Resin composition, film, and multilayer structure

Abstract

To provide a resin composition that is excellent in gas barrier properties under high humidity conditions, especially oxygen barrier properties under high humidity conditions.SOLUTION: A resin composition contains a hydrophilic resin and a metallic compound, where the metallic compound satisfies the general formula (1): Ma(OH)bAn-(2a-b) / n (1). (In the formula, M represents a metal species; A represents an anionic ligand other than a hydroxy ligand with a valence of n-, provided that A is not O (oxo ligand); n is an integer greater than or equal to 1; and a and b are numbers greater than 0 and satisfy a / b=0.1 to 10.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, and more particularly to a resin composition capable of obtaining a film having high gas barrier properties under high humidity conditions.

Background Art

[0002] Hydrophilic resins such as polyvinyl alcohol-based resins are excellent in strength, transparency, gas barrier properties, etc., so they are formed into films and widely used as various packaging materials, particularly packaging materials for foods, pharmaceuticals, etc. that require suppression of deterioration by oxygen. However, since hydrophilic resins have many hydroxyl groups, they are easily affected by humidity, and their gas barrier properties significantly deteriorate in a high humidity environment.

[0003] As a film with improved gas barrier properties, for example, in Patent Document 1, water-insoluble inorganic fine particles with an average particle size of 500 nm or less, and a water-soluble or water-dispersible polymer compound are included, and the above water insoluble inorganic fine particles are an inorganic compound or a salt thereof having one or more selected from aluminum, silicon, zinc, zirconium, silver, and tin as essential components, and an organic acid, an inorganic acid, and a gas barrier film material which is an ionic crystal synthesized by reacting one or more compounds selected from their salts is disclosed.

[0004] Also, in Patent Document 2, a gas barrier layer forming composition containing a water-soluble polymer, at least one of a metal alkoxide, its hydrolyzate, and tin chloride and a compound represented by the general formula (R 1 Si(OR 2 )3)n (wherein R 1 is an organic functional group, R 2 is CH3, C2H5, or C2H4OCH3) is disclosed.​​​​ A product is disclosed.

[0005] Furthermore, in Patent Document 3, on the surface of a base film or a laminate containing the same, a coating film containing zinc ions, at least one of a metal alkoxide and its hydrolyzate, and a water-soluble polymer is formed, and a step of forming a gas barrier layer on the above surface is included. A method for manufacturing a gas barrier laminate is disclosed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Disclosure of the Invention

Problems to be Solved by the Invention

[0007] However, the gas barrier films disclosed in the above Patent Documents 1 to 3 do not have sufficient gas barrier properties under high humidity, and further improvement is required.

[0008] Therefore, under such circumstances, the present invention aims to provide a resin composition having excellent gas barrier properties, particularly oxygen barrier properties, under high humidity.

Means for Solving the Problems

[0009] However, the inventors of the present invention have found that by further containing a specific metal compound in a resin composition containing a hydrophilic resin, it has excellent gas barrier properties under high humidity. ​​​​​​​ .

[0010] That is, the present invention relates to a resin composition containing a hydrophilic resin and a metal compound, and the metal compound satisfies the following general formula (1) as a first gist. The resin composition satisfying the following general formula (1) is the first gist. M a (OH) b A n- (2a-b) / n ···(1) (In the above formula, M represents a metal species, and A represents an anionic ligand other than a hydroxy ligand having a valence of n−. However, O (oxo ligand) is excluded as A. n is an integer of 1 or more, and a and b are numbers greater than 0, and a / b satisfies 0.1 to 10.) In addition, the present invention has a second gist of a film containing the resin composition of the first gist, and a third gist of a multilayer structure having at least one layer made of the film of the second gist. That is, the present invention has a second gist of a film containing the resin composition of the first gist, and a third gist of a multilayer structure having at least one layer made of the film of the second gist. Further, the present invention has a second gist of a film containing the resin composition of the first gist, and a third gist of a multilayer structure having at least one layer made of the film of the second gist. Furthermore, the present invention has a second gist of a film containing the resin composition of the first gist, and a third gist of a multilayer structure having at least one layer made of the film of the second gist. That is, the present invention has a second gist of a film containing the resin composition of the first gist, and a third gist of a multilayer structure having at least one layer made of the film of the second gist.

Effects of the Invention

[0011] The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity. The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity. The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity. The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity. The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity. That is, the resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the above general formula (1). When hydrophilic resin molecules or water molecules are present around the metal compound satisfying the general formula (1), the layers of the metal compound are peeled off, and as a result of the interaction of these fine layered structural units with the hydrophilic resin at the molecular level, the film containing this resin composition is presumed to be excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity.

Embodiments for Carrying Out the Invention

[0012] Hereinafter, embodiments for carrying out the present invention will be specifically described, but the present invention is not limited thereto. That is, the present invention is not limited thereto.

[0013] The resin composition of the present invention contains a hydrophilic resin and a metal compound, and the metal compound satisfies the following general formula (1). M a (OH) b A n- (2a-b) / n ···(1) (In the above, M represents a metal species, and A represents an anionic ligand other than a hydroxy ligand with a valence of n-. However, O (oxo ligand) is excluded as A. n is an integer of 1 or more, and a and b are numbers greater than 0 and satisfy a / b = 0.1 to 10.) Hereinafter, each component will be described.

