Gas barrier laminated film

Abstract

To provide a gas barrier film which maintains adhesion even after heat-resistant and moisture-resistance tests, is excellent in durability and is transparent.SOLUTION: A gas barrier laminate film 10 has a resin base material 11, a primer layer 12 and a vapor deposition film layer 13, in which the primer layer 12 and the vapor deposition film layer 13 are laminated in this order on at least one surface of the resin base material 11, the primer layer 12 is formed of a composite of polyol and an isocyanate-based compound, and the polyol contains a repeating unit having a partial structure represented by a specific chemical formula.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a gas barrier laminate film that protects an object from gas. [Background technology]

[0002] Gas barrier laminated films protect objects from moisture in the air, oxygen, carbon dioxide, and other gases, preventing deterioration in quality and performance. They are being considered for use as packaging materials for food and pharmaceuticals, as well as in replacement of glass and aluminum foil in the electronics field, such as solar cell backsheets, electronic paper, and organic light-emitting diodes (OLEDs).

[0003] Currently, the main types of gas barrier laminate films include single films such as ethylene vinyl alcohol copolymer resin, co-extruded multilayer nylon (Ny) films, and wet-coated films such as polyvinylidene chloride (PVDC) and polyvinyl alcohol (PVA). However, even films with high gas barrier properties have a water vapor permeability of 3 g / m. 2 / day, making it difficult to use as packaging material or electronic components, which require higher gas barrier properties. Therefore, when higher barrier properties are required, it has been necessary to laminate metal foil such as aluminum.

[0004] However, packaging materials using films laminated with metal foil have problems such as the contents being invisible and the contents not being able to be inspected using a metal detector.

[0005] To overcome these problems, for example, Patent Document 1 proposes a transparent gas barrier film in which an inorganic compound such as aluminum oxide, magnesium oxide, or silicon oxide is vapor-deposited onto a polymer resin substrate.

[0006] Furthermore, in order to improve the adhesion of the vapor-deposited layer to the resin substrate, many proposals have been made to provide a primer layer between the resin substrate and the vapor-deposited layer. Acrylic resins are often used as the material for these primer layers, and in particular, reaction compounds of acrylic polyols and isocyanate compounds or compounds to which a silane coupling agent has been added have been used to achieve gas barrier films with high boiling and retort resistance that do not deteriorate in physical properties even after boiling sterilization or retort sterilization and do not cause delamination or the like (e.g., Patent Documents 2 to 4). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 63-28017 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-106443 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-69456 [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-36419 Summary of the Invention [Problem to be solved by the invention]

[0008] However, these films have difficulty maintaining adhesion even after high-temperature tests (JIS C8917, C8938, C8990, C8991), which are common durability tests for solar cell modules, making them difficult to use in applications requiring high durability.

[0009] Therefore, an object of the present invention is to provide a transparent gas barrier laminate film that has excellent durability and maintains adhesion even after high-temperature testing. [Means for solving the problem]

[0010] As a result of extensive research, the inventors have found that the use of a specific polyol having excellent heat resistance in the primer layer is important in order to solve the above problems.

[0011] One aspect of the present invention for solving the above-mentioned problems is a gas barrier laminate film comprising a resin substrate, a primer layer, and a vapor-deposited film layer, wherein the primer layer is laminated directly on the corona-treated surface of the resin substrate that has been subjected to a corona treatment so as to have a film thickness of 30 nm to 300 nm, and the vapor-deposited film is laminated directly on the primer layer, and the primer layer is formed from a composite of a polyol and an isocyanate-based compound, and the polyol contains a repeating unit having a partial structure represented by the following general formula (I) or (II): and the following general formula (III): The gas barrier laminate film is characterized by comprising: [ka] In formula (I), Q A represents the ester bond shown in the formula, and R A represents a substituent, n1 represents an integer of 1 to 5, * represents the bonding site to the rest of the repeating unit, and ** represents the bonding site to the phenyl group in the formula. [ka] In formula (II), Q B is Q in formula (I) A represents a linking group other than an ester bond or a single bond, and R B represents a substituent, n2 represents an integer of 1 to 5, and * represents a bonding site to the rest of the repeating unit. However, at least one R B represents a hydroxyl group. [ka]

[0012] The content of the repeating unit in the polyol may be 2 mol % or more and 50 mol % or less based on the total repeating units in the polyol.

