Resin composition, molded article using the same, and method for producing resin composition

Abstract

A resin composition which contains a resin (A) containing 30% by mole or more of a structural unit that is represented by formula (1), and a boron compound (B), wherein the elemental boron contained in the boron compound (B) is 0.01 to 2,000 micromoles relative to 1 g of the resin (A).

Description

Technical Field

[0001] The present invention relates to a resin composition containing a resin containing a polymethallyl alcohol unit and a molded article using the same. The present invention also relates to a method for producing the resin composition.

Background Art

[0002] Gas barrier materials using resins excellent in the performance of blocking gases such as oxygen (gas barrier property) are widely used mainly in the field of packaging materials containing foods, pharmaceuticals, etc. as contents. Since molded articles such as packaging materials are usually manufactured by heat-melting molding, in addition to the gas barrier property, the above resins are required to have heat stability such as color resistance (property that coloring such as yellowing does not occur due to heat) and long-run property (property that physical properties such as viscosity do not change even in long-time melt molding). Further, when laminating another layer on the layer made of the above resin, interlayer adhesiveness is also required so that the layers do not easily peel off.

[0003] As resins having good gas barrier properties, vinyl alcohol polymers represented by ethylene-vinyl alcohol copolymers (hereinafter sometimes abbreviated as EVOH) and methallyl alcohol polymers have been reported (Patent Document 1, Patent Document 2). Further, polymethallyl alcohol (hereinafter sometimes abbreviated as PMAL) is known as a resin showing better gas barrier properties (Patent Document 3).

[0004] EVOH is suitably used as a gas barrier material, but the thermal stability, interlayer adhesiveness, and gas barrier property of EVOH in a high-humidity environment have not been satisfactory. For example, Patent Document 1 discloses that an EVOH composition containing a predetermined amount of a carboxylic acid and an alkaline earth metal has less coloring and film surface unevenness and is excellent in appearance even during coextrusion molding or co-injection molding with a resin having a high melting point such as polyamide or polyester, or during melt molding at a high temperature, and is excellent in long-term properties and low odor. However, since the gas barrier property of the above EVOH composition deteriorates in a high-humidity environment, there are limitations in applications and usage forms. Further, since EVOH has a small water vapor barrier property, when a water vapor barrier property is required, it has been necessary to use it as a multilayer structure with a material having an excellent water vapor barrier property.

[0005] Patent Document 2 discloses that a gas barrier material made of a resin containing a methallyl alcohol unit exhibits excellent gas barrier properties even under high humidity and is excellent in transparency and melt moldability. However, there is room for improvement in thermal stability such as coloring resistance and long-term properties, and further in interlayer adhesiveness.

[0006] As a material for solving the above problems, a polymethallyl alcohol resin composition excellent in gas barrier properties and thermal stability (coloring resistance and long-term properties) under high humidity, and a molded article using the same have been reported. (Patent Document 3) However, in this report, in order to improve physical properties, it is necessary to add at least one of an acid component having a logarithm value pKa of the reciprocal of the acid dissociation constant at 25 °C of 3.5 to 7.5 and an anion of the acid component. (Patent Document 3) Therefore, for example, when sodium acetate is added, there is a risk of acetic acid elution from the resin, and corrosion of stainless steel or the like used in the equipment is a concern ( Non-Patent Document 1 and Patent Document 4).

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, an object of the present invention is to provide a resin composition excellent in coloring resistance, long-term properties, interlayer adhesion, and gas barrier properties under high humidity, a molded article using the same, and a method for producing the resin composition.

Means for Solving the Problems

[0009] As a result of intensive studies by the present inventors, it has been found that a resin containing a structural unit represented by the following formula (1) in a predetermined amount or more and a resin composition containing a boron compound in a predetermined amount are excellent in thermal stability and have excellent gas barrier properties. Based on this finding, further studies were repeated to complete the present invention.

[0010] That is, the present invention provides the following [1] to

[11] . [1] A resin composition containing a resin (A) containing 30 mol% or more of a structural unit represented by the following formula (1) and a boron compound (B), wherein the boron element contained in the boron compound (B) is 0.01 to 2,000 micromoles per 1 g of the resin (A).

Chemical Formula

Chemical formula

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a resin composition excellent in color resistance, long-term stability, interlayer adhesion, and gas barrier properties under high humidity, a molded article using the same, and a method for producing the resin composition.

Modes for Carrying Out the Invention

[0012] Hereinafter, the present invention will be described in detail. In this specification, the specified preferred regulations can be arbitrarily adopted, and the combination of preferred ones can be said to be more preferred. In this specification, the description of "XX to YY" means "XX or more and YY or less". In the following production examples, examples, and comparative examples, unless otherwise specified, "parts" means parts by mass.

[0013] <Resin composition> The resin composition of the present invention contains a resin (A) containing 30 mol% or more of a structural unit represented by the following formula (1), and a boron compound (B), and the boron element contained in the boron compound (B) is 0.01 to 2,000 micromoles with respect to 1 g of the resin (A).

[0014] [Chemical formula]

[0015] Since the resin (A) containing 30 mol% or more of the structural unit represented by the formula (1) has a quaternary carbon in the main chain, the rotational movement of the main chain is suppressed. As a result, the diffusion of gas molecules in the resin is slowed down, and high barrier properties are exhibited even under high humidity. Further, the resin composition of the present invention contains a predetermined amount of boron element contained in the boron compound (B) with respect to 1 g of the resin (A), so that the hydroxyl group in the structural unit represented by the formula (1) coordinates with the boron element. Although the reason for the improvement in thermal stability is not clear, it is assumed that by blending the boron compound (B), the hydroxyl group and boron contained in the structural unit represented by the formula (1) form a coordination bond, the hydroxyl group is protected, and the thermal stability (color resistance and long-term stability) is improved.

[0016] [Resin (A)] The resin (A) contains 30 mol% or more of the structural unit represented by the above formula (1).

[0017] From the viewpoint of gas barrier properties, the content of the structural unit represented by the formula (1) contained in the resin (A) is preferably 45 mol% above and more preferably 70 mol %The above is more preferable, 80 mol% or more is even more preferable, 90 mol% or more is still even more preferable, 95 mol% or more is particularly preferable, and it may contain 99.9 mol% or more. Also, the content may be 100 mol%, but considering moldability and the like, 99.9 mol% or less is preferable, and it may be 99 mol% or less, 98 mol% or less, or even 95 mol% or less.

[0018] The resin (A) may be a copolymer containing a structural unit represented by the formula (1) and a structural unit other than the structural unit represented by the formula (1). As other structural units other than the structural unit represented by the formula (1), there is no particular limitation as long as it does not significantly adversely affect gas barrier properties and thermal stability, and it may contain a structural unit derived from the monomer (M) exemplified below. Examples of the monomer (M) include hydroxyl group-containing monomers such as allyl alcohol, vinyl alcohol, 3,4-diol-1-butene, and 2-methylene-1,3-propanediol; (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; carboxyl group-containing monomers such as (meth)acrylic acid and crotonic acid; olefin monomers such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, and 1-octene; diene monomers such as butadiene and isoprene; aromatic vinyl monomers such as styrene, α-methylstyrene, o-, m-, p-methylstyrene, and vinylnaphthalene; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; vinyl halide monomers such as vinyl chloride and vinyl fluoride; vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride; nitrile monomers such as acrylonitrile and methacrylonitrile; and maleic acid derivative monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and dimethyl maleate. The resin (A) may contain only one type or two or more types of other structural units in addition to the structural unit represented by the formula (1).

[0019] The lower limit value of the melt flow rate (MFR) of resin (A) is the measured value at a temperature of 210 °C and a load of 2160 g, preferably 0.01 g / 10 min, more preferably 0.05 g / 10 min, still more preferably 0.1 g / 10 min, and particularly preferably 0.3 g / 10 min. On the other hand, the upper limit value of MFR is the measured value under the same conditions, preferably 200 g / 10 min, more preferably 50 g / 10 min, still more preferably 30 g / 10 min, particularly preferably 15 g / 10 min, and most preferably 10 g / 10 min. By adjusting the MFR within the above range, the melt molding of the resin composition can be easily performed, and the color resistance and long-term properties of the resin composition can be enhanced. Examples of the method for adjusting the MFR within the above range include a method of adjusting the degree of polymerization of resin (A) and a method of adjusting the type of copolymerization component. In view of the gas barrier properties, color resistance, long-term properties, etc. of the resin composition and the molded article obtained therefrom, not only resin (A) itself but also the resin composition and the molded article containing the same preferably have an MFR within the above range. The number average degree of polymerization of resin (A) is preferably 100 to 10,000.

[0020] Resin (A) can be produced by a known method. Although there is no particular limitation on the production method, for example, the following first to third methods can be mentioned as production methods.

[0021] The first method is a method of homopolymerizing the monomer represented by the following formula (2) or copolymerizing the monomer represented by the following formula (2) with the above monomer (M), and reducing the obtained polymer or copolymer.

[0022]

Chemical formula

[0023] In the above formula (2), X represents any one selected from the group consisting of a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, and a halogen atom.

[0024] Specific examples of the monomer represented by the above formula (2) include methacrylic acid, methacrylic acid halides, methacrylic acid esters such as methyl methacrylate, and methacrolein.

[0025] Examples of the polymerization method of the above-mentioned monomer include known polymerization methods such as radical polymerization and anionic polymerization.

[0026] Examples of the radical polymerization initiator include azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4'-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4'-dimethylvaleronitrile); peroxide initiators such as isobutyl peroxide, di-n-propyl peroxydicarbonate, and t-butyl peroxypivalate. The polymerization temperature is usually about room temperature to 100°C.

[0027] As the initiator for anionic polymerization, basic alkali metal or alkaline earth metal derivatives such as butyllithium, lithium aluminum hydride, methylmagnesium bromide, ethylmagnesium chloride, and triphenylmethyl calcium chloride can be used. Anionic polymerization is usually carried out at a low temperature of about -100°C to room temperature in an aprotic solvent such as tetrahydrofuran, dimethoxyethane, or diethyl ether.

[0028] As a method for reducing the obtained polymer or copolymer, methods using metal hydrides such as lithium aluminum hydride, sodium borohydride, lithium borohydride, and diborane as reducing agents; methods of hydrogenating with transition metal catalysts such as ruthenium-based, rhodium-based, nickel-based, palladium-based, and platinum-based catalysts can be mentioned. The reduction reaction solvent is appropriately selected in consideration of the solubility of the polymer or copolymer and the reactivity with the reducing agent. Specific examples of the reduction reaction solvent include tetrahydrofuran, N-methylmorpholine, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dimethoxyethane, methanol, ethanol, propanol, and the like. The temperature of the reduction reaction is usually about room temperature to 200 °C, preferably 50 to 150 °C. When a polymer or copolymer regulated to syndiotactic or isotactic is reduced, a resin (A) maintaining its stereoregularity can be obtained.