[0014] 〔Hydrophilic resin〕 Specific examples of the hydrophilic resin used in the present invention include, for example, water-soluble resins such as vinyl alcohol-based resins, polysaccharides , acrylic resins, and polyether resins. The above hydrophilic resins may be used alone or in combination of two or more.

[0015] In addition, the above hydrophilic resin preferably has the following characteristics when formed into a film, for example. That is, when a film with a thickness of 30 μm is prepared using the above hydrophilic resin and allowed to stand and immerse in water at 25°C for 2 hours, the area change rate is preferably 105% or more. The area change rate can be obtained by the following formula. That is, when a film with a thickness of 30 μm is prepared using the above hydrophilic resin and allowed to stand and immerse in water at 25°C for 2 hours, the area change rate is preferably 105% or more. The area change rate can be obtained by the following formula. Specifically, when a film with a thickness of 30 μm is prepared using the above hydrophilic resin and allowed to stand and immerse in water at 25°C for 2 hours, the area change rate is preferably 105% or more. The area change rate can be obtained by the following formula. Area change rate (%) = Film area after immersion / Film area before immersion × 100 Area change rate (%) = Film area after immersion / Film area before immersion × 100 Hereinafter, specific hydrophilic resins will be described in detail.

[0016] [Vinyl alcohol-based resin] The above vinyl alcohol-based resin generally excludes resins known as ethylene-vinyl alcohol copolymer resins (ethylene content 20 to 60 mol%), and includes, for example, poly ethylene-vinyl alcohol copolymer resins (ethylene content 20 to 60 mol%), and includes, for example, poly Examples include vinyl alcohol (hereinafter referred to as "PVA") - based resins and the like.

[0017] The above PVA - based resin is preferably an unmodified PVA resin, but a modified PVA - based resin may also be used.

[0018] The above unmodified PVA resin can usually be produced by polymerizing a vinyl ester - based monomer and then saponifying it. In addition, the above modified PVA - based resin can be produced by saponifying a copolymer of a vinyl ester - based monomer and another unsaturated monomer, or by post - modifying an unmodified PVA resin.

[0019] Examples of the above vinyl ester - based monomer include aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl versatate, vinyl trichloroacetate, etc., and aromatic vinyl esters such as vinyl benzoate, etc. Among them, aliphatic vinyl esters having 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms are preferred, and vinyl acetate is particularly preferred. These are usually used alone, but a plurality

[0020] Examples of the above other unsaturated monomers include olefins such as ethylene, propylene, isobutylene, α - octene, α - dodecene, α - octadecene, etc., unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, Salts, or nitriles such as acrylonitrile, methacrylonitrile, amides such as acrylamide, methacrylamide, ethylenesulfonic acid, olefinsulfonic acids such as allylsulfonic acid, methallylsulfonic acid or salts thereof, alkyl vinyl ethers, N - acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N - vinyl pyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth)allyl ether , polyoxypropylene (meth)allyl ether and other polyoxyalkylene (meth)allyl ethers, polyoxyethylene (meth)acrylate, polyoxypropylene (meth) acrylate and other polyoxyalkylene (meth)acrylates, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth)acrylamide and other polyoxyalkylene (meth) acrylamides, polyoxyethylene (1 - (meth)acrylamide - 1 ,1 - dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allyl amine, polyoxyethylene vinylamine, polyoxypropylene vinylamine and the like can be mentioned. These can be used alone or in combination of two or more. Note that the above “( meth)allyl” means allyl or methallyl, “(meth)acrylate” means acrylate or methacrylate, and “(meth)acryl” means acrylic or methacrylic respectively.

[0021] The above PVA - based resin can be obtained by any known polymerization method, saponification method, and post - modification method. It is possible.

[0022] Note that the introduction amount of the above-mentioned other unsaturated monomer and the modification amount by post-modification are appropriately set depending on the type of monomer, but are usually 15 mol% or less, particularly 10 mol% or less. If the introduction amount and the modification amount are too large, the crystallinity of the PVA-based resin decreases, and the gas barrier property when formed into a film tends to decrease. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726.

[0023] The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726. The average saponification degree of the above PVA-based resin is usually 70 to 100 mol%, preferably 80 to 100 mol%, particularly preferably 85 to 100 mol%, and more preferably 90 to 99.99 mol%. If the average saponification degree is less than 70 mol%, the oxygen permeability under high humidity tends to increase. The above average saponification degree is measured in accordance with JIS K 6726.

[0024] The average degree of polymerization of the above PVA-based resin is usually 100 to 4,000, preferably 200 to 3,000, and particularly preferably 250 to 2,500. If such an average degree of polymerization is too low, the mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to form an aqueous solution, and the handling becomes difficult. The above average degree of polymerization is measured in accordance with JIS K 6726. The average degree of polymerization of the above PVA-based resin is usually 100 to 4,000, preferably 200 to 3,000, and particularly preferably 250 to 2,500. If such an average degree of polymerization is too low, the mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to form an aqueous solution, and the handling becomes difficult. The above average degree of polymerization is measured in accordance with JIS K 6726. The average degree of polymerization of the above PVA-based resin is usually 100 to 4,000, preferably 200 to 3,000, and particularly preferably 250 to 2,500. If such an average degree of polymerization is too low, the mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to form an aqueous solution, and the handling becomes difficult. The above average degree of polymerization is measured in accordance with JIS K 6726. The average degree of polymerization of the above PVA-based resin is usually 100 to 4,000, preferably 200 to 3,000, and particularly preferably 250 to 2,500. If such an average degree of polymerization is too low, the mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to form an aqueous solution, and the handling becomes difficult. The above average degree of polymerization is measured in accordance with JIS K 6726. The average degree of polymerization of the above PVA-based resin is usually 100 to 4,000, preferably 200 to 3,000, and particularly preferably 250 to 2,500. If such an average degree of polymerization is too low, the mechanical properties such as film strength tend to decrease, and if it is too high, it tends to be difficult to form an aqueous solution, and the handling becomes difficult. The above average degree of polymerization is measured in accordance with JIS K 6726.