[0013] The repeating unit may be any one of a repeating unit derived from a (meth)acrylate monomer, a repeating unit derived from a (meth)acrylamide monomer, and a repeating unit derived from an N-substituted maleimide monomer.

[0014] The primer layer may further contain an organic additive.

[0015] Furthermore, a gas barrier coating layer, which is a thin, dried film made of a coating liquid containing a water-soluble polymer and an alkoxysilane or a hydrolysis product thereof, may be provided on the surface of the vapor-deposited film layer. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a transparent gas barrier laminate film having excellent durability and which retains adhesion even after high-temperature testing. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a cross-sectional view of one embodiment of the gas barrier laminate film of the present invention. [Figure 2] 1 is a cross-sectional view of one embodiment of the gas barrier laminate film of the present invention. [Figure 3] 1 is a cross-sectional view of a double-sided laminate structure in one embodiment of the gas barrier laminate film of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail.

[0019] 1, the gas barrier laminate film 10 of the present invention comprises a resin substrate 11, a primer layer 12, and a vapor-deposited film layer 13, with the primer layer 12 and the vapor-deposited film layer 13 laminated in that order on one side of the resin substrate 11. The gas barrier laminate film may also have a configuration in which the primer layer 12 and the vapor-deposited film layer 13 are laminated in that order on both sides of the resin substrate 11 in order to achieve higher water vapor barrier properties.

[0020] Examples of resin substrate 11 include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, and biodegradable plastic films such as polyethersulfone (PES), polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, and polylactic acid. There are no particular limitations on the thickness of resin substrate 11, but in practice it is preferably about 6 μm to 200 μm, more preferably 12 μm to 125 μm, and even more preferably 12 μm to 25 μm.

[0021] Furthermore, in order to improve adhesion, the surface of the resin substrate 11 on which another layer is to be laminated may be subjected to physical treatment such as corona treatment, plasma treatment, or flame treatment, or chemical treatment such as chemical treatment with an acid or alkali.

[0022] The primer layer 12 is provided on the resin substrate 11 to increase adhesion between the resin substrate 11 and the vapor-deposited film layer 13, and to prevent peeling of the vapor-deposited layer due to various sterilization processes such as boiling sterilization and retort sterilization, or due to long-term outdoor installation.

[0023] The primer layer 12 is formed using a composite of a polyol and an isocyanate compound, thereby improving the adhesion between the resin substrate 11 and the vapor-deposited film layer 13 .

[0024] Polyol is a general term for compounds having multiple hydroxyl groups in the molecule, and reacts with the isocyanate groups of isocyanate compounds. Major polyols include polyether polyols having ether bonds in the main chain, polyester polyols having ester bonds in the main chain, polymeric compounds obtained by polymerizing (meth)acrylic acid derivative monomers, and acrylic polyols, which are polymeric compounds obtained by copolymerizing (meth)acrylic acid derivative monomers with other monomers.

[0025] Examples of polyether polyols include polyoxyalkylene polyols obtained by addition polymerization of alkylene oxides using polyhydric alcohols or polyamines as initiators, and polyoxytetramethylene glycols obtained by cationic polymerization of tetrahydrofuran.

[0026] Polyester polyols include self-polymerized polyester polyols obtained from dibasic acids and glycols, and polycaprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. Dibasic acids used in self-polymerized polyester polyols include adipic acid, terephthalic acid, and isophthalic acid, while glycols include ethylene glycol, neopentyl glycol, and 3-methyl-1,5-pentanediol.

[0027] Acrylic polyol is a polymer compound obtained by copolymerizing (meth)acrylic acid derivative monomers with each other or (meth)acrylic acid derivative monomers with other monomers by radical polymerization, and has a hydroxyl group at the end.

[0028] In this case, it is preferable to select a polyol containing a repeating unit (a) having a partial structure represented by the following general formula (I) or (II). [ka]

[0029] In formula (I), Q Arepresents the ester bond shown in the formula, and R A represents a substituent, n1 represents an integer of 1 to 5, * represents the bonding site to the rest of the repeating unit (a), and ** represents the bonding site to the phenyl group in the formula. [ka]

[0030] In formula (II), Q B is Q in formula (I) A represents a linking group other than an ester bond or a single bond, and R B represents a substituent, n2 represents an integer of 1 to 5, and * represents a bonding site with the remainder of the repeating unit (a), provided that at least one R B represents a hydroxyl group.

