Laminate, and packaging material

Abstract

To provide a laminate excellent in a gas barrier property, and a packaging material.SOLUTION: A laminate includes a first base material having a vapor-deposited layer, a first extrusion resin layer, and a gas barrier anchor coat layer arranged between the first extrusion resin layer and the vapor-deposited layer, wherein the gas barrier anchor coat layer contains a polyol composition (X) containing polyester polyol (A), and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), and the polyester polyol (A) is a cured coating film of a two-pack curable type anchor coat agent containing at least one kind selected from polyester polyol (A1) obtained by polycondensation of a polyvalent carboxylic acid containing an ortho-directing polyvalent carboxylic acid and polyhydric alcohol, polyester polyol (A2) having an isocyanuric ring, and polyester polyol (A3) having a polymerizable carbon-carbon double bond.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate having excellent gas barrier properties and a packaging material obtained using the laminate. [Background technology]

[0002] Packaging materials used for packaging food and daily necessities typically consist of a laminate made by laminating a heat-sealable film, such as polyethylene or polypropylene, with a resin film, such as polyester or nylon, that has excellent heat resistance and strength. When the contents are susceptible to deterioration due to oxygen, films with vapor-deposited layers of metals or inorganic oxides that have excellent gas barrier properties are sometimes used as the film that makes up the laminate to prevent deterioration of the contents. Another known method for manufacturing laminates is the extrusion lamination method (Reference 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2023-148620 Summary of the Invention [Problem to be solved by the invention]

[0004] Packaging materials made by making bags from such laminates have excellent gas barrier properties, but because the vapor-deposited layer is hard, cracks are likely to occur when the vapor-deposited layer is formed on the base film and then wound into a roll, or when the laminate passes through conveyor rolls during production. Even after the laminate has been made into a packaging material, cracks and pinholes may occur in the vapor-deposited layer due to repeated bending or collisions during transportation, etc. If cracks or pinholes occur in the vapor-deposited layer of the metal or inorganic oxide for these reasons, the gas barrier properties of the laminate, and ultimately the packaging material, may be reduced, and the originally expected performance may not be achieved. The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate and a packaging material that have excellent gas barrier properties. [Means for solving the problem]

[0005] The present invention relates to a laminate comprising a first substrate having a vapor-deposited layer, a first extruded resin layer, and a gas-barrier anchor coat layer disposed between the first extruded resin layer and the vapor-deposited layer, the gas-barrier anchor coat layer comprising a polyol composition (X) containing a polyester polyol (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), the polyester polyol (A) being a cured coating film of a two-component curing anchor coating agent containing at least one selected from polyester polyol (A1) obtained by polycondensation of a polycarboxylic acid containing an ortho-orienting polycarboxylic acid and a polyhydric alcohol, polyester polyol (A2) having an isocyanuric ring, and polyester polyol (A3) having a polymerizable carbon-carbon double bond, and a laminate; and a packaging material obtained by forming the laminate into a bag. [Effects of the Invention]

[0006] According to the laminate of the present invention, it is possible to provide a laminate and a packaging material having excellent gas barrier properties. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a schematic diagram showing an example of a laminating device used in the present invention. [Figure 2] FIG. 2 is a schematic diagram showing another example of a laminating device used in the present invention. [Figure 3] FIG. 2 is a schematic diagram showing another example of a laminating device used in the present invention. [Figure 4] FIG. 2 is a schematic diagram showing another example of a laminating device used in the present invention. [Figure 5] FIG. 2 is a schematic diagram showing another example of a laminating device used in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Laminate> The laminate of the present invention includes a first substrate having a vapor-deposited layer, an extruded resin layer, and a gas-barrier anchor coat layer disposed between the extruded resin layer and the vapor-deposited layer. The laminate of the present invention will be described in detail below.

[0009] (First substrate) The first substrate includes a film or sheet (hereinafter, unless otherwise specified, film is a general term for film and sheet) that has excellent chemical and physical strength, and a vapor-deposited layer provided on the film. The film may be a single-layer film or a multi-layer laminate film. It can be appropriately selected depending on the conditions of use, such as the contents and type of the packaging material, and whether or not to perform a heat treatment after filling the contents, as described below.

[0010] Specific examples of films include, but are not limited to, resin films such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; K-coated stretched polypropylene film; K-coated stretched nylon film; and composite films formed by laminating two or more of these films.

[0011] It is also preferable to use a film made of a material containing biomass-derived components. Biomass films are commercially available from various companies, and for example, sheets such as those listed in the list of biomass-certified products listed by the Japan Organics Recycling Association can be used.

[0012] Specifically, well-known films are made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0013] Alternatively, products made from biomass materials are also available, classified by their biomass plastic content as specified by ISO 16620 or ASTM D6866. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 1012 particles, and this rate remains the same for atmospheric carbon dioxide, so this rate remains the same even in plants that fix this carbon dioxide through photosynthesis. Therefore, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the plant-derived resin content, or biomass plastic content, can be determined. Examples of plant-derived low-density polyethylene that is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866 include products manufactured by Braskem under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0014] The thickness of the film is not particularly limited and may be appropriately selected from the range of 1 to 300 μm from the viewpoints of formability and transparency. The range is preferably 1 to 100 μm. If the thickness is less than 1 μm, the strength may be insufficient, and if it exceeds 300 μm, the rigidity may be too high, making processing difficult.

[0015] The film may be subjected to any surface treatment, such as a physical treatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, or glow discharge treatment, or a chemical treatment such as oxidation treatment using chemicals, or other treatments.

[0016] The film can be produced by a conventional film-forming method such as extrusion, cast molding, T-die molding, cutting, or inflation using one or more resins selected from the above-mentioned resins. Alternatively, the film can be produced by a multilayer co-extrusion film-forming method using two or more resins selected from the above-mentioned resins. From the viewpoint of film strength, dimensional stability, and heat resistance, the film may be stretched uniaxially or biaxially using a tenter system, tubular system, or the like.

[0017] The film may contain additives as needed. Specifically, plastic compounding agents and additives such as lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments may be added for the purpose of improving or modifying processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, mildew resistance, electrical properties, strength, etc. The amount of additive added is adjusted within a range that does not affect other properties.

[0018] The vapor-deposited layer can be formed on the film directly or via a layer formed using an anchor coating agent, etc., by a conventionally known method. Examples of methods for forming the vapor-deposited layer include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0019] The vapor-deposited layer can be formed from any material, such as various metals and their oxides, including metals such as aluminum, inorganic oxides such as alumina (aluminum oxide) and silica (silicon oxide), and combinations of these (e.g., silica and alumina).

[0020] The thickness of the vapor-deposited layer is preferably 1 to 200 nm. When the vapor-deposited layer is an aluminum vapor-deposited layer, the thickness is more preferably 1 to 100 nm, and even more preferably 15 to 60 nm. When the vapor-deposited layer is silica, alumina, or a binary vapor-deposited layer thereof, the thickness is preferably 1 to 100 nm, more preferably 10 to 50 nm, and even more preferably 20 to 30 nm.

[0021] An anchor coat layer may be provided on the film prior to the formation of the vapor-deposited layer. The anchor coat layer can be formed by applying an anchor coating agent to the film and drying it. This not only increases the adhesion between the film and the vapor-deposited layer, but also improves the flatness of the surface on which the vapor-deposited layer is formed due to the leveling action of the anchor coating agent, allowing for the formation of a uniform vapor-deposited layer with few film defects such as cracks.

