Gas-barrier laminated body, packaging material, packaging body, and packaged article

Abstract

According to an embodiment of the present invention, a gas barrier laminate is provided, which sequentially comprises a substrate, an inorganic vapor-deposited layer containing inorganic oxides, and a coating layer. The coating layer contains a carboxyl-containing polymer (a), particles containing a multivalent metal (b), a surfactant (c), and a silicon-containing compound (d). The silicon-containing compound (d) is at least one selected from the group consisting of silane coupling agents having a specific structure, their hydrolysis products, and their condensates, wherein the silicon-containing compound (d) is present in a molar quantity (d...). t ) / The number of moles of carboxyl groups in the carboxyl-containing polymer (a) t The molar ratio (d) represented by )] t ) / (a t The content of the coating is 0.15% to 6.10%, and the film thickness of the coating layer is 230 nm to 600 nm. In the above molar ratio (d) / (a), (d) is the mass obtained by converting the silicon-containing compound (d) into a silane coupling agent.

Description

TECHNICAL FIELD

[0001] The present application relates to a gas barrier laminate, a packaging material, a packaging body, and a packaged article. BACKGROUND

[0002] When an article such as a food, a pharmaceutical product, a cosmetic, a pesticide, and an industrial product is stored for a long period of time, the quality can be deteriorated by oxygen. Therefore, as a packaging material for such an article, a film or a sheet having oxygen barrier properties is used.

[0003] As such a packaging material, a packaging material provided with an aluminum foil as a gas barrier coating layer has been used conventionally. However, when a packaging material including an aluminum foil is used, the contents cannot be visually recognized, and a metal detector cannot be used. Therefore, in particular, in the food field and the pharmaceutical product field, development of a packaging material having excellent gas barrier properties and transparency is required.

[0004] Under such a requirement, a gas barrier laminate formed by applying a coating liquid containing polyvinylidene chloride (PVDC) on a substrate to provide a layer composed of PVDC is used. The layer composed of PVDC is transparent and has gas barrier properties.

[0005] However, PVDC can generate dioxin at the time of incineration. Therefore, a shift from PVDC to a non-chlorine-based material is required. Under such a requirement, for example, a scheme of using a polyvinyl alcohol (PVA)-based polymer instead of PVDC is proposed.

[0006] A layer composed of a PVA-based polymer is densified by hydrogen bonding of hydroxyl groups, and exerts high gas barrier properties in a low-humidity atmosphere. However, a layer composed of a PVA-based polymer has a problem that the hydrogen bonding is weakened and the gas barrier properties are greatly reduced due to moisture absorption in a high-humidity atmosphere. Therefore, a gas barrier laminate in which a layer composed of a PVA-based polymer is used as a gas barrier coating layer cannot be used for a packaging material for a food or the like containing a large amount of moisture, and the use is limited to a packaging material for a dry product or the like.

[0007] In order to further improve the gas barrier properties, a scheme of adding an inorganic layered compound to a PVA-based polymer is proposed (for example, refer to Patent Literature 1). However, even if an inorganic layered compound is added, the water resistance of the PVA-based polymer itself is not improved, and thus the problem of reduction in the gas barrier properties in a high-humidity atmosphere still remains.

[0008] In order to improve the gas barrier properties in a high-humidity atmosphere, a scheme of manufacturing a gas barrier laminate by applying a coating liquid containing a PVA-based polymer and a polymer capable of forming a crosslinked structure therewith on a substrate and performing heat treatment is proposed (for example, refer to Patent Literatures 2 and 3).

[0009] However, in these techniques, in order to obtain sufficient gas barrier properties, heat treatment after coating of the coating liquid is required at a high temperature, for example, 150°C or higher, to form a crosslinked structure. Such heat treatment causes rapid deterioration of the substrate in the case where the material of the substrate is a polyolefin such as polypropylene (OPP) or polyethylene (PE), for example. Therefore, the material of the substrate is limited, or a gas barrier laminate that can be produced under milder conditions is required.

[0010] As a method of forming a gas barrier coating layer, a method of forming a layer containing a polycarboxylic acid-based polymer such as polyacrylic acid and ionically crosslinking the polycarboxylic acid-based polymer by a polyvalent metal ion has also been proposed (for example, refer to Patent Documents 4 to 6).

[0011] In this method, the high-temperature heat treatment performed in the methods described in Patent Documents 2 and 3 is not required. Therefore, a polyolefin can be used as the substrate. In addition, the obtained gas barrier coating layer has excellent gas barrier properties even under a high-humidity atmosphere. Therefore, a gas barrier laminate containing the gas barrier coating layer can also be used for applications in which a heating sterilization treatment such as boiling or steaming is performed.

[0012] However, when a polycarboxylic acid-based polymer and a polyvalent metal compound coexist in a coating liquid, the polycarboxylic acid-based polymer and the polyvalent metal compound easily react in the coating liquid to produce a precipitate. When a precipitate is produced in a liquid, a uniform film cannot be formed. Therefore, in this method, when a gas barrier coating layer is formed, a layer containing a polycarboxylic acid-based polymer and a layer containing a polyvalent metal compound are formed separately, or an aqueous solution of a polyvalent metal salt is brought into contact with a layer containing a polycarboxylic acid-based polymer. Therefore, in the case where this method is used, the number of steps is increased in terms of making the gas barrier coating layer a two-layer structure.

[0013] Patent Document 7 discloses a gas barrier film containing a polycarboxylic acid-based polymer and a polyvalent metal compound particle in the same gas barrier coating layer. Here, as a coating liquid for forming a gas barrier coating layer, a proposal is made to set the water content to 1000 ppm or less in a coating liquid containing a polycarboxylic acid-based polymer, a polyvalent metal compound particle, a surfactant, and an organic solvent. In this coating liquid, since the water content is 1000 ppm or less, the reaction of the polycarboxylic acid-based polymer and the polyvalent metal compound is suppressed.

[0014] Prior Art Documents

[0015] Patent Documents

[0016] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 6-093133

[0017] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2000-289154

[0018] Patent Document 3: Japanese Patent Application Publication No. 2000-336195

[0019] Patent Document 4: International Publication No. 2003 / 091317

[0020] Patent Document 5: International Publication No. 2005 / 053954

[0021] Patent Document 6: Japanese Patent Application Publication No. 2013-252618

[0022] Patent Document 7: Japanese Patent Application Publication No. 2005-126528 Summary of the Invention

[0023] The problem that the invention aims to solve

[0024] Patent document 7 describes that the coating liquid disclosed therein can form a film with excellent gas barrier properties even under high humidity conditions. However, in more severe high temperature and high humidity environments, in the laminate formed by coating with this coating liquid, peeling occurs between the gas barrier coating layer and the adjacent layer, such as the film substrate, which may reduce the gas barrier properties.

[0025] When a silane coupling agent is added to the gas barrier coating to improve the lamination strength between the film substrate and the gas barrier coating, the transparency decreases. This makes it difficult to obtain a gas barrier laminate that exhibits both excellent transparency and gas barrier properties under high temperature and high humidity conditions.

[0026] The purpose of this invention is to provide a gas barrier laminate, packaging material, packaging body, and packaged articles that combine transparency with high gas barrier properties under high temperature and high humidity conditions.

[0027] Methods for solving problems

[0028] According to a first aspect of the present invention, a gas barrier laminate is provided, comprising sequentially a substrate, an inorganic vapor-deposited layer containing an inorganic oxide, and a coating layer, wherein the coating layer contains a carboxyl-containing polymer (a), particles containing a multivalent metal (b), a surfactant (c), and a silicon-containing compound (d), wherein the silicon-containing compound (d) is at least one selected from the group consisting of silane coupling agents represented by the following general formulas (1) and (2), their hydrolysis products, and their condensates, and the molar number (d) of the silicon-containing compound (d) is [not specified]. t ) relative to the number of moles of carboxyl groups contained in the above-mentioned carboxyl-containing polymer (a) (a t molar ratio (d) t ) / (a t The content of the coating layer is between 0.15% and 6.10%, and the film thickness is between 230 nm and 600 nm. The molar ratio (d) mentioned above... t ) / (at (d) t The mass is obtained by converting the silicon-containing compound (d) into a silane coupling agent.

