JPH07276576A - Resin composition and film excellent in water resistance and gas barrier properties - Google Patents

Abstract

PURPOSE:To obtain a gas barrier molded product or film excellent in water resistance and having high-level gas barrier properties from a resin compsn. or film obtained by exchanging a compsn. consisting of a highly hydrogen- bondable resin and an inorg. laminar compd. with an exchangeable cation with a specific ion exchange selection index. CONSTITUTION:A compsn. consisting of a highly hydrogen-bondable resin and an inorg. laminar compd. is exchanged with a exchangeable cation with an ion exchange selection index of 19 or more to obtain a resin compsn. or a film formed therefrom. The inorg. laminar compd. has a laminar structure wherein unit crystal layers are mutually stacked. The cation used in ion exchange pref. has an ion exchange selection index of 19 or more and, for example, Ca<2a> and Ba<2+> are designated. After ion exchange, it is desirable to perform washing carefully in order to remove an excessive residual ion. After washing, sufficient drying is performed so as not to leave moisture in a resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a film which are excellent in water resistance and gas barrier property by an ion exchange treatment.

[0002]

BACKGROUND OF THE INVENTION Although various functions are required for packaging, various gas barrier properties for protecting contents are important properties that affect the storability of foods. Distribution forms, diversification of packaging technology, regulation of additives However, due to changes in tastes and the like, the need for it is increasing. The gas barrier property was also a weak point of general plastic materials. Degradation factors of food include oxygen, light, heat, water, etc., and oxygen is particularly important as a substance causing it. The barrier material is a material that is indispensable for effectively blocking oxygen and at the same time controlling the deterioration of foods such as gas filling and vacuum packaging.In addition to oxygen gas, various gases, organic solvent vapors, fragrances, etc. By having a barrier function,
It can be used for rust prevention, deodorization, and sublimation prevention, and is used in many fields such as confectionery bags, skipjack packs, retort pouches, carbon dioxide beverage containers, and other food products, cosmetics, agricultural chemicals, medical care, and the like.

Among the films made of thermoplastic resin, particularly oriented films of polypropylene, polyester, polyamide and the like have excellent mechanical properties, heat resistance and transparency and are widely used as packaging materials. There is. However, when these films are used for food packaging, they have insufficient oxygen and other gas barrier properties,
Various problems such as oxidative deterioration and alteration of contents due to aerobic microbes, permeation of aroma components, loss of flavor, and moistening of contents by external moisture, resulting in poor mouthfeel. Tend to occur. Therefore, a method such as stacking another film layer having a good gas barrier property is usually adopted.

Conventionally, various transparent plastic materials having a large gas barrier property have been known. For example, although there are films made of polyvinyl alcohol, polyethylene vinyl alcohol copolymer and polyvinylidene chloride resin, they can be bottled or bottled. While the metal and glass materials used have almost zero oxygen permeability, these plastic materials are still permeable to oxygen that cannot be ignored.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a molded article or film having excellent water resistance and gas barrier properties having a high level of gas barrier property.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in a resin composition and a film comprising an inorganic layered compound and a resin, the aspect ratio of the inorganic layered compound is extremely increased. It has been found that a significantly excellent gas barrier property is exhibited by doing so, and as a result of further studies, it was found that excellent water resistance can be imparted by ion exchange, and the present invention was achieved.

That is, the present invention provides a resin composition or a film comprising the resin composition obtained by cation exchange of a composition comprising a high hydrogen-bonding resin and an inorganic layered compound with an exchangeable cation having an ion exchange selectivity index of 19 or more. It is provided.