[0022] Examples of anchor coating agents include those containing solvent-soluble or water-soluble polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl-modified resins, epoxy resins, oxazoline group-containing resins, modified styrene resins, modified silicone resins, and alkyl titanates, etc. These can be used alone or in combination of two or more.

[0023] The thickness of the anchor coat layer is not particularly limited, but is preferably about 5 nm to 5 μm, and more preferably 10 nm to 1 μm, which allows a uniform layer with reduced internal stress to be formed on the sealant film.

[0024] When an anchor coat layer is provided, it is also preferable to subject the surface of the sealant film to a discharge treatment prior to the formation of the anchor coat layer in order to improve the applicability and adhesiveness of the anchor coat agent.

[0025] (Gas barrier anchor coat layer) The gas barrier anchor coat layer is disposed on the vapor deposition layer of the first substrate. The gas barrier anchor coat layer is formed from a two-component curing anchor coating agent containing a polyol composition (X) containing a polyester polyol (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), and the polyester polyol (A) contains at least one selected from a polyester polyol (A1) obtained by polycondensation of a polycarboxylic acid containing an ortho-orienting polycarboxylic acid with a polyhydric alcohol, a polyester polyol (A2) having an isocyanuric ring, and a polyester polyol (A3) having a polymerizable carbon-carbon double bond (hereinafter, the anchor coating agent used to form the gas barrier anchor coat layer is also referred to as a gas barrier anchor coating agent).

[0026] Examples of ortho-oriented polycarboxylic acids used in the synthesis of polyester polyol (A1) include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracene carboxylic acid or its anhydride. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group, an amino group, a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

[0027] The polycarboxylic acid used in the synthesis of the polyester polyol (A1) may contain a polycarboxylic acid other than the ortho-oriented polycarboxylic acid. Examples of polycarboxylic acids other than ortho-oriented polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and acid anhydrides or ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids. These may be used alone or in combination of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid and acid anhydrides thereof are preferred.

[0028] When the polycarboxylic acid contains a polycarboxylic acid other than an ortho-oriented polycarboxylic acid, the proportion of the ortho-oriented polycarboxylic acid in the total amount of polycarboxylic acids is preferably 40 to 100 mass %.

[0029] The polyhydric alcohol used in the synthesis of the polyester polyol (A1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably contains ethylene glycol.

[0030] The polyhydric alcohol may be used in combination with polyhydric alcohols other than those mentioned above. Examples of the polyhydric alcohol include aliphatic diols such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, and tetramethylbiphenol; ethylene oxide-extended products of these; and aromatic polyhydric phenols such as hydrogenated alicyclic alcohols.

[0031] When the polyester polyol (A1) has three or more hydroxyl groups (referred to as polyester polyol (a1) for convenience), some of the hydroxyl groups may be modified with acid groups. Such polyester polyols are hereinafter also referred to as polyester polyol (A1'). The polyester polyol (A1') is obtained by reacting the polyester polyol (a1) with a polycarboxylic acid or its acid anhydride. The proportion of hydroxyl groups modified with the polycarboxylic acid is preferably 1 / 3 or less of the hydroxyl groups in the polyester polyol (a1). Examples of polycarboxylic acids used for modification include, but are not limited to, succinic anhydride, maleic acid, fumaric acid, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, oleic acid, and sorbic acid.

[0032] The polyester polyol (A2) can be obtained, for example, by reacting a triol having an isocyanuric ring with a polycarboxylic acid including an ortho-oriented aromatic polycarboxylic acid and a polyhydric alcohol. Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris(2-hydroxyethyl)isocyanuric acid and 1,3,5-tris(2-hydroxypropyl)isocyanuric acid. The ortho-oriented aromatic polycarboxylic acid, polycarboxylic acid, and polyhydric alcohol can be the same as those used for the polyester polyol (A1).

[0033] As the triol compound having an isocyanuric ring, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid or 1,3,5-tris(2-hydroxypropyl)isocyanuric acid is preferably used. As the ortho-oriented aromatic polycarboxylic acid, orthophthalic anhydride is preferably used. As the polyhydric alcohol, ethylene glycol is preferably used.

[0034] The polyester polyol (A3) can be obtained by using a component having a polymerizable carbon-carbon double bond as a polycarboxylic acid or a polyhydric alcohol.

[0035] Examples of polycarboxylic acids having a polymerizable carbon-carbon double bond include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and its anhydride, etc. Maleic anhydride, maleic acid, and fumaric acid are preferred because it is believed that the fewer the number of carbon atoms, the less flexible the molecular chain becomes and the less oxygen permeates. Examples of polyhydric alcohols having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol.

[0036] In addition to the above, polycarboxylic acids and polyhydric alcohols not having a polymerizable carbon-carbon double bond may be used in combination. The same polycarboxylic acids and polyhydric alcohols as those used in the polyester polyols (A1) and (A2) can be used. The polycarboxylic acid is preferably at least one selected from the group consisting of succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, orthophthalic acid anhydride, and isophthalic acid, and more preferably at least one of orthophthalic acid and its acid anhydride. The polyhydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably ethylene glycol.

[0037] The hydroxyl value of the polyester polyol (A) is preferably 20 mgKOH / g or more and 400 mgKOH / g or less, and more preferably 100 mgKOH / g or more and 400 mgKOH / g or less. When the polyester polyol (A) has an acid group, the acid value is preferably 200 mgKOH / g or less. The hydroxyl value of the polyester polyol (A) can be measured by the hydroxyl value measurement method described in JIS-K0070, and the acid value can be measured by the acid value measurement method described in JIS-K0070.

[0038] The number average molecular weight of the polyester polyol (A) is, for example, 300 to 5000. The number average molecular weight can be calculated from the obtained hydroxyl value and the designed number of functional hydroxyl groups.

[0039] The glass transition temperature of the polyester polyol (A) is preferably from -30°C to 80°C, more preferably from 0°C to 60°C, and even more preferably from 25°C to 60°C, in view of the balance between adhesion to the extruded resin and gas barrier properties.

[0040] The polyester polyol (A) may be a polyester polyurethane polyol having a number average molecular weight of 1,000 to 15,000 obtained by urethane elongation of the polyester polyols (A1) to (A3) through reaction with a diisocyanate compound.

[0041] The isocyanate compound (B) can be any known compound without particular limitation, and examples thereof include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret, nurate, adduct, allophanate, carbodiimide-modified, uretdione-modified, iminooxadiazinedione, and polyurethane polyisocyanate of these diisocyanates, and these compounds can be used alone or in combination of two or more.

[0042] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also known as polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also known as PPDI), and 2,4-toluene. Examples of diisocyanates include, but are not limited to, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0043] The aromatic aliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0044] Examples of aliphatic diisocyanates include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI).

[0045] Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI), but are not limited to these.

[0046] Compounds that can be used to synthesize the adduct include low-molecular-weight active hydrogen compounds such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine.

[0047] Compounds used in the synthesis of polyurethane polyisocyanates include alkylene oxide adducts of the above-mentioned low-molecular-weight active hydrogen compounds, various polyester resins, and high-molecular-weight active hydrogen compounds of polyamides. It is also preferable to use polyester polyisocyanates obtained by reacting polyester polyols (A1) to (A3) with diisocyanates in an isocyanate excess ratio relative to hydroxyl groups and isocyanate groups. These compounds can be used alone or in combination of two or more.

[0048] Among these, it is more preferable to use an isocyanate compound having a skeleton derived from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, or diphenylmethane diisocyanate, since good gas barrier properties can be obtained.