[0029] Si(OR1)3Z1···(1)

[0030] Si(R2)(OR3)2Z2···(2)

[0031] In general formula (1), R1 can be the same or different and is an alkyl group with 1 to 6 carbon atoms, and Z1 is a group containing an epoxy group. In general formula (2), R2 is a methyl group, R3 can be the same or different and is an alkyl group with 1 to 6 carbon atoms, and Z2 is a group containing an epoxy group.

[0032] In embodiments of the present invention, the carboxyl-containing polymer (a) may contain at least one α,β-mono-olefinic unsaturated carboxylic acid unit selected from the group consisting of acrylic acid, methacrylic acid, butenoic acid, itaconic acid, maleic acid and fumaric acid.

[0033] Furthermore, in embodiments of the present invention, the multivalent metal constituting the above-mentioned multivalent metal-containing particle (b) can be a divalent metal.

[0034] Furthermore, in embodiments of the present invention, the gas barrier laminate may further include an anchoring coating between the substrate and the inorganic vapor-deposited layer.

[0035] According to a second aspect of the present invention, a packaging material comprising the above-described gas barrier laminate is provided.

[0036] According to a third aspect of the present invention, a packaging body comprising the above-described packaging material is provided.

[0037] According to a fourth aspect of the present invention, a packaged article comprising the aforementioned package body and contents contained therein is provided.

[0038] The effects of the invention

[0039] According to the present invention, a gas barrier laminate, packaging material, packaging body, and packaged articles can be provided that combine transparency with high gas barrier properties under high temperature and high humidity conditions. Attached Figure Description

[0040] [ Figure 1 ] Figure 1 This is a schematic cross-sectional view of the gas barrier laminate according to the first embodiment of the present invention.

[0041] [ Figure 2 ] Figure 2 This is a schematic cross-sectional view of the gas barrier laminate according to the second embodiment of the present invention. DETAILED DESCRIPTION

[0042] Hereinafter, the present embodiment will be described with reference to the drawings. Note that, for elements having the same or similar functions, the same reference signs are assigned, and overlapping descriptions will be omitted.

[0043] Figure 1 is a cross-sectional view schematically showing a gas barrier laminate according to the first embodiment of the present application. Figure 1 The gas barrier laminate 10 shown has a substrate 1, an inorganic vapor deposition layer 2 containing an inorganic oxide, and a coating layer 3.

[0044] The coating layer 3 contains a carboxyl group-containing polymer (a) described in detail below, a polyvalent metal-containing particle (b), a surfactant (c), and a silicon compound (d). The carboxyl group-containing polymer (a) is ionically crosslinked by polyvalent metal ions from the polyvalent metal-containing particle (b), and thus exhibits excellent gas barrier properties even in a high humidity atmosphere. Moreover, since the coating layer 3 contains the silicon compound (d), the gas barrier properties are further improved. On the other hand, by adjusting the blending amount of the silicon compound (d) so that the molar ratio represented by [the number of moles of the silicon compound (d) (d t ) / the number of moles of the carboxyl groups contained in the carboxyl group-containing polymer (a) (a t )] falls within a range of 0.15% or more and 6.10% or less, and the film thickness of the coating layer 3 is set to 230 nm or more and 600 nm or less, the transparency is improved. Further, by providing the inorganic vapor deposition layer 2 between the coating layer 3 and the substrate 1 in the gas barrier laminate 10, the gas barrier properties are further improved, and the transparency and high gas barrier properties can be combined.

[0045] <Coating Layer>

[0046] [Carboxyl Group-Containing Polymer (a)]

[0047] The carboxyl group-containing polymer (a) contained in the coating layer 3 is a polymer having two or more carboxyl groups in the molecule, and is hereinafter sometimes referred to as "polycarboxylic acid-based polymer". As described above, the carboxyl group-containing polymer (a) forms ionic crosslinking with metal ions from the polyvalent metal-containing particle (b) described later in the coating layer 3, and thus exhibits excellent gas barrier properties. As the carboxyl group-containing polymer (a), representative examples include homopolymers of carboxyl group-containing unsaturated monomers, copolymers of two or more kinds of carboxyl group-containing unsaturated monomers, copolymers of carboxyl group-containing unsaturated monomers and other polymerizable monomers, and polysaccharides having carboxyl groups in the molecule (also referred to as "carboxyl group-containing polysaccharides" or "acidic polysaccharides").

[0048] The carboxyl group includes not only a free carboxyl group but also an anhydride group (specifically, a dicarboxylic anhydride group). The anhydride group can be partially ring-opened to become a carboxyl group. A part of the carboxyl group can be neutralized with a base. In this case, the degree of neutralization is preferably 20% or less.

[0049] Here, the "degree of neutralization" is a value obtained by the following method. That is, the carboxyl group is partially neutralized by adding a base (f t ) to the carboxyl group-containing polymer (a). At this time, the ratio of the number of moles of the base (f t ) to the number of moles of the carboxyl group contained in the carboxyl group-containing polymer (a) (a t ) is the degree of neutralization.

[0050] In addition, a graft polymer obtained by graft-polymerizing a carboxyl group-containing unsaturated monomer onto a polymer such as a polyolefin, which does not contain a carboxyl group, can also be used as the carboxyl group-containing polymer (a). A polymer obtained by hydrolyzing a polymer having a hydrolyzable ester group such as an alkoxycarbonyl group (for example, a methoxycarbonyl group) to convert it into a carboxyl group can also be used.

[0051] As the carboxyl group-containing unsaturated monomer, an α,β-monoethylenically unsaturated carboxylic acid is preferable. Therefore, the carboxyl group-containing polymer (a) contains: a homopolymer of an α,β-monoethylenically unsaturated carboxylic acid, a copolymer of two or more kinds of α,β-monoethylenically unsaturated carboxylic acids, and a copolymer of an α,β-monoethylenically unsaturated carboxylic acid and another polymerizable monomer. As the other polymerizable monomer, an ethylenically unsaturated monomer is representative.

[0052] As the α,β-monoethylenically unsaturated carboxylic acid, for example, an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and crotonic acid; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, and itaconic acid; an unsaturated dicarboxylic anhydride such as maleic anhydride and itaconic anhydride; and a mixture of two or more kinds thereof can be exemplified. Among these, at least one kind of α,β-monoethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid is preferable, and at least one kind of α,β-monoethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid is more preferable.

[0053] As other polymerizable monomers, particularly ethylenically unsaturated monomers, which are copolymerizable with the α,β-monoethylenically unsaturated carboxylic acid, for example, the following can be listed: ethylene; α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene; saturated carboxylic acid vinyl esters such as vinyl acetate; alkyl acrylates such as methyl acrylate and ethyl acrylate; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; chlorine-containing vinyl monomers such as vinyl chloride and vinylidene chloride; fluorine-containing vinyl monomers such as vinyl fluoride and vinylidene fluoride; unsaturated nitriles such as acrylonitrile and methacrylonitrile; aromatic vinyl monomers such as styrene and α-methylstyrene; and alkyl itaconates. These ethylenically unsaturated monomers can each be used alone or in combination of two or more. In addition, in the case where the carboxyl group-containing polymer is a copolymer of an α,β-monoethylenically unsaturated carboxylic acid and a saturated carboxylic acid vinyl ester such as vinyl acetate, a copolymer obtained by saponifying this copolymer to convert the saturated carboxylic acid vinyl ester units into vinyl alcohol units can also be used.

[0054] As the carboxyl group-containing polysaccharides, for example, the following acidic polysaccharides having carboxyl groups within the molecule can be listed: alginic acid, carboxymethyl cellulose, and pectin. These acidic polysaccharides can each be used alone or in combination of two or more. In addition, the acidic polysaccharides can also be used in combination with a (co)polymer of an α,β-monoethylenically unsaturated carboxylic acid.

[0055] In the case where the carboxyl group-containing polymer is a copolymer of an α,β-monoethylenically unsaturated carboxylic acid and another ethylenically unsaturated monomer, from the viewpoint of the gas barrier property, hot water resistance, and water vapor resistance of the resulting film, the proportion of the number of moles of the α,β-monoethylenically unsaturated carboxylic acid monomer to the total number of moles of these monomers in the copolymer is preferably 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0056] From the viewpoint of easily obtaining a film which is excellent in gas barrier property, moisture resistance, water resistance, hot water resistance, and water vapor resistance, and which is also excellent in gas barrier property under high humidity conditions, the carboxyl group-containing polymer (a) is preferably a homopolymer or copolymer obtained only by polymerization of an α,β-monoethylenically unsaturated carboxylic acid. In the case where the carboxyl group-containing polymer (a) is a (co)polymer composed only of an α,β-monoethylenically unsaturated carboxylic acid, preferred specific examples thereof are a homopolymer, a copolymer, and a mixture of two or more of these, obtained by polymerization of at least one kind of α,β-monoethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Among these, more preferred are a homopolymer and a copolymer of at least one kind of α,β-monoethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid.