The inorganic layered compound used in the present invention is
There is no particular limitation as long as it is an inorganic compound in which unit crystal layers are stacked on each other to have a layered structure and has a particle size of 5 μm or less and an aspect ratio of 50 or more and 5000 or less. Regarding gas barrier properties, the aspect ratio is 200
The range of up to 3000 is more preferable. Aspect ratio is 50
If it is less than 500, the gas barrier property is not sufficiently expressed,
Those larger than 0 are technically difficult and economically expensive. From the viewpoint of transparency, those having a particle size of 3 μm or less are preferable, and those having a particle size of 1 μm or less are more preferable. Specific examples of the inorganic layered compound include graphite, phosphate-based derivative-type compounds (zirconium phosphate-based compounds), chalcogenides [Group IV (Ti, Z
r, Hf), Group V (V, Nb, Ta) and Group VI (M
o, W) dichalcogenide and is represented by the formula MX ₂ . Here, X represents chalcogen (S, Se, Te). ], Clay-based minerals and the like can be mentioned.

The particle size of the inorganic layered compound used in the present invention refers to the particle size determined by the dynamic light scattering method in a solvent.
It is extremely difficult to measure the true particle size in the resin composition, but when the resin is swelled sufficiently with the same solvent as the solvent used in the dynamic light scattering method to form a composite with the resin, the inorganic layered compound in the resin is used. The particle size of can be considered to be close to the particle size in the solvent.

The aspect ratio (Z) of the inorganic layered compound used in the present invention is represented by the relationship of Z = L / a.
[L is a particle size obtained by a dynamic light scattering method in a solvent, and a is a unit thickness of the inorganic layered compound (unit thickness a is a measurement of the inorganic layered compound alone by a powder X-ray diffraction method or the like. It is a value determined by.)]. However, Z = L / a
, The interplanar spacing d obtained from powder X-ray diffraction of the composition
Exists and satisfies the relationship of a <d. Here, it is necessary that the value of da is larger than the width of the resin single chain in the composition. Z cannot necessarily be said to be the true aspect ratio of the inorganic layered compound in the resin composition, but is considerably appropriate for the following reasons.

Direct measurement of the aspect ratio of the inorganic layered compound in the resin composition is extremely difficult. Composition powder X
There is a relation of a <d between the interplanar spacing d obtained by the line diffraction method and the unit thickness a determined by the powder X-ray diffraction measurement of the inorganic layered compound alone, and the value of da is the resin 1 in the composition. If the width is equal to or larger than the width of the main chain, it means that the resin is inserted between the layers of the inorganic layered compound in the resin composition, and thus it is clear that the thickness of the inorganic layered compound is the unit thickness a. . In addition, it is extremely difficult to measure the true particle size in the resin composition, but in the case of swelling sufficiently with a solvent of the same kind as the solvent used in the dynamic light scattering method to form a composite with the resin, It can be considered that the particle size of the inorganic layered compound in is substantially close to that in the solvent (however, the particle size L determined by the dynamic light scattering method is the major axis Lmax of the inorganic layered compound).
It is considered that the true aspect ratio Lmax / a cannot theoretically fall below the definition Z of the aspect ratio in the present invention. ). From the above two points,
The definition of aspect ratio of the present invention is considered to be relatively relevant. Of course, in the present invention, the aspect ratio and particle size as defined in the present invention are used, and they are not necessarily true values.

As the inorganic layered compound having a large aspect ratio, an inorganic layered compound which swells and cleaves in a solvent is preferably used. Among these, swelling clay minerals are preferable, and clay-based minerals have a central metal such as aluminum or magnesium at the top of the tetrahedral layer of silica.
The type consisting of a two-layer structure having a face layer and silica 4
The face layer is classified into a type having a three-layer structure in which an octahedron layer having a central metal such as aluminum or magnesium is sandwiched from both sides. Examples of the former include kaolinites and antigorites, and examples of the latter include smectites, vermiculites and mica depending on the number of interlayer cations. Specifically, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilylic mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite. , Xanthophyllite, chlorite, etc.

The solvent for swelling the inorganic layered compound is not particularly limited. For example, in the case of natural swelling clay mineral,
Examples thereof include water, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol, dimethylformamide, dimethyl sulfoxide, acetone and the like, and alcohols such as water and methanol are more preferable.