[0029] As a method for adjusting the content of the structural unit represented by the formula (1) in the resin (A), for example, adjusting the amount of the reducing agent in the above reduction reaction or changing the hydrogenation conditions can be mentioned.

[0030] The second method is a method of homopolymerizing the monomer represented by the following formula (3) or copolymerizing the monomer represented by the following formula (3) with the above monomer (M).

[0031]

Chemical formula

[0032] When polymerizing the monomer represented by the formula (3), the hydrogen atom of the hydroxyl group in the monomer may be substituted with an acyl group. As the polymerization method, the polymerization method described in the above first method can be adopted. After the polymerization, by subjecting to saponification treatment, the resin (A) containing the structural unit represented by the formula (1) can be obtained. As the polymerization method of methallyl alcohol, for example, the methods described in U.S. Patent No. 3,285,897, U.S. Patent No. 3,666,740 and Japanese Patent Publication No. 47-40308 corresponding thereto, British Patent No. 854,207, etc. can be used.

[0033] The third method is a method of homopolymerizing the monomer represented by the following formula (4) or copolymerizing the monomer represented by the following formula (4) with the above monomer (M), and converting Z which is a halogen atom in the following formula (4) into a hydroxyl group. For the third method, for example, the method described in U.S. Patent No. 4,125,694 can be used.

[0034] [Chemical formula]

[0035] In the formula (4), Z represents a halogen atom.

[0036] [Boron compound (B)] The resin composition of the present invention contains a boron compound (B), and the boron element contained in the boron compound (B) is 0.01 to 2,000 micromoles with respect to 1 g of the resin (A). By containing the boron element, the resin composition and the molded article containing the same can significantly improve the thermal stability (color resistance and long-term properties).

[0037] In the resin composition of the present invention, the boron compound (B) may contain other elements as long as the effects of the present invention are not impaired. Examples of other elements include lithium, sodium, aluminum, etc.

[0038] The boron compound (B) is not particularly limited. For example, boric acids such as orthoboric acid (H3BO3), metaboric acid, and tetraboric acid; boric acid esters such as triethyl borate and trimethyl borate; borates such as alkali metal salts of the above boric acids, alkaline earth metal salts of the above boric acids, and borax; diborane, borane-dimethyl sulfide complex, borane-tetrahydrofuran complex, borane-triethylamine complex; boron hydride compounds such as sodium borohydride, lithium borohydride, nickel borohydride, zinc borohydride, lithium tri(sec-butyl)borohydride, sodium triacetoxyborohydride, and lithium triethylborohydride can be mentioned.

[0039] Among these, as the boron compound (B), from the viewpoints of availability and simplicity of addition as an aqueous solution, any one selected from the group consisting of orthoboric acid (H3BO3), metaboric acid, tetraboric acid, alkali metal salts of orthoboric acid, alkaline earth metal salts of orthoboric acid, borax, and sodium borohydride is preferable, and any one selected from the group consisting of orthoboric acid (H3BO3), borax, and sodium borohydride is more preferable.

[0040] In the resin composition of the present invention, the content of boron element contained in the boron compound (B) is 0.01 micromol or more per 1 g of the resin (A). From the viewpoint of improving thermal stability, the content of the boron element is preferably 0.1 micromol or more, more preferably 0.2 micromol or more, and still more preferably 2 micromol or more. The content of the boron element is 2,000 micromol or less. From the viewpoint of significantly improving thermal stability (color resistance and / or long-term stability), the content of the boron element is preferably 1,500 micromol or less, more preferably 1,000 micromol or less, still more preferably 800 micromol or less, still more preferably 500 micromol or less, still more preferably 300 micromol or less, and particularly preferably 200 micromol or less. When the content of the boron element contained in the boron compound (B) is less than 0.01 micromol per 1 g of the resin (A), no improvement in thermal stability is observed. Further, when the content of the boron element contained in the boron compound (B) exceeds 2,000 micromol per 1 g of the resin (A), the thermal stability decreases.

[0041] [Other Components] The resin composition of the present invention may contain other components other than the resin (A) and the boron compound (B) as needed. Examples of the other components include additives such as antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, metal-free heat stabilizers, lubricants, colorants, fillers, other polymer compounds (for example, other thermoplastic resins), solvents (water or various organic solvents). The other components can be blended and contained in one or more kinds within a range that does not inhibit the effects of the present invention. The content of the other polymer compound is usually 50% by mass or less, preferably 20% by mass or less, based on the content of the resin (A).

[0042] The melt flow rate (MFR) of the resin composition of the present invention is not particularly limited, but the melt flow rate (MFR) at a temperature of 230°C and a load of 2.16 kg is preferably 3.0 g / 10 min or more, more preferably 6.0 g / 10 min, and still more preferably 7.0 g / 10 min. Thereby, the processability during secondary molding is improved without impairing the effects of the present invention.

[0043] The ratio ((B) / (OH)) of the content (B) of the boron element contained in the resin composition of the present invention to the hydroxyl group content (OH) contained in the resin (A) represents the molar amount of the boron element per 1 mol of the hydroxyl group, and although there is no particular limitation, it is 0.005×10 -6 The following is preferable, and 0.003×10 -6 The following is more preferable, and 0.001×10 -6 The following is even more preferable. Thereby, without impairing the effects of the present invention, the processability during melt molding is improved.

[0044] The oxygen permeability of the resin composition at a temperature of 20°C and a relative humidity of 100% is preferably 60 mL·20 μm / (m 2 ·day·atm) or less, more preferably 40 mL·20 μm / (m 2 ·day·atm) or less, still more preferably 20 mL·20 μm / (m 2 ·day·atm) or less, and particularly preferably 10 mL·20 μm / (m 2 ·day·atm) or less, from the viewpoint of gas barrier properties in a high humidity environment. The lower the oxygen permeability of the resin composition, the better the barrier performance can be obtained in a high humidity environment even when a multilayer structure is formed.

[0045] <Formed body> The formed body of the present invention contains the resin composition of the present invention. Thereby, a formed body excellent in color resistance, long-term properties, interlayer adhesiveness, and gas barrier properties under high humidity can be obtained.

[0046] The formed body of the present invention may be a single-layer structure or a multilayer structure including other layers.

[0047] The molded article of the present invention includes one or more layers containing the resin composition of the present invention (preferably, a layer made of the above resin composition), a single-layer structure having only the layer containing the resin composition; a multilayer structure including one or more layers containing the resin composition and one or more other layers different from the layer; a multilayer structure including one or more layers containing the resin composition and a thermoplastic resin layer laminated on one or both sides of the layer; and a multilayer structure including two or more layers containing the resin composition and no other layers can be cited as specific examples.

[0048] As a preferred layer configuration of the above multilayer structure, when the layer containing the resin composition of the present invention described above is P, the layer made of an adhesive resin (adhesive resin layer) is Ad, and the layer made of a thermoplastic resin (thermoplastic resin layer) is T, P / T, T / P / T, P / Ad / T, T / Ad / P / Ad / T, etc. can be cited. Each of these layers may be a single layer or a multilayer. An adhesive layer can also be interposed instead of the adhesive resin layer.

[0049] Among them, a molded article which is a multilayer structure including one or more layers containing the resin composition of the present invention and one or more other layers different from the layer is excellent in coloring resistance, long-term stability, interlayer adhesion, and gas barrier properties under high humidity.

[0050] In addition, a molded article which is a multilayer structure including one or more layers containing the resin composition of the present invention and a thermoplastic resin layer laminated on one or both sides of the layer is excellent in coloring resistance, long-term stability, interlayer adhesion, and gas barrier properties under high humidity.

[0051] The thickness of the layer containing the resin composition constituting the molded article is preferably 0.01 to 1000 μm. When the thickness of the above layer is within the above numerical range, a molded article excellent in coloring resistance, long-term stability, interlayer adhesion, and gas barrier properties under high humidity can be obtained.

[0052] The method for manufacturing the multilayer structure is not particularly limited, and for example, the following methods (i) to (iv) can be cited. i) A method of melt-extruding a thermoplastic resin onto layer P (film, sheet, etc.) to form a thermoplastic resin layer T on layer P. ii) A method of co-extruding or co-injecting the resin composition of the present invention and another thermoplastic resin to form a layer structure of P / T or T / P / T. iii) A method of laminating layer P and a thermoplastic resin layer T (film, sheet, etc.) via an adhesive resin layer Ad or an adhesive layer. When using the adhesive resin layer Ad, a multilayer structure can also be manufactured by co-extrusion or co-injection in the same manner as in method ii). Also, another substrate (film, sheet, etc.) can be used instead of the thermoplastic resin layer T. iv) A method of forming layer P by coating a uniform solution composed of the resin composition and a solvent onto a substrate and evaporating the solvent from the formed coating surface. The substrate is not particularly limited and may be a thermoplastic resin layer T (film, sheet, etc.), an adhesive resin layer Ad coated on the thermoplastic resin layer T, or another substrate (film, sheet, etc.).

[0053] Thermoplastic resins used for other layers in the multilayer structure include linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, propylene-α-olefin copolymer (α-olefin having 4 to 20 carbon atoms), polybutene, polypentene, etc., alone or as a copolymer thereof; ethylene-vinyl alcohol copolymer; polyesters such as polyethylene terephthalate; polyester elastomers; polyamides such as nylon 6 and nylon 66; polystyrene; polyvinyl chloride; polyvinylidene chloride; (meth)acrylic resins; vinyl ester resins; polyurethane elastomers; polycarbonate; chlorinated polyethylene; chlorinated polypropylene, etc. Among these, polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, polyester, polyamide, and polystyrene are preferably used.