[0049] Furthermore, when a composition containing a polyester polyol having residual carboxylic acid groups, such as polyester polyol (A1′), is used as polyol composition (X), polyisocyanate composition (Y) may contain an epoxy compound. Examples of the epoxy compound include diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl. ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

[0050] When an epoxy compound is used, a commonly known epoxy curing accelerator may be added as needed to accelerate curing, provided that the object of the present invention is not impaired.

[0051] When a composition containing a polyol having a polymerizable carbon-carbon double bond, such as polyester polyol (A3), is used as the polyol composition (X), a known polymerization catalyst can be used in combination to promote the polymerization of the carbon-carbon double bond. Examples of the transition metal complex include a transition metal complex. The transition metal complex is not particularly limited as long as it is a compound capable of oxidatively polymerizing the polymerizable double bond. For example, salts of metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, and copper with octylic acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, and soybean oil fatty acid can be used. The amount of the transition metal complex to be added is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass, based on the resin solids content of the polyol composition (X).

[0052] The polyol composition (X) and the polyisocyanate composition (Y) are preferably blended so that the equivalent ratio of hydroxyl groups contained in the polyol composition (X) to isocyanate groups contained in the polyisocyanate composition (Y) is 1 / 0.5 to 1 / 10, and more preferably 1 / 1 to 1 / 5.

[0053] The gas barrier anchor coating agent may contain various additives within the range that does not impair the adhesiveness and gas barrier properties of the extruded resin.

[0054] As such an additive, an inorganic filler may be used. Examples of the inorganic filler include silica, alumina, aluminum flakes, and glass flakes. In particular, using a plate-like inorganic compound as the inorganic filler is preferred because it improves adhesive strength, gas barrier properties, light-shielding properties, etc. Examples of plate-like inorganic compounds include hydrous silicates (such as phyllosilicate minerals), kaolinite-serpentine clay minerals (such as halloysite, kaolinite, endelite, dickite, nacrite, antigorite, and chrysotile), pyrophyllite-talc clay minerals (such as pyrophyllite, talc, and keroli), smectite clay minerals (such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite), vermiculite clay minerals (such as vermiculite), mica or mica clay minerals (such as muscovite and phlogopite, margarite, tetrasilylic mica, and taeniolite), chlorite (such as cookeite, sudoite, clinochlore, chamosite, and nimite), hydrotalcite, plate-like barium sulfate, boehmite, and aluminum polyphosphate. These minerals may be natural or synthetic clay minerals. The plate-like inorganic compounds can be used alone or in combination of two or more.

[0055] The plate-like inorganic compound may be ionic, having an interlayer charge, or nonionic, having no charge. The presence or absence of an interlayer charge does not have a significant direct effect on the gas barrier properties of the gas barrier anchor coat layer. However, ionic plate-like inorganic compounds and inorganic compounds that swell in water have poor dispersibility in organic solvents, and increasing the amount added may increase the viscosity of the gas barrier anchor coat agent or cause it to become thixotropic, resulting in reduced coatability. For this reason, it is preferable that the plate-like inorganic compound be nonionic, having no interlayer charge.

[0056] The average particle size of the plate-like inorganic compound is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. If it is smaller than 0.1 μm, the bypass path for oxygen molecules will not be long, and sufficient improvement in gas barrier properties cannot be expected. There is no particular upper limit to the average particle size, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle size is preferably 100 μm or less, and more preferably 20 μm or less. In this specification, the average particle size of the plate-like inorganic compound refers to the particle size that appears most frequently when the particle size distribution of the plate-like inorganic compound is measured using a light scattering measurement device.

[0057] The aspect ratio of the plate-like inorganic compound is preferably high in order to improve gas barrier properties due to the oxygen labyrinth effect, specifically, 3 or more, more preferably 10 or more, and most preferably 40 or more.

[0058] The amount of the plate-like inorganic compound to be blended is arbitrary, but as an example, the amount of the plate-like inorganic compound to be blended is 5 to 50 parts by mass when the total mass of the solid contents of the polyol composition (X), the polyisocyanate composition (Y), and the plate-like inorganic compound is 100 parts by mass.

[0059] The gas barrier anchor coating agent may contain an adhesion promoter. Examples of adhesion promoters include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are expected to improve adhesion to various film materials.

[0060] When the gas barrier anchor coating layer requires acid resistance, the gas barrier anchor coating agent may contain a known acid anhydride, such as phthalic anhydride, succinic anhydride, HET anhydride, HIMIC anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5-(2,5-oxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, or styrene-maleic anhydride copolymer.

[0061] If necessary, a compound having an oxygen-scavenging function may be further added. Examples of the compound having an oxygen-scavenging function include low-molecular-weight organic compounds that react with oxygen, such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and transition metal compounds, such as cobalt, manganese, nickel, iron, and copper.

[0062] The gas barrier anchor coating agent may contain a compound represented by the following general formula (1) or (2).

[0063] [ka] (In general formula (1), R1 to R3 are groups selected from a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth)acryloyl group, a phenyl group which may have a substituent, and an alkyl group having 1 to 4 carbon atoms which has a (meth)acryloyloxy group, and at least one of them is a hydrogen atom, and n is an integer of 1 to 4.)

[0064] [ka] (In general formula (2), R4 and R5 each represent a group selected from a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth)acryloyl group, a phenyl group which may have a substituent, and an alkyl group having 1 to 4 carbon atoms and having a (meth)acryloyloxy group; m and l each represent an integer of 1 to 4, p represents an integer of 0 to 30, and q represents an integer of 0 to 30, except when both p and q are 0.)

[0065] Specific examples of the compounds represented by the above general formulas (1) and (2) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate.

[0066] The compound represented by the general formula (1) or (2) is preferably blended in an amount of 0.005 to 10 mass %, more preferably 0.01 to 1 mass %, based on the total solid content of the two-component curing anchor coating agent.

[0067] If necessary, a tackifier such as a xylene resin, a terpene resin, a phenol resin, a rosin resin, etc. may be added. When these are added, the amount thereof is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y).

[0068] When the polyol composition (X) contains a polyester polyol (A3), active energy rays can be used as a method for reacting the polymerizable carbon-carbon double bonds. Known techniques can be used for the active energy rays, and curing can be achieved by irradiating with ionizing radiation such as electron beams, ultraviolet rays, or gamma rays. When curing with ultraviolet rays, known ultraviolet irradiation devices equipped with high-pressure mercury lamps, excimer lamps, metal halide lamps, etc. can be used.

[0069] When curing is performed by irradiation with ultraviolet rays, it is preferable to add, as necessary, about 0.1 to 20 parts by mass of a photo (polymerization) initiator that generates radicals upon irradiation with ultraviolet rays per 100 parts by mass of the polyester polyol (A3).

[0070] Examples of radical-generating photo(polymerization) initiators include hydrogen abstraction types such as benzil, benzophenone, Michler's ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone, and photocleavage types such as benzoin ethyl ether, diethoxyacetophenone, benzil methyl ketal, hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl phenyl ketone. These can be used alone or in combination.

[0071] In addition, the gas barrier anchor coating agent may contain stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, etc. These various additives may be added in advance to either or both of the polyol composition (X) and the polyisocyanate composition (Y), or may be added when the polyol composition (X) and the polyisocyanate composition (Y) are mixed.

[0072] The gas barrier anchor coating agent used in the present invention contains an organic solvent. Examples of solvents that can be used include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene, xylol, n-hexane, and cyclohexane. Either or both of the polyol composition (X) and the polyisocyanate composition (Y) contain the organic solvent. The solvent used as a reaction medium during the production of the components of the polyol composition (X) or the polyisocyanate composition (Y) may also be used as a diluent during coating.