[0057] As the carboxyl group-containing polymer (a), polyacrylic acid, polymethacrylic acid, polymaleic acid, and a mixture of two or more thereof are particularly preferable. As the acidic polysaccharide, alginic acid is preferable. Among these, polyacrylic acid is particularly preferable from the viewpoint of being easily available and easily obtaining a film having various excellent properties.

[0058] The number average molecular weight of the carboxyl group-containing polymer (a) is not particularly limited, but from the viewpoint of film formability and film properties, the number average molecular weight is preferably in the range of 2,000 to 10,000,000, more preferably in the range of 5,000 to 1,000,000, further preferably in the range of 10,000 to 500,000.

[0059] Here, the "number average molecular weight" is a value obtained by gel permeation chromatography (GPC) measurement. In the GPC measurement, the number average molecular weight of the polymer is generally measured in a manner of being converted into a standard polystyrene.

[0060] 〔Multivalent metal-containing particle (b)〕

[0061] The multivalent metal-containing particle (b) contained in the coating layer 3 is preferably a particle containing one or more multivalent metals having a valence of 2 or more. The multivalent metal-containing particle (b) can be a particle composed of a multivalent metal having a valence of 2 or more, a particle composed of a compound of a multivalent metal having a valence of 2 or more, or a mixture thereof.

[0062] As specific examples of the multivalent metal, there can be mentioned beryllium, magnesium, calcium, and the like, which are metals of Group 2A of the short-period type element periodic table; titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, which are transition metals; and aluminum, but not limited thereto.

[0063] The multivalent metal is preferably a metal having a valence of 2. In addition, the multivalent metal preferably forms a compound.

[0064] As specific examples of the compound of the multivalent metal, there can be mentioned oxides, hydroxides, carbonates, organic acid salts, and inorganic acid salts of the multivalent metal, but not limited thereto. As the organic acid salt, there can be mentioned, for example, acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, and monoethylenically unsaturated carboxylate, but not limited thereto. As the inorganic acid salt, there can be mentioned, for example, chloride, sulfate, nitrate, but not limited thereto. As the multivalent metal compound, an alkyl alcoholate of the multivalent metal can also be used. These multivalent metal compounds can be used individually or in combination of two or more.

[0065] Among the multivalent metal compounds, from the viewpoint of the gas barrier property of the gas barrier layered body 10, compounds of beryllium, magnesium, calcium, copper, cobalt, nickel, zinc, aluminum, and zirconium are preferable, and compounds of 2-valent metals such as beryllium, magnesium, calcium, copper, zinc, cobalt, and nickel are more preferable.

[0066] As the preferable 2-valent metal compound, for example, oxides such as zinc oxide, magnesium oxide, copper oxide, nickel oxide, and cobalt oxide; carbonates such as calcium carbonate; organic acid salts such as calcium lactate, zinc lactate, and calcium acrylate; and alcoholates such as magnesium methoxide can be exemplified, but are not limited to these.

[0067] The multivalent metal or the multivalent metal compound is used in the form of particles. As the multivalent metal particles (b), from the viewpoint of the dispersion stability of the coating liquid for forming the coating layer 3 (hereinafter, referred to as "coating liquid for coating layer formation" or simply as "coating liquid") to be described later and the gas barrier property of the gas barrier layered body 10, particles in the range of 10 nm to 10 μm (or 10,000 nm) are preferably used, in terms of the average particle diameter in the coating liquid. As the multivalent metal particles (b), in terms of the average particle diameter in the coating liquid, it is more preferable to be in the range of 12 nm to 1 μm (or 1,000 nm), further preferable to be in the range of 15 nm to 500 nm, and particularly preferable to be in the range of 15 nm to 50 nm.

[0068] When the average particle diameter of the multivalent metal-containing particles (b) is too large, the uniformity of the film thickness of the coating layer 3, the planarity of the surface, the ionic cross-linking reactivity with the carboxyl group-containing polymer (a), and the like easily become insufficient. When the average particle diameter of the multivalent metal-containing particles (b) is too small, the ionic cross-linking reaction with the carboxyl group-containing polymer (a) can proceed too early. In addition, when the average particle diameter of the multivalent metal-containing particles (b) is too small, it is sometimes difficult to uniformly disperse in the coating liquid.

[0069] In the case where the sample is a solid after drying, the average particle diameter of the multivalent metal-containing particles (b) can be determined by measurement and counting using a scanning electron microscope or a transmission electron microscope. The average particle diameter of the multivalent metal-containing particles (b) in the coating liquid can be determined by a light scattering method (Reference: "Kogaku System", Vol. I, pp. 362 to 365, Fuji Techno system (2001)").

[0070] The multivalent metal-containing particles in the coating liquid exist in the form of primary particles, secondary particles, or a mixture thereof, but from the viewpoint of the average particle diameter, it is presumed that most of the cases exist in the form of secondary particles.

[0071] [Surfactant (c)]

[0072] The coating layer 3 contains a surfactant (c) in order to improve the dispersibility of the particles (b) containing multivalent metal. The surfactant is a compound having both a hydrophilic group and a lipophilic group in the molecule. The surfactant includes anionic, cationic and amphoteric ionic surfactants and nonionic surfactants. In the coating layer 3, any surfactant can be used.

[0073] The anionic surfactant includes, for example, carboxylic acid type, sulfonic acid type, sulfate type and phosphate type. As the carboxylic acid type anionic surfactant, for example, there are aliphatic monocarboxylic acid salt, polyoxyethylene alkyl ether carboxylic acid salt, N-acyl sarcosinic acid salt and N-acyl glutamic acid salt. As the sulfonic acid type anionic surfactant, for example, there are dialkyl sulfosuccinic acid salt, alkyl sulfonic acid salt, a-olefin sulfonic acid salt, linear alkylbenzene sulfonic acid salt, alkyl (branched) benzene sulfonic acid salt, naphthalene sulfonic acid salt-formaldehyde condensate, alkyl naphthalene sulfonic acid salt and N-methyl-N-acyl taurine salt. As the sulfate type anionic surfactant, for example, there are alkyl sulfate, polyoxyethylene alkyl ether sulfate and oil and fat sulfate. As the phosphate type anionic surfactant, for example, there are alkyl phosphate type, polyoxyethylene alkyl ether phosphate and polyoxyethylene alkyl phenyl ether phosphate.

[0074] As the cationic surfactant (c), for example, there are alkyl amine salt type and quaternary ammonium salt type. As the alkyl amine salt type cationic surfactant, for example, there are monoalkyl amine salt, dialkyl amine salt and trialkyl amine salt. As the quaternary ammonium salt type cationic surfactant, for example, there are halogenated (chlorinated, brominated or iodinated) alkyl trimethyl ammonium salt and alkyl benzalkonium chloride.

[0075] As the amphoteric surfactant, for example, there are carboxybetaine type, 2-alkyl imidazoline derivative type, glycine type and amine oxide type. As the carboxybetaine type amphoteric surfactant, for example, there are alkyl betaine and fatty acid amide propyl betaine. As the 2-alkyl imidazoline derivative type amphoteric surfactant, for example, there is 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine. As the glycine type amphoteric surfactant, for example, there is alkyl or dialkyl diethylene triamino acetic acid. As the amine oxide type amphoteric surfactant, for example, there is alkyl amine oxide.

[0076] As the nonionic surfactant, for example, there are ester type, ether type, ester ether type, and alkanolamide type. As the nonionic surfactant of the ester type, for example, there are glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester. As the nonionic surfactant of the ether type, for example, there are polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene polyoxypropylene glycol. As the nonionic surfactant of the ester ether type, for example, there are fatty acid polyethylene glycol and fatty acid polyoxyethylene sorbitan. As the nonionic surfactant of the alkanolamide type, for example, there are fatty acid alkanolamides.