[0031] R A Examples of the substituent represented by the formula include an alkyl group (e.g., an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkoxy group (e.g., a methoxy group or an ethoxy group), a hydroxyl group, an acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, a halogen atom, etc. As mentioned above, n1 represents an integer of 1 to 5, and may be an integer of 1 to 3. When n1 is an integer of 2 or more, a plurality of R A may all be the same, may all be different, or may be partly the same.

[0032] Q B As mentioned above, Q A Q represents a single bond or a linking group other than an ester bond represented by the formula: A Examples of linking groups other than the ester bond represented by the formula (II) include -CONR- (where R represents a hydrogen atom or an alkyl group), an alkylene group (for example, an alkylene group having 1 to 4 carbon atoms), a urethane bond, an ether bond, and an ester bond represented by *-O-CO-** (where ** represents the bonding site with the phenyl group in formula (II)).

[0033] R BExamples of the substituent represented by the formula include an alkyl group (e.g., an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkoxy group (e.g., a methoxy group, an ethoxy group), a hydroxyl group, an acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, a halogen atom, etc. However, as described above, at least one R B represents a hydroxyl group.

[0034] As described above, n2 represents an integer of 1 to 5, or may be an integer of 1 to 3. When n2 is an integer of 2 or more, a plurality of R B may all be the same, may all be different, or may be partly the same. B If all are the same, R B are all hydroxyl groups.

[0035] The repeating unit (a) may be any unit as long as it has a partial structure represented by the above-mentioned general formula (I) or (II), and may be, for example, a repeating unit derived from a (meth)acrylate-based monomer, a repeating unit derived from a (meth)acrylamide-based monomer, a repeating unit derived from an N-substituted maleimide-based monomer, or a repeating unit derived from a styrene-based monomer.

[0036] When the repeating unit (a) is a repeating unit derived from a (meth)acrylate monomer, examples of the (meth)acrylate monomer include 4-methoxyphenyl(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, 2,6-di-tert-butylphenyl(meth)acrylate, 2,6-di-tert-butyl-4-methoxyphenyl(meth)acrylate, 2-tert-butyl-4-hydroxyphenyl(meth)acrylate, 3-tert-butyl-4-hydroxyphenyl(meth)acrylate, 2,6-di-tert-butyl-4-methylphenyl(meth)acrylate, 2-hydroxy-4-tert-butylphenyl(meth)acrylate, and 2,4-di-methyl-6-tert-butylphenyl(meth)acrylate.

[0037] When the repeating unit (a) is a repeating unit derived from a (meth)acrylamide-based monomer, examples of the (meth)acrylamide-based monomer include N-(4-hydroxyphenyl)(meth)acrylamide.

[0038] When the repeating unit (a) is a repeating unit derived from an N-substituted maleimide monomer, examples of the N-substituted maleimide monomer include 4-hydroxyphenylmaleimide and 3-hydroxyphenylmaleimide.

[0039] When the repeating unit (a) is a repeating unit derived from a styrene-based monomer, examples of the styrene-based monomer include α-methyl-p-hydroxystyrene.

[0040] Monomers copolymerizable with (meth)acrylic acid derivative monomers having terminal hydroxyl groups include monomers having terminal alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and t-butyl (meth)acrylate, (meth)acrylic acid derivative monomers having terminal carboxyl groups such as (meth)acrylic acid, and (meth)acrylic acid derivative monomers having terminal aromatic rings or cyclic structures such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate. Other than (meth)acrylic acid derivative monomers, examples include styrene monomers, cyclohexylmaleimide monomers, and phenylmaleimide monomers.

[0041] In this embodiment, the polyol is preferably a binary or ternary copolymer further containing one or more repeating units different from the repeating unit (a). In this case, the content of the repeating unit (a) in the polyol is preferably in the range of 2 mol% to 50 mol% based on the total repeating units in the polyol. When the content of the repeating unit (a) in the polyol is 2 mol% or more, thermal decomposition of the polyol can be more effectively suppressed.

