion exceeds 300 ° C., the oxidation of the thermoplastic resin (B) proceeds, the oxygen absorbing ability of the resin composition is reduced, and the gas barrier property and the oxygen scavenging property are likely to be reduced. . 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 delamination resistance (delamination resistance) and transparency of a multilayer container obtained by stretch blow molding the bottomed parison, the PES of the parison and the gas barrier resin at the time of the injection molding are required. It is important to suppress 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 gas barrier resin (A), it is preferable to set the mold temperature within the range of 0 ° C. to 70 ° C.
C. to 50.degree. C., more preferably 10 to 3C.
More preferably, it is within the range of 0 ° C. Mold temperature is 0
If the temperature is lower than 0 ° C., the appearance of the parison is impaired due to condensation in the mold, and a good molded product cannot be obtained. On the other hand, when the mold temperature exceeds 70 ° C., the crystallization of the parison PES and the gas barrier resin (A) is promoted, so that uniform stretchability cannot be obtained. The delamination resistance is reduced, and it is difficult to obtain a molded article shaped into an intended shape. Furthermore, crystallization of PES impairs transparency.

Regarding the thickness of the parison, the total thickness is 2 to 2.
5 mm, the resin composition layer of the present invention has a total of 10 to 500 μm.
m is preferred.

The multilayer parison thus obtained is reheated to 75 to 150 ° C. directly at a high temperature or by a heating element such as a block heater or an infrared heater, and then sent to a stretching blow step. After being stretched 1 to 5 times in the longitudinal direction, it is blow-molded 1 to 4 times with compressed air or the like, and the PES resin layer and the resin composition layer of the present invention are uniaxially or biaxially stretched. 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 resin composition layer of the present invention is 2 to
It is preferably in the range of 200 μm,
More preferably, it is within the range of m.

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

[0199]

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

(1) Polyvinyl alcohol resin (A
1) Ethylene content and degree of saponification of ethylene content and degree of saponification of polyvinyl alcohol resin (A1) was deuterated dimethyl sulfoxide as a solvent ¹ H-
NMR (nuclear magnetic resonance) spectrum ("JN" manufactured by JEOL Ltd.
M-GX-500 type ").

(2) Polyvinyl alcohol resin (A
Phosphate content in 1): The phosphate content was obtained as a phosphate ion (PO ₄ ³⁻ ) content according to the method described below. Dried polyvinyl alcohol resin 1 as a sample
0 g was added to 50 ml of 0.01N hydrochloric acid aqueous solution, and 9 g
Stirred at 5 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to obtain a phosphate ion content. The chromatography column used was CIS-A23 manufactured by Yokogawa Electric Corporation, and the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium hydrogen carbonate. Note that a calibration curve prepared with a phosphoric acid aqueous solution was used for the quantification.

(3) 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 Na ion, K ion and Mg ion thus obtained, the amounts of alkali metal salt and alkaline earth metal salt in the dried chip were obtained in terms of metal.

(4) Styrene content, vinyl bond content, and carbon-carbon double bond content of the thermoplastic resin (B): ¹ H-NMR (nuclear magnetic resonance) spectrum using deuterated chloroform as a solvent (Japan "JNM-GX-50" manufactured by Denshi
Thermoplastic resin (B) was measured according to “type 0”), and the structure of the resin was identified. Thereby, the content was calculated.

Here, the styrene content is the proportion (mol%) of styrene in all the monomers constituting the resin, and the vinyl bond content is the content of all the diene monomers in the diene block. Of those that formed vinyl bonds in (%)
Say. The content of the carbon-carbon double bond was determined by calculating the number of moles (eq / g) of the double bond contained in 1 g of the resin.

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

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

(7) Intrinsic viscosity of polyester: A film layer of a sample was cut out from 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).

(8) 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.

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

(10) Refractive index of resin: A film to be measured was subjected to film extrusion molding to obtain a non-stretched film having a thickness of 20 μm. Using the resulting film, the refractive index was measured using an Abbe refractometer (4T type, manufactured by Atago Co., Ltd., SL-Na-1 lamp, manufactured by Toshiba Corporation). The extrusion temperature of the film was 210 ° C. for EVOH resin.