[0073] The thickness of the gas barrier anchor coat layer can be adjusted as appropriate, but is, for example, from 0.05 μm to 1 μm.

[0074] (First extruded resin layer) The first extruded resin layer is a layer formed by laminating an extruded resin on the anchor coat layer by an extrusion lamination method (extrusion lamination method, co-extrusion lamination method, sandwich lamination method).

[0075] Examples of the extrusion resin include polyethylene resin, polypropylene resin, and acid-modified versions of these. Examples of the polyethylene resin include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene. Examples of the polypropylene resin include homo-type polypropylene, random-type polypropylene, and block-type polypropylene. Examples of the acid-modified polyethylene resin include linear low-density polyethylene, high-density polyethylene or medium-density polyethylene, high-density polyethylene or medium-density polyethylene, acrylic acid and / or methacrylic acid derivatives, and ethylene copolymers containing vinyl acetate or vinyl ester. Examples of the acid-modified polypropylene resin include random-type polypropylene, homo-type polypropylene, and block-type polypropylene, all of which are grafted with unsaturated carboxylic acid.

[0076] The thickness of the first extruded resin layer is, for example, 10 μm or more and 250 μm or less.

[0077] (Printing layer) The laminate of the present invention may have a printed layer provided at any position, for example, on the surface of the first substrate opposite to the vapor-deposited layer. The printed layer is a layer on which characters, figures, symbols, or other desired designs are printed using printing ink.

[0078] The printing method and printing ink are not particularly limited, and known printing methods and printing inks can be used. Specific examples include, but are not limited to, printing inks using gravure printing, flexographic printing, lithographic offset printing, inkjet recording printing, etc. Printing inks that combine these printing methods with methods of curing using active energy rays such as ultraviolet (UV), LED, and electron beam (EB), or methods of curing using heat, can also be used. Depending on the solvent used in the printing ink, it may be referred to as water-based ink or organic solvent-based ink.

[0079] Specific examples include gravure printing ink, flexographic printing ink (in some industries, gravure printing ink and flexographic printing ink are sometimes called liquid ink), ultraviolet-curable ink for lithographic offset printing, electron-beam-curable ink for lithographic offset printing, ultraviolet-curable ink for inkjet recording and printing, electron-beam-curable ink for inkjet recording and printing, etc. Biomass inks made from biomass raw materials are also used as appropriate.

[0080] The printing ink may contain a resin, a colorant, and a solvent as essential components, or may be a so-called clear ink that contains a resin and a solvent but does not substantially contain a colorant. The printing layer may be provided over the entire surface or only a part of the surface.

[0081] Taking the case where the printing ink is gravure printing ink or flexographic printing ink as an example, the resin used in the printing ink is not particularly limited and includes, for example, acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one or more of these can be used in combination. Preferably, at least one or more selected from polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, and cellulose-based resin is used.

[0082] Colorants used in printing inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.

[0083] The organic solvent used in the printing ink preferably does not contain an aromatic hydrocarbon organic solvent. More specifically, examples of the organic solvent include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol, ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, and n-octane, and alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane, and these can be used alone or in combination.

[0084] In consideration of the establishment of a recycling-oriented society that should continue to develop (sustainability), it is also preferable that the liquid printing ink used in the present invention is a gravure printing ink or a flexographic printing ink that uses plant-derived raw materials.

[0085] Examples of plant-derived raw materials include cellulose resins such as cellulose acetate propionate resin and nitrocellulose; polyamide resins using dimer acids or polymerized fatty acids derived from natural oils such as soybean oil, palm oil, and rice bran oil; polycarboxylic acids such as succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dimer acid, glutaric acid, and malic acid; polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, pentylene glycol, 1,10-dodecanediol, dimer diol, and isosorbide; and polyisocyanates such as 1,5-pentamethylene diisocyanate and dimer diisocyanate. These polycarboxylic acids include succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dimer acid, glutaric acid, and malic acid; and rosin resins.

[0086] As the biomass gravure printing ink or flexographic printing ink, commercially available products listed by the Japan Organics Recycling Association can also be used.

[0087] (Second substrate, third substrate) The laminate of the present invention may include a second substrate and a third substrate in addition to the first substrate. As the second substrate and the third substrate, any film having excellent chemical and physical strength can be used without any particular limitation. As such a film, the same films as those exemplified as the film constituting the first substrate can be used. Similarly to the first substrate, the second substrate and the third substrate may each include a film and a vapor deposition layer provided on the film.

[0088] (Second extruded resin layer) The laminate of the present invention may include a second extruded resin layer in addition to the first extruded resin layer. The second extruded resin layer is a layer formed by laminating an extruded resin at any position of the laminate using an extrusion lamination method. The extruded resin may be the same as that of the first extruded resin layer. The film thickness of the second extruded resin layer can be adjusted as appropriate, but is, for example, 10 μm or more and 250 μm or less.

[0089] (Example of laminate configuration) Examples of the structure of the laminate of the present invention include: (1) First substrate (vapor deposition layer) / gas barrier anchor coat layer / first extruded resin layer (2) First substrate (vapor deposition layer) / gas barrier anchor coat layer / first extruded resin layer / second substrate (3) First substrate (vapor deposition layer) / gas barrier anchor coat layer / first extruded resin layer / second substrate / second extruded resin layer (4) First substrate (vapor deposition layer) / gas barrier anchor coat layer / first extruded resin layer / second substrate / second extruded resin layer / third substrate (5) Second substrate / first extruded resin layer / gas barrier anchor coat layer / (vapor deposition layer) First substrate / second extruded resin layer (6) Second substrate / first extruded resin layer / gas barrier anchor coat layer / (vapor deposition layer) First substrate / second extruded resin layer / third substrate (7) Second substrate / second extruded resin layer / third substrate / first extruded resin layer / gas barrier anchor coat layer / (vapor deposition layer) first substrate These include, but are not limited to:

[0090] Examples of the first substrate used in the configuration examples (1) to (4) include an MDOPE film, an OPE film, an OPP film, a PET film, and an Ny film each having a vapor-deposited layer of a metal or inorganic oxide, with a PET film having a vapor-deposited metal layer being preferred. In all of the configuration examples, a printed layer may be provided on the side of the first substrate opposite the vapor-deposited layer. When a printed layer is provided, a coating may be provided between the first substrate and the printed layer for the purpose of improving ink receptivity when providing the printed layer.

[0091] Examples of the second substrate used in configuration example (2) include an LLDPE film, a VM-LLDPE film, a CPP film, a VM-CPP film, a gas barrier heat seal film, an MDOPE film provided with a heat seal layer, an OPE film, an OPP film, a VM-OPP film, a PET film, a VM-PET film, and an Ny film.

[0092] Examples of the second substrate used in the configuration examples (3) and (4) include MDOPE film, OPE film, OPP film, PET film, Ny film, films in which a metal or inorganic oxide vapor deposition layer is provided on these films, K-OPP film, K-PET film, etc., and any of these can be preferably used.

[0093] In the configuration examples (2) to (4), when the adhesion between the first extruded resin layer and the second substrate is low, for example, when the first extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the second substrate is an OPP film, a PET film, an Ny film, or the like, it is preferable to provide an anchor coat layer between the first extruded resin layer and the second substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coat agent.

[0094] In the configuration examples (3) and (4), when the adhesion between the second substrate and the second extruded resin layer is low, for example, when the second extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the second substrate is an OPP film, a PET film, an Ny film, or the like, it is preferable to provide an anchor coat layer between the first extruded resin layer and the second substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coat agent.