[0077] A surfactant having a polymer skeleton such as a styrene-acrylic acid copolymer can also be used.

[0078] Among these surfactants, anionic surfactants such as phosphate esters and surfactants having a polymer skeleton such as styrene-acrylic acid copolymers are preferred.

[0079] 〔Silicon-containing compound (d)〕

[0080] The coating layer 3 contains a silicon-containing compound (d) in order to improve the peeling strength. The silicon-containing compound (d) is at least one compound selected from the group consisting of a silane coupling agent represented by the following general formula (1), a silane coupling agent represented by the following general formula (2), a hydrolysis product thereof, and a condensate thereof.

[0081] Si(OR1)3Z1... (1)

[0082] Si(R2)(OR3)2Z2... (2)

[0083] In the general formula (1), R1may be the same or different and is an alkyl group having 1 to 6 carbon atoms, and Z1is a group containing an epoxy group. Also, in the general formula (2), R2is a methyl group, R3may be the same or different and is an alkyl group having 1 to 6 carbon atoms, and Z2is a group containing an epoxy group.

[0084] The silane coupling agent is easily hydrolyzed, and a condensation reaction easily occurs in the presence of an acid or a base. Therefore, in the coating layer 3, the silicon-containing compound (d) is rarely present in the form of only the silane coupling agent represented by the general formula (1) or (2), in the form of only the hydrolysis product thereof, or in the form of only the condensate thereof. That is, in the coating layer 3, the silicon-containing compound (d) is generally present in the form of a mixture of at least one of the silane coupling agent represented by the general formula (1) and the silane coupling agent represented by the general formula (2), the hydrolysis product thereof, and the condensate thereof.

[0085] R1and R3in General Formulae (1) and (2) can each be an alkyl group having 1 to 6 carbon atoms, and are preferably a methyl group or an ethyl group. Z1and Z2may each be a group containing an epoxy group, and for example, can be an organic group having an epoxy propoxy group.

[0086] As specific examples of the silane coupling agent represented by General Formula (1) or (2), 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane, 3-epoxy propoxy propyl methyldimethoxysilane, 3-epoxy propoxy propyl trimethoxysilane, 3-epoxy propoxy propyl methyldiethoxysilane, and 3-epoxy propoxy propyl triethoxysilane can be given, and 3-epoxy propoxy propyl methyldimethoxysilane and 3-epoxy propoxy propyl trimethoxysilane are preferred. One or two or more kinds of silane coupling agents can be used.

[0087] The hydrolysis product of the silane coupling agent represented by General Formula (1) or (2) can be a partial hydrolysis product, a complete hydrolysis product, or a mixture thereof.

[0088] The condensate included in the coating layer 3 as at least a part of the silicon-containing compound (d) is two or more kinds of a hydrolysis condensate of the silane coupling agent represented by General Formula (1), a hydrolysis condensate of the silane coupling agent represented by General Formula (2), and a condensate of the hydrolysis product of the silane coupling agent represented by General Formula (1) and the hydrolysis product of the silane coupling agent represented by General Formula (2). These hydrolysis condensates are produced by the following reaction. That is, first, the silane coupling agent is hydrolyzed. As a result, one or more alkoxyl groups included in the molecule of the silane coupling agent are replaced with a hydroxyl group, becoming a hydrolysis product. Next, by condensing these hydrolysis products, a compound in which silicon atoms (Si) are bonded via an oxygen bond is formed. By repeating this condensation, a hydrolysis condensate is obtained.

[0089] [Composition]

[0090] The coating layer 3 preferably contains the carboxyl group-containing polymer (a) and the multivalent metal-containing particle (b) in the following blending ratio. That is, the ratio of the product of the number of moles of the multivalent metal contained in the multivalent metal-containing particle (b) and the valence number of the multivalent metal (b t ) to the number of moles of the carboxyl group contained in the carboxyl group-containing polymer (a) (a t ) ((b t ) / (a t ) (hereinafter also referred to as equivalent ratio) is preferably 0.6 or more. This ratio is more preferably 0.8 or more, and particularly preferably 1.0 or more. The upper limit of this ratio is usually 10.0, and is preferably 2.0. When this ratio becomes too small, various properties of the gas barrier laminate 10 such as gas barrier properties, hot water resistance, and water vapor resistance tend to decrease.

[0091] The aforementioned equivalence ratio can be determined in the following way. An example will be given using the case where the carboxyl-containing polymer (a) is polyacrylic acid and the polyvalent metal compound particles (b) are magnesium oxide.

[0092] The monomer unit of polyacrylic acid has a molecular weight of 72, and each monomer molecule has one carboxyl group. Therefore, the amount of carboxyl groups in 100g of polyacrylic acid is 1.39 moles. The above-mentioned equivalent ratio of 1.0 in the coating liquid containing 100g of polyacrylic acid means that the coating layer 3 contains magnesium oxide of an amount that neutralizes 1.39 moles of carboxyl groups. Therefore, in order to make the above-mentioned equivalent ratio in the coating layer 3 containing 100g of polyacrylic acid 0.6, it is only necessary to incorporate magnesium oxide of an amount that neutralizes 0.834 moles of carboxyl groups into the coating layer 3. Here, the valence of magnesium is divalent, and the molecular weight of magnesium oxide is 40. Therefore, in order to make the above-mentioned equivalent ratio in the coating layer 3 containing 100g of polyacrylic acid 0.6, it is only necessary to incorporate 16.68g (0.417 moles) of magnesium oxide into the coating layer 3.

[0093] The surfactant (c) is used in an amount sufficient to stably disperse the multivalent metal particles in the coating solution. Therefore, when its formulation amount is described in terms of concentration in the coating solution for coating layer formation, it is typically set in the range of 0.0001 to 70% by mass, preferably in the range of 0.001 to 60% by mass, and more preferably in the range of 0.1 to 50% by mass.

[0094] Without the addition of surfactant (c), it is difficult to disperse the polyvalent metal-containing particles (b) in the coating solution in a manner that minimizes their average particle size. As a result, it is difficult to obtain a coating solution in which the polyvalent metal-containing particles (b) are uniformly dispersed. In this case, it is difficult to obtain a coating layer 3 with a uniform film thickness in the coating layer 3 obtained by coating the inorganic vapor-deposited layer 2 with the coating solution and then drying it.

[0095] From the perspective of the high gas barrier properties and transparency of the gas barrier laminate 10, the coating layer 3 has a molar number (d) of silicon-containing compound (d). t ) relative to the number of moles of carboxyl groups contained in the carboxyl-containing polymer (a) t molar ratio (d) t ) / (a t The content of silicon-containing compound (d) is between 0.15% and 6.10%. Here, the molar ratio (d) t ) / (a t (d) t ) is the number of moles obtained by converting silicon-containing compound (d) into silane coupling agent.

[0096] When the amount of silicon-containing compound (d) added is too small, the above molar ratio (d) will be affected. t ) / (at When the content is below 0.15%, the peel strength of the gas barrier laminate 10 decreases. Therefore, careful handling is required to prevent interlayer peeling, which leads to a reduction in productivity.

[0097] From the above perspective, the number of moles of silicon-containing compound (d) (d t ) relative to the number of moles of carboxyl groups contained in the carboxyl-containing polymer (a) t molar ratio (d) t ) / (a t The content is preferably 0.3% or more, more preferably 0.46% or more, and particularly preferably 0.61% or more.

[0098] On the other hand, when the amount of silicon-containing compound (d) added is too large, the above molar ratio (d) becomes too large. t ) / (a t When the molar ratio (d) is higher than 6.10%, the transparency of the gas-barrier laminate 10 decreases. Furthermore, the silicon-containing compound (d) does not possess gas-barrier properties. Therefore, when the above molar ratio (d) is higher than 6.10%, the transparency of the laminate decreases. t ) / (a t When the content is higher than 6.10%, not only does the transparency of the laminate decrease, but the gas barrier properties also decrease.

[0099] From the above perspective, the number of moles of silicon-containing compound (d) (d t ) relative to the number of moles of carboxyl groups contained in the carboxyl-containing polymer (a) t molar ratio (d) t ) / (a t The content is preferably 4.57% or less, more preferably 3.66% or less, and particularly preferably 2.13% or less.