The resin used in the present invention is a high hydrogen-bonding resin having a weight percentage of hydrogen-bonding groups or ionic groups per unit weight of resin of 20% to 60%. A more preferable example is one in which the weight percentage of hydrogen-bonding groups or ionic groups per unit weight of the resin of the high hydrogen-bonding resin satisfies the ratio of 30% to 50%. Among the hydrogen-bonding groups or ionic groups of the high hydrogen-bonding resin, more preferable ones are a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group and a phosphoric acid group, and the ionic group is a carboxylate. Group, sulfonate ion group, phosphate ion group, ammonium group, phosphonium group and the like. Specific examples include, for example, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of 41 mol% or more, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan. Polysaccharides such as cellulose, pullulan, chitosan, polyacrylic acid, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine, its ammonium salts polyvinylthiol, polyglycerin, etc. Can be mentioned.

More preferred examples of the high hydrogen bond resin include polyvinyl alcohol and polysaccharides.
The polyvinyl alcohol as used herein is obtained by hydrolyzing (saponifying) the acetic ester portion of a vinyl acetate polymer, and is a vinyl alcohol / vinyl acetate copolymer to be precise. Here, the saponification ratio is preferably 70% or more, more preferably 85% or more, in terms of molar percentage. The degree of polymerization is 100 or more and 50
00 or less is preferable.

The term "polysaccharide" as used herein refers to a biopolymer synthesized in a biological system by polycondensation of various monosaccharides, and includes those chemically modified based on them. For example, cellulose and cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin,
Examples include chitosan.

When the resin used in the present invention is a high hydrogen-bonding resin, a hydrogen-bonding group cross-linking agent may be used for the purpose of improving its water resistance (meaning barrier property after a water resistance environment test). it can.

The crosslinking agent for hydrogen-bonding group is not particularly limited, but examples thereof include titanium coupling agents, silane coupling agents, melamine coupling agents, epoxy coupling agents, isocyanate coupling agents,
A copper compound, a zirconia compound, etc. are mentioned, More preferably, a zirconia compound is mentioned.

Specific examples of zirconia compounds include zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride, zirconium halides such as zirconium bromide, zirconium sulfate, basic zirconium sulfate, zirconium nitrate and other mineral acids. Zirconium salts of organic acids such as salts, zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate, zirconium stearate, ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, sodium zirconium citrate, citric acid Zirconium complex salts such as zirconium ammonium,
And so on.

The amount of the cross-linking agent for hydrogen-bonding groups added is the ratio (K) of the number of moles of cross-linking groups (CN) of the cross-linking agent to the number of moles of hydrogen-bonding groups (HN) of the high hydrogen-bonding resin [K]. That is, K = C
N / HN] is usually in the range of 0.001 or more and 10 or less,
The range is preferably 0.01 or more and 1 or less.

The cation that can be used for ion exchange is an ion exchange selectivity index (product of atomic number and ionic valence).
Is preferably 19 or more. For example Ca ²⁺ , B
Preferred examples include a ²⁺ . Further, it is desirable to wash with water after the ion exchange, and it is also desirable to carefully perform it for removing excess residual ions. However, after washing with water, care should be taken to ensure that water molecules do not remain in the resin by sufficient drying.

After ion exchange, it is also possible to immerse in hot water at 40 to 80 ° C. This further removes excess ions, improves the smoothness of the film surface, and has a favorable effect on the gas barrier property. However, after washing with water, care should be taken to ensure that water molecules do not remain in the resin by sufficient drying.

The composition ratio (volume ratio) of the inorganic layered compound and the resin used in the present invention is not particularly limited,
Generally, the volume ratio of (inorganic layered compound / resin) is 5/95.
To 90/10, preferably 5/95 to 50/50. The volume ratio of (inorganic layered compound / resin) is 5/95.
In the range of ~ 30/70, the flexibility of the membrane becomes good, and 7/93 ~ 17/8
In the range of 3, there are advantages such as a decrease in barrier property due to bending and a decrease in peel strength. Further, when the volume fraction of the inorganic layered compound is smaller than 5/95, the barrier performance is insufficient, and when it is larger than 90/10, the film forming property is not good.