[0095] Examples of the third substrate used in configuration example (4) include LLDPE film, VM-LLDPE film, CPP film, VM-CPP film, gas-barrier heat-sealable film, MDOPE film provided with a heat-sealable layer, OPE film, OPP film, VM-OPP film, PET film, VM-PET film, and Ny film. When the adhesion between the second extruded resin layer and the third substrate is low, for example, when the second extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the third substrate is a CPP film, gas-barrier heat-sealable film, OPP film provided with a heat-sealable layer, PET film, or Ny film, it is preferable to provide an anchor coat layer between the second extruded resin layer and the third substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coating agent.

[0096] Examples of the second substrate used in the configuration examples (5) to (7) include MDOPE film, OPE film, OPP film, PET film, Ny film, films obtained by providing a metal or inorganic oxide vapor-deposited layer on these films, K-OPP film, K-PET film, etc., and any of these can be preferably used. In any of the configuration examples, a printed layer may be provided on either side of the first substrate. When a printed layer is provided, a coating may be provided between the first substrate and the printed layer for the purpose of improving ink receptivity when providing the printed layer.

[0097] In configuration examples (5) and (6), when the adhesion between the second substrate and the first extruded resin layer is low, for example, when the first extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the second substrate is an OPP film, a PET film, an Ny film, a K-OPP film, a K-PET film, etc., it is preferable to provide an anchor coat layer between the first extruded resin layer and the second substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coat agent.

[0098] Examples of the first substrate used in the configuration examples (5) and (6) include an MDOPE film, an OPE film, an OPP film, a PET film, an Ny film, and the like, each having a vapor-deposited layer of a metal or inorganic oxide. In the configuration examples (5) and (6), when the adhesion between the first substrate and the second extruded resin layer is low, for example, when the second extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the first substrate is an OPP film, PET film, Ny film, or the like, having a vapor-deposited layer of a metal or inorganic oxide, it is preferable to provide an anchor coat layer between the second extruded resin layer and the first substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coat agent.

[0099] Examples of the third substrate used in configuration example (6) include LLDPE film, VM-LLDPE film, CPP film, VM-CPP film, gas-barrier heat-sealable film, MDOPE film provided with a heat-sealable layer, OPE film, OPP film, VM-OPP film, PET film, VM-PET film, and Ny film. When the adhesion between the second extruded resin layer and the third substrate is low, for example, when the second extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the third substrate is a CPP film, gas-barrier heat-sealable film, OPP film provided with a heat-sealable layer, PET film, or Ny film, it is preferable to provide an anchor coat layer between the second extruded resin layer and the third substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coating agent.

[0100] Examples of the third substrate used in configuration example (7) include MDOPE film, OPE film, OPP film, PET film, Ny film, films in which a metal or inorganic oxide vapor deposition layer is provided on these films, K-OPP film, K-PET film, etc., and any of these can be preferably used. In configuration example (7), if the adhesion between the third substrate and the first extruded resin layer and / or the second extruded resin layer is low, for example, if the first extruded resin layer and / or the second extruded resin layer is a polyethylene resin or an acid-modified polyethylene resin and the material of the third substrate facing these resin layers is an OPP film, a PET film, an Ny film, etc., it is preferable to provide an anchor coat layer between the first extruded resin layer and / or the second extruded resin layer and the third substrate to improve the adhesion therebetween. In this case, the anchor coat layer can be formed using a conventionally known anchor coating agent.

[0101] Examples of the first substrate used in the configuration example (7) include a VM-LLDPE film, a VM-CPP film, a VM-OPP film provided with a heat seal layer, and a VM-PET film.

[0102] According to the present invention, even if there are pinholes or cracks in the vapor-deposited layer of the first substrate used in manufacturing the laminate, it is possible to obtain a laminate with extremely high gas barrier properties, more specifically, an oxygen permeability of 0.3 cc / m at 1 atmosphere and 0% RH. 2 / day or less, oxygen permeability at 1 atmosphere and 90% RH is 0.5cc / m 2 / day or less, water vapor transmission rate at 1 atmosphere and 90% RH is 1.5g / m 2 It can be less than / day.

[0103] Furthermore, the laminate and the packaging material obtained by making a bag from the laminate have excellent gas barrier properties even when a bending load is applied to the laminate. More specifically, the laminate has an oxygen permeability of 0.7 cc / m at 1 atmosphere and 0% RH after being subjected to a bending load of 10 times using a Gelbo flex tester. 2 / day or less, the increase in oxygen permeability is 0.5cc / m 2 / day or less, oxygen permeability at 1 atmosphere and 90% RH is 1.5cc / m 2 / day or less, the increase in oxygen permeability is 1.5cc / m 2 It can be less than / day.

[0104] <Method of manufacturing laminate> The laminate of the present invention can be obtained by applying the above-mentioned two-component curing anchor coating agent onto the vapor-deposited layer of the first substrate, and then extrusion laminating a molten extruded resin onto the anchor coating agent. Several embodiments of the method for producing the laminate of the present invention will be described in detail below, but the method for producing the laminate of the present invention is not limited to these.

[0105] (Manufacturing method 1) 1 is a schematic diagram showing an example of a laminating apparatus 100 used in one embodiment of the laminate manufacturing method of the present invention. The laminating apparatus 100 includes a first unwinding roller 101, a coating device 102, a drying device 103, a first extruder 104, a first laminator 105, and a take-up roller 106.

[0106] The first substrate is unwound from a first unwind roller 101 and delivered to a coating device 102 .

[0107] The coating device 102 is a device that applies the above-mentioned two-component curing anchor coating agent to the vapor deposition layer of the first substrate. The coating device 102 is, for example, a gravure coater that has a transfer roll 102a equipped with a gravure plate, an impression cylinder 102b, an anchor coating agent tank 102c, and a doctor blade. The coating device 102 can also be a gravure coater that has a chamber doctor blade instead of the anchor coating agent tank 102c and the doctor blade, or a roll coater that uses a transfer roll without a gravure plate instead of the transfer roll 102a equipped with a gravure plate and does not have a doctor blade.

[0108] The gas-barrier anchor coating agent in the anchor coating agent tank 102c is transferred to the vapor deposition layer of the first substrate via the transfer roll 102a. At this time, excess two-component curing anchor coating agent adhering to the transfer roll 102a is scraped off by a doctor blade. The impression cylinder 102b is a rotating body that applies pressure between the transfer roll 102a and the first substrate while wrapping it around it, thereby adhering the two-component curing anchor coating agent adhering to the transfer roll 102a to the first substrate. The smoothing roll is a rotating body that smoothes the coating surface of the gas-barrier anchor coating agent transferred to the first substrate, and rotates in the opposite direction to the running direction of the first substrate.

[0109] The transport speed of the first substrate can be set arbitrarily, but is, for example, 80 m / min to 350 m / min, preferably 150 m / min or more, and more preferably 200 m / min or more.

[0110] The gas-barrier anchor coating agent contained in the anchor coating agent tank 102c is a mixture of the polyol composition (X) and the polyisocyanate composition (Y). The amount of the gas-barrier anchor coating agent to be applied is adjusted appropriately. For example, the amount of the gas-barrier anchor coating agent to be applied is adjusted to a solid content of 0.03 g / m. 2 More than 0.8g / m 2 The following is the result.