[0042] Furthermore, when the content of the repeating unit (a) in the polyol is 50 mol % or less, it is possible to maintain the effect of suppressing thermal decomposition of the polyol and the additives used in combination, while effectively suppressing yellowing of the gas barrier film when heated and hardening and brittleness of the primer layer 12. From the same viewpoint, the content of the repeating unit (a) in the resin may be 2 mol % or more and 30 mol % or less, or 2 mol % or more and 20 mol % or less.

[0043] In the present embodiment, when the polyol is a copolymer, examples of the repeating unit (hereinafter referred to as a "copolymerization component") that may be contained and that is different from the repeating unit (a) include a (meth)acrylate repeating unit, an olefin repeating unit, a halogen atom-containing repeating unit, a styrene repeating unit, a vinyl acetate repeating unit, and a vinyl alcohol repeating unit.

[0044] Examples of the (meth)acrylate repeating unit that is a copolymerization component include a repeating unit derived from a (meth)acrylate monomer having a linear or branched alkyl group on the side chain, and a repeating unit derived from a (meth)acrylate monomer having a hydroxyl group (excluding phenolic hydroxyl groups) on the side chain.

[0045] Examples of the (meth)acrylate repeating unit having a linear or branched alkyl group on the side chain include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and isooctyl (meth)acrylate. Examples of monomer-derived components include 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, and octadecyl (meth)acrylate. These may be used alone or in combination of two or more. Among the above, (meth)acrylate-based repeating units having a linear or branched alkyl group having 1 to 4 carbon atoms in the side chain are preferred.

[0046] Examples of the olefin repeating unit that is a copolymerization component include components derived from olefin monomers such as ethylene, propylene, isoprene, butadiene, etc. These may be used alone or in combination of two or more.

[0047] Examples of the halogen atom-containing repeating unit that is a copolymerization component include components derived from monomers such as vinyl chloride, vinylidene chloride, etc. These may be used alone or in combination of two or more.

[0048] Examples of the styrene repeating unit that is a copolymerization component include components derived from styrene monomers such as styrene, α-methylstyrene, vinyltoluene, etc. These may be used alone or in combination of two or more.

[0049] The molecular weight of the polyol is not particularly limited, but specifically, it is 3,000 or more and 200,000 or less, preferably 5,000 or more and 100,000 or less, and more preferably 5,000 or more and 40,000 or less.

[0050] Examples of (meth)acrylic repeating units having a hydroxyl group other than a phenolic hydroxyl group in a side chain include components derived from monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0051] However, when the repeating unit (a) does not contain a hydroxyl group, it is necessary to contain 2 mol % or more of a component having a hydroxyl group as a copolymerization component.

[0052] The copolymer may have any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer structure. If the copolymer has a random copolymer structure, the manufacturing process and preparation with the cyanine dye are easy. Therefore, a random copolymer is preferable to other copolymers.

[0053] Radical polymerization can be used as a polymerization method for obtaining the copolymer. The use of radical polymerization is preferred because it is easy to produce industrially. The radical polymerization method may be solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, or the like, with solution polymerization being particularly preferred. The use of solution polymerization makes it easy to control the molecular weight of the copolymer.

[0054] In radical polymerization, the above-mentioned monomers may be diluted with a polymerization solvent, and then a polymerization initiator may be added to polymerize the monomers. Examples of the polymerization solvent include ester-based solvents, alcohol ether-based solvents, ketone-based solvents, aromatic solvents, amide-based solvents, and alcohol-based solvents. Examples of the ester-based solvent include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, and ethyl lactate. Examples of the alcohol ether-based solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the aromatic solvent include benzene, toluene, and xylene. The amide solvent may be, for example, formamide, dimethylformamide, etc. The alcohol solvent may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, diacetone alcohol, 2-methyl-2-butanol, etc. The above-mentioned polymerization solvents may be used alone or in combination of two or more.

[0055] In radical polymerization, the amount of polymerization solvent used is not particularly limited. When the total amount of monomers is set to 100 parts by mass, the amount of polymerization solvent used is preferably 1 part by mass or more and 1,000 parts by mass or less, and more preferably 10 parts by mass or more and 500 parts by mass or less.