The method of blending the composition comprising the inorganic layered compound and the resin is not particularly limited. For example, a solution in which the resin is dissolved and a dispersion in which the inorganic layered compound has been swollen and cleaved in advance are mixed, and then the solvent is added. Method of removing, the dispersion liquid obtained by swelling and cleaving the inorganic layered compound is added to the resin, the method of removing the solvent, the inorganic layered compound is added to the liquid in which the resin is dissolved,
Examples include a method in which the dispersion is swollen and cleaved, the solvent is removed, and the resin and the inorganic layered compound are heat-kneaded. In particular, the former three methods are preferably used as a method for easily obtaining a large aspect ratio.

In the above-mentioned former three methods, the water resistance of the film (meaning the barrier property after the water resistance environment test) is particularly improved by removing the solvent from the system and then heat aging at 110 ° C. or higher and 220 ° C. or lower. To do. Although the aging time is not limited, it is necessary that the film reaches at least the set temperature, and in the case of a method using a heating medium contact such as a hot air dryer, it is preferably 1 second or more and 100 minutes or less. The heat source is also not particularly limited, and includes heat roll contact, heat medium contact (air, oil, etc.), infrared heating, microwave heating,
Various other types can be applied.

The resin composition of the present invention is molded into various forms for use. The form of the molded product is not particularly limited,
When used for packaging, such as films, sheets, containers (tray, bottles, etc.), the gas barrier property is sufficiently exhibited. Also, they are often used in stacked form.

The base material of the laminate is not particularly limited,
Typical base materials such as resin, paper, aluminum foil, wood, cloth and non-woven fabric can be mentioned. As the resin used as the base material, polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene- Vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, polyolefin resin such as ionomer resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6, nylon-6,6, meta-xylene Diamine-adipic acid condensation polymer, amide resin such as polymethylmethacrylimide, acrylic resin such as polymethylmethacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene Copolymers, styrene such as polyacrylonitrile, acrylonitrile resins, hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resins such as Teflon, polyvinyl Alcohol, ethylene-vinyl alcohol copolymer, hydrogen bonding resin such as cellulose derivative, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyphenylene oxide resin, polymethylene oxide resin, liquid crystal resin, etc. Examples include engineering plastic resins.

Among these, in the film-form laminate, the outer layer is biaxially stretched polypropylene,
Polyethylene terephthalate, nylon or K-coated polyvinylidene chloride-coated biaxially stretched polypropylene, polyethylene terephthalate, nylon, etc. are preferably arranged, and the inner layer generally has a good heat-sealing property. , For example, polyethylene (low density, high density), ethylene-
Propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer,
Ethylene-methyl methacrylate copolymer and the like are preferably used.

The method for laminating the composition of the present invention on the substrate is not particularly limited. When the substrate is, for example, a film or sheet, a coating method of applying a coating liquid of the composition on the surface of the substrate, drying and heat treatment, a method of laminating the composition film afterwards, and the like are preferable.
Further, the interface between the two may be treated with corona treatment, anchor coating agent or the like. As a coating method,
Roll coating methods such as direct gravure method, reverse gravure method and micro gravure method, two roll beat coating method, bottom feed three reverse coating method,
Examples thereof include a doctor knife method, a die coating method, a dip coating method, a bar coating method, and a coating method combining these methods.

The thickness of the coating film varies depending on the type of the substrate and the desired barrier performance, but the dry thickness is preferably 10 μm or less, more preferably 1 μm or less (1 μm or less has the advantage that the transparency of the laminate is extremely high). It is also preferable for applications that require transparency).
The lower limit is not particularly limited, but is preferably 1 nm or more in order to obtain an effective gas barrier effect.

In addition, in the range which does not impair the effects of the present invention, the resin composition and the film include an ultraviolet absorber,
Various additives such as colorants and antioxidants may be mixed. The present invention comprises at least one of the above-mentioned film layers.
It includes a laminated film having layers and a laminated body.

[0032]

According to the present invention, in a mixed system of a resin and an inorganic layered compound, the particle size of the inorganic layered compound is 5 μm.
It is possible to obtain a gas barrier film having an unprecedentedly high level of gas barrier property and water resistance by using an aspect ratio of 50 or more and 5000 or less and subjecting the composition to ion exchange treatment. Become.