[0100] From the viewpoint of combining transparency and gas barrier properties, the film thickness of the coating layer 3 is 230 nm to 600 nm. Specifically, the film thickness of the coating layer 3 is the film thickness measured by the film thickness measurement method described later. The film thickness of the coating layer 3 is preferably 250 nm to 500 nm, and more preferably 300 nm to 450 nm.

[0101] <Inorganic vapor deposition layer>

[0102] The gas barrier laminate 10 of this embodiment has an inorganic vapor-deposited layer 2 between the substrate 1 and the coating layer 3. This further improves the gas barrier properties of the gas barrier laminate 10 with the coating layer 3, thereby achieving both transparency and high gas barrier properties.

[0103] The inorganic vapor deposition layer 2 contains an inorganic oxide. As the inorganic oxide, for example, aluminum oxide, silicon oxide, magnesium oxide, tin oxide, and the like can be listed. Among these, from the viewpoint of combining transparency and gas barrier properties, aluminum oxide, silicon oxide, magnesium oxide, or a mixture of any two or more thereof is preferable.

[0104] The thickness of the inorganic vapor deposition layer 2 can be, for example, in the range of 5 to 100 nm, or in the range of 10 to 50 nm. From the viewpoint of forming a uniform thin film, the thickness of the inorganic vapor deposition layer 2 is preferably 5 nm or more. When the thin film as a gas barrier material is uniform, the function required of the gas barrier material can be sufficiently exerted. From the viewpoint of flexibility of the thin film, the thickness of the inorganic vapor deposition layer 2 is preferably 100 nm or less. When the gas barrier material is poor in flexibility, it can be possible to cause cracking due to external factors such as bending or stretching.

[0105] [Substrate]

[0106] The substrate 1 provided to the gas barrier layered body 10 according to the present embodiment is not particularly limited, and various substrates can be used. The material constituting the substrate 1 is not particularly limited, and various materials can be used, for example, plastic or paper can be listed.

[0107] The substrate 1 can be a single layer composed of a single material, or can be a multilayer composed of a plurality of materials. As an example of a multilayer substrate, a substrate in which a film composed of plastic is laminated on paper can be listed.

[0108] As the material constituting the substrate 1, among the above, from the viewpoint of being able to be shaped into various shapes and further expanding the use by imparting gas barrier properties, plastic is preferable.

[0109] As the plastic, there is no particular limitation, and for example, polyolefin-based resins such as polyethylene and polypropylene; polyester-based resins such as polyethylene terephthalate, polyethylene 2,6-naphthalate, polybutylene terephthalate, and copolymers thereof; polyamide-based resins such as nylon-6, nylon-66, nylon-12, m-xylylene adipamide, and copolymers thereof; styrene-based resins such as polystyrene, styrene-butadiene copolymer, and styrene-butadiene-acrylonitrile copolymer; poly(meth)acrylate; polyacrylonitrile; polyvinyl acetate; ethylene-vinyl acetate copolymer; ethylene-vinyl alcohol copolymer; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulfone; polyethersulfone; polyether ketone; and ionomer resin can be listed.

[0110] In the case where the gas barrier layered body is used for a food packaging material, as the substrate 1, a substrate composed of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66 is preferable.

[0111] As the plastic constituting the base material 1, one kind can be used alone, or two or more kinds can be used in combination.

[0112] An additive can also be incorporated in the plastic. As the additive, a known additive such as a pigment, an antioxidant, an antistatic agent, an ultraviolet absorber, and a lubricant can be appropriately selected according to the use. As the additive, one kind can be used alone, or two or more kinds can be used in combination.

[0113] The form of the base material 1 is not particularly limited, and examples thereof include a film, a sheet, a cup, a dish, a tube, and a bottle. Among these, a film is preferred.

[0114] In the case where the base material 1 is a film, the film can be a stretched film or an unstretched film.

[0115] The thickness of the film is not particularly limited, but from the viewpoint of the mechanical strength and the process adaptability of the resulting gas barrier laminate, it is preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 100 μm.

[0116] In order to enable the coating liquid to be coated to the surface of the base material 1 without being repelled by the base material, plasma treatment, corona treatment, ozone treatment, flame treatment, or radical activation treatment using ultraviolet (UV) or electron beam, or the like can be performed on the surface of the base material 1. The treatment method can be appropriately selected according to the kind of the base material.

[0117] [Other Layer]

[0118] As needed, the gas barrier laminate according to the present embodiment can further have one or more layers other than the base material 1, the inorganic vapor deposition layer 2, and the coating layer 3.

[0119] For example, the gas barrier laminate according to the present embodiment can have only the above-described coating layer 3 as the gas barrier coating layer, or can further include one or more layers other than the coating layer 3. For example, a layer composed of an inorganic compound such as alumina, silica, and aluminum can be formed on the surface of the base material by a sputtering method or an ion plating method, or the like.

[0120] In addition, in order to improve the adhesion between the layers, or in order to enable the coating liquid for forming the coating layer to be coated without being repelled by the inorganic vapor deposition layer, the gas barrier laminate according to the present embodiment can further have an anchor coating layer between the base material 1 and the inorganic vapor deposition layer 2, or between the inorganic vapor deposition layer 2 and the coating layer 3.

[0121] Figure 2 is a cross-sectional view schematically showing a gas barrier laminate according to a second embodiment of the present application. With respect to the gas barrier laminate 10 according to the above-described first embodiment, Figure 2The gas barrier layered body 20 shown further has an anchor coat layer 4 between the base material 1 and the inorganic vapor deposition layer 2.

[0122] The anchor coat layer 4 can be formed using a publicly known anchor coat liquid and by a conventional method. As the anchor coat liquid, for example, a coating liquid containing a resin such as a urethane resin, an acrylic resin, a melamine resin, a polyester resin, a phenol resin, an amino resin, and a fluorine resin can be cited.

[0123] In addition to the resin, the anchor coat liquid can further contain an isocyanate compound in order to improve adhesion and hot water resistance. The isocyanate compound can be, for example, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and toluene diisocyanate, as long as it has one or more isocyanate groups in the molecule.

[0124] The anchor coat liquid can further contain a liquid medium for dissolving or dispersing the resin and the isocyanate compound.

[0125] The thickness of the anchor coat layer 4 is not particularly limited. The thickness of the anchor coat layer 4 can be, for example, in the range of 0.01 to 2 μm, or in the range of 0.05 to 1 μm. When the film thickness is less than 0.01 μm, it is very thin, and thus it can not be possible to sufficiently exert the performance as an anchor coat layer. On the other hand, from the viewpoint of flexibility, the film thickness is preferably 2 μm or less. When the flexibility is reduced, the anchor coat layer can be cracked by external factors.

[0126] As needed, the gas barrier layered body according to the present embodiment can further have other layers laminated via an adhesive on the covering layer 3, or on the surface of the base material 1 or the inorganic vapor deposition layer 2, or can further have other layers extrusion-laminated with an adhesive resin.

[0127] The other layers laminated can be appropriately selected according to the purpose of imparting strength, imparting sealability, imparting easy openability at the time of sealing, imparting designability, imparting light-shielding property, and imparting moisture-proof property, and the like, and are not particularly limited, and for example, the same materials as the above-described plastics related to the base material can be cited. In addition thereto, paper or an aluminum foil can also be used.

[0128] The thickness of the other layers laminated is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, further preferably in the range of 5 to 200 μm, and particularly preferably in the range of 5 to 150 μm.

[0129] The other layers laminated can be one, or two or more.

[0130] According to necessity, the gas barrier layered body according to the present embodiment can further have a print layer. The print layer can be formed on the coating layer provided on the substrate, or on the surface of the substrate on which no coating layer is provided. In addition, in the case where other layers are laminated, the print layer can be formed on the laminated other layers.

[0131] [Method for manufacturing gas barrier layered body]

[0132] The gas barrier layered body according to the present embodiment can be manufactured by a manufacturing method including a step of forming the inorganic vapor deposition layer, and a step of forming the coating layer using the coating layer forming coating liquid shown below. According to necessity, the manufacturing method can further include a step of forming other layers such as the anchor coating layer, and / or a step of forming a print layer, and the like.