[0025] Also, as the PVA-based resin, two or more kinds having different modification types, modification amounts, average saponification degrees, average degrees of polymerization, etc. may be used in combination. Also, as the PVA-based resin, two or more kinds having different modification types, modification amounts, average saponification degrees, average degrees of polymerization, etc. may be used in combination.

[0026] [Polysaccharide] Examples of the above polysaccharide include starch, cellulose, etc. Examples of the above starch include natural starches such as corn starch and potato starch, and ethers Modified starches such as gelatinized starch, esterified starch, crosslinked starch, grafted starch, roasted dextrin, enzyme-modified dextrin, alpha-starch, oxidized starch, etc. are included. Examples of the above cellulose include carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose , hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, nitrocellulose, cationized cellulose, etc., and metal salts such as their sodium salts. are included.

[0027] [Acrylic resin] Examples of the above acrylic resin include polyacrylamide, polyacrylic acid, and metal salts such as their sodium salts.

[0028] [Polyether resin] Examples of the above polyether resin include polyethylene glycol, polypropylene glycol, etc.

[0029] Among the above hydrophilic resins, vinyl alcohol-based resins and polysaccharides are preferable from the viewpoint of excellent oxygen barrier properties under high humidity conditions, and more preferably PVA-based resins, modified starches (especially modified starches), hydroxypropyl methyl cellulose, and most preferably unmodified PVA resin. is.

[0030] The above hydrophilic resin is preferably the main component of the resin composition of the present invention, and the content of the hydrophilic resin in the entire resin composition is usually 80% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more. The upper limit is usually 99.99% by weight. is.

[0031] 〔Metal compound〕 The metal compound used in the present invention has a structure in which specific structural units are layered at specific interplanar spacings. It has the following structure.

[0032] The above structural unit contains a metal, a hydroxy ligand, and an anionic ligand other than the hydroxy ligand. It is represented by the following chemical formula (1). M a (OH) b A n- (2a-b) / n ···(1) (In the above formula, M represents a metal species, and A represents an anionic ligand other than the hydroxy ligand with a valence of n-. However, O (oxo ligand) is excluded as A. n is an integer of 1 or more, and a and b are numbers greater than 0. They satisfy a / b = 0.1 to 10.)

[0033] In the above chemical formula (1), examples of M include Na, K, Ca, Mg, Si, Al. , Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, etc. These metal species may be contained alone or in combination of two or more. Among them, Al, Si, Mg, Ni, Co, Zn are preferred from the viewpoint of excellent oxygen barrier properties under high humidity. Ni, Co, Zn are particularly preferred, and Zn is especially preferred.

[0034] In the above chemical formula (1), examples of A include RO (alkoxy ligand), ROCO (carboxylic acid ligand), CO3, NO3, SO3, PO4, BO3, F, Br, Cl. etc. (R is an alkyl chain, C m H 2m+1 ; It is generally represented by the chemical formula m = 1 to 20. However, as long as the effects of the present invention are not inhibited, the alkyl chain may have a functional group such as an OH group. ). However, O (oxo ligand) is excluded as A. These ani The ionic ligand may be contained alone or in combination with two or more kinds of the hydrophilic resin. From the viewpoint of interaction, NO3, Cl, RO, and ROCO are preferred, and ROCO is particularly preferred. Among these, CH3OCO is particularly preferred.

[0035] The metal compound used in the present invention may contain water molecules.

[0036] Specific examples of the metal compounds include layered compounds containing Zn as a metal species. Among these, the compound with the chemical formula [Zn5(O A Zn-containing layered compound represented by the formula (H)8(CH3CO2)2·2H2O) is preferred.

[0037] The metal compounds can be obtained, for example, by reacting metal-containing compounds under specific conditions. It is possible.

[0038] Examples of the metal-containing compound include organic acid metal salts and inorganic metal salts.

[0039] Examples of the organic acid constituting the organic acid metal salt include monocarboxylic acids such as acetic acid, Dicarboxylic acids such as citric acid, oxalic acid, and tartaric acid, citric acid, and ethylenediaminetetraacetic acid These may be used alone or in combination of two or more kinds. The organic acid metal salt may be a hydrate or an anhydrous salt. As the organic acid metal salt, monovalent carbohydrate is preferred because it has excellent oxygen barrier properties under high humidity. Metal phosphates are preferred, metal acetates are particularly preferred, and zinc acetate or is its hydrate.

[0040] Examples of the inorganic metal salts include metal fluorides, chlorides, bromides, iodides, and oxides. Examples include sulfuric acid and the like. These may be used alone or in combination of two or more. In addition, the inorganic metal salt may be a hydrate or an anhydride. As the above inorganic metal salt, metal chlorides and oxoacids are preferred from the viewpoint of excellent oxygen barrier properties under high humidity conditions, and zinc chloride, zinc nitrate or their hydrates are particularly preferred.