[0056] The radical polymerization initiator may be, for example, a peroxide or an azo compound. The peroxide may be, for example, benzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, or di-t-butyl peroxide. The azo compound may be, for example, azobisisobutyronitrile, azobisamidinopropane salt, azobiscyanovaleric acid (salt), or 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0057] The amount of radical polymerization initiator used is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 15 parts by mass, and even more preferably 0.005 to 10 parts by mass, when the total amount of monomers is set to 100 parts by mass. The radical polymerization initiator may be added to the monomers and polymerization solvent before the start of polymerization, or may be added dropwise to the polymerization reaction system. Adding the radical polymerization initiator dropwise to the monomers and polymerization solvent in the polymerization reaction system is preferred because it can suppress heat generation due to polymerization.

[0058] The reaction temperature for radical polymerization is appropriately selected depending on the types of radical polymerization initiator and polymerization solvent, and is preferably 60° C. or higher and 110° C. or lower from the viewpoints of ease of production and reaction controllability.

[0059] An isocyanate compound is one that has two or more isocyanate groups in its molecule. Examples of monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bisisocyanatomethylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI), and aromatic aliphatic isocyanates such as xylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI). Polymers or derivatives of these monomeric isocyanates can also be used. Examples include nurate types (trimers to pentamers), adduct types reacted with 1,1,1-trimethylolpropane, and biuret types reacted with biuret.

[0060] The isocyanate compound may be selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and one or more of them may be used in combination.

[0061] In addition to the polyol and isocyanate compound, additives may be added depending on the application. Examples include catalysts that accelerate the curing reaction, light stabilizers such as ultraviolet absorbers (UVA) and hindered amine light stabilizers (HALS), antioxidants, antistatic agents, plasticizers, and silane coupling agents. In particular, in this embodiment, the use of a polyol containing repeating unit (a) and exhibiting excellent heat resistance can also suppress thermal degradation of organic additives. Here, the term "organic additive" refers to an additive selected from compounds containing carbon atoms, and may be a low-molecular-weight compound, a high-molecular-weight compound, an oligomer, or an organic metal salt. Specific examples of additives are shown in Table 1.

[0062] [Table 1]

[0063] The use of a polyol containing the repeating unit (a) can suppress thermal degradation of additives. For example, when a light stabilizer is used as an additive, the resulting gas barrier laminate film has good light resistance even after heating.

[0064] The primer layer 12 is formed by applying a solution consisting of a composite of the polyol and the isocyanate compound and a solvent onto the resin substrate 11, followed by reactive curing. The solvent used may be any solvent that dissolves the polyol and the isocyanate compound, such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, or acetone, and these solvents may be used alone or in combination of two or more.

[0065] The primer layer 12 can be formed by a conventional coating method, such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, or gravure offset. The drying method can be one or a combination of two or more heat application methods, such as hot air drying, heat roll drying, high frequency irradiation, infrared irradiation, or UV irradiation.

[0066] The thickness of the primer layer 12 is desirably 30 nm to 200 nm, and preferably 100 nm to 200 nm. If the thickness is thinner than this, the adhesion between the resin substrate 11 and the vapor-deposited film layer 13 will be insufficient, and if the thickness is thicker than 300 nm, the influence of internal stress will be greater, the vapor-deposited film layer 13 will not be laminated neatly, and the barrier properties will not be sufficiently exhibited.

[0067] The vapor-deposited film layer 13 is provided on the primer layer 12 to impart gas barrier properties to the entire film.

[0068] It is preferable to use a deposition material containing metallic silicon and silicon dioxide as the material for the deposited film layer 13. Alternatively, the material for the deposited film layer 13 may be a deposition material containing other metallic tin or metal oxide.

[0069] By depositing a deposition material containing metallic silicon and silicon dioxide, it is possible to impart high gas barrier properties to the entire film. Furthermore, by depositing a deposition material that is a mixture of metallic silicon and silicon dioxide with metallic tin or tin oxide, a deposited film layer 13 with high film density is formed, which exhibits high water vapor barrier properties. In addition, a gas barrier film that combines high gas barrier properties and high durability is obtained due to the synergistic effect with the primer layer 12 formed from a composite of polyol and an isocyanate compound.

[0070] It is desirable to mix metallic silicon and silicon dioxide so that the element ratio O / Si is 1 or more and 1.8 or less, and preferably 1.2 or more and 1.7 or less.