(11) Haze value (cloudiness value): The resin or resin composition to be measured was extruded to obtain a non-stretched film having a thickness of 20 μm. Using the obtained film, AS
According to TM D1003-61, a Poick integrating sphere type light transmittance / total light reflectance meter (“H” manufactured by Murakami Color Research Laboratory)
R-100 type ") was used to measure the internal haze value. The measurement was similarly performed for the multilayer film. Furthermore, for the multi-layer bottle, the center of the bottle body was divided into four on the circumference.
For the location, measure the internal haze value at each location,
The average value was taken as the haze value (cloudiness value) of the bottle.

(12) Oxygen absorption rate of resin composition: Extrusion molding was performed using the resin composition to obtain a film having a thickness of 20 μm. The obtained single-layer film 0.9 m ² (0.2 m
× 4.5 m; surface area 1.8 m ² ) was wound into a roll 5 hours after film formation, and placed in a 375 ml Erlenmeyer flask filled with air at 20 ° C. and 65% RH. The air in the Erlenmeyer flask contains 21:79 by volume oxygen and nitrogen. The mouth of the Erlenmeyer flask was sealed with an epoxy resin using a multilayer sheet containing an aluminum layer, and then left at 20 ° C. 96 hours after encapsulation, 168
After time and 336 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 10 days from 4 days to 14 days by the number of days and the surface area.

(13) Oxygen Permeation Rate of Gas Barrier Resin (A) The gas barrier resin (A) was extruded to a thickness of 20 μm.
Was obtained. 20 ° C
The temperature and humidity are adjusted to 65% RH, and an oxygen permeation amount measuring device (OX-TRAN-10 / 50A, manufactured by Modern Control Co., Ltd.)
Was used to measure the amount of oxygen permeation. The extrusion temperature of the film was 210 ° C. for the EVOH resin.

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

(Example 1) EVOH which is a polyvinyl alcohol-based resin (A1) as the gas barrier resin (A)
It was used. This EVOH has an ethylene content of 44 mol%, a saponification degree of 99.5%, and a melt flow rate (210
C.-2160 g load) 13 g / 10 min. This 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. Furthermore, this EV
The measured refractive index of OH was 1.528.
The oxygen transmission rate of the EVOH is 1.5 ml · 2
It was 0 μm / m ² · day · atm.

Next, a thermoplastic resin (B) to which an antioxidant was added was prepared by the following method.

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

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

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

Thermoplastic resin (B) containing the above antioxidant
The refractive index and the haze value (cloudiness value) of the sample were 1.531 and 1.0%, respectively.

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

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

An extrusion temperature of 2 was obtained by using the obtained resin composition.
Film extrusion was performed at 10 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of the obtained single-layer film was measured, it was 7.8%. Next, when the oxygen absorption amount of the film was measured, the result shown in FIG. 1 was obtained. The oxygen absorption rate of the resin composition calculated from the measurement results after 4 days (96 hours) and 14 days (336 hours) was 1.744 ml / m ² · day.

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

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

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

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

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

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

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

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

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

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

Using the above-prepared single-layer film, the film was left in a screw-tube glass bottle at 40 ° C. for 4 hours in the same manner as in Example 1, and then the odor of the film was smelled. Felt.

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

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

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

Using the monolayer film prepared above, the film was left in a screw-tube glass bottle at 40 ° C. for 4 hours in the same manner as in Example 1, and then the film was smelled. Felt.

Next, a laminated film was produced in the same manner as in Example 1. The haze of this laminated film was 2.0%.

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

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

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

[0243]

[Table 1]

Example 3 The laminated film produced in Example 1 was punched into a gasket shape to fit a polypropylene screw cap body having an outer diameter of 65 mm and a bottom thickness of 1.2 mm, and was attached to the screw cap body. Was. Next, the obtained cap with a gasket is supplied to a mold of a gasket molding machine for compression molding, and an ethylene-1-butene copolymer ("POLYBUTYLEN" manufactured by Shell Chemical Co., Ltd.) is supplied to the gasket molding machine for compression molding.
E 8240 ": 1-butene (99 mol% or more), ethylene (1 mol% or less) copolymer, density 0.908 g /
cm ³ , MFR = 2.0 g / 10 min (210 ° C., 216
A cap with a multilayer gasket was produced by supplying 0 g load)) and compression molding. At this time, the cylinder temperature of the compression molding machine was 245 ° C, the nozzle temperature was 235 ° C,
The mold temperature was adjusted to 30 ° C.