[0041] The metal compound used in the present invention can be obtained, for example, by using the above metal-containing compound and (I) reacting the metal-containing compound under a base, (II) heating the metal-containing compound and reacting it, and the like. Hereinafter, each method will be described in detail.

[0042] [Method (I)] The method (I) is a method of reacting a metal-containing compound under a base.

[0043] Examples of the base used in the method (I) include hydroxides of alkali metals or alkaline earth metals. Among them, alkali metal hydroxides are preferred because of their excellent reactivity with metal-containing compounds, and sodium hydroxide is particularly preferred.

[0044] In the reaction between the metal-containing compound and the base, usually, the metal-containing compound and the base may be mixed and reacted in a solution. The method of mixing the metal-containing compound and the base is not particularly limited. For example, a method of mixing a solution in which the metal-containing compound is dissolved and a solution in which the base is dissolved, a method of mixing a slurry solution in which the metal-containing compound is dispersed and a solution in which the base is dissolved, and the like can be mentioned. Among them, from the viewpoint of reaction efficiency, a solution in which the metal-containing compound is dissolved and a solution in which the base is dissolved ​​​​​​A method of mixing with a liquid is preferred. Furthermore, an organic acid metal salt is used as the metal-containing compound. In the case of using an organic acid metal salt, a method of adding and mixing a solution in which the organic acid metal salt is dissolved to a solution in which a base is dissolved is preferred. In the case of using an inorganic metal salt, a method of adding and mixing a solution in which a base is dissolved to a solution in which the inorganic metal salt is dissolved is preferred.

[0045] As the solvent for dissolving the metal-containing compound and the base, there is no particular limitation as long as it can dissolve the metal-containing compound and the base. For example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and other lower alcohols having 1 to 5 carbon atoms can be mentioned. These may be used alone or in combination of two or more. Among them, water is preferred from the viewpoint of easy post-treatment.

[0046] The concentration of the metal-containing compound in the solution in which the metal-containing compound is dissolved is usually 0.5 to 3 mol / L, preferably 1 to 2 mol / L. Also, the concentration of the base in the solution in which the base is dissolved in the solvent is usually 0.01 to 100 mol / L, preferably 0.1 to 30 mol / L, and particularly preferably 1 to 10 mol / L. If the concentrations of the metal-containing compound and the base are too low compared to the above ranges, the reaction tends not to proceed sufficiently. On the other hand, if the concentrations of the metal-containing compound and the base are too high compared to the above ranges, side reactions tend to occur.

[0047] The molar ratio of the metal-containing compound to the base (metal-containing compound: base) is usually 0.5:2 to 2:0.5, preferably 0.8:1.5 to 1.5:0.8, and particularly preferably 0.9:1.2 to 1:1. If the molar ratio is outside the above range, the reaction does not proceed sufficiently.

[0047] The molar ratio of the metal-containing compound to the base (metal-containing compound: base) is usually 0.5:2 to 2:0.5, preferably 0.8:1.5 to 1.5:0.8, and particularly preferably 0.9:1.2 to 1:1. When the molar ratio is outside the above range, the reaction does not proceed sufficiently. There is a tendency not to.

[0048] Also, the pH when reacting the metal-containing compound with the base is usually 4 to 9, preferably it is 5 to 8. When the pH is too low compared to the above range, the reaction tends not to proceed sufficiently. Also, when the pH is too high compared to the above range, the formed metal compound tends to decompose. Note that the pH adjustment is performed by adjusting the amounts of the solution in which the metal-containing compound is dissolved and the solution in which the base is dissolved. to be used.

[0049] The reaction temperature in the above reaction is usually 15 to 60 °C, preferably 20 to 40 °C. If the reaction temperature is too low, the reaction tends not to proceed sufficiently, and if the reaction temperature is too high, the metal containing compound decomposes due to heat, and there is a tendency that the target metal compound cannot be obtained. Also, the reaction time is usually 0.5 to 5 hours, preferably 1 to 3 hours, and the pressure during the reaction may be normal pressure.

[0050] After the above reaction, the metal compound is obtained as a precipitate. The obtained metal compound may be used as it is, but it is preferable to purify the metal compound by washing, grinding operations, etc. and then use it.

[0051] [Method of (II)] The method of (II) above is a method of heating and reacting a metal-containing compound.

[0052] The method of (II) above is usually carried out by heating the solution in which the metal-containing compound is dissolved while stirring. to do.

[0053] As the solvent for dissolving the metal-containing compound, the solvents listed in the method of (I) above are used. It is possible. Among them, water and alcohols are preferable, and a mixed solvent of water and 1-propanol is particularly preferable. The medium is particularly preferred.

[0054] As the above heating conditions, the temperature of the solution is usually 20 to 100 °C, preferably 50 to 95 °C , particularly preferably heated at 70 to 90 °C. If the reaction temperature is too low, the reaction tends not to proceed sufficiently , and if the reaction temperature is too high, the metal-containing compound decomposes due to heat, and the target metal compound tends not to be obtained. In addition, the reaction time is usually 0.1 to 100 hours, preferably 0.5 to 30 hours, particularly preferably 1 to 10 hours, and the pressure during the reaction may be normal pressure.

[0055] After the above reaction, the metal compound is obtained as a precipitate. The obtained metal compound may be used as it is , or the metal compound may be purified by washing, pulverization operation, etc. and then used.