[0054] As the adhesive resin for forming the adhesive resin layer Ad, there is no particular limitation as long as it has adhesiveness to the resin composition and thermoplastic resin of the present invention, but an adhesive resin containing a carboxylic acid-modified polyolefin is preferred. As the carboxylic acid-modified polyolefin, a modified olefin-based polymer containing a carboxyl group obtained by chemically bonding (for example, addition reaction, graft reaction, etc.) an ethylenically unsaturated carboxylic acid, its ester or its anhydride to an olefin-based polymer can be preferably used. The olefin-based polymer referred to here means polyolefins such as polyethylene (low pressure, medium pressure, high pressure), linear low-density polyethylene, polypropylene, polybutene, and copolymers of olefins and other monomers (vinyl esters, unsaturated carboxylic acid esters, etc.) (for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc.). Among these, linear low-density polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate content 5 to 55% by mass), ethylene-ethyl acrylate copolymer (ethyl acrylate content 8 to 35% by mass) are preferred, and linear low-density polyethylene and ethylene-vinyl acetate copolymer are more preferred. Examples of the ethylenically unsaturated carboxylic acid, its ester or its anhydride include ethylenically unsaturated monocarboxylic acids or their esters, ethylenically unsaturated dicarboxylic acids, their monoesters or diesters, or their anhydrides. Among these, ethylenically unsaturated dicarboxylic acid anhydrides are preferred. Specifically, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, etc. can be mentioned, and in particular, maleic anhydride is suitable.

[0055] As the adhesive for forming the adhesive layer, known adhesives containing organic titanium compounds, isocyanate compounds, polyester-based compounds, etc. as adhesive components can be used.

[0056] Among the above methods (i) to (iv), the method of co-extruding the resin composition of the present invention and another thermoplastic resin is preferably used. The co-extrusion method is not particularly limited, and examples thereof include a multi-manifold confluence type T-die method, a feed block confluence type T-die method, an inflation method, and the like.

[0057] Also, among the above methods (i) to (iv), the method of coating a uniform solution composed of a resin composition and a solvent on a substrate is also preferable. There is no particular limitation on the concentration of the resin composition in the uniform solution, but a concentration of 5 to 50% by mass is preferable. If the concentration is less than 5% by mass, the drying load may increase. On the other hand, when the concentration exceeds 50% by mass, the viscosity becomes high and handling may be problematic. The solvent is not particularly limited as long as it can dissolve the resin composition, but ethanol, 1-propanol, etc. are preferably used. The temperature of the coating agent during coating is preferably 20 to 80°C. The coating method is not particularly limited, and for example, known methods such as a gravure roll coating method, a reverse gravure coating method, a reverse roll coating method, and a Meyer bar coating method are preferably used.

[0058] The multilayer structure may be secondarily processed to obtain a molded body. The shape and form of the molded body obtained by secondary processing are not particularly limited, and typical molded bodies include the following a) to d).

[0059] a) A multilayer stretched sheet or film obtained by stretching and heat-treating a multilayer structure (sheet, film, etc.) in a uniaxial or biaxial direction. b) A multilayer rolled sheet or film obtained by rolling a multilayer structure (sheet, film, etc.). c) A multilayer tray or cup-shaped container obtained by thermoforming a multilayer structure (sheet, film, etc.) such as vacuum forming, pressure-air forming, and vacuum-pressure-air forming. d) A bottle or cup-shaped container obtained by stretch blow molding or the like of a multilayer structure (pipe, etc.). In addition, the secondary processing method is not limited to each method exemplified when obtaining the above-mentioned molded article, and for example, known secondary processing methods other than the above, such as blow molding, can be appropriately used.

[0060] Since the molded article which is the above-mentioned single-layer structure or multi-layer structure is excellent in gas barrier properties, it is suitable for applications that take advantage of such characteristics. Examples of the uses of the molded article include single-layer or multi-layer films or sheets, pipes, tubes, containers (deep-drawn containers, bottles, cups, tanks, pouches, bags, blister packs, etc.), fibers, and the like. In these applications, the shape and form of the molded article are not particularly limited. Further, the molded article applied to these applications may have a single-layer or multi-layer structure. The molded article of the present invention can be suitably used as a packaging material for food, a packaging material for pharmaceuticals, and the like.

[0061] Among these applications, it can be suitably used as a film in terms of achieving both gas barrier properties and moldability, and the film containing the molded article of the present invention is one form of the present invention.

[0062] [Molding method of molded article] The molding method of the above-mentioned molded article is not particularly limited, and various molding methods such as melt molding (extrusion molding, injection molding, blow molding, etc.), solution molding, and powder molding can be used. Preferably, it is melt molding. According to the resin composition of the present invention, even when producing a molded article by melt molding, it is possible to stably and continuously produce the molded article while suppressing coloring such as yellowing, and further, the interlayer adhesiveness when forming a molded article that is a multi-layer structure can be improved, thereby improving the durability of the molded article. In addition, the molded article of the present invention can have few occurrences of fish eyes, streaks, gels, lumps, etc., and can also be excellent in appearance characteristics other than coloring. By using the molded article of the present invention, it is also possible to obtain a multi-layer structure excellent in excellent appearance characteristics, long-term performance, and interlayer adhesiveness. The temperature at which the resin composition is melted in melt molding is preferably about 100 to 300°C. If it exceeds 300°C, the resin (A) in the resin composition may be thermally deteriorated or decomposed. If it is less than 100°C, it may be difficult to melt the resin composition.

[0063] [Use] The use of the molded article of the present invention will be described. The molded article of the present invention can be suitably used as a packaging material. The packaging material containing the above-described film is one form of the present invention. The packaging material may be composed only of the molded article of the present invention, or may be composed of a multilayer structure other than the present invention and other members.

[0064] The packaging material of the present invention can be produced by a known method. For example, a container (packaging material) may be produced by joining a sheet-like multilayer structure containing a layer containing the resin composition of the present invention or a film material containing the multilayer structure (hereinafter, also simply referred to as "film material") and molding it into a predetermined container shape. The packaging material of the present invention can be applied to various uses by taking advantage of its excellent gas barrier property and water vapor barrier property. This packaging material is preferably used for applications that require a barrier property against oxygen and for applications where the inside of the packaging material is replaced with various functional gases. For example, the packaging material of the present invention is preferably used as a food packaging material. In addition to food packaging materials, the packaging material of the present invention is also preferably used as packaging materials for chemicals such as agricultural chemicals and pharmaceuticals; medical devices; industrial materials such as machine parts and precision materials; and clothing.

[0065] In addition, the molded article of the present invention may be used for electronic devices such as solar cells and displays. For example, when used for a solar cell, the molded article of the present invention is used as a member of the solar cell. When used for a display, the molded article of the present invention is used as a member of the display.

[0066] The molded article or film of the present invention may be secondary-processed into various molded products. Examples of such molded products include vertical form-fill-seal bags, pouches, vacuum heat insulators, vacuum packaging bags, bottles, cup-shaped containers, blister packs, tanks, bags, laminated tube containers, infusion bags, lid materials for containers, paper containers, strip tapes, or in-mold labels. Hereinafter, each molded product will be described.

[0067] (Vertical form-fill-seal bag) The molded body or film of the present invention can be used as a vertical form-fill-seal bag. The vertical form-fill-seal bag is formed by sealing the multilayer structure constituting the molded body on three sides: two end portions and a body portion. The vertical form-fill-seal bag can be manufactured by a vertical form-fill-sealing machine. Various methods are applicable to the bag-making by the vertical form-fill-sealing machine. In any method, the content is supplied into the bag from the opening above the bag, and then the opening is sealed to manufacture the vertical form-fill-seal bag. The vertical form-fill-seal bag is composed of, for example, a single film material heat-sealed on three sides: the upper end, the lower end, and the side portion. The vertical form-fill-seal bag as a container according to the present invention is excellent in gas barrier properties and water vapor barrier properties, and the barrier performance is maintained even after retort treatment. Therefore, according to the vertical form-fill-seal bag, deterioration of the content quality can be suppressed over a long period of time.

[0068] (Pouch) The molded body or film of the present invention can be used as a pouch. In this specification, "pouch" means a container having a film material as a wall member and mainly containing food, daily necessities, or pharmaceuticals as contents. Examples of the pouch include, depending on its shape and use, a pouch with a spout, a pouch with a chuck seal, a flat pouch, a stand-up pouch, a horizontal form-fill-seal pouch, a retort pouch, etc. For example, a flat pouch is formed by joining the peripheral portions of the multilayer structures constituting two molded bodies to each other. The pouch may be formed by laminating a barrier multilayer structure and at least one other layer. The pouch is excellent in gas barrier properties, and its barrier performance is maintained even after retort treatment. Therefore, by using the pouch, it is possible to prevent the deterioration of the content over a long period of time even after transportation or long-term storage. Further, in an example of the pouch, since good transparency can be maintained, it is easy to check the content and the deterioration of the content due to deterioration.

[0069] (Vacuum insulator) The molded article or film of the present invention can also be used as a vacuum heat insulator. A vacuum heat insulator is produced by disposing a core material inside a multilayer structure and bonding the peripheral portions. At this time, by evacuating the inside, the multilayer structure adheres to the core material due to the pressure difference. The material and shape of the core material are not particularly limited as long as they are suitable for heat insulation. Examples of the core material include perlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, artificial (synthetic) wool, and resin foams (e.g., styrene foam, urethane foam). As the core material, a hollow container formed into a predetermined shape, a honeycomb structure, or the like can also be used, and it may be in the form of particles.

[0070] The above vacuum heat insulator makes it possible to achieve heat insulation characteristics equivalent to those of a heat insulator made of urethane foam with a thinner and lighter heat insulator. Since the vacuum heat insulator can maintain the heat insulation effect for a long time, it can be used as a heat insulating material for home appliances such as refrigerators, water heaters, and rice cookers, a heat insulating material for houses used for wall parts, ceiling parts, attic parts, and floor parts, a vehicle roof material, a heat storage device, a heat insulating panel for vending machines, and a heat transfer device such as a heat pump application device.

[0071] (Electronic device) In addition to gas barrier properties, the molded article or film of the present invention also has excellent barrier properties against water vapor. In particular, when the molded article or film of the present invention is used in an electronic device, this property may greatly contribute to the durability of the electronic device. Examples of the electronic device include a photoelectric conversion device such as a solar cell; an information display device having a display such as an organic EL display, a liquid crystal display (LCD), and electronic paper; and a lighting device such as an organic EL light emitting element. Examples of solar cells include silicon-based solar cells, compound semiconductor solar cells, organic thin-film solar cells, etc. Examples of silicon-based solar cells include single-crystalline silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, etc. Examples of compound semiconductor solar cells include III-V compound semiconductor solar cells, II-VI compound semiconductor solar cells, I-III-VI compound semiconductor solar cells, etc. Examples of organic thin-film solar cells include pn heterojunction organic thin-film solar cells, bulk heterojunction organic thin-film solar cells, etc. Further, the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series.