[0111] The first substrate is then transported to the drying device 103. The drying device 103 is a device for evaporating the diluent solvent in the gas barrier anchor coating agent transferred to the first substrate by heating. A hot air blowing method is widely used as a heating method, but is not limited to this. The interior of the drying device may be maintained at a substantially constant temperature throughout, or may be divided into multiple areas with different temperatures. If the interior of the drying device is divided into multiple areas with different temperatures, it is preferable that the temperature gradually increases from the area located upstream to the area located downstream in the transport direction of the first substrate. The temperature inside the drying device is preferably 50°C or higher and 100°C or lower.

[0112] The first substrate that has passed through the drying device 103 is sent to a first laminator 105. The first laminator 105 includes a cooling roll 105a, a pressure roll 105b, and a backing roll. The cooling roll is equipped with a cooling mechanism (not shown) and is kept at a constant temperature. An example of a cooling mechanism is a method in which water is passed through the inside of the roll, but this is not limiting. In the first laminator 105, a molten extruded resin is extruded from the first extruder 104 onto a coating film of the gas barrier anchor coating agent (hereinafter also referred to as a gas barrier anchor coating layer for convenience), and when the first substrate passes between the cooling roll 105a and the pressure roll 105b, the extruded resin is cooled and solidified by the cooling roll 105a, and a first extruded resin layer is formed on the gas barrier anchor coating layer.

[0113] The laminate that has passed through the first laminator 105 is wound up under tension by a winding roller 106. Aging is performed as necessary to obtain a laminate of the first substrate / gas barrier anchor coat layer / first extruded resin layer. For example, the aging temperature is room temperature to 80°C, and the aging time is 1 to 240 hours.

[0114] (Manufacturing method 2) 2 is a schematic diagram showing an example of a laminating apparatus 200 used in another embodiment of the laminate manufacturing method of the present invention. The laminating apparatus 200 includes a first unwinding roller 201, a coating device 202, a drying device 203, a first extruder 204, a first laminator 205, a take-up roller 206, and a second unwinding roller 207.

[0115] The laminating apparatus 200 is the same as the laminating apparatus 100 except that it is equipped with a second unwinding roller 207, and therefore can be carried out in the same manner as manufacturing method 1 until the first substrate unwound from the first unwinding roller 201 is transported to the first laminator 205.

[0116] The second substrate is fed from the second unwinding roller 207 to the first laminator 205. In the first laminator 205, a molten extruded resin is extruded from the first extruder 204 onto the gas barrier anchor coat layer, and as the extruded resin is sandwiched between the first substrate and the second substrate and passes between the cooling roll 205a and the pressure roll 205b, the extruded resin is cooled and solidified by the cooling roll 205a, and a first extruded resin layer is formed on the gas barrier anchor coat layer. Accordingly, the first substrate (gas barrier anchor coat layer) and the second substrate are bonded together by the first extruded resin layer.

[0117] The laminate that has passed through the first laminator 205 is wound up under tension by a winding roller 206, and if necessary, is aged under the same conditions as in production method 1, to obtain a laminate of first substrate / gas barrier anchor coat layer / first extruded resin layer / second substrate.

[0118] In this embodiment, the laminating apparatus 200 may include a coating device and a drying device (not shown) between the second unwinding roller 207 and the first extruder 204. When the adhesion between the second substrate and the extruded resin is low, the adhesion between the second substrate and the first extruded resin layer can be improved by providing an anchor coat layer on the second substrate using the coating device and the drying device.

[0119] (Manufacturing method 3) 3 is a schematic diagram showing an example of a laminating apparatus 300 used in another embodiment of the laminate manufacturing method of the present invention. The laminating apparatus 300 includes a first unwinding roller 301, a coating device 302, a drying device 303, a first extruder 304, a first laminator 305, a second unwinding roller 307, a second extruder 308, a second laminator 309, a third unwinding roller 310, and a take-up roller 306.

[0120] Laminating apparatus 300 is similar to laminating apparatus 200 except that it includes second extruder 308, second laminator 309, and third unwinding roller 310, and therefore can be carried out in the same manner as in manufacturing method 2 until the first substrate unwound from first unwinding roller 301 is conveyed to second laminator 309. Like first laminator 305, second laminator 309 includes a cooling roll 309a equipped with a cooling mechanism (not shown), a pressure roll 309b, and a backing roll.

[0121] The third substrate is sent from the third unwinding roller 310 to the second laminator 309. In the second laminator 309, the molten extruded resin is extruded from the second extruder 308 onto the second substrate, and as the extruded resin is sandwiched between the second substrate and the third substrate and passes between the cooling roll 309a and the pressure roll 309b, the extruded resin is cooled and solidified by the cooling roll 309a, and a second extruded resin layer is formed on the second substrate. Accordingly, the second substrate and the third substrate are bonded together by the second extruded resin layer.

[0122] The laminate that has passed through the second laminator 309 is wound up under tension by a winding roller 306, and if necessary, is aged under the same conditions as in production method 1, to obtain a laminate of first substrate / gas barrier anchor coat layer / first extruded resin layer / second substrate / second extruded resin layer / third substrate.

[0123] (Manufacturing Method 3, Modified Example) In manufacturing method 3, laminating apparatus 300 may further include a coating device and a drying device (not shown) between second unwinding roller 307 and first extruder 304. When the adhesion between the second substrate and the extruded resin is low, the adhesion between the second substrate and the first extruded resin layer can be improved by providing an anchor coat layer on the second substrate using the coating device and the drying device.

[0124] In manufacturing method 3, laminating apparatus 300 may further include a coating device and a drying device (not shown) between first laminator 305 and second extruder 308 or between third unwinding roller 310 and second extruder 308. This can improve the adhesion between the second substrate and the second extruded resin layer, and between the third substrate and the second extruded resin layer.

[0125] The laminating apparatus 300 may not be provided with the third unwinding roller 310, or the substrate may not be transported from the third unwinding roller 310 to the second laminator 309. In such cases, a laminate of the first substrate / gas barrier anchor coat layer / first extruded resin layer / second substrate / second extruded resin layer is obtained.

[0126] (Manufacturing method 4) 4 is a schematic diagram showing an example of a laminating apparatus 400 used in another embodiment of the laminate manufacturing method of the present invention. The laminating apparatus 400 includes a first unwinding roller 401, a coating device 402, a drying device 403, a first extruder 404, a first laminator 405, a second unwinding roller 407, a second extruder 408, a second laminator 409, a third unwinding roller 410, and a take-up roller 406.

[0127] In manufacturing method 4, the first substrate having a vapor deposition layer is unwound from a second unwinding roller 407 and sent to a coating device 402. In the coating device 402, a gas barrier anchor coating agent is applied to the vapor deposition layer of the first substrate in the same manner as in manufacturing method 1, and the resulting substrate is then transported to a drying device 403.

[0128] In the drying device 403, the dilution solvent in the gas barrier anchor coating agent transferred to the first substrate is evaporated by heating, in the same manner as in production method 1. The first substrate that has passed through the drying device 403 is sent to a first laminator 405.

[0129] In the first laminator 405, a molten extruded resin is extruded from a first extruder 404 between the second substrate unwound from a first unwinding roller 401 and the gas barrier anchor coat layer applied to the first substrate, and as the extruded resin is sandwiched between the first substrate and the second substrate and passes between a cooling roll 405a and a pressure roll 405b, the extruded resin is cooled and solidified by the cooling roll 405a, and a first extruded resin layer is formed on the gas barrier anchor coat layer. Accordingly, the first substrate (gas barrier anchor coat layer) and the second substrate are bonded together by the first extruded resin layer, and the resulting laminate is sent to a second laminator 409.