[0056] Generally, the metal compound refers to, for example, a metal salt, a metal oxide, a metal complex, a metal simple substance or an alloy, etc. However, the metal compound obtained by each of the above methods has, as described above, a structure in which the layered structural unit represented by the above chemical formula (1) is layered at a specific interplanar spacing. Therefore, in the presence of hydrophilic resin molecules or water molecules around the metal compound, the layers of the metal compound are peeled off, and as a result of the interaction of the peeled fine layered structural units with the hydrophilic resin at the molecular level, excellent oxygen barrier properties are presumed to be obtained. The metal compound used in the present invention is excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity conditions. Therefore, when measured by wide-angle X-ray diffraction using CuKα rays, X-ray diffraction occurs at 2θ = 2 to 15°. Since the metal compound used in the present invention is excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity conditions, when measured by wide-angle X-ray diffraction using CuKα rays, X-ray diffraction occurs at 2θ = 2 to 15°. When the layers of the metal compound are peeled off and the peeled fine layered structural units interact with the hydrophilic resin at the molecular level, excellent oxygen barrier properties are presumed to be obtained. As a result of the interaction of the peeled fine layered structural units with the hydrophilic resin at the molecular level, excellent oxygen barrier properties are presumed to be obtained.

[0057] The metal compound used in the present invention is excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity conditions. Therefore, when measured by wide-angle X-ray diffraction using CuKα rays, X-ray diffraction occurs at 2θ = 2 to 15°. Preferably having a main peak of the fold, more preferably having a main peak at 2θ = 2 to 9°, even more preferably having a main peak at 2θ = 3 to 8°. When the X-ray diffraction has a main peak within the above range, the metal compound and the hydrophilic resin interact, and the polarity of the hydrophilic resin increases, resulting in excellent oxygen barrier properties

[0058] under high humidity. The interlayer distance (distance between layers) of the above metal compound is preferably 0.01 to 50 nm, more preferably 0.1 to 30 nm, from the viewpoint of the interaction with the molecules of the hydrophilic resin and water molecules. The interlayer distance of the above metal compound can be calculated from Bragg's equation based on the diffraction position of the peak with the strongest intensity in the range of 2θ = 2 to 15° when analyzed by the X-ray diffraction method.

[0059] The molecular weight of the layered structural unit exfoliated from the above metal compound is preferably 100 to 10,000, and particularly preferably 200 to 2,000, from the viewpoint that

[0060] mutual interaction is possible at the molecular level of the hydrophilic resin. Also, the above layered structural unit is preferably hydrophilic from the viewpoint of the interaction with the molecules of the hydrophilic resin. Furthermore, it is preferable that the above layered structural unit does not decompose even when

[0061] allowed to stand for 1,000 hours in an environment of 20°C and 90% RH. The metal conversion content of the metal compound in the resin composition of the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, and particularly preferably The raw barrier property tends to decrease. When the content of the metal compound is too high, whitening occurs and the transparency tends to decrease when made into a film or the like. In the case of, there is a tendency for whitening to occur and the transparency to decrease. In addition, when the resin composition contains a plurality of metal compounds having different metal species, the total amount of all the metal compounds contained in the resin composition is defined as the content. is used as the content. Also, the content of the above metal compound can be determined by the standard addition method using ICP-MS. is possible.

[0062] [Other components] In the resin composition of the present invention, within a range that does not inhibit the effects of the present invention, generally, compounding agents that are compounded in resin compositions, such as heat stabilizers, antioxidants, antistatic agents, coloring agents, ultraviolet absorbers, lubricants, plasticizers, light stabilizers, surfactants, antibacterial agents, desiccants, antiblocking agents, flame retardants, crosslinking agents, curing agents, foaming agents, crystal nucleating agents, antifogging agents, biodegradable additives, silane coupling agents, oxygen absorbers, etc. may be contained. These can be used alone or in combination of two or more. is possible. is possible. can be used.

[0063] The resin composition of the present invention can be obtained by mixing a hydrophilic resin, a metal compound, and, if necessary, other components. is possible.

[0064] [Resin composition] The resin composition of the present invention contains the above hydrophilic resin and a metal compound that satisfies the following general formula (1). is. M a (OH) b A n- (2a-b) / n ···(1) (In the above, M represents a metal species, and A represents an anionic ligand other than a hydroxy ligand having a valence of n-. However, O (oxo ligand) is excluded as A. n is an integer of 1 or more, and a and b are 0 is a larger number and satisfies a / b = 0.1 to 10.)

[0065] The layered structure of the metal compound satisfying the general formula (1) interacts with the hydrophilic resin and it is presumed that the effect of excellent oxygen barrier properties under high humidity is obtained by increasing the polarity of the hydrophilic resin is obtained.