The present invention has, as a resin composition, a high level of barrier properties that cannot be imagined from conventional materials. Oxygen permeability per 1 μm thickness is 31 ° C, 61% R
Even ethylene-vinyl alcohol copolymer, which has the best oxygen barrier property of commercially available resins under H condition, is 15cc
/ M ² · day · atm, while in the present invention, oxygen permeability is 2 or less, or even more excellent is 0.2.
The following is obtained: The resin composition of the present invention has a barrier property that greatly exceeds that of the resin and approaches the barrier properties of metals and ceramics. Therefore, from the viewpoint of barrier properties, applications in which metals such as aluminum foil and glass and inorganic materials are essential It can be used as well and can be said to be a material that breaks the common sense of barrier resin compositions up to now. Regarding weaknesses such as opacity of metal and brittleness of ceramics,
It goes without saying that the present invention, which is a resin composition, is superior to them.

As a use as a packaging material of the present invention, as a film, it is used for miso, bonito flakes, confectionery, ramen, ham / sausage, Tetra Pak, etc., and for boiled food such as packed rice, curry, stew, etc. and food for retort. For bottles, squeeze bottles such as mayonnaise, juice, soy sauce, sauce, edible oil, etc.
As trays, such as yogurt and pudding cups, microwave food trays, etc., as well as infusion packs, semiconductor packaging, oxidizing chemical packaging, precision material packaging such as medical, electronic, chemical, machinery and other industrial material packaging. , Is used in a wide range of applications in various shapes.

[0035]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

The methods for measuring various physical properties are described below. [Oxygen permeability] Oxygen permeability measuring device (OX-TRAN
It was measured at a temperature of 24.1 ° C. (humidity-controlled thermostat 21 ° C.) (10 / 50A, manufactured by MOCON) (relative humidity was about 93.3%). [Thickness measurement] It was measured by a digital thickness meter. [Measurement of Particle Size] Ultrafine particle size analyzer (BI-90, manufactured by Brookhaven Co., Ltd.) was used under the conditions of a temperature of 25 ° C. and a water solvent. The central diameter determined by the photon correlation method by the dynamic light scattering method was defined as the particle diameter L. [Aspect ratio calculation] X-ray diffractometer (XD-5A,
Diffraction measurement was performed on the inorganic layered compound alone and the resin composition by a powder method using Shimadzu Corporation. Thus, the interplanar spacing (unit thickness) a of the inorganic layered compound was determined, and it was further confirmed from the diffraction measurement of the resin composition that the interplanar spacing of the inorganic layered compound was wide. Using the particle size L obtained by the above method, the aspect ratio Z is Z = L /
It was determined by the formula a.

[Example 1] Natural montmorillonite (Kunipia F; manufactured by Kunimine Industries Co., Ltd.) was used as the inorganic layered compound (A). The particle size of natural montmorillonite (Kunipia F) is 560 nm, and the a value obtained from powder X-ray diffraction is 1.
It is 2156 nm and the aspect ratio Z is 461. In addition, polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree; 99.6%, degree of polymerization 1700) was dissolved in ion-exchanged water (0.7 μS / cm or less) to a concentration of 4.0 wt%, and this was used as a resin solution. (Solution B). Inorganic layered compound / resin = 2 in the solid component ratio (volume ratio) of liquids A and B
/ 8 to mix and mix this (solid content 6 wt
%). Into the mixed solution obtained above, as a hydrogen-bonding cross-linking agent, zirconium ammonium carbonate (manufactured by Daiichi Rare Element Industry Co., Ltd .; Zircosol AC7 (aqueous solution containing 15 wt% in terms of zirconium oxide)) was added to the hydroxyl group of polyvinyl alcohol in an amount of 15 mol. The zirconium element was added to the mixed solution in a ratio of 1 mol to prepare a coating solution.
Then, a coating solution is gravure-coated (test coater; tester;
Yasui Seiki Co., Ltd .: Microgravure coating method, coating speed 3 m / min, drying temperature 100 ° C.). The dry thickness of the coating layer was 0.8 μm. The obtained coated film was immersed in a BaCl ₂ aqueous solution whose ionic strength was adjusted to 1.5 for 5 minutes, washed with pure water at 23 ° C., and dried in an oven at 60 ° C. Further, it was heat-treated at 180 ° C. for 10 minutes. The oxygen permeability of the above ion exchange film at 24.1 ° C. and 93.3% RH was measured. The results are shown in Table 1.