[0072] Examples of the molded body or film used for electronic devices include display members such as a substrate film for LCD, a substrate film for organic EL display, a substrate film for electronic paper, a sealing film for electronic devices, a film for PDP, etc.; solar cell members related to electronic devices such as a film for LED, a film for IC tag, a solar cell module, a backsheet for solar cell, a protective film for solar cell, etc.; members for optical communication, a flexible film for electronic equipment, a separator for fuel cell, a sealing film for fuel cell, a substrate film for various functional films, etc. When using the multilayer structure as a member of the display, it is used as, for example, a low-reflectivity film.

[0073] An electronic device including the molded article or film of the present invention includes, as an example, an electronic device main body, a sealing material, and a protective sheet including the above-described multilayer structure, and the protective sheet may be arranged to protect the surface of the electronic device main body. The protective sheet may be directly arranged on one surface of the electronic device main body, or may be arranged on the electronic device main body via other members such as a sealing material. The protective sheet may be composed only of the multilayer structure, or may include the multilayer structure and other members (for example, other layers) laminated on the multilayer structure. The protective sheet is not particularly limited in terms of its thickness and material as long as it is a layered laminate suitable for protecting the surface of the electronic device and includes the above-described multilayer structure. The sealing material may cover the entire surface of the electronic device main body and is an arbitrary member appropriately added according to the type and use of the electronic device main body. As the sealing material, ethylene-vinyl acetate copolymer, polyvinyl butyral, or the like is used. The protective sheet may also be arranged on the surface opposite to the surface on which the protective sheet is arranged.

[0074] Depending on its type, the electronic device main body can be manufactured by a so-called roll-to-roll method. In the roll-to-roll method, a flexible substrate (for example, a stainless steel substrate, a resin substrate, etc.) wound around a feed roll is fed out, and an electronic device main body is manufactured by forming elements on this substrate, and the obtained electronic device main body is wound up by a take-up roll. In this case, the protective sheet may also be prepared in the form of a long flexible sheet, more specifically, in the form of a wound body of a long sheet. In one example, the protective sheet fed out from the feed roll is laminated on the electronic device main body before being wound up by the take-up roll and is wound up together with the electronic device main body. In another example, the electronic device main body wound up by the take-up roll may be fed out from the roll again and the protective sheet may be laminated. In one example of a preferred form of the present invention, the electronic device itself has flexibility.

[0075] (Blister pack) The molded article or film of the present invention can also be used for blister packs. In this specification, a blister pack means a tablet package particularly used for pharmaceuticals. The shape as a tablet package is not particularly limited, but by adhering a lid material to the edge of a tray having a storage portion, a sealed space capable of storing the contents can be provided. The method for molding the tray is not particularly limited, but by secondarily molding and denting the molded article or film of the present invention, a storage space and the edge portion around it can be provided. Specifically, for example, vacuum molding, pressure-air molding, pressure-air vacuum molding, plug-assisted pressure-air molding, plug-assisted vacuum molding, plug-assisted pressure-air vacuum molding, plug molding, press molding, etc. can be used. The lid material is not particularly limited as long as it adheres to the tray. For example, the molded article or film of the present invention, aluminum, a transparent vapor-deposited film, etc. can be used. The blister pack using the molded article or film of the present invention is excellent in gas barrier properties, so it is possible to prevent the deterioration of the contents over a long period of time. Further, in an example of the blister pack, since good transparency can be maintained, it is easy to confirm the contents and the deterioration of the contents due to deterioration.

[0076] <Method for producing resin composition> In the production of the resin composition of the present invention described above, a known method can be adopted. For example, by bringing the boron compound (B) into contact with the resin (A) or by reducing it with sodium borohydride, a structural unit derived from the formula (1) is contained in the resin and used as it is as the resin composition. However, it can also be obtained by the method for producing the resin composition of the present invention described later.

[0077] The method for producing the resin composition of the present invention includes a step of bringing a resin (A) containing 30 mol% or more of the structural unit represented by the above formula (1), a boron compound (B), and water into contact with each other. By adopting the production method of the present invention, a resin composition excellent in thermal stability and further in interlayer adhesiveness can be more reliably produced. Hereinafter, the resin (A) containing 30 mol% or more of the structural unit represented by the above formula (1) may be simply abbreviated as resin (A).

[0078] The resin (A) containing 30 mol% or more of the structural unit represented by the above formula (1) and the boron compound (B) are the same as above and are omitted here. From the viewpoints of ensuring the treatment and simplicity, the boron compound (B) is preferably sodium borohydride or borax.

[0079] In the step of bringing the resin (A) containing 30 mol% or more of the structural unit represented by the above formula (1), the boron compound (B), and water into contact, the order of contacting the respective components is not limited as long as the effects of the present invention are not impaired, but preferably, the resin (A) is immersed in an aqueous solution containing the boron compound (B).

[0080] In the aqueous solution containing the boron compound (B), the boron compound (B) may be dissolved in water or may be dispersed in water.

[0081] In the above step, as long as the effects of the present invention are not impaired, a solvent other than water may be used. When using a solvent other than water, a solvent other than water may be added to the aqueous solution containing the boron compound (B), or the boron compound may be added to water and a solvent other than water and used.

[0082] In the above step, other components may be blended. Examples of other components are the same as above and are omitted here. As long as the effects of the present invention are not impaired, there is no limitation on the order of adding other components.

[0083] The treatment of immersing the resin (A) in the aqueous solution containing the boron compound (B) may be in a batch system or a continuous system. When carried out in a batch system, the mass ratio (bath ratio) of the aqueous solution containing the boron compound (B) to the resin (A) is preferably 3 or more, more preferably 10 or more, and even more preferably 20 or more. In a continuous system, a tower-type apparatus can be preferably used. The immersion time varies depending on the shape and form of the resin (A), but when the resin (A) is in the form of granules having an average diameter of about 1 to 10 mm, it is 1 hour or more, preferably 2 hours or more.

[0084] The resin composition obtained by the production method of the present invention can be used as it is as a material for a molded article, but it is preferable to remove water (or a solvent) from the resin composition and dry it. From the viewpoint of preventing molding troubles such as the generation of voids due to foaming during molding, the water content of the dried resin composition is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less with respect to the whole resin composition.

[0085] There is no particular limitation on the drying method, and static drying, fluidized drying, etc. can be mentioned as suitable ones. The drying method may use a single method, or a plurality of methods may be combined, for example, static drying may be performed after fluidized drying. The drying treatment may be either continuous or batch type. When combining a plurality of drying methods, the continuous type and the batch type can be freely selected for each drying method. It is also preferable to perform drying under a low oxygen concentration or an oxygen-free state or in a nitrogen atmosphere in terms of reducing the deterioration of the resin composition due to oxygen during drying. Among them, drying under a nitrogen atmosphere is preferable.

[0086] When the content of the boron compound (B) in the obtained resin composition is excessively high, the thermal stability decreases. Therefore, washing may be performed as necessary to adjust the content of the boron compound (B). There is no particular limitation on the washing method, but methods such as stirring the resin composition in water and applying steam to the resin composition are industrially easy to use.

[0087] In the production method of the resin composition of the present invention, in the above step, after reacting the resin (A) with the boron compound (B), the reaction solution may be added to water. When the reaction solution comes into contact with water, the resin composition is obtained as a precipitate. In the reaction of the resin (A) and the boron compound (B), a solvent such as tetrahydrofuran, toluene, methanol, or other components may be blended. The solvent and other components may be used alone or in combination of two or more. Further, the reaction temperature of the resin (A) and the boron compound (B) is preferably 60 to 150°C, more preferably 80 to 130°C. If it is within the above reaction temperature range, the reaction proceeds well.

[0088] In the method for producing the resin composition of the present invention, in the above step, the resin (A) can also be applied even in a molten state. When producing the resin composition of the present invention with the resin (A) in a molten state, devices such as a kneader or an extruder are used.

[0089] When supplying the raw materials to the above device, the resin (A) may be melted in the device, and an aqueous solution containing the boron compound (B) may be brought into contact with the melted resin (A). Alternatively, the resin (A) and the boron compound (B) may be dry-blended, heated or melted, and water may be added thereto. At this time, the resin (A) and the boron compound (B) may be dissolved or dispersed in water.

[0090] Even when producing the resin composition with the resin (A) in a molten state, a solvent other than water or other components may be blended. The blending order of the solvent other than water and other components is not particularly limited. Also, the solvent other than water and other components may be prepared as a plurality of liquids each containing them alone, or may be prepared as a liquid containing two or more components (for example, a liquid containing all the components to be mixed).

[0091] The temperature at which the resin (A) is melted is preferably about 100 to 300°C. If it is 300°C or lower, there is no risk of thermal degradation and decomposition of the resin (A). Also, since the melting point of the water-containing resin (A) is lower than that of the dry resin (A), melting at a lower temperature is possible. If it is 100°C or higher, the resin (A) is likely to melt.

[0092] Even when producing the resin composition of the present invention with the resin (A) in a molten state, by drying according to the solvent and moisture content, a resin composition with less void generation can be obtained. The drying method is the same as above and is omitted here.

Examples

[0093] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Each evaluation in the examples and comparative examples was carried out according to the method shown below.

[0094] · Method for identifying the structure of resin (A) The structure of resin (A) was 1 identified by 1H-NMR and 13 13C-NMR. The measurement conditions are shown below. ( 1 Measurement conditions for 1H-NMR) Observation frequency: 600 MHz Solvent: DMSO-d6 Polymer concentration: 5 mass% Measurement temperature: 80 °C Number of integrations: 512 times Pulse delay time: 2.8 seconds Sample rotation speed: 10 - 12 Hz Pulse width (90° pulse): 15 μsec. ( 13 Measurement conditions for 13C-NMR) Observation frequency: 150 MHz Solvent: DMSO-d6 Polymer concentration: 10 mass% Measurement temperature: 80 °C Number of integrations: 8000 times Measurement mode: Inverse gated decoupling method Pulse delay time: 1.2 seconds Sample rotation speed: 10 - 12 Hz Pulse width (90° pulse): 16 μsec.