[0066] In addition, in the present invention, from the viewpoint of excellent gas barrier properties, particularly oxygen barrier properties, under high humidity when measured by wide-angle X-ray diffraction using CuKα rays, it preferably has a main peak of X-ray diffraction at 2θ = 2 to 15°, more preferably has a main peak at 2θ = 2 to 9° and particularly preferably has a main peak at 2θ = 3 to 8°

[0067] The main peak of X-ray diffraction observed at 2θ = 2 to 15° when measured by wide-angle X-ray diffraction using the above CuKα rays is preferably a peak derived from the metal compound satisfying the general formula (1)

[0068] The wide-angle X-ray diffraction is measured under the following conditions [Measurement conditions] · Equipment used: D8 DISCOVER (manufactured by Bruker Japan) · Detector: 2D detector VANTEC-500 (manufactured by Bruker Japan) · Voltage: 50 kV · Current: 100 mA · Camera length: 100 mm · Measurement method: Reflection method · Integration time: 30 minutes · Wavelength: CuKα ray (Kα1 and Kα2 are not separated) · Detector position: 2θ = 10° · X-ray incident angle: θ = 0.3° · Conditions for one-dimensionalization in the 2θ direction: 2θ = 0 to 35°, azimuth angle (chi) = -95 to -85°​​​ · One-dimensionalization in the azimuth direction: Azimuth (chi) = -180 to 0° When one-dimensionalizing in the azimuth direction, the peak with the strongest diffraction intensity within the range of 2θ = 2 to 15° is included and one-dimensionalized in the azimuth direction within a range of 1.0°. At this time, the azimuth -18 If a peak is observed within the range of 0 to 0°, it is determined that a diffraction peak is observed within the range of 2θ = 2 to 15°. For example, when a diffraction peak is observed at 2θ = 6.8°, when one-dimensionalized in the azimuth direction within the range of 2θ = 6.0 to 7.0°, if a peak is observed within the range of azimuth = -180 to 0°, it can be determined that a diffraction peak is observed within the range of 2θ = 2 to 15°. For the sample used in the above wide-angle X-ray diffraction, the resin composition in the film state described later can be used as it is. Also, when the film of the above resin composition is laminated with another substrate and the resin composition layer can be peeled off, the resin composition layer is peeled off for measurement. If it cannot be peeled off, measurement can be performed in the state laminated with the other substrate. Note that during measurement the thickness of the resin composition layer (film) is preferably 30 μm or more. If the film thickness is insufficient, the film may be laminated.

[0069] <Film containing a resin composition> The film containing the resin composition of the present invention is obtained by forming a film of the composition containing the above resin composition, and preferably, it is obtained by forming a film of the above resin composition. As a method for forming the above film, for example, a solution of a composition containing a resin composition( is used. The thickness of the resin composition layer (film) is preferably 30 μm or more. If the film thickness is insufficient, the film may be laminated.

[0070] <Film containing a resin composition> The film containing the resin composition of the present invention is obtained by forming a film of the composition containing the above resin composition, and preferably, it is obtained by forming a film of the above resin composition. As a method for forming the above film, for example, a solution of a composition containing a resin composition( is used.

[0071] As a method for forming the above film, for example, a solution of a composition containing a resin composition( ​A method using a coating solution, a pellet-like composition containing the resin composition of the present invention, Examples include a method of melt molding using an extruder. Among them, a method using a solution (coating solution) of a composition containing the resin composition is preferred. Further, when using the above coating solution The solid content concentration is usually 0.5 to 30% by weight, preferably 5 to 20% by weight.

[0072] The preparation of the above coating solution can be carried out, for example, by charging all components into a solvent at once and mixing them, or by adding and mixing other components to a solution in which some components are dissolved in a solvent. Examples include Among them, from the viewpoint of workability, a method of adding and mixing other components to a solution in which a hydrophilic resin is dissolved in a solvent is preferred. In addition, in the method for obtaining the above metal compound, when reacting a metal-containing compound, it is also preferable to dissolve a hydrophilic resin in a solvent This is particularly preferred when obtaining a metal compound by the method of (II) above from the viewpoint of workability. As the above solvent, the solvents mentioned for the above metal compound can be used.

[0073] As the above film-forming method, for example, known methods such as a melt extrusion method, an endless belt method, a drum method, and a casting method by a casting method such as a coating method can be adopted. Among them, a method by a casting method is preferred, and a method by a coating method is particularly preferred.

[0074] Examples of the above coating method include known methods such as a bar coater, roll coating, die coating gravure coating, comma coating, screen printing, etc.

[0075] After coating, it is dried by heat treatment at, for example, 60 to 105 °C for 0.5 to 10 minutes ​​Thus, a film made of the resin composition can be obtained. Further, the film may be subjected to stretching operations such as uniaxial stretching or biaxial stretching as needed.

[0076] The film may be a single-layer film or a multilayer structure. The above-mentioned multi- layer structure preferably has at least one layer made of the above-mentioned film. Further, the above- mentioned multilayer structure may be formed by laminating the formed film, or may be laminated with other base resins.

[0077] The thickness of the film is usually 1 to 200 μm, preferably 1 to 100 μm, and particularly preferably 1 to 50 μm. When the formed film is a multilayer structure, the total thickness of all the films made of the resin composition is taken as the thickness of the film.

[0078] Examples of the base resin include polyethylene resins such as linear low-density polyethylene, low-density polyethylene, ultra- low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, ethylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymers, polypropylene, propylene-α-ole fin (α-olefin having 4 to 20 carbon atoms) copolymers, etc., polypropylene resins, polybut tene, polypentene, polycyclic olefin resins (polymers having a cyclic olefin structure in at least one of the main chain and side chains), etc. (unmodified) polyolefin resins, and modified olefin resins such as unsaturated carboxylic acid-modified polyolefin resins obtained by graft-modifying these polyolefins with unsaturated carboxylic acids or their esters, etc. including polyolefin resins in a broad sense. ​​Fats, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, e thylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polysty rene, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, aromatic or aliphatic polyketones, etc. These may be used alone or in combination of two or more. Further, these base resins may be subjected to surface treatment such as corona treatment.