[Example 2] The coating film prepared in Example 1
Rum, CaCl adjusted to an ionic strength of 1.5 ₂Water soluble
After soaking in the solution for 5 minutes, wash with pure water at 23 ° C and turn it on at 60 ° C.
Oven dried. Furthermore, heat treatment at 180 ° C for 10 minutes
I understood The other conditions are the same as in Example 1.

Comparative Example 1 The coated film prepared in Example 1 was heat-treated at 180 ° C. for 10 minutes without being subjected to the ion exchange treatment. The other conditions are the same as in Example 1.

Comparative Example 2 Natural montmorillonite (Kunipia F; manufactured by Kunimine Industries Co., Ltd.) is used as the inorganic layered compound (A). The particle size of natural montmorillonite (Kunipia F) is 560 nm, and the a value obtained from powder X-ray diffraction is 1.
It is 2156 nm and the aspect ratio Z is 461. In addition, polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., saponification degree; 99.6%, degree of polymerization 1700) was dissolved in ion-exchanged water (0.7 μS / cm or less) to a concentration of 4.0 wt%, and this was used as a resin solution. (Solution B). Inorganic layered compound / resin = 2 in the solid component ratio (volume ratio) of liquids A and B
/ 8 so that the coating liquid (solid content 6 wt
%). Then, a 25 μm thick polyethylene terephthalate (PET) film (Lumirror; Toray Industries, Inc.)
The coating solution was applied to the surface of the surface corona-treated by (gravure coating) (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m / min, drying temperature 100 ° C.). The dry thickness of the coating layer was 0.8 μm. Coating film 2
The oxygen permeability at 4.1 ° C. and 93.3% RH was measured. The results are shown in Table 1.

[Comparative Example 3] EVOH-F film (15
Oxygen permeability of μm, ethylene content 32 mol%; Kuraray Co., Ltd., at 24.1 ° C., 93.3% RH was measured. The results are shown in Table 1.

[0042]

[Table 1] ・ PET: Biaxial polyethylene terephthalate film (water vapor transmission rate 50 g / m ² · day, manufactured by Toray Industries, Inc .: Lumirror, thickness 25 μm) ・ K: Natural montmorillonite (Kunipia F; manufactured by Kunimine Industries Co., Ltd.) ・ H: PVA117H ( Degree of saponification: 99.6%, degree of polymerization 1700;
Kuraray Co., Ltd.) ・ Annealing conditions: 180 ° C., 600 sec ・ Crosslinking agent: ammonium zirconium carbonate (Zircozol AC7: manufactured by Daiichi Rare Element Industry Co., Ltd.)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Funabashi 2-10-1 Tsukahara, Takatsuki City, Osaka Sumitomo Chemical Co., Ltd.

Claims (5)

[Claims] 1. A resin composition comprising a composition comprising a high hydrogen-bonding resin and an inorganic layered compound, which is cation-exchanged with an exchangeable cation having an ion exchange selectivity index of 19 or more, or a film comprising the same. 2. The resin composition or film according to claim 1, wherein the exchangeable cations are Ca ²⁺ ions and Ba ²⁺ ions. 3. A resin composition or film obtained by immersing the resin composition or film according to claim 1 in hot water at 40 to 80 ° C. 4. A laminate comprising at least one layer selected from biaxially oriented polypropylene, biaxially oriented nylon and biaxially oriented polyethylene terephthalate, and the resin composition or film according to any one of claims 1 to 3. A laminated film made of. 5. The resin composition according to claim 1, wherein the oxygen permeability per 1 μm in thickness at 31 ° C. and 61% RH is 0.2 cc / m ² · day · atm or less. Thing or film.