[0095] · Quantification of boron element contained in boron compound (B) The resin composition was pretreated with a microwave decomposition apparatus, and boron element derived from boron compound (B) contained in the resin composition was quantified using ICP-MS measurement. 0.1 g of the resin composition was weighed into a quartz insert, and 6 mL of nitric acid (specific gravity 1.42 g) was added. The quartz insert was placed into a decomposition vessel containing 5 mL of water and 2 mL of hydrogen peroxide, sealed, and subjected to microwave decomposition (using "Microwave Decomposition Apparatus ETHOS-1" manufactured by Milestone General Co., Ltd., decomposition conditions: heat up to 70 °C in 3 minutes, then cool to 50 °C in 2 minutes. Subsequently, heat up to 230 °C in 20 minutes and maintain at 230 °C for 15 minutes). After cooling, it was made up to 50 mL in volume, and the filtrate filtered through a 0.45 μm pore size filter was subjected to ICP-MS measurement. (Measurement method of ICP-MS) Apparatus name: "Agirent7900" manufactured by Agilent Technologies, Inc. RF output: 1500 W Carrier gas flow rate: 0.7 L / min Plasma mode: Hot plasma Elements measured in NoGas mode: B, Na Standard solution: "XSTC-622" manufactured by SPEX Industries, Inc. Standard solution for calibration curve: 1.4 mol / L nitric acid solutions of 0, 0.5, 5.0, 10.0, 30.0, 50.0 ng / mL

[0096] ·Measurement of weight average molecular weight and molecular weight distribution The weight average molecular weight and molecular weight distribution were measured using gel permeation chromatography (GPC) and calculated as values converted to the molecular weight of standard polymethyl methacrylate. The measurement conditions were as follows. (Measurement conditions of GPC) Apparatus: "LC-20AT" manufactured by Shimadzu Corporation Detector: Differential refractive index detector Column: Two "TSKgel AWM-M" columns manufactured by Tosoh Corporation connected in series Mobile phase: 10 mmol / L lithium bromide DMF solution Sample concentration: 0.1 wt% Flow rate: 0.5 mL / min Column temperature: 40 °C

[0097] · Evaluation method and evaluation criteria for color fastness In the evaluation of interlayer adhesion described below, the prepared multilayer film was wound around a paper tube, and the end face of the layer made of the resin composition was visually observed, and the color fastness was evaluated based on the following evaluation criteria. (Evaluation criteria for color fastness) A: No coloring is observed B: Slight coloring is observed C: Colored light yellow D: Colored yellow E: Heavily colored and showing orange

[0098] · Evaluation method and evaluation criteria for long-run property The long-run property was evaluated using MFR (Model "L260" manufactured by Tateyama Kagaku Co., Ltd.). After holding the resin composition in a melt indexer at a temperature of 210 °C and a load of 2160 g for 3 minutes, it was discharged for 1 minute, and the discharged weight at that time was defined as MFR3. Similarly, after holding for 15 minutes and discharging for 1 minute, the discharged weight at that time was defined as MFR15. The ratio MFR15 / MFR3 of MFR15 to MFR3 was calculated, and the long-run property was evaluated based on the following evaluation criteria. The closer MFR15 / MFR3 is to 1, the better the stability of the melt viscosity and the better the long-run property. (Evaluation criteria for long-run property) A: Less than 1.2 and 0.8 or more B: 0.6 or more and less than 0.8, or 1.2 or more and less than 1.4 C: 0.4 or more and less than 0.6, or 1.4 or more and less than 1.6 D: 0.3 or more and less than 0.4, or 1.6 or more and less than 1.7 E: 0.2 or more and less than 0.3, or 1.7 or more and less than 1.8 F: Less than 0.2, or 1.8 or more

[0099] · Evaluation method and evaluation criteria for interlayer adhesion A resin composition, linear low-density polyethylene (LLDPE, "UltraZex 2022L" manufactured by Mitsui Chemicals, Inc.), and an adhesive resin ("Bondine TX8030" manufactured by Sumitomo Chemical Co., Ltd., hereinafter also referred to as Ad) were used to produce a three-kind five-layer multilayer film (LLDPE / Ad / resin composition / Ad / LLDPE, thickness 50 μm / 10 μm / 10 μm / 10 μm / 50 μm) by a multilayer film extruder under the following manufacturing method and manufacturing conditions. The obtained multilayer film was cut out in the MD direction by 150 mm and in the TD direction by 15 mm immediately after multilayer film formation, and then the peel strength between the resin composition layer and the Ad layer was measured in the T-peel mode immediately by an autograph ("DCS-50M" manufactured by Shimadzu Corporation), and the interlayer adhesiveness was evaluated based on the following evaluation criteria according to the strength of the peel strength. (Manufacturing Method and Manufacturing Conditions of Multilayer Film) 〈Extruder〉 For resin composition: 20 mmφ extruder, Labo Machine ME type CO-EXT, manufactured by Toyo Seiki Seisaku-sho, Ltd. For Ad: 20 mmφ extruder, SZW20GT-20MG-STD, manufactured by Technovel Corporation For LLDPE: 32 mmφ extruder, GT-32-A, manufactured by Plastic Engineering Laboratory Co., Ltd. 〈Die〉 300 mm width coat hanger die, manufactured by Plastic Engineering Laboratory Co., Ltd. Extrusion temperature of resin composition: Feeding section / Compression section / Metering section / Die = 175 / 210 / 210 / 210 °C Extrusion temperature of Ad: Feeding section / Compression section / Metering section / Die = 100 / 160 / 220 / 220 °C Extrusion temperature of LLDPE: Feeding section / Compression section / Metering section / Die = 150 / 200 / 210 / 220 °C (Evaluation Criteria for Interlayer Adhesiveness) A: 300 g / 15 mm or more B: 200 g / 15 mm or more and less than 300 g / 15 mm C: 100 g / 15 mm or more and less than 200 g / 15 mm D: Less than 100 g / 15 mm

[0100] · Evaluation Method and Criteria for Gas Barrier Property (Oxygen Permeability) For the evaluation of the above-mentioned interlayer adhesion, the multilayer film prepared was measured for oxygen permeability using the oxygen permeation measuring device "MOCON OX-TRAN2 / 20 type" manufactured by MODERN CONTROLS INC. according to the method described in JIS K7126 (isobaric method) under the conditions of 20 °C and 100% RH, and the gas barrier property was evaluated based on the following evaluation criteria. (Evaluation Criteria for Gas Barrier Property) A: Less than 10 mL·20 μm / (m 2 ·day·atm) B: 10 mL·20 μm / (m 2 ·day·atm) or more and less than 20 mL·20 μm / (m 2 ·day·atm) C: 20 mL·20 μm / (m 2 ·day·atm) or more and less than 40 mL·20 μm / (m 2 ·day·atm) D: 40 mL·20 μm / (m 2 ·day·atm) or more and less than 60 mL·20 μm / (m 2 ·day·atm) E: 60 mL·20 μm / (m 2 ·day·atm) or more

[0101] · Melt Flow Rate (MFR) 5 g of dry pellets made of the resin composition were placed in a melt flow rate (manufactured by Tateshima Kagaku Co., Ltd. "L260") and held for 6 minutes under a load of 2.16 kg at the measurement temperature. Then, the resin weight discharged from the melt flow rate was collected and weighed 3 times at regular intervals. The average value was obtained and the MFR at a holding time of 6 minutes was calculated (the unit is g / 10 min).

[0102] [Production Example 1] (1) Synthesis of Polymethyl Methacrylate In a nitrogen atmosphere, 100 parts by mass of methyl methacrylate, 0.0053 parts by mass of 2,2'-azobis(2-methylpropionitrile), and 0.20 parts by mass of n-octyl mercaptan were placed in an autoclave equipped with a stirrer and a sampling tube. While blowing nitrogen, stirring was carried out to remove dissolved oxygen, and a raw material solution was obtained. Next, the raw material solution was put into a tank-type reactor connected to the autoclave up to 2 / 3 of its capacity, and the temperature was maintained at 140°C. First, the polymerization reaction was started in a batch mode. When the polymerization conversion rate reached 48% by mass, the raw material solution was supplied from the autoclave to the tank-type reactor at a flow rate corresponding to an average residence time of 150 minutes, and at the same time, the reaction solution was withdrawn from the tank-type reactor at a flow rate corresponding to the supply flow rate of the raw material solution, and the temperature was maintained at 140°C, and the polymerization reaction was switched to a continuous flow mode. The polymerization conversion rate in the steady state after switching was 48% by mass. The reaction solution withdrawn from the tank-type reactor in the steady state was supplied to a multi-tubular heat exchanger with an internal temperature of 230°C at a flow rate corresponding to an average residence time of 2 minutes for heating. Then, the heated reaction solution was introduced into an adiabatic flash evaporator to remove volatile components mainly composed of unreacted monomers, and a molten resin was obtained. The molten resin from which the volatile components were removed was supplied to a twin-screw extruder with an internal temperature of 260°C and discharged in a strand shape, and cut with a pelletizer to obtain pellet-shaped polymethyl methacrylate. As a result of GPC analysis, the weight-average molecular weight of the obtained polymethyl methacrylate was 117,000 g / mol, and the molecular weight distribution was 2.35.

[0103] [Production Example 2] (2) Synthesis of Resin (A1) Charge 250 parts of lithium aluminum hydride into a reaction vessel equipped with a cooler, replace the air with nitrogen, add 3000 parts of N-methylmorpholine, and then heat to 130 °C and reflux. Add a solution consisting of 600 parts of the polymethyl methacrylate synthesized in Production Example 1 and 6000 parts of N-methylmorpholine thereto, and reflux for an additional 4 hours after the dropping is completed. Then, dropwise add 1000 parts of ethyl acetate to deactivate the unreacted hydride, and further dropwise add 5000 parts of a 50% aqueous phosphoric acid solution. After cooling, separate into supernatant and solid by centrifugation. Polymer (its 1) was precipitated in the obtained supernatant in addition to distilled water. Also, add 10000 parts of ethanol to the obtained solid content, heat and dissolve at 60 °C for 1 hour, filter through a glass filter, concentrate the obtained filtrate with an evaporator, and then add to distilled water to precipitate polymer (its 2). The polymers (its 1 and its 2) obtained by precipitation were combined, added to distilled water at 100 °C, and thoroughly washed by boiling. After washing, resin (A1) was obtained by filtration.

[0104] Structure identification of resin (A1) 1 1H-NMR: δ = 0.9 to 1.2 (3H, side-chain methyl), 1.2 to 1.6 (2H, main-chain methylene), 3.1 to 3.5 (2H, side-chain methylene), 4.6 (1H, hydroxyl group) 13 13C-NMR: δ = 21 to 27 (side-chain primary carbon), 38 to 43 (main-chain quaternary carbon), 43 to 52 (main-chain secondary carbon), 67 to 73 (carbon to which the hydroxyl group in the side chain is bonded)

[0105] [Production Examples 3 to 8] (3) Synthesis of resins (A2) to (A7) Resins (A2) to (A7) were obtained in the same manner as in Production Example 2, except that the (co)polymer obtained by radical polymerization of the monomer shown in Table 1 was used instead of polymethyl methacrylate in Production Example 2.