[0071] The deposition film layer 13 may be formed by any known method, such as vacuum deposition, sputtering, plasma vapor deposition, or atomic layer deposition, but vacuum deposition is preferred. To increase the transparency of the deposition film layer 13, reactive deposition may be used, in which evaporated particles react with oxygen gas or the like introduced into the atmosphere when the deposition material is deposited. By reactive deposition with oxygen gas or argon gas, the metal components in the deposition material are oxidized, improving the transparency of the deposition film layer 13. When introducing the gas, the pressure in the deposition chamber should be 2×10 -1 It is desirable to keep the pressure in the deposition chamber below 2×10 Pa. -1 If it is greater than Pa, the vapor-deposited film layer 13 will not be laminated neatly, and the water vapor barrier properties will be reduced.

[0072] The thickness of the vapor-deposited film layer 13 is preferably 0.005 μm or more and 0.3 μm or less, and more preferably 0.03 μm or more and 0.05 μm or less. If it is less than 0.005 μm, sufficient barrier properties are not exhibited, and if it exceeds 0.3 μm, it becomes brittle and prone to cracking, resulting in the problem of not exhibiting barrier properties.

[0073] The gas barrier laminate film of the present invention may be, as in the gas barrier laminate film 20 shown in Figure 2, provided on the vapor-deposited film layer 13 of the gas barrier laminate film 10 with a gas barrier coating layer 21 which is a thin, dried coating made of a coating liquid containing a water-soluble polymer and an alkoxysilane or a hydrolysis product thereof.

[0074] The gas barrier coating layer 21 is provided to protect the hard and brittle vapor-deposited film layer 13 and prevent cracks from occurring due to rubbing or bending, and is made of a component containing a water-soluble polymer and an alkoxysilane or its hydrolysis product. The gas barrier coating layer 21 is formed by applying a coating liquid containing the water-soluble polymer and the alkoxysilane or its hydrolysis product onto the vapor-deposited film layer 13 and drying it.

[0075] The gas barrier coating layer 21 can be formed by a conventional coating method, similar to the primer layer 12. For example, well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, and gravure offset can be used. As a drying method, one or a combination of two or more heat application methods such as hot air drying, heat roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

[0076] As the water-soluble polymer, polyvinyl alcohol resin (PVA), ethylene-vinyl alcohol copolymer resin (EVOH), polyvinylpyrrolidone resin (PVP), etc. can be used, and these may be used alone or in combination.

[0077] Examples of alkoxysilanes that can be used include tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, and methyltrimethoxysilane. Examples of hydrolysis products of alkoxysilanes include those prepared by dissolving an alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction.

[0078] A silane coupling agent may be added to improve adhesion to the vapor-deposited film layer 13. Examples of silane coupling agents include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, those having a mercapto group such as 3-mercaptopropyltrimethoxysilane, and those having an isocyanate group such as 3-isocyanatepropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0079] The gas barrier laminate film of the present invention may be configured as shown in FIG. 3, in which a laminate resin layer 32 is provided on both sides of the gas barrier laminate film 20 via an adhesive layer 31, resulting in a highly practical gas barrier laminate film. The laminate resin layer 32 is used as an adhesive when forming a bag-shaped package by laminating a heat-sealable sealant film thereon. The laminate resin layer 32 may be made of, for example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, or a metal-crosslinked product thereof. The thickness of the laminate resin layer 32 is determined depending on the purpose, but is generally in the range of 15 μm to 200 μm. The laminate resin layer 32 may be provided on only one side of the gas barrier laminate film 20 via the adhesive layer 31.

[0080] Furthermore, by laminating a polyethylene terephthalate film or a polyethylene naphthalate film on one or both sides of the gas barrier laminate film 10, 20, or 30 of the present invention, the film can also be used as an encapsulant for transparent conductive sheets used in liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, and the like. [Example]

[0081] <Synthesis of polyol> Nineteen types of polyols were synthesized, and named Pa to Pp, respectively. The structural formulas of the repeating units contained in polyols Pa to Pp are shown in Chemical Formula 5-1 and Chemical Formula 5-2. The synthesis methods for each are described below.