[0079] The film containing the resin composition of the present invention has excellent gas barrier properties under high humidity. However, when this film is allowed to stand under high humidity, it can be made into a film having even more excellent gas barrier properties, particularly oxygen barrier properties under high humidity, which is preferable. The principle by which such an effect is obtained is not clear, but it is presumed that the molecules of the hydrophilic resin are plasticized by

[0080] standing under high humidity, and the metal compounds dispersed in the film interact with the hydrophilic resin or localize on the surface of the film. In the present invention, high humidity means 20 ± 5°C and 90 ± 10% RH.

[0081] Also, the oxygen permeability of the film made of the resin composition is 80 cc·3μm / m 2 ·day ·Preferably, it is below ·atm, 70 cc·3 μm / m 2 ·day·atm or less ·day·atm or less is more preferable, 55 cc·3 μm / m 2 ·day·atm or less is even more preferably, 40 cc·3 μm / m 2 ·day·atm or less is even more preferable 、35 cc·3 μm / m 2 ·day·atm or less is even more preferable, 30 cc ·3 μm / m 2 ·day·atm or less is even more preferable, 25 cc·3 μm / m 2 ·day·atm or less is particularly preferable. The oxygen permeability is measured at 23 °C 、in an environment of 80% RH, and the lower limit of the oxygen permeability is usually 0 cc·3 μm / m 2 ·day·atm. Also, the above oxygen permeability can be obtained by an oxygen permeability measuring device .

[0082] The film containing the resin composition of the present invention is extremely excellent in transparency, and its transparency is much superior to that of a film containing an inorganic layered compound or a filler. Specifically 、the film containing the resin composition of the present invention preferably has a haze of 1% or less 、more preferably 0.6% or less, even more preferably 0.3% or less, and particularly preferably 0 .2% or less. The above haze is the HAZE value measured in accordance with the standard of JIS K7361-1 . For example, 10 test pieces of 50 mm × 50 mm are cut out from the film 、and measured using a haze meter (NDH-4000 manufactured by Nippon Denshoku Co., Ltd.), and the average value of the 10 pieces is taken as the haze (%). 、and the average value of the 10 pieces is taken as the haze (%). .

[0083] The resin composition of the present invention and the film made of the resin composition are useful as packaging materials, and can be preferably used particularly as packaging materials for foods, pharmaceuticals, and the like.

Examples

[0084] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist. In the following, "parts" means a weight basis. standard.

[0085] Prior to the examples, the following hydrophilic resins were prepared.

[0086] 〔Hydrophilic resin〕 [PVA-based resin] ·PVA (unmodified PVA resin, average degree of polymerization 300, average saponification degree 99 mol%)

[0087] Also, the synthesis of the metal compound was carried out according to the following procedure.

[0088] <Synthesis of Zn-containing layered compound> The synthesis of the Zn-containing layered compound was carried out according to the method described in Inorg. Chem. 2013, 52, 95-102. Specifically, while stirring 900 parts of a 1.5 mol / L aqueous sodium hydroxide solution at 27°C, 900 parts of a 1.5 mol / L aqueous solution of zinc acetate dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at 27°C for 2 hours to cause a reaction. After the reaction, the precipitated white precipitate was filtered off under reduced pressure. Thereafter, the obtained white solid and 750 parts of water were stirred and filtered again to wash the white solid. This washing operation was performed a total of 3 times while replacing the water. Finally, the filtered white solid was dried at 60°C overnight (10 hours) under normal pressure to obtain a Zn-containing layered compound.

[0089] <Identification of the synthesized Zn-containing layered compound> The above Zn-containing layered compound was measured by solid-state NMR and wide-angle X-ray diffraction to identify the Zn-containing layered compound.

[0090] 〔Solid-state NMR ( 13 C-CP / MS) measurement〕 The above Zn-containing layered compound was filled into a 4 mm φ zirconia rotor and sealed with a polyethylene drive tip to obtain a measurement sample. This measurement sample was measured by solid-state NMR [AVANCEI II 400WB ( 1 H: 400 MHz, 13 C: 100 MHz), manufactured by Bruker Japan 〕using a CP / MAS probe. The measurement conditions were as follows: after rotation at 5000 Hz, a 90° pulse width of 45 μs, a contact time of 2 m s, an integration time of 485 times, an acquisition time of 50 ms, and a delay time of 5 s.

[0091] 〔Wide-angle X-ray diffraction (XRD) measurement〕 The above Zn-containing layered compound was measured by wide-angle X-ray diffraction (XRD) under the following conditions. [Measurement conditions] Equipment used: D8 DISCOVER (manufactured by Bruker Japan) Voltage: 50 kV Current: 100 mA Camera length: 150 mm Measurement method: Reflection method Integration time: 20 minutes As a result of the measurement, peaks were mainly detected at 2θ = 6.8°, 13.5°, and 20.2°.

[0092] From the measurement results of the above solid-state NMR and wide-angle X-ray diffraction, since they were consistent with the Zn-containing layered compound described in Inorg. Chem. 201 3, 52, 95-102, the obtained Zn-containing layered compound was identified as [Zn5(OH)8(CH3CO2)2·2H2O].

[0093] Further, based on the diffraction position at 2θ = 6.8° where the peak intensity was the strongest when the above Zn-containing layered compound [Zn5(OH)8(CH3CO2)2·2H2O] was measured by wide-angle X ray diffraction, the interlayer distance was calculated from the Bragg's formula. As a result, the above Zn-containing layered compound [Zn5(OH)8(CH 3CO2)2·2H2O] was a layered compound with an interlayer distance of 1.3 nm.