[0106]

Table 1

[0107] [Production Example 9] (4) Synthesis of Resin (A8) In Production Example 2, Resin (A8) was obtained in the same manner as in Production Example 2, except that "Parapet (registered trademark) GF brand, methacrylic resin" manufactured by Kuraray Co., Ltd. was used instead of polymethyl methacrylate. Resin (A8) contained 88 mol% of the structural unit represented by the formula (1) and also contained a structural unit derived from allyl alcohol.

[0108] [Example 1] 450 g of water was added to 0.1 g of sodium borohydride and stirred to prepare Solution 1. 50 g of Solution 1 was measured out, 3 g of Resin (A1) was added thereto, and it was immersed at room temperature for 5 days while stirring occasionally. After immersion, the resin composition was recovered and dried under reduced pressure at 80°C for 12 hours to obtain a resin composition.

[0109] The Resin (A1) contained in the resin composition obtained in Example 1 had 99.9 mol% or more of the structural unit represented by the formula (1). The content of boron element contained in the resin composition was 2 μmol / g with respect to Resin (A1). Also, MFR15 / MFR3 in the long-term property evaluation was 0.92, the peel strength in the interlayer adhesion evaluation was 530 g / 15 mm, and the oxygen permeability in the gas barrier property evaluation was less than the detection limit of 0.01 mL / (m 2 ·day·atm). No fish eyes, streaks, gels, or lumps were observed in the resin composition layer of the multilayer film prepared for the evaluation of interlayer adhesion. Each evaluation result is shown in Table 2.

[0110] [Example 2] A resin composition was obtained in the same manner as in Example 1, except that Solution 2 prepared by adding 1 g of aqueous ammonia to 0.1 g of boric acid and then adding 450 g of water was used instead of Solution 1. The resin contained in the resin composition obtained in Example 2 contained 99.9 mol% or more of the structural unit represented by the formula (1). The content of boron element contained in the resin composition was 2 μmol / g. Each evaluation result is shown in Table 2.

[0111] [Example 3] A solution 3 prepared by adding 10 g of aqueous ammonia to 1 g of boric acid and then adding 90 g of water was used in place of solution 1, and a resin composition was obtained in the same manner as in Example 1. The resin contained in the resin composition obtained in Example 3 contained 99.9 mol% or more of the structural unit represented by formula (1). The content of boron element contained in the resin composition was 30 μmol / g. The results of each evaluation are shown in Table 2.

[0112] [Example 4] A solution 4 prepared by adding 25 g of aqueous ammonia to 4 g of boric acid and then adding 75 g of water was used in place of solution 1, and a resin composition was obtained in the same manner as in Example 1. The resin contained in the resin composition obtained in Example 4 contained 99.9 mol% or more of the structural unit represented by formula (1). The content of boron element contained in the resin composition was 161 μmol / g. The results of each evaluation are shown in Table 2.

[0113] [Examples 5 to 9] In Example 1, a resin composition was obtained in the same manner as in Example 1, except that resin (A1) was changed to resin (A2), resin (A3), resin (A4), resin (A5), and resin (A8) in Table 1, respectively. The content of the structural unit of formula (1), the content of boron element contained in the resin composition, and the results of each evaluation are shown in Table 2.

[0114] [Comparative Examples 1 and 2] In Example 1, a resin composition was obtained in the same manner as in Example 1, except that resin (A1) was changed to resin (A6) and resin (A7) in Table 1, respectively. The content of the structural unit of formula (1), the content of boron element contained in the resin composition, and the results of each evaluation are shown in Table 2.

[0115] [Comparative Example 3] Each evaluation was carried out without treating resin (A1) with boron compound (B). The content of the structural unit of formula (1), the content of boron element contained in the resin composition, and the results of each evaluation are shown in Table 2.

[0116] [Example 10] 200 g of THF, 8 g of sodium borohydride, and 5 g of the polymethyl methacrylate produced in Production Example 1 were charged into a SUS autoclave. After purging with nitrogen, the temperature was raised to 120°C. 80 g of methanol was added dropwise thereto over 1 hour. When the internal pressure increased due to the addition of methanol, the pressure was appropriately released. After completion of the dropwise addition, the reaction temperature was maintained at 120°C, and stirring was continued for an additional 1 hour. After allowing it to cool, the reaction solution was added to 2000 g of distilled water, and the product was precipitated by reprecipitation. After obtaining the product by filtration, it was washed by stirring in distilled water for 2 hours again. The resin composition was obtained by filtering this. The resin composition had 90 mol% of the structural unit represented by the formula (1). Further, the content of boron element contained in the resin composition was 2 μmol / g. Each evaluation result is shown in Table 2.

[0117] [Example 11] A resin composition was obtained in the same manner as in Example 10, except that the amount of sodium borohydride used was changed to 12 g. The resin composition had 97 mol% of the structural unit represented by the formula (1). Further, the content of boron element contained in the resin composition was 6 μmol / g. Each evaluation result is shown in Table 2.

[0118] [Example 12] A resin composition was obtained in the same manner as in Example 10, except that the amount of sodium borohydride used was changed to 15 g. The resin composition had 99.9 mol% of the structural unit represented by the formula (1). Further, the content of boron element contained in the resin composition was 18 μmol / g. Each evaluation result is shown in Table 2.

[0119] [Example 13] The operation was carried out as in Example 12 until the polymer was precipitated by reprecipitation. After obtaining the polymer by filtration, it was washed by stirring in distilled water for 30 minutes again, and the resin composition was obtained by filtration. The resin composition had 99.9 mol% of the structural unit represented by the formula (1). Further, the content of boron element contained in the resin composition was 113 μmol / g. Each evaluation result is shown in Table 2.

[0120] [Example 14] The resin (A1) obtained in Production Example 2 was dried in a vacuum dryer at 60°C for 5 hours. The dried resin (A1) was fed into the cylinder barrel of a twin-screw extruder from the first raw material supply section at 10 kg / hr, the resin temperature at the discharge port was set to 130°C, and an aqueous solution (solution 5) in which 0.1 kg of sodium borohydride was dissolved in 450 kg of water was fed to the molten resin (A1) at 0.83 L / hr from the second raw material supply section located near the tip of the discharge port side. The strand-shaped molten resin composition discharged from the die was cut with a strand cutter. The obtained resin composition was dried in a hot air dryer at 80°C for 3 hours and then at 120°C for 15 hours. The obtained resin composition had 99.9 mol% of the structural unit represented by formula (1). The content of boron element contained in the resin composition was 2 μmol / g. The measurement results of this resin composition are shown in Table 2.

[0121] The twin-screw extruder and kneading conditions used in the preparation of the resin composition of Example 14 are as follows: (Details of twin screw extruder specifications) Diameter 30mmφ L / D 45.5 Screw Same direction full intermeshing type Screw rotation speed: 300 rpm Die: 3mmφ, 5-hole strand die Take-up speed: 5m / min

[0122] [Comparative Example 4] A resin composition was obtained in the same manner as in Example 14, except that ion-exchanged water was supplied from the second raw material supply unit instead of solution 5. The obtained resin composition had 99.9 mol% of the structural unit represented by formula (1). In addition, the resin composition did not contain boron element. The measurement results are shown in Table 2.

[0123] [Table 2]

[0124] Next, the melt flow rate (MFR) of the resin composition of the present invention was measured.

[0125] [Example 15] Into an SUS autoclave, 200 g of THF, 15 g of sodium borohydride, and 5 g of the polymethyl methacrylate produced in Production Example 1 were charged. After purging with nitrogen, the temperature was raised to 120°C. 80 g of methanol was added dropwise thereto over 1 hour. When the internal pressure increased due to the addition of methanol, the pressure was released as appropriate. After completion of the addition, the reaction temperature was maintained at 120°C and stirring was continued for another 1 hour. After allowing it to cool, the reaction solution was added to 2000 g of distilled water, and the product was precipitated by reprecipitation. After the product was obtained by filtration, as a washing step, stirring was carried out in 2000 g of distilled water for 2 hours and then filtration was repeated 3 times to obtain a resin composition. The resin composition had 99.9 mol% of the structural unit represented by the formula (1). Further, the content of the boron element contained in the resin composition was 0.1 μmol / g. The MFR (load 2.16 kg, 230°C) of the obtained resin composition was measured. The results are shown in Table 3.

[0126] [Example 16] It was the same as in Example 15 except that the amount of washing water was changed to 1900 g in the washing step. The results are shown in Table 3.

[0127] [Example 17] It was the same as in Example 15 except that the amount of washing water was changed to 1800 g in the washing step. The results are shown in Table 3.

[0128] [Example 18] It was the same as in Example 15 except that the amount of washing water was changed to 1700 g in the washing step. The results are shown in Table 3.

[0129] [Example 19] It was the same as in Example 15 except that the amount of washing water was changed to 1600 g in the washing step. The results are shown in Table 3.

[0130] [Example 20] It was the same as in Example 15 except that the amount of washing water was changed to 1500 g in the washing step. The results are shown in Table 3.

[0131] [Example 21] It is the same as Example 15 except that the amount of washing water was changed to 1000 g in the washing step. The results are shown in Table 3.

[0132] [Reference Example 1] The MFR (load 2.16 kg, 230 °C) of the resin (A1) obtained in Production Example 2 was measured. Let the obtained MFR value be MFR0. The results are shown in Table 3.

[0133]

Table 3

[0134] Generally, when a boron compound is added to a polymer containing a hydroxyl group, the hydroxyl group coordinates to the boron atom, resulting in a decrease in the mobility of the polymer. That is, the fluidity of the resin composition decreases. However, surprisingly, in the resin composition of the present invention, even when the amount of the boron compound is increased, the decrease in fluidity is relatively suppressed. For example, as described in Example 21, even with a relatively high content of boron element, the MFR is 3 or more, so melt processing is possible. Although the details of this are unclear, the hydroxy site of the hydroxymethylene group in the side chain of the polymer coordinates relatively strongly to boron, while the degree of freedom of rotation around the carbon of the methylene site is high, so that decoordination is likely to occur. As a result, coordination / decoordination is likely to occur, and this behavior may contribute to the excellent fluidity of the resin composition.

[0135] Hereinafter, examples of the molded body using the resin composition of the present invention will be described.

[0136] [Example 22] · Production of a single-layer film The resin composition obtained in Example 1 was melt-extruded and pelletized at 220°C using a Laboplastmill manufactured by Toyo Seiki Seisaku-sho, Ltd., equipped with a twin-screw extruder having a screw diameter of 20 mm. Using the obtained pellets, a single-layer film with a thickness of 15 μm was obtained by single-layer film formation at a die temperature of 220°C using a Laboplastmill manufactured by Toyo Seiki Seisaku-sho, Ltd., equipped with a single-screw extruder having a screw diameter of 20 mm and a coat hanger die with a width of 300 mm and a lip gap of 0.3 mm. The obtained single-layer film was colorless and transparent, and had a good appearance.