[0130] The third substrate is sent from the third unwinding roller 410 to the second laminator 409. In the second laminator 409, the molten extruded resin is extruded from the second extruder 408 onto the first substrate, and as the extruded resin is sandwiched between the first substrate and the third substrate and passes between the cooling roll 409a and the pressure roll 409b, the extruded resin is cooled and solidified by the cooling roll 409a, and a second extruded resin layer is formed on the second substrate. Accordingly, the first substrate and the third substrate are bonded together by the second extruded resin layer.

[0131] The laminate that has passed through the second laminator 409 is wound up under tension by a winding roller 406, and if necessary, is aged under the same conditions as in manufacturing method 1, to obtain a laminate of second substrate / first extruded resin layer / gas barrier anchor coat layer / first substrate / second extruded resin layer / third substrate.

[0132] (Manufacturing Method 4, Modified Example) In this embodiment, the laminating apparatus 400 may further include a coating device and a drying device (not shown) at least in one of the following locations: between the first unwinding roller 401 and the first extruder 404, between the first laminator 405 and the second extruder 408, and between the second unwinding roller 410 and the second extruder 408. This may provide an anchor coat layer that improves adhesion between the extruded resin layer and the substrate. This improves adhesion between the second substrate and the first resin layer, between the first substrate and the second extruded resin layer, and between the third substrate and the second extruded resin layer.

[0133] (Manufacturing method 5) 5 is a schematic diagram showing an example of a laminating apparatus 500 used in another embodiment of the laminate manufacturing method of the present invention. The laminating apparatus 500 includes a first unwinding roller 501, a coating device 502, a drying device 503, a first extruder 504, a first laminator 505, a second unwinding roller 507, a second extruder 508, a second laminator 509, a third unwinding roller 510, and a take-up roller 506.

[0134] In manufacturing method 5, a second substrate is unwound from first unwinding roller 501 and a third substrate is unwound from second unwinding roller 507, and then sent to first laminator 505. In first laminator 505, molten extruded resin is extruded from first extruder 504 between the second substrate and the third substrate, and as the extruded resin is sandwiched between the second substrate and the third substrate and passes between cooling roll 505a and pressure roll 505b, the extruded resin is cooled and solidified by cooling roll 505a, forming a second extruded resin layer. The second substrate and the third substrate bonded together by the second resin layer are sent to second laminator 509.

[0135] In production method 5, the first substrate having a vapor deposition layer is unwound from a third unwinding roller 510 and sent to a coating device 502. In the coating device 502, a gas barrier anchor coating agent is applied to the vapor deposition layer of the first substrate in the same manner as in production method 1, and the substrate is then transported to a drying device 503.

[0136] In the drying device 503, the diluting solvent in the gas barrier anchor coating agent transferred to the first substrate is evaporated by heating, in the same manner as in Production Method 1. The first substrate that has passed through the drying device 503 is sent to a second laminator 509.

[0137] In the second laminator 509, a molten extruded resin is extruded from a second extruder 508 between the third substrate of the laminate transported from the first laminator 505 and the gas barrier anchor coat layer applied to the first substrate, and as the extruded resin is sandwiched between the first substrate and the third substrate and passes between a cooling roll 509a and a pressure roll 509b, the extruded resin is cooled and solidified by the cooling roll 509a, and a first extruded resin layer is formed on the gas barrier anchor coat layer. Accordingly, the first substrate (gas barrier anchor coat layer) and the third substrate are bonded together by the first extruded resin layer.

[0138] The laminate that has passed through the second laminator 509 is wound up under tension by a winding roller 506, and if necessary, is aged under the same conditions as in production method 1, to obtain a laminate of second substrate / second extruded resin layer / third substrate / first extruded resin layer / gas barrier anchor coat layer / first substrate.

[0139] (Manufacturing Method 5, Modified Example) In this embodiment, the laminating apparatus 500 may further include a coating device and a drying device (not shown) at least in one location between the first unwinding roller 501 and the first extruder 504, between the second unwinding roller 507 and the first extruder 504, or between the first laminator 505 and the second extruder 508, and may provide an anchor coat layer that improves adhesion between the extruded resin layer and the substrate. This can improve adhesion between the second substrate and the first resin layer, adhesion between the first substrate and the second extruded resin layer, and adhesion between the third substrate and the second extruded resin layer.

[0140] <Packaging material> The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting food, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use.

[0141] The packaging material of the present invention can be obtained, for example, by overlapping the heat-sealable layers of the laminate of the present invention so that they face each other, and then heat-sealing the peripheral edges. Examples of bag-making methods include folding or overlapping the laminate of the present invention so that the inner layer surfaces (sealant film surfaces) face each other, and heat-sealing the peripheral edges using, for example, a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a flared seal type, a flat-bottom seal type, a square-bottom seal type, a gusset seal type, or other heat seal type. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage form. Self-standing packaging materials (standing pouches) are also possible. Heat-sealing methods can be known, such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0142] The packaging material of the present invention is filled with contents through its opening, and the opening is then heat-sealed to produce a product using the packaging material of the present invention. The contents to be filled include confectioneries such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snack foods; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and fish ham and sausages. Examples of suitable packaging materials include processed seafood products such as fish paste products, kamaboko (fish paste), nori (seaweed paste), tsukudani (simmered foods in soy sauce), dried bonito flakes, salted fish, smoked salmon, and spicy cod roe, fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes, prepared foods such as frozen and chilled prepared foods, including hamburger steaks, meatballs, fried seafood, gyoza (dumplings), and croquettes, dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula, liquid seasonings, retort curry, and pet food. The packaging material of the present invention can also be used as a packaging material for cigarettes, pharmaceuticals such as disposable body warmers and infusion packs, cosmetics, and vacuum insulation materials.

[0143] Alternatively, the packaging material of the present invention may be a lid material using the laminate of the present invention.

[0144] <Recycled plastics> The laminate and packaging material of the present invention can be used as raw materials for recycled plastics. The recycled plastics of the present invention are produced by regenerating the laminate and packaging material of the present invention as raw materials. The method for recycling the laminate and packaging material is not particularly limited, and known methods can be used. Examples include a method in which the laminate and packaging material are crushed, melt-kneaded, and then pelletized and molded, and a method in which the crushed laminate and packaging material are directly fed into an extrusion molding machine without being melt-kneaded or pelletized, and melt-kneaded in the heating barrel of the molding machine to form a molding raw material.

[0145] The laminate and packaging material can be crushed using a known crusher. The crusher is not particularly limited, and examples include methods using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, or hammer mill. The size of the fragments of the printed matter or laminate is preferably 1 mm to 40 mm in side length, more preferably 8 mm to 20 mm.

[0146] The crushed laminate and packaging material are preferably washed before being subjected to heat melting. Examples of the washing method include a batch method and a continuous method, and water, detergent, neutralizing agent, and alkaline aqueous solution may be used. The washed laminate and packaging material are preferably dehydrated and dried. A centrifugal dehydration method is suitable for the dehydration method, and a hot air drying method is suitable for the drying method.

[0147] Dehydration and drying can adjust the moisture content of the laminate to be heated and melted. This prevents foaming during the production of recycled plastics. If bubbles form during pellet production, the pressure in the cylinder changes, causing the extrusion volume and extrusion pressure to fluctuate, potentially resulting in irregular pellet shapes and dimensions. Furthermore, when using the pellets to produce molded products through secondary molding, unevenness is likely to occur on the surface, potentially deteriorating the surface condition of the molded product.

[0148] In one embodiment, dehydration and drying are carried out until the moisture content of the laminate to be used in the production of recycled plastic is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the total mass of the laminate.