The sealing performance of the thus prepared cap container was evaluated as follows.

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

[0247]

According to the present invention, a resin composition having excellent gas barrier properties, particularly excellent oxygen gas barrier properties and oxygen absorption properties, and further having excellent low odor properties can be obtained. Further, by appropriately selecting the resin, good transparency can be obtained. Such a resin composition can be prepared into a molded article of any shape. Molded articles prepared using these, for example, films and containers, have excellent gas barrier properties and oxygen absorption properties, and furthermore have good transparency. Therefore, the resin composition or resin of the present invention is useful as a container for storing articles that are susceptible to deterioration by oxygen, such as foods and pharmaceuticals.

A multilayer structure using the above resin composition, for example, a packaging material made of a multilayer film is also preferably used because it has the above excellent performance. In particular, the total layer thickness is 300μ
m or a multilayer container laminated with a thermoplastic polyester layer is suitably used for a container requiring transparency in addition to the oxygen absorbing or gas barrier properties.

[Brief description of the drawings]

FIG. 1 is a graph plotting the amount of oxygen absorption of a resin composition of Example 1 and an EVOH resin or a resin composition of Comparative Examples 1 and 2 against time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 81/26 B65D 81/26 J C08K 3/00 C08K 3/00 5/09 5/09 5/098 5 / 098 C08L 29/04 C08L 29/04 S 101/02 101/02 F term (reference) 3E067 AA03 AA11 AB01 AB26 AB81 BA03A BB14A BB25A CA05 CA06 FA01 FC01 GB13 GB15 3E086 AB01 AD04 BA04 BA15 BA35 BA40 BB15 BB90 BB15 CA28 4F100 AK01A AK41B AK69A BA02 BA15 CA30A DE01A GB15 GB16 JA20A JB16A JB16B JB20A JD03A JD14A YY00A 4J002 AA001 AA032 BB221 BC052 BD031 BD101 BE031 BG101 BL012 BL022 BP012 CL001 CL011 CL031 CL051 DD076 DD077 DD087 DE107 DE247 DF037 DG047 DH047 DJ007 DJ017 EF017 EF077 EF117 EG046 EG047 EG057 FA087 FD060 FD070 FD150 FD207 GG00

Claims (10)

[Claims] 1. An oxygen transmission rate of 500 ml · 20 μm /
Gas barrier resin (A) having m ² · day · atm (20 ° C., 65% RH) or less, thermoplastic resin having a carbon-carbon double bond (B), transition metal salt (C), and deodorant (D) A gas barrier resin composition comprising: 2. An oxygen absorption rate of 0.01 ml / m ² · d
The resin composition according to claim 1, which is at least ay. 3. An oxygen transmission rate of 500 ml · 20 μm /
Gas barrier resin composition comprising gas barrier resin (A) having m ² · day · atm (20 ° C., 65% RH) or less, thermoplastic resin (B) having a carbon-carbon double bond, and deodorant (D) And the oxygen absorption rate is 0.01 ml
/ M ² · day or more, a gas barrier resin composition. 4. The resin composition according to claim 1, wherein the thermoplastic resin (B) contains a carbon-carbon double bond at a rate of 0.0001 eq / g or more. 5. The gas-barrier resin (A) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.
The resin composition according to any one of the above items. 6. The method according to claim 1, wherein the transition metal salt (C) is contained at a ratio of 1 to 5000 ppm in terms of a metal element.
The resin composition according to any one of items 2, 4, and 5. 7. The resin composition according to claim 1, wherein the deodorant (D) has a particle size of 0.5 to 10 μm. 8. The method according to claim 1, wherein the gas barrier resin (A) is 60 to 9
9.8% by weight, the thermoplastic resin (B) is 30 to 0.1%
The resin composition according to any one of claims 1 to 7, wherein the resin composition comprises 10% by weight and 0.1% by weight of the deodorant (D). 9. A multilayer structure having a layer containing the gas barrier resin composition according to any one of claims 1 to 8. 10. A multilayer container having a layer made of the gas barrier resin composition according to claim 1 and a layer made of thermoplastic polyester.