[0137] [Example 23] ·Production of laminated film A low-density polyethylene (LDPE) film with a thickness of 50 μm, whose bonding surfaces were treated with corona, was laminated on both sides of the single-layer film obtained in Example 22 via a urethane-based adhesive, thereby obtaining a laminated film having a configuration of LDPE / resin composition / LDPE = 50 μm / 15 μm / 50 μm. Two films with a size of 10 cm square were cut out from the obtained laminated film, 20 g of ketchup was placed between these films, heat-sealed and enclosed in a nitrogen box, and a storage test was conducted at 40°C and a relative humidity of 50% for 180 days. As a result, no discoloration was observed in the ketchup.

[0138] [Example 24] ·Application of resin composition to adhesive A laminated film having a configuration of LDPE / EF-F / LDPE was obtained in the same manner as in Example 23, except that a film with a thickness of 15 μm made of "EF-F" manufactured by Kuraray Co., Ltd. was used instead of the intermediate layer made of the resin composition, and a urethane-based adhesive obtained by adding the resin composition to the urethane-based adhesive used in Example 23 so that its content was 10% by mass of the total adhesive was used. When the same evaluation as in Example 23 was conducted, no discoloration was observed in the ketchup.

[0139] [Example 25] ·Production of pouch On one side of a biaxially oriented polypropylene film (OPP, "Tosero OP U-1" manufactured by Toppan Printing Co., Ltd., melting point 155°C, thickness 20 μm), a urethane-isocyanate-based adhesive ("Takelac A-385" / "Takenate A-10" manufactured by Takeda Pharmaceutical Company Limited) was applied at a solid content of 2.5 g / m 2 After coating at a basis weight of, the single-layer film obtained in Example 22 was laminated on the coated surface by the dry lamination method. Next, a linear low-density polyethylene film (LLDPE, "Tosero TUX-TC" manufactured by Toppan Printing Co., Ltd., density 0.92 g / cm 3 , thickness 65 μm) was laminated by the same dry lamination method as above to produce a multilayer structure (laminated film with a total thickness of 100 μm) having a structure of OPP / resin composition / LLDPE. Then, the LLDPE surface was sealed as the sealing surface to produce a pouch, and the following items (1) and (2) were evaluated.

[0140] (1) Bag-making processability Using a high-speed automatic bag-making machine "HSE-500A type" manufactured by Nishi Machinery Co., Ltd., a three-side sealed bag (pouch, 150×230 mm, seal width 15 mm) was made at a bag-making speed of 85 bags / min at a seal bar temperature of 180°C. The appearance (presence or absence of appearance defects such as darts, pinholes, waviness, whitening, seal deviation, etc.) and seal strength of the sealed surface of the made pouch were good. (2) Appearance When the appearance of the three-side sealed bag (pouch) was visually judged comprehensively from the presence or absence of appearance defects such as gels, fish eyes, streaks, wood grain patterns, coloring, etc. and transparency (cloudiness), it was good.

[0141] [Example 26] · Fabrication of a hollow molded container Using a TB-ST-6P type direct blow multi-layer hollow molding machine manufactured by Suzuki Iron Works Co., Ltd., with the resin composition obtained in Example 1 as the intermediate layer, polypropylene (PP, "B200" manufactured by Mitsui Chemicals, Inc.) as the inner and outer layers, and maleic anhydride-modified polypropylene (M-PP, "Admer QB550" manufactured by Mitsui Chemicals, Inc.) as the adhesive layer, a 3-kind 5-layer hollow molded container (capacity 350 mL) with a total thickness of 700 μm and a thickness configuration of the container body of PP (320 μm, outer layer) / M-PP (10 μm) / resin composition / M-PP (10 μm) / PP (350 μm, inner layer) was molded by the direct blow molding method. The moldability and the appearance of the molded body were extremely good. The die temperature during molding was set at 220 °C, and the blow mold temperature was set at 25 °C.

[0142] [Example 27] · Fabrication of a vacuum insulator A vacuum insulator was fabricated using the multi-layer structure having the OPP / resin composition / LLDPE configuration obtained in Example 25. Specifically, first, two pieces of the above multi-layer structure were cut out into a predetermined shape. Next, the two pieces of the above multi-layer structure were overlapped so that the OPP layer was on the inside, and a bag was formed by heat-sealing three sides of a rectangle. Next, a heat-insulating core material was filled from the opening of the bag, and the bag was sealed at a temperature of 20 °C and an internal pressure of 10 Pa using a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH). In this way, the vacuum insulator could be fabricated without problems. Note that silica fine powder dried at 120 °C for 4 hours was used as the heat-insulating core material.

[0143] [Example 28] · Fabrication of a coating film A coating film was prepared using the resin composition obtained in Example 1. Specifically, 0.5 g of the resin composition obtained in Example 1 was dissolved in 9.5 g of 1-propanol to prepare a coating solution. Subsequently, the above coating solution was applied onto the corona-treated surface of "Lumirror" (registered trademark) "P60" manufactured by Toray Industries, Inc., which is a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm and one side corona-treated, using a bar coater so that the thickness after drying would be 1.0 μm. The coated film was dried at 100 °C for 5 minutes and then at 140 °C for 10 minutes to form a layer of the resin composition on the polyethylene terephthalate film. In this way, a coating film (multilayer structure) having a structure of a polyethylene terephthalate / resin composition layer with good appearance was obtained.

[0144] [Example 29] ·Fabrication of a solar cell module A solar cell module was fabricated using the multilayer structure obtained in Example 28. Specifically, first, an amorphous silicon solar cell installed on a 10 cm square tempered glass was sandwiched between ethylene-vinyl acetate copolymer films with a thickness of 450 μm. Next, the above multilayer structure was bonded onto the film such that the polyethylene terephthalate layer of the multilayer structure was on the outside to fabricate a solar cell module. The bonding was carried out by performing vacuum pumping at 150 °C for 3 minutes and then pressure bonding for 9 minutes. The solar cell module fabricated in this way operated well and exhibited good electrical output characteristics over a long period.

[0145] [Example 30] ·Application of the resin composition to powder coating The resin composition obtained in Example 1 was subjected to cryogenic grinding (using liquid nitrogen), passed through a 20-mesh wire netting, and the powder remaining on a 100-mesh wire netting was obtained. The obtained powder was put into a thermal spraying facility, sprayed onto a 150×250×2 mm steel plate that had been degreased and washed with a solvent, and allowed to cool in the air. As a result, a steel plate with an average layer thickness of the resin composition of 55 μm and a steel plate with an average layer thickness of the resin composition of 400 μm were obtained. For both steel plates, the glossiness and smoothness of the layer of the resin composition were good.

[0146] [Example 31] ·Manufacture of a paper container for liquid packaging After flame-treating both sides of the paper (paperboard) serving as the base material, low-density polyethylene (LDPE) with a thickness of 50 μm was laminated on both sides of the paper by the extrusion coating method to produce a three-layer structure having an LDPE / paper / LDPE configuration. After corona-treating the low-density polyethylene layer on one side of this three-layer structure, the resin composition obtained in Example 1 was laminated at a thickness of 15 μm on the corona-treated surface by the extrusion coating method to produce a multilayer structure having a four-layer configuration. From the multilayer structure having the four-layer configuration, a paper container having a gabled top with a length of 7 cm, a width of 7 cm, and a height of 19 cm was produced with the layer of the resin composition as the inner layer, filled with orange juice, nitrogen-substituted, and then the upper part was heat-sealed and sealed. As a result of conducting a sensory test on the taste change after storage for 10 weeks in an environment of 20°C and 100% RH, the quality of the content had hardly changed compared to before storage.

[0147] [Example 32] ·Manufacture of a thermoformed container Using the resin composition obtained in Example 1 as the intermediate layer, homopolypropylene [PP, "J103" manufactured by Grand Polymer, MI = 3.0 g / 10 min (230 °C, 2160 g load), Vicat softening point 155 °C] for the inner and outer layers, and maleic anhydride-modified polypropylene ["Admer QF500" manufactured by Mitsui Chemicals, Inc., MI = 5.3 g / 10 min (230 °C, 2160 g load)] as the adhesive (Ad) layer, a thermoforming sheet with an overall thickness of 860 μm was obtained in a 3-layer 5-layer structure (PP / Ad / resin composition / Ad / PP = thickness 400 μm / 20 μm / 20 μm / 20 μm / 400 μm) using a co-extrusion machine equipped with a T-die. The obtained sheet was thermoformed (compressed air: 5 kg / cm 2 , plug: 45φ × 65 mm, syntactic foam, plug temperature: 150 °C, mold temperature: 70 °C) at a sheet temperature of 150 °C using a thermoforming machine (manufactured by Asano Seisakusho), and a thermoformed container with good appearance was obtained.

[0148] [Example 33] · Preparation of blister pack Using the resin composition obtained in Example 1 as the intermediate layer, polypropylene [PP, "Novatec EA7AD" manufactured by Japan Polypropylene Corporation] for the inner and outer layers, and maleic anhydride-modified polypropylene ["Admer QF500" manufactured by Mitsui Chemicals, Inc.] as the adhesive (Ad) layer, melt film formation was carried out using a feed block type multilayer film extrusion molding machine consisting of three extruders, and a 3-layer 5-layer multilayer structure (PP / Ad / resin composition / Ad / PP = thickness 130 μm / 10 μm / 10 μm / 10 μm / 130 μm, overall thickness 290 μm) was obtained. Using the obtained multilayer structure, a blister pack was produced. The appearance of the molded blister pack was good, and the oxygen permeability was less than 0.01 mL / (m 2 ·day·atm). The manufacturing conditions of the multilayer structure, the extrusion conditions of each resin, and the manufacturing conditions of the blister pack were as follows, respectively.