[0149] The crushed laminate and packaging material are heated to melt at 120 to 280°C and then kneaded. The temperature at which the laminate and packaging material are melted can be adjusted taking into consideration the glass transition temperature and melting temperature of the laminate or packaging material, the shape to be pelletized, and the pressure to be applied in the molding process. The screw rotation speed during kneading is, for example, 50 to 1000 RPM.

[0150] The melt-kneaded laminate and packaging material are cooled and shredded into pellets. Examples of pelletizing methods include, but are not limited to, hot cutting and strand cutting. To prevent foreign matter from being mixed into the pellets, it is preferable that a screen mesh be provided at the discharge port of the melt-kneaded laminate and packaging material. Examples of screen mesh include plain weave, twill weave, plain dutch weave, and twill dutch weave, as well as punched metal types. Taking into consideration the pressure and clogging of the discharge port, the screen mesh size is preferably 40 mesh or larger, more preferably 80 mesh or larger, and even more preferably 120 mesh or larger. Examples of cooling methods include air cooling, wind cooling, and water cooling. In the present invention, a water cooling step is preferably included. Cooling to 20°C to 80°C is preferable, and cooling to 30°C to 60°C is more preferable.

[0151] When the substrate and extruded resin layer constituting the laminate are made of the same resin type, the laminate of the present invention can be used as is for the production of recycled plastics as described above, or it can be used for the production of recycled plastics after being immersed in a release agent (for example, an alkaline solution such as an aqueous sodium hydroxide solution) for a certain period of time to peel off the layers of the laminate. An example of a laminate in which the substrate and extruded resin layer constituting the laminate are made of the same resin type is a laminate consisting of a first substrate / anchor coat layer / first extruded resin layer, in which the first substrate is a biaxially oriented polypropylene film having a vapor deposition layer and the first extruded resin layer is made of polypropylene.

[0152] When the substrate and the extruded resin layer constituting the laminate of the present invention are made of different resin types, it is preferable to immerse the laminate in a release agent for a certain period of time to peel off each layer of the laminate, and then separate the laminate by resin type for use in the production of recycled plastics. Conventionally known release agents can be used.

[0153] The printed layer may be removed before use in the production of recycled plastics. The printed layer can be removed by a known method. The printed layer itself may be formed using a printing ink that is easily peeled from the substrate by immersion in a release agent, or a release layer may be formed between the printed layer and the substrate by applying a coating agent containing a resin that is easily peeled from the substrate by immersion in a release agent, and the printed layer may be provided on the release layer.

[0154] The recycled plastic of the present invention may contain known additives, such as at least one antioxidant selected from the group consisting of phenolic and phosphorus-based additives, at least one lubricant selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters, a hindered amine weathering stabilizer, a wax having an acid value of 5 mgKOH / g or less, and at least one antistatic agent selected from the group consisting of fatty acid sulfonates and fatty acid esters.

[0155] The recycled plastic of the present invention may contain virgin plastic as a raw material in addition to the laminate and packaging material of the present invention. The virgin plastic to be added is of the same resin type as each layer of the laminate of the present invention (first substrate to third substrate, first extruded resin layer, second extruded resin layer). The virgin plastic may be added when pelletizing the laminate and packaging material of the present invention, or when molding the pelletized recycled plastic of the present invention. The virgin plastic may be added both when pelletizing and when molding the recycled plastic. The amount of virgin plastic used in combination when pelletizing the laminate and packaging material of the present invention is, for example, in a laminate / packaging material:virgin plastic ratio of 100:0 to 25:75 (mass ratio). The amount of virgin plastic used when molding the pelletized recycled plastic of the present invention is, for example, in a recycled plastic:virgin plastic ratio of 100:0 to 25:75 (mass ratio).

[0156] The recycled plastic of the present invention can be used as a raw material for various plastic products. Examples of plastic products include, but are not limited to, automobile parts such as bumpers and interior materials, components for home appliances, transportation pallets and containers, containers such as bottles, hangers, stationery, pots and cups, disposable cutlery, and play equipment. The recycled plastic can also be recycled as a film, or the recycled film can be molded and used as, for example, cushioning material for transporting fruit, but this is not limited to this. Methods for converting the recycled plastic of the present invention into a film and producing a recycled film include known methods such as T-die molding, inflation molding, solution casting molding, and calendar molding. Methods for molding the recycled film include known methods such as vacuum molding and hot press molding. [Explanation of symbols]

[0157] 100, 200, 300, 400, 500: laminating device, 101, 201, 301, 401, 501: first unwinding roller, 102, 202, 302, 402, 502: coating device, 102a, 202a, 302a, 402a, 502a: transfer roll, 102b, 202b, 302b, 402b, 502b: impression cylinder, 102c, 202c, 302c, 402c, 502c: anchor coating agent tank, 103, 203, 303, 403, 503: drying device, 104, 204, 304, 404, 504: first extruder, 105, 205, 305, 405, 505: first laminator, 105a, 205a, 305a, 309a, 405a, 409a, 505a, 509a: cooling roll, 105b, 205b, 305b, 309b, 405b, 409b, 505b, 509b: pressure roll, 106, 206, 306, 406, 506: take-up roller, 207, 307, 407, 507: second unwinding roller, 308, 408, 508: second extruder, 309, 409, 509: second laminator, 310, 410, 510: third unwinding roller

Claims

1. a first substrate having a vapor-deposited layer; a first extruded resin layer; a gas barrier anchor coat layer disposed between the first extruded resin layer and the vapor deposition layer, The gas barrier anchor coat layer is a laminate that is a cured coating film of a two-component curing anchor coat agent that includes a polyol composition (X) containing a polyester polyol (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), wherein the polyester polyol (A) is at least one selected from the group consisting of a polyester polyol (A1) obtained by polycondensing a polycarboxylic acid including an ortho-orienting polycarboxylic acid with a polyhydric alcohol, a polyester polyol (A2) having an isocyanuric ring, and a polyester polyol (A3) having a polymerizable carbon-carbon double bond.

2. 2. The laminate according to claim 1, wherein the thickness of the gas barrier anchor coat layer is 0.05 μm or more and 1 μm or less.

3. 2. The laminate according to claim 1, wherein the vapor-deposited layer is a vapor-deposited layer of a metal.

4. 2. The laminate according to claim 1, wherein the vapor-deposited layer is a vapor-deposited layer of an inorganic oxide.

5. The laminate according to claim 1 , further comprising a second substrate disposed on the surface of the extruded resin layer opposite to the first substrate.

6. a step of applying, onto the vapor-deposited layer of a first substrate having the vapor-deposited layer, a gas-barrier anchor coating agent containing: a polyol composition (X) containing at least one polyester polyol (A) selected from polyester polyol (A1) obtained by polycondensation of a polycarboxylic acid including an ortho-orienting polycarboxylic acid with a polyhydric alcohol, polyester polyol (A2) having an isocyanuric ring, and polyester polyol (A3) having a polymerizable carbon-carbon double bond; and a polyisocyanate composition (Y) containing a polyisocyanate compound (B); and extruding a molten extrusion resin onto the gas barrier anchor coating agent.

7. The solid content of the anchor coating agent was 0.03 g / m ２ 0.8g / m or more ２ The method for producing a laminate according to claim 6, wherein the following is true:

8. The method for producing a laminate according to claim 6, wherein the vapor-deposited layer is a vapor-deposited layer of a metal.

9. 2. The laminate according to claim 1, wherein the vapor-deposited layer is a vapor-deposited layer of an inorganic oxide.

10. The method for producing a laminate according to claim 6 , further comprising the step of bonding the first substrate and the second substrate together via the olefin resin.

11. A packaging material comprising the laminate according to any one of claims 1 to 5.

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