[0133] As one example of the manufacturing method of the gas barrier layered body according to the present embodiment, the manufacturing method of the gas barrier layered body 20 shown below will be described. Figure 2

[0134] In the manufacturing method of the gas barrier layered body 20, the anchor coating layer 4 is formed on the substrate 1. The anchor coating layer 4 can be formed by applying the anchor coating liquid described above on the substrate 1 and drying the formed coating film. The method of applying the anchor coating liquid is not particularly limited, and a known printing method such as offset printing, gravure printing, screen printing, or the like; or a known coating method such as roll coating, knife coating, gravure coating, or the like can be used. By drying the formed coating film, removal of the solvent and curing are performed, thereby forming the anchor coating layer 4.

[0135] In the manufacturing method of the gas barrier layered body 20, the inorganic vapor deposition layer 2 is formed on the anchor coating layer 4. As the method of forming the inorganic vapor deposition layer 2, various methods such as vacuum evaporation, sputtering, ion plating, chemical vapor deposition (CVD), or the like are known, and any method can be used, but generally vacuum evaporation is used.

[0136] As the heating means of the vacuum evaporation device using vacuum evaporation, an electron beam heating method, a resistance heating method, an induction heating method, or the like can be used, and any heating means can be used.

[0137] In addition, in order to improve the adhesion of the inorganic vapor deposition layer 2 to the anchor coating layer 4 and the density of the inorganic vapor deposition layer 2, a plasma assistance method or an ion beam assistance method can also be used.

[0138] In addition, in order to improve the transparency of the inorganic vapor deposition layer 2, reactive evaporation by blowing oxygen or the like can be performed.

[0139] ​In the method for manufacturing the gas barrier layered body 20, the coating layer 3 is formed on the inorganic vapor deposition layer 2. The coating layer 3 can be formed by applying a coating liquid for coating layer formation prepared by the method described below on the inorganic vapor deposition layer 2 and drying the formed coating film.

[0140] • Preparation method of the coating liquid for coating layer formation

[0141] In the coating liquid for coating layer formation, an organic solvent (e) is used as a solvent or a dispersion medium. That is, the coating liquid is a dispersion liquid containing the carboxyl group-containing polymer (a), the multivalent metal-containing particles (b), the surfactant (c), the silicon compound (d), and the organic solvent, and the multivalent metal-containing particles (b) are dispersed.

[0142] The organic solvent (e) is used in an amount sufficient to uniformly dissolve the carboxyl group-containing polymer (a) and uniformly disperse the multivalent metal-containing particles. Therefore, as the organic solvent, an organic solvent that dissolves the carboxyl group-containing polymer but does not substantially dissolve the multivalent metal compound so as to disperse it in the form of particles can be used.

[0143] In addition, as the organic solvent (e), a polar organic solvent that dissolves the carboxyl group-containing polymer (a) is generally used, but an organic solvent that does not have a polar group (hetero atom or atom group having a hetero atom) can also be used together with the polar organic solvent.

[0144] As the organic solvent (e) that can be preferably used, for example, alcohols such as methanol, ethanol, isopropanol, n-propanol, and n-butanol; polar organic solvents such as dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethyl urea, hexamethyl phosphoric triamide, and γ-butyrolactone can be listed.

[0145] As the organic solvent (e), in addition to the above-described polar organic solvents, hydrocarbons such as benzene, toluene, xylene, hexane, heptane, and octane; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as dichloromethane; esters such as methyl acetate; and ethers such as diethyl ether can be appropriately used. A hydrocarbon such as benzene that does not have a polar group is generally used together with a polar organic solvent.

[0146] The above-described coating liquid can contain only the organic solvent (e) as a solvent or a dispersion medium, but can further contain water. By containing water, the solubility of the carboxyl group-containing polymer (a) can be improved, and the coatability and handleability of the coating liquid can be improved. The water content of the coating liquid can be 100 ppm or more, can be 1,000 ppm or more, can be 1,500 ppm or more, or can be 2,000 ppm or more in terms of mass fraction.

[0147] The water content of the coating liquid is preferably 50,000 ppm or less, more preferably 10,000 ppm or less, and further preferably 5,000 ppm or less, in terms of mass fraction.

[0148] To prepare the coating liquid for the coating layer, on one hand, after the carboxyl group-containing polymer (a) is uniformly dissolved in the organic solvent (e), a silicon compound (d) is added thereto, thereby preparing a carboxyl group-containing polymer solution.

[0149] Then, on the other hand, the multivalent metal-containing particle (b), the surfactant (c), and the organic solvent (e) are mixed, and a dispersion treatment is performed as necessary, thereby preparing a dispersion liquid. The dispersion treatment is performed in a manner such that the average particle diameter of the multivalent metal-containing particle (b) becomes a predetermined value. In a case where the average particle diameter of the multivalent metal-containing particle (b) in the mixed liquid before the dispersion treatment is 10 μm or less, the dispersion treatment can not be performed, but even in this case, the dispersion treatment is preferably performed. By performing the dispersion treatment, the aggregation of the multivalent metal-containing particle (b) is resolved, the coating liquid becomes stable, and at the same time, the transparency of the gas barrier layered body obtained by coating the coating liquid is improved. Furthermore, when the coating liquid is coated and the coating film is dried, the crosslinking of the carboxyl group-containing polymer (a) with the multivalent metal ions from the multivalent metal-containing particle (b) is easily performed, and thus a gas barrier layered body having a good gas barrier property is easily obtained.

[0150] As a method of the dispersion treatment, a method using a high-speed stirrer, a homogenizer, a ball mill, or a bead mill can be cited. In particular, when the dispersion is performed using a ball mill or a bead mill, the dispersion can be performed with high efficiency, and thus the coating liquid in which the dispersion state is stable can be obtained in a short time. In this case, the diameter of the balls or beads can be small, and is preferably 0.1 to 1 mm.

[0151] The coating liquid can be prepared by mixing the carboxyl group-containing polymer solution prepared according to the above-described preparation method and the dispersion liquid of the multivalent metal-containing particle (b). Note that in the above-described preparation method, the silicon compound (d) is added to the carboxyl group-containing polymer solution in advance, but the silicon compound (d) can not be added to the carboxyl group-containing polymer solution, and the silicon compound (d) can be mixed, for example, at the time of mixing the carboxyl group-containing polymer solution and the dispersion liquid of the multivalent metal-containing particle (b).

[0152] In the above-described coating liquid, the total concentration of the components other than the above-described organic solvent (e) is preferably in the range of 0.1 to 60% by mass, more preferably in the range of 0.5 to 25% by mass, and particularly preferably in the range of 1 to 20% by mass, which is preferable in terms of obtaining a coating film and a coating layer having a desired film thickness with high operability.

[0153] The coating liquid described above can contain, as necessary, various additives such as other polymers, tackifiers, stabilizers, ultraviolet absorbers, anti-blocking agents, softening agents, inorganic layered compounds (e.g., montmorillonite), and colorants (dyes, pigments), and the like.

[0154] As the coating method of the coating liquid, there is no particular limitation, and for example, a method in which coating is performed using an air knife coater; a direct gravure coater; a gravure offset printer; an arc gravure coater; a reverse roll coater such as a top feed reverse coater, a bottom feed reverse coater, or a nozzle feed reverse coater; a 5-roll coater; a lip coater; a bar coater; a bar reverse coater; or a die coater can be exemplified.

[0155] As the drying method of the coating film, there is no particular limitation, and for example, a method in which drying is performed in an oven set to a predetermined temperature by natural drying, and a method in which a drying machine attached to a coater, such as an arched drying machine, a floating type drying machine, a drum drying machine, or an infrared drying machine, or the like is used can be exemplified.

[0156] The drying conditions can be appropriately selected depending on the drying method and the like. For example, in the method in which drying is performed in an oven, the drying temperature is preferably in the range of 40 to 150°C, more preferably in the range of 45 to 150°C, and particularly preferably in the range of 50 to 140°C. The drying time varies depending on the drying temperature, and is preferably in the range of 0.5 seconds to 10 minutes, more preferably in the range of 1 second to 5 minutes, and particularly preferably in the range of 1 second to 1 minute.

[0157] It is presumed that, during or after drying, the carboxyl group-containing polymer (a) contained in the coating film reacts with the multivalent metal-containing particles (b) to introduce an ionically crosslinked structure. In order to sufficiently perform the ionically crosslinked reaction, it is preferable to age the film after drying in an atmosphere having a relative humidity of preferably 20% or more, more preferably in the range of 40 to 100%, and under temperature conditions in the range of 5 to 200°C, more preferably in the range of 20 to 150°C, for 1 second to about 10 days.