[0149] (Manufacturing conditions of multilayer structure) Equipment: Feed block type multilayer film extrusion molding machine Die: Manufactured by Plastic Engineering Research Institute Co., Ltd., 300 mm wide coat hanger die Die temperature: 210 °C Cooling roll temperature: 80 °C Take-up speed: 1.5 m / min

[0150] (Extrusion conditions of resin composition) Equipment: Toyo Seiki Seisakusho Co., Ltd. Labo Machine ME type CO-EXT (20 mm φ single screw extruder) Screw rotation speed: 7 rpm Extrusion temperature: Feeding section / Compression section / Measuring section = 170 °C / 210 °C / 210 °C

[0151] (Extrusion conditions of polypropylene) Equipment: GT-32-A manufactured by Plastic Engineering Research Institute Co., Ltd. (32 mm φ single screw extruder) Screw rotation speed: 70 rpm Extrusion temperature: Feeding section / Compression section / Measuring section = 170 °C / 210 °C / 210 °C

[0152] (Extrusion conditions of adhesive resin) Equipment: SZW20GT-20MG-STD manufactured by Technovel Corporation (20 mm φ single screw extruder) Screw rotation speed: 12 rpm Extrusion temperature: Feeding section / Compression section / Measuring section = 170 °C / 210 °C / 210 °C

[0153] (Manufacturing conditions of blister pack) Equipment: Ez Blister manufactured by Sepha Void size: Length 22 mm, width 8 mm, height 8 mm Elongation ratio: Length 0.36, width 1.0 Temperature: 168 °C During preheating: 0.075 MPa / 4 s During thermoforming: 0.10 MPa / 4 s

[0154] [Example 34] · Production of shrink film The resin composition obtained in Example 1 was melt-extruded and pelletized at 210°C using a Laboplastmill manufactured by Toyo Seiki Seisaku-sho, Ltd. equipped with a twin-screw extruder having a screw diameter of 20 mm. Using the obtained pellets, a three-layer five-layer co-extrusion apparatus was used to produce a multilayer sheet (ionomer resin layer / adhesive resin layer / resin composition layer / adhesive resin layer / ionomer resin layer). The thickness of each layer constituting the sheet was such that the ionomer resin (Himilan 1652 manufactured by Mitsui DuPont Polychemical Co., Ltd.) layers of both outermost layers were each 250 μm, the adhesive resin (Admer NF518 manufactured by Mitsui Chemicals, Inc.) layers were each 30 μm, and the resin composition layer was 90 μm. The obtained sheet was subjected to a pantograph-type biaxial stretching machine, and simultaneous biaxial stretching was performed at a stretching ratio of 4×4 times at 90°C to obtain a shrink film having a thickness configuration of 15 / 2 / 6 / 2 / 15 μm for each layer and a total thickness of 40 μm. The obtained multilayer shrink film had no unevenness or thickness deviation, and had relatively good appearance and transparency. Further, the above multilayer shrink film was folded in two, heat-sealed in two directions (both sides) to form a bag, and after putting processed meat, the inlet was heat-sealed under vacuum. Then, the vacuum packaging bag was immersed in 85°C warm water for 5 seconds to thermally shrink the film. As a result, the film adhered to the processed meat had no wrinkles and little abnormal deformation of the contents, and was relatively good.

[0155] [Example 35] · Production of pipe Using the resin composition obtained in Example 1, a four-layer five-layer co-extrusion multilayer pipe molding apparatus was used to produce a pipe having an outer diameter of 20 mm. The configuration of the pipe was an outermost layer with a thickness of 450 μm made of 12 polyamide (UBE Nylon 30200 manufactured by Ube Industries, Ltd.) / an adhesive resin layer with a thickness of 50 μm (Admer VF500 manufactured by Mitsui Chemicals, Inc.) / a 6 polyamide layer with a thickness of 100 μm (Amilan CM1046 manufactured by Toray Industries, Inc.) / a resin composition layer with a thickness of 150 μm / an innermost layer with a thickness of 250 μm made of 6 polyamide (Amilan CM1046 manufactured by Toray Industries, Inc.).

[0156] Next, water from which dissolved oxygen had been removed using a packed tower filled with metallic tin was circulated through the pipe prepared above, and the rate of increase in the concentration of dissolved oxygen in the water was measured at a temperature of 70°C. The rate of increase μg / (L·hr) referred to here indicates the rate of increase in μg / hr of dissolved oxygen per 1 L of water in the pipe. That is, when the volume of water in the entire apparatus including the pipe is V mL and the volume of water in the above pipe is V' mL, and the increase in the oxygen concentration of the circulating water in the apparatus per unit time is B μg / (L·hr), the above rate of increase in dissolved oxygen A μg / (L·hr) indicates a value calculated by A = B·(V / V'). When the rate of increase in the concentration of dissolved oxygen in the pipe was measured at a relative humidity of 80% in the external atmosphere, the rate of increase in dissolved oxygen was 1 μg / (L·hr), and good results were obtained.

[0157] [Example 36] ·Production of fuel tank (blow-molded container) The blow-molded container was produced using the resin composition obtained in Example 1 and the following recovered resin prepared from this resin composition.

[0158] (1) Preparation of recovered resin 4 parts by mass of the resin composition obtained in Example 1, 86 parts by mass of high-density polyethylene ("HZ8200B" manufactured by Mitsui Chemicals, Inc., melt flow rate (MFR) = 0.01 g / 10 min at 190°C and 2160 g load), and 10 parts by mass of an adhesive resin ("Admer GT-6A" manufactured by Mitsui Chemicals, Inc., melt flow rate = 0.94 g / 10 min at 190°C - 2160 g) were dry-blended. Then, using a twin-screw extruder ("2D25W" manufactured by Toyo Seiki Seisakusho Co., Ltd., 25 mmφ, die temperature 220°C, screw rotation speed 100 rpm), pelletization by extrusion was carried out under a nitrogen atmosphere. Further, in order to obtain a model recovered resin, this extruded pellet was extruded again using the same extruder and under the same conditions, and pelletization was carried out. This operation was carried out a total of 4 times (the blending in the extruder was carried out 5 times in total) to obtain a recovered resin.

[0159] (2) Production of fuel tank (blow-molded container) Using the dried pellets of the above resin composition, the above high-density polyethylene, the above adhesive resin, and the above recycled resin, a blow-molded container having a four-layer and six-layer structure of (inner) high-density polyethylene / adhesive resin / resin composition / adhesive resin / recycled resin / resin composition (outer) was produced at 210 °C using a blow molding machine "TB-ST-6P" of Suzuki Manufacturing Works. In the production of the blow-molded container, it was cooled at a mold temperature of 15 °C for 20 seconds, and a 3L tank with an average thickness of 1000 μm for all layers ((inner) high-density polyethylene / adhesive resin / resin composition / adhesive resin / recycled resin / resin composition (outer) = (inner) 340 / 50 / 40 / 50 / 400 / 120 μm (outer)) was molded. The bottom diameter of this tank was 100 mm and the height was 400 mm. When the appearance of the obtained blow-molded container was evaluated, it was a good container with few streaks and the like.

[0160] [Example 37] · Preparation of a single-layer film blended with nylon, a laminated film and a pouch using the same 80 parts by mass of the resin composition obtained in Example 1 and 20 parts by mass of polyamide ("Ny1018A" (nylon 6) manufactured by Ube Industries, Ltd.) were dry-blended, and then using a twin-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., 2D25W, 25 mm φ), under extrusion conditions of a die temperature of 250 °C and a screw rotation speed of 100 rpm, extrusion pelletization was carried out under a nitrogen atmosphere. Next, using a single-screw extrusion device (Toyo Seiki Seisakusho Co., Ltd., D2020, D (mm) = 20, L / D = 20, compression ratio = 2.0, screw: full flight), a single-layer film with a thickness of 20 μm was produced from the above extrusion pellets. The extrusion conditions are as shown below. (Extrusion conditions) Extrusion temperature: 250 °C Screw rotation speed: 40 rpm Die width: 30 cm Take-up roll temperature: 80 °C Take-up roll speed: 3.1 m / min

[0161] The obtained monolayer film, a commercially available biaxially oriented nylon 6 film ("EMBLEM ON" manufactured by Unitika Co., Ltd., average thickness 15 μm), and a commercially available non-oriented polypropylene film ("TO-CELLO CP" manufactured by Mitsui Chemicals Tocello Co., Ltd., average thickness 60 μm) were each cut into A4 size. A dry lamination adhesive was applied to both sides of the monolayer film, and dry lamination was performed so that the outer layer was a nylon 6 film and the inner layer was a non-oriented polypropylene film, and the film was dried at 80°C for 3 minutes to obtain a transparent laminate film consisting of three layers. The dry lamination adhesive used was "Takelac A-385" manufactured by Mitsui Chemicals Co., Ltd. as the main agent, "Takenet A-50" manufactured by Mitsui Chemicals Co., Ltd. as the hardener, and ethyl acetate as the diluent. The amount of application of this adhesive was 4.0 g / m. After lamination, the film was cured at 40°C for 3 days.

[0162] Using the laminate film obtained above, a pouch with four sealed sides and inner dimensions of 12 x 12 cm was produced. The content was water. This was subjected to retort treatment at 120°C for 20 minutes using a retort device (Hisaka Manufacturing Co., Ltd.'s high-temperature, high-pressure cooking sterilization tester "RCS-40RTGN"). After retort treatment, the surface water was wiped off and the pouch was left in a high-temperature, high-humidity room at 20°C and 65% RH for one day, after which the appearance characteristics were evaluated as an evaluation of retort resistance. There was no significant change and it was judged to be good.

Claims

1. A resin composition containing a resin (A) containing 30 mol% or more of a structural unit represented by the following formula (1) and a boron compound (B), wherein the boron element contained in the boron compound (B) is 0.01 to 2,000 micromoles per 1 g of the resin (A). 【Chemical 1】

2. A molded article containing the resin composition according to Claim 1.

3. The molded article according to Claim 2, which is a multilayer structure including one or more layers containing the resin composition according to Claim 1 and one or more other layers.

4. The molded article according to Claim 2 or 3, which is a multilayer structure including one or more layers containing the resin composition according to Claim 1 and a thermoplastic resin layer laminated on one or both sides thereof.

5. The molded article according to Claim 2 or 3, wherein the thickness of the layer containing the resin composition according to Claim 1 is 0.01 to 1000 μm.

6. A film containing the molded article according to Claim 2 or 3.

7. A packaging material containing the film according to Claim 6.

8. A method for producing a resin composition, including a step of bringing a resin (A) containing 30 mol% or more of a structural unit represented by the following formula (1), a boron compound (B), and water into contact with each other. 【Chemical Formula 2】

9. The method for producing a resin composition according to Claim 8, wherein the boron compound (B) is sodium borohydride or borax.

10. The method for producing a resin composition according to Claim 8 or 9, wherein the resin (A) is in a molten state in the step.

11. The method for producing a resin composition according to Claim 8 or 9, wherein the resin (A) is immersed in an aqueous solution containing the boron compound (B) in the step.

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