[0094] <Example 1> To 900 parts of water, 100 parts of PVA was added, and the mixture was heated and stirred at 90 °C for 1 hour to completely dissolve the PVA. This solution was cooled to 60 °C, and 0.5 part of the Zn-containing layered compound obtained above was added per 100 parts of PVA in terms of metal conversion, and the mixture was stirred at 60 °C for 1 hour to prepare a resin composition (coating solution). The obtained coating solution was applied to the corona-treated surface of a PET substrate with a thickness of 38 μm using a wire bar #18, and dried at 80 °C for 5 minutes to obtain a two-layer film with a 3-μm-thick film layer laminated on the PET substrate. The obtained film was allowed to stand for 200 hours under the humidity control conditions of 23 °C and 80% RH to condition the film.

[0095] <Example 2> In Example 1, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity control conditions, except that the amount of the Zn-containing layered compound to be added was changed to 1 part in terms of metal conversion per 100 parts of PVA.

[0096] <Example 3> In Example 1, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity control conditions, except that the amount of the Zn-containing layered compound to be added was changed to 3 parts in terms of metal conversion per 100 parts of PVA. ​​​​​​​

[0097] <Example 4> In Example 1, except that the amount of the Zn-containing layered compound to be added was changed to 5 parts in terms of metal based on 100 parts of PVA, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity conditions. and prepared.

[0098] <Comparative Example 1> In Example 1, except that no Zn-containing layered compound was added, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity conditions.

[0099] <Comparative Example 2> In Example 1, except that zinc oxide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added in an amount of 1 part in terms of metal based on 100 parts of PVA instead of the Zn-containing layered compound, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity conditions.

[0100] <Comparative Example 3> In Example 1, except that zinc chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added in an amount of 1 part in terms of metal based on 100 parts of PVA instead of the Zn-containing layered compound, a film was prepared in the same manner as in Example 1 and conditioned under the same humidity conditions.

[0101] Using the films of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above, wide-angle X-ray diffraction and oxygen barrier properties were measured under the following conditions. The results are shown in Table 1 below.

[0102] [Wide-angle X-ray diffraction (XRD) measurement of the film] The resin composition film obtained above was peeled off from the PET film and laminated to a thickness of 30 μm or more to obtain a sample. The wide-angle X-ray diffraction measurement of this sample was carried out under the following conditions. [Measurement conditions] ​​​​​​​​Machine used: D8 DISCOVER (manufactured by Bruker Japan Co., Ltd.) Detector: 2D detector VANTEC-500 (manufactured by Bruker Japan Co., Ltd.) Voltage: 50 kV Current: 100 mA Camera length: 100 mm Measurement method: Reflection method Integration time: 30 minutes Wavelength: CuKα ray (Kα1 and Kα2 are not separated) Detector position: 2θ = 10° X-ray incident angle: θ = 0.3° Condition for one-dimensionalization in the 2θ direction: 2θ = 0 to 35°, azimuth angle (chi) = -95 to -85° One-dimensionalization in the azimuth angle direction: 2θ = 6.0 to 7.0°, azimuth angle (chi) = -180 to 0° After X-ray diffraction measurement, the obtained diffraction image was one-dimensionalized in the azimuth angle direction in the range of 2θ = 6.0 to 7.0° and -180 to 0° to confirm the azimuth angle dependence of the diffraction intensity. At this time If a diffraction peak is observed at the azimuth angle of -90°, it was determined that the resin composition has a diffraction peak at 2θ = 6.0 to 7.0°.

[0103] 〔Oxygen barrier property〕 The oxygen permeability of the obtained resin composition film was measured under the conditions of 23°C and 80% RH using an oxygen permeability measuring device (OX-TRAN1 00A, manufactured by MOCON).

[0104]

Table 1

[0105] As can be seen from Table 1 above, Examples 1 to 4 containing a hydrophilic resin and a metal compound satisfying the general formula (1) had excellent oxygen barrier properties under high humidity conditions. On the other hand, Comparative Examples 1 to 3 that did not contain a metal compound satisfying the general formula (1) all had oxygen barriers ​​It was inferior in reality.

Industrial Applicability

[0106] The resin composition of the present invention is excellent in gas barrier properties, particularly oxygen barrier properties, under high humidity conditions. Therefore, it is useful as a packaging material, and can be suitably used particularly as a packaging material for foods, pharmaceuticals, etc. It can be used.

Claims

1. A resin composition comprising a hydrophilic resin and a metal compound, wherein the metal compound satisfies the following general formula (1). (In the formula, M represents a metal species, and A represents an anionic ligand other than a hydroxy ligand having a valence of n−. However, O (oxo ligand) is excluded as A.) M a (OH) b A n- (2a-b) / n ...(1) n is an integer of 1 or more, and a and b are numbers greater than 0, and a / b satisfies 0.1 to 10.)

2. The resin composition according to claim 1, wherein the metal content in terms of metal of the metal compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydrophilic resin.

3. A film comprising the resin composition according to claim 1 or 2.

4. The film according to claim 3, wherein... is... per day·atm or less.

5. A multilayer structure having at least one layer made of the film according to claim 3 or 4. ​ The oxygen permeability of the above film under the conditions of 23°C and 80% RH is 80 cc·3μm / m 2 ​ ​ ​ ​

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