[0158] The gas barrier layered body thus obtained is ionically crosslinked, and thus has excellent moisture resistance, water resistance, hot water resistance, and water vapor resistance. Furthermore, the gas barrier layered body has excellent gas barrier properties not only under low humidity conditions but also under high humidity conditions. The oxygen permeability of the gas barrier layered body, which is measured according to the method described in JIS K-7126B (isobaric method) and ASTM D3985 under conditions of a temperature of 30°C and a relative humidity of 70%, is preferably 10 cm 3 / (m 2 ·day·MPa) or less.

[0159] <Packaging material, packaging body, and packaged article>

[0160] The packaging material according to the present embodiment contains the gas barrier laminate described above. The packaging material is used, for example, for manufacturing a packaging body of a packaged article.

[0161] The packaging body according to the present embodiment contains the packaging material described above.

[0162] The packaging body can be composed of the packaging material described above, or can contain the packaging material described above and other components. In the former case, the packaging body is formed, for example, by shaping the packaging material described above into a bag shape. In the latter case, the packaging body is, for example, a container composed of the packaging material described above as a lid body and a bottomed tubular container main body.

[0163] In the packaging body, the packaging material described above can be a shaped product. As described above, the shaped product can be a container such as a bag, or a part of a container such as a lid body. As specific examples of the packaging body or a part thereof, a bag-forming product, a bag with a spout, a laminated tube, an infusion bag, a lid material for a container, and a paper container can be given.

[0164] The use of the packaging body is not particularly limited. The packaging body can be used for packaging various articles.

[0165] The packaged article according to the present embodiment contains the packaging body described above and a content housed therein.

[0166] As described above, the gas barrier laminate described above has excellent gas barrier properties and transparency. Therefore, the packaging material and the packaging body containing the gas barrier laminate are respectively used as packaging materials and packaging bodies for articles that are likely to deteriorate due to the influence of oxygen, water vapor, and the like, and are particularly preferably used as packaging materials and packaging bodies for foods. These packaging materials and packaging bodies are also preferably used as packaging materials and packaging bodies for packaging industrial materials such as agricultural chemicals, pharmaceuticals, medical devices, mechanical parts, and precision materials.

[0167] The gas barrier laminate described above does not deteriorate in gas barrier properties and interlayer adhesion when subjected to a heat sterilization treatment such as a boiling treatment and a retort treatment, and tends to improve instead. Therefore, these packaging materials and packaging bodies can be heat-sterilization packaging materials and heat-sterilization packaging bodies, respectively.

[0168] The heat-sterilization packaging material and the heat-sterilization packaging body are used for packaging an article that is subjected to a heat sterilization treatment after packaging.

[0169] As the article that is subjected to a heat sterilization treatment after packaging, for example, foods such as curry, stew, soup, sauce, and processed meat products can be given.

[0170] As the heat sterilization treatment, for example, a boiling treatment and a retort treatment can be given.

[0171] The retort treatment is a treatment for sterilizing by moist heat for the purpose of preserving food and the like. In the retort treatment, depending on the contents, the packaged article in which the contents of food and the like are packaged in the above-mentioned packaging body is subjected to a moist heat sterilization treatment for 10 to 120 minutes at a temperature of 60 to 100°C under atmospheric pressure. The retort treatment is usually performed using a hot water tank. In the retort treatment, there are a batch type in which the packaged article is immersed in a hot water tank at a certain temperature and taken out after a certain time, and a continuous type in which the packaged article is passed through the hot water tank in a tunnel shape to perform sterilization.

[0172] The retort treatment is a treatment for sterilizing by moist heat for the purpose of preserving food and the like. In the retort treatment, depending on the contents, the packaged article in which the contents of food and the like are packaged in the above-mentioned packaging body is subjected to a moist heat sterilization treatment for 10 to 120 minutes at a temperature of 60 to 100°C under atmospheric pressure. The retort treatment is usually performed using a hot water tank. In the retort treatment, there are a batch type in which the packaged article is immersed in a hot water tank at a certain temperature and taken out after a certain time, and a continuous type in which the packaged article is passed through the hot water tank in a tunnel shape to perform sterilization.

[0173] Example

[0174] A specific example of the present application is described below.

[0175] Preparation of anchor coating solution

[0176] In a dilution solvent (ethyl acetate), 5 parts by mass of an acrylic polyol was mixed with respect to 1 part by mass of γ-isocyanatopropyltrimethoxysilane, and stirring was performed. Next, toluene diisocyanate (TDI) was added as an isocyanate compound so that the NCO group was made equal to the OH group of the acrylic polyol. The resulting mixed solution was diluted with the above-mentioned dilution solvent to a concentration of 2% by mass, whereby an anchor coating solution was obtained.

[0177] As the acrylic polyol, GS-5756 manufactured by Mitsubishi Rayon Co., Ltd. was used.

[0178] Preparation of coating solution for forming coating layer

[0179] (Coating solution 1)

[0180] A carboxyl group-containing polymer was heated and dissolved in 2-propanol. As the carboxyl group-containing polymer, polyacrylic acid (PAA) (Jurymer (registered trademark) AC-10LP manufactured by Toagosei Co., Ltd., number average molecular weight 50,000) was used. In this way, a polyacrylic acid solution containing polyacrylic acid at a concentration of 10% by mass was prepared.

[0181] A polyether phosphoric acid ester (Disparlon (registered trademark) DA-375 manufactured by Nippon Shokubai Co., Ltd., solid content 100 mass%) of 1.8 g was dissolved in 2-propanol of 26.2 g. Next, to this, zinc oxide (FINEX (registered trademark)-30 manufactured by Sakai Chemical Industry Co., Ltd.) of 12 g of which the average diameter of primary particles was 35 nm was added and stirred. The resulting liquid was subjected to dispersion treatment for 1 hour using a planetary ball mill (P-7 manufactured by Fritsch Co.). In the dispersion treatment, zirconia beads of 0.2 mm in diameter were used. Then, the beads were sieved out of the liquid, whereby a dispersion liquid containing zinc oxide at a concentration of 30 mass% was obtained.

[0182] Next, a coating liquid 1 was prepared by mixing a polyacrylic acid (PAA) solution of 31.20 g, the zinc oxide dispersion liquid of 5.79 g, a silane coupling agent (SC agent) of 0.08 g as a silicon-containing compound (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane) and 2-propanol of 23.57 g. In the coating liquid 1, the mole ratio ((d t ) / (a t )) of the number of moles (d t ) of the silicon-containing compound (d) to the number of moles (a t ) of the carboxyl group contained in the carboxyl group-containing polymer (a) was 0.78%.

[0183] (Coating liquid 2)

[0184] The coating liquid 2 was prepared by the same method as described above for the coating liquid 1 except that the addition amount of the above-described silicon-containing compound was changed to 0.164 g. In the coating liquid 2, the mole ratio ((d t ) / (a t )) of the number of moles (d t ) of the silicon-containing compound (d) to the number of moles (a t ) of the carboxyl group contained in the carboxyl group-containing polymer (a) was 1.60%.

[0185] (Coating liquid 3)

[0186] The coating liquid 3 was prepared by the same method as described above for the coating liquid 1 except that the addition amount of the above-described silicon-containing compound was changed to 0.499 g. In the coating liquid 3, the mole ratio ((d t ) / (a t )) of the number of moles (d t ) of the silicon-containing compound (d) to the number of moles (a t ) of the carboxyl group contained in the carboxyl group-containing polymer (a) was 4.87%.

[0187] (Coating liquid 4)

[0188] A coating liquid 4 was prepared by the same method as described above for the coating liquid 1 except that the addition amount of the above-described silicon-containing compound was changed to 0.655 g. In this coating liquid 4, the mole ratio ((d t ) / (a t )) of the number of moles of the silicon-containing compound (d t ) to the number of moles of the carboxyl group contained in the carboxyl group-containing polymer (a t ) was 6.40%.

[0189] (Coating liquid 5)

[0190] A coating liquid 5 was prepared by the same method as described above for the coating liquid 1 except that no silicon-containing compound was added. In this coating liquid 5, the mole ratio ((d t ) / (a t )) of the number of moles of the silicon-containing compound (d t ) to the number of moles of the carboxyl group contained in the carboxyl group-containing polymer (a t ) was 0%.