[0082] Synthesis Example 1: Synthesis of polyol Pa 80 parts by weight of cyclohexanone was prepared as a polymerization solvent. 5 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 14 parts by weight of methyl methacrylate (MMA), and 1 part by weight of 4-methoxyphenyl methacrylate (MPhMA) were prepared as acrylic monomers. 0.22 parts by weight of benzoyl peroxide (BPO) was also prepared as a polymerization initiator. These components were placed in a reaction vessel equipped with a stirrer and a reflux condenser. While introducing nitrogen gas into the reaction vessel, the mixture was stirred and refluxed for 8 hours while heated to 80°C. This yielded a polymer solution containing an acrylic copolymer formed from repeating units derived from HEMA, repeating units derived from MMA, and repeating units derived from MPhMA. The resulting polymer solution was added dropwise to a large amount of methanol for reprecipitation purification, and then dried under reduced pressure at room temperature for 24 hours to obtain polyol Pa.

[0083] Synthesis Example 2: Synthesis of Polyol Pb Polyol Pb was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxyphenyl methacrylate (HPMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0084] Synthesis Example 3: Synthesis of polyol Pc Polyol Pc was obtained in the same manner as in Synthesis Example 2, except that the amounts of 2-hydroxyethyl methacrylate (HEMA) and 4-hydroxyphenyl methacrylate (HPMA) were changed to 5.6 parts by mass and 0.4 parts by mass, respectively.

[0085] Synthesis Example 4: Synthesis of polyol Pd Polyol Pd was obtained in the same manner as in Synthesis Example 2, except that the amounts of 2-hydroxyethyl methacrylate (HEMA) and 4-hydroxyphenyl methacrylate (HPMA) were changed to 4 parts by mass and 2 parts by mass, respectively.

[0086] Synthesis Example 5: Synthesis of polyol Pe Polyol Pe was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxyphenyl methacrylamide (HPMAA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0087] Synthesis Example 6: Synthesis of polyol Pf Polyol Pf was obtained in the same manner as in Synthesis Example 1, except that 4-hydroxyphenylmaleimide (HPhMI) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0088] Synthesis Example 7: Synthesis of polyol Pg Polyol Pg was obtained in the same manner as in Synthesis Example 1, except that 2,6-di-tert-butylphenyl methacrylate (t-BuPhMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0089] Synthesis Example 8: Synthesis of Polyol Ph Polyol Ph was obtained in the same manner as in Synthesis Example 1, except that 2,6-di-tert-butyl-4-methoxyphenyl methacrylate (t-BuMPhMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0090] Synthesis Example 9: Synthesis of polyol Pi 80 parts by weight of cyclohexanone was prepared as a polymerization solvent. 5 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 14 parts by weight of methyl methacrylate (MMA), and 1 part by weight of 4-acetoxystyrene (AcSt) were prepared as acrylic monomers. Furthermore, 0.22 parts by weight of benzoyl peroxide (BPO) was prepared as a polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux condenser. While introducing nitrogen gas into the reaction vessel, the mixture was stirred and refluxed for 8 hours while heated to 80°C. This yielded a polymer solution containing an acrylic copolymer formed from repeating units derived from HEMA, repeating units derived from MMA, and repeating units derived from AcSt. The resulting polymer solution was added dropwise to a large amount of methanol for reprecipitation purification, and then dried under reduced pressure at room temperature for 24 hours to obtain a HEMA / MMA / AcSt copolymer. To 1 part by weight of the obtained HEMA / MMA / AcSt copolymer, 2 parts by weight of a 1 mol / L sodium hydroxide ethanol solution and 10 parts by weight of tetrahydrofuran were added and stirred for 2 hours. This solution was added dropwise to a large amount of methanol to obtain polyol Pi.

[0091] Synthesis Example 10: Synthesis of polyol Pj Polyol Pj was obtained in the same manner as in Synthesis Example 1, except that 6 parts by mass of 2-hydroxyethyl methacrylate (HEMA) was used and 4-methoxyphenyl methacrylate (MPhMA) was not used.

[0092] Synthesis Example 11: Synthesis of Polyol Pk Polyol Pk was obtained in the same manner as in Synthesis Example 1, except that styrene (St) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0093] Synthesis Example 12: Synthesis of polyol Pl Polyol Pl was obtained in the same manner as in Synthesis Example 1, except that phenyl methacrylate (PhMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0094] Synthesis Example 13: Synthesis of polyol Pm Polyol Pm was obtained in the same manner as in Synthesis Example 1, except that phenyl methacrylamide (PhMAA) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0095] Synthesis Example 14: Synthesis of polyol Pn Polyol Pn was obtained in the same manner as in Synthesis Example 1, except that phenylmaleimide (PhMI) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0096] Synthesis Example 15: Synthesis of polyol Po A polyol Po was obtained in the same manner as in Synthesis Example 1, except that 4-methoxystyrene (MSt) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0097] Synthesis Example 16: Synthesis of polyol Pp Polyol Pp was obtained in the same manner as in Synthesis Example 1, except that 2,4,6-trimethylstyrene (TMSt) was used instead of 4-methoxyphenyl methacrylate (MPhMA).