[0191] <Manufacture of gas barrier laminate>

[0192] [Example 1]

[0193] An anchor coating layer was formed by using a bar coater to coat the anchor coating liquid 1 on one face of a 2-axis stretched polypropylene film (manufactured by Mitsui Chemicals Tohcello, Inc., trade name: ME-1, thickness: 20 μm) in such a manner that the thickness after drying became 0.2 μm, and drying at 150°C for 1 minute.

[0194] An inorganic vapor deposition layer having a thickness of 20 nm was formed by evaporating silicon using a vacuum evaporation device of an electron beam heating type, introducing oxygen thereto, and vapor depositing silicon oxide on the anchor coating layer.

[0195] A coating layer was formed by using a bar coater (wire bar) to coat the coating liquid 1 on the inorganic vapor deposition layer. The coating film was dried in an oven at 50°C for 1 minute, thereby forming a coating layer having a film thickness of 500 nm. In this manner, a laminate 1 was obtained. Note that the film thickness of the coating layer was measured by the method described later.

[0196] [Example 2]

[0197] A laminate 2 was obtained by the same method as described above for the laminate 1 of Example 1 except that the coating amount of the coating liquid 1 was changed to change the film thickness of the coating layer.

[0198] [Example 3]

[0199] In addition to changing the inorganic vapor-deposited layer from silicon oxide to aluminum oxide and changing the coating amount of the coating liquid 1 to change the film thickness of the coated layer, the laminate 3 was obtained by the same method as described above for the laminate 1 of Example 1.

[0200] [Example 4]

[0201] In addition to changing the coating liquid 1 to the coating liquid 2 and changing the coating amount of the coating liquid to change the film thickness of the coated layer, the laminate 4 was obtained by the same method as described above for the laminate 1 of Example 1.

[0202] [Example 5]

[0203] In addition to changing the coating liquid 1 to the coating liquid 3 and changing the coating amount of the coating liquid to change the film thickness of the coated layer, the laminate 5 was obtained by the same method as described above for the laminate 1 of Example 1.

[0204] [Comparative Example 1]

[0205] In addition to not forming the inorganic vapor-deposited layer and changing the coating amount of the coating liquid 1 to change the film thickness of the coated layer, the laminate 1C was obtained by the same method as described above for the laminate 1 of Example 1.

[0206] [Comparative Example 2]

[0207] In addition to changing the coating amount of the coating liquid 1 to change the film thickness of the coated layer, the laminate 2C was obtained by the same method as described above for the laminate 1 of Example 1.

[0208] [Comparative Example 3]

[0209] In addition to not forming the inorganic vapor-deposited layer and changing the coating amount of the coating liquid 2 to change the film thickness of the coated layer, the laminate 3C was obtained by the same method as described above for the laminate 4 of Example 4.

[0210] [Comparative Example 4]

[0211] In addition to not forming the inorganic vapor-deposited layer, the laminate 4C was obtained by the same method as described above for the laminate 5 of Example 5.

[0212] [Comparative Example 5]

[0213] In addition to not forming the inorganic vapor-deposited layer and changing the coating liquid 1 to the coating liquid 4, the laminate 5C was obtained by the same method as described above for the laminate 1 of Example 1.

[0214] [Comparative Example 6]

[0215] The laminate 6C was obtained by the same method as described above for the laminate 1 of Example 1, except that the coating liquid 1 was changed to the coating liquid 4.

[0216] [Comparative Example 7]

[0217] The laminate 7C was obtained by the same method as described above for the laminate 1 of Example 1, except that the inorganic vapor deposition layer was not formed and the coating liquid 1 was changed to the coating liquid 5.

[0218] [Measurement of the film thickness of the coating layer]

[0219] The obtained laminate was embedded with an embedding resin, and a cross section was exposed using a microtome. The cross section of the laminate was observed using a scanning electron microscope (SEM). From the obtained SEM image, the thickness of the coating layer at 10 points in the planar portion was measured and averaged, and the average was taken as the thickness of the coating layer.

[0220] [Evaluation]

[0221] [Transparency]

[0222] For each of the obtained laminates, the haze of the coating layer was measured according to JIS-K7105-1981 using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). A case where the haze value was 10% or less was evaluated as A, and a case where the haze value exceeded 10% was evaluated as B. When the haze value was 10% or less, the laminate had the desired transparency. These results are shown in Table 1.

[0223] [Oxygen permeability]

[0224] Each of the obtained laminates was cut to a size of 20 cm x 20 cm, and subjected to a cooking treatment at 0.2 MPa, 120°C for 30 minutes using a hot water immersion type retort. The oxygen permeability of each of the samples after the cooking treatment was measured using an oxygen permeability tester OXTRAN (registered trademark) 2 / 20 manufactured by Modern Control Co., Ltd., under conditions of a temperature of 30°C and a relative humidity of 70%. The measurement method was according to JIS K-7126B method (isobaric method) and ASTM D3985, and the measured value was expressed in units of cm 3 / (m 2 · day · MPa). A case where the oxygen permeability was 10 cm 3 / (m 2 · day · MPa) or less was evaluated as A, and a case where the oxygen permeability exceeded 10 cm 3 / (m 2 · day · MPa) was evaluated as B. When the oxygen permeability was 10 cm 3 / (m 2 · day · MPa) or less, the laminate had the desired gas barrier property under a high-temperature high-humidity environment. These results are shown in Table 1.

[0225]

[0226] As shown in Table 1, the laminates 1 to 5 (Examples 1 to 5) according to the present embodiment are excellent in both transparency and gas barrier properties under high temperature and high humidity environment.

[0227] Note that the present application is not limited to the above-described embodiments, and various modifications can be made in the implementation stage without departing from the gist thereof. In addition, the respective embodiments can be appropriately combined, and in this case, the effects of the combination can be obtained. Furthermore, the above-described embodiments include various inventions, and various inventions can be extracted by combining the disclosed plurality of constituent elements in an appropriate manner. For example, in the case where the problem can be solved and the effect can be obtained even if several constituent elements are deleted from all the constituent elements shown in the embodiments, the constitution in which the constituent elements are deleted can be extracted as an invention.

[0228] Explanation of symbols

[0229] 1 • • • substrate

[0230] 2 • • • inorganic vapor deposition layer

[0231] 3 • • • coating layer

[0232] 4 • • • anchor coating layer

[0233] 10, 20 • • • gas barrier laminate

Claims

1. A gas barrier laminate comprising, in order, a substrate, an inorganic vapor-deposited layer containing an inorganic oxide, and a coating layer, the coating layer containing a carboxyl group-containing polymer (a), a polyvalent metal-containing particle (b), a surfactant (c), and a silicon compound (d), the silicon compound (d) being at least one selected from the group consisting of silane coupling agents represented by general formulae (1) and (2) below, hydrolyzates thereof, and condensates thereof, The mole ratio d t / a t of the number of moles (d t ) of the silicon-containing compound (d) to the number of moles (a t ) of the carboxyl group contained in the carboxyl group-containing polymer (a) is 0.15% or more and 6.10% or less. the coating layer having a film thickness of 230 nm or more and 600 nm or less, the coating layer being only one layer, wherein, The molar ratio d t / a t d in the formula (1) t is the number of moles obtained by converting the silicon-containing compound (d) into a silane coupling agent, Si(OR1)3Z1 (1) Si(R2)(OR3)2Z2 (2) in general formula (1), R1 can be the same or different and is an alkyl group having 1 to 6 carbon atoms, and Z1 is a group containing an epoxy group, and in general formula (2), R2 is a methyl group, R3 can be the same or different and is an alkyl group having 1 to 6 carbon atoms, and Z2 is a group containing an epoxy group. the carboxyl group-containing polymer (a) containing at least a constitutional unit derived from at least one α,β-monoethylenic unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.

2. The gas barrier laminate according to claim 1, wherein the polyvalent metal constituting the polyvalent metal-containing particle (b) is a divalent metal.

3. The gas barrier laminate according to claim 1 or 2, wherein an anchor coating layer is further provided between the substrate and the inorganic vapor-deposited layer.

4. The gas barrier laminate according to any one of claims 1 to 3, wherein 5. A packaging material comprising the gas barrier laminate according to any one of claims 1 to 4.

6. A packaging body comprising the packaging material according to claim 5.

7. A packaged article comprising the packaging body according to claim 6 and contents contained in the packaging body. ​

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