[0098] [ka] [ka]

[0099] <Preparation of gas barrier laminated film> Gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8 were produced according to the following steps (1) to (6).

[0100] (1) Preparation of primer layer solution

[0101] Example 1 A methyl ethyl ketone solution of polyol Pa adjusted to a solids concentration of 5% and a methyl ethyl ketone solution of an isocyanate compound adjusted to a solids concentration of 5% were mixed at a ratio of 7:3 to prepare a solution. The isocyanate compound used was a tolylene diisocyanate adduct (Tosoh Corporation, Coronate T-65).

[0102] Example 2 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pb adjusted to a solids concentration of 5% was used.

[0103] Example 3 A methyl ethyl ketone solution of polyol Pb adjusted to a solids concentration of 5% was mixed with a methyl ethyl ketone solution of an isocyanate compound adjusted to a solids concentration of 5% in a ratio of 7:3, and then a light stabilizer (Tinuvin (registered trademark) 292, manufactured by BASF Japan Ltd.) was added as an additive at 1% by weight of the solids content, to prepare a primer layer solution in the same manner as in Example 1.

[0104] Example 4 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pc adjusted to a solids concentration of 5% was used.

[0105] Example 5 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pd adjusted to a solids concentration of 5% was used.

[0106] Example 6 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pe adjusted to a solids concentration of 5% was used.

[0107] Example 7 A methyl ethyl ketone solution of polyol Pe adjusted to a solids concentration of 5% was mixed with a methyl ethyl ketone solution of an isocyanate compound adjusted to a solids concentration of 5% in a ratio of 7:3, and then a light stabilizer (Tinuvin 292, manufactured by BASF Japan Ltd.) was added as an additive at 1% by weight of the solids content, and the primer layer solution was prepared in the same manner as in Example 1.

[0108] Example 8 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pf adjusted to a solids concentration of 5% was used.

[0109] Example 9 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pg adjusted to a solids concentration of 5% was used.

[0110] Example 10 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Ph adjusted to a solids concentration of 5% was used.

[0111] Example 11 A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pi adjusted to a solids concentration of 5% was used.

[0112] (Comparative Example 1) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pj adjusted to a solids concentration of 5% was used.

[0113] (Comparative Example 2) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pk adjusted to a solids concentration of 5% was used.

[0114] (Comparative Example 3) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pl adjusted to a solids concentration of 5% was used.

[0115] Comparative Example 4 A methyl ethyl ketone solution of polyol Pl adjusted to a solids concentration of 5% was mixed with a methyl ethyl ketone solution of an isocyanate compound adjusted to a solids concentration of 5% in a ratio of 7:3, and then a light stabilizer (Tinuvin 292, manufactured by BASF Japan Ltd.) was added as an additive in an amount of 1% by weight of solids, to prepare a primer layer solution in the same manner as in Example 1.

[0116] (Comparative Example 5) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pm adjusted to a solids concentration of 5% was used.

[0117] (Comparative Example 6) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pn adjusted to a solids concentration of 5% was used.

[0118] (Comparative Example 7) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Po adjusted to a solids concentration of 5% was used.

[0119] (Comparative Example 8) A primer layer solution was prepared in the same manner as in Example 1, except that a methyl ethyl ketone solution of polyol Pp adjusted to a solids concentration of 5% was used.

[0120] The components of the polyols and the additives used in Examples 1 to 11 and Comparative Examples 1 to 8 are shown in Table 2.

[0121] [Table 2-1] [Table 2-2]

[0122] (2) Primer layer solution coating process The resin substrate used was a 12 μm-thick biaxially stretched PET film (P60, manufactured by Toray Advanced Film Co., Ltd.) with one side corona-treated. Primer layer solutions of Examples 1 to 11 and Comparative Examples 1 to 8 were applied to the corona-treated surface of the resin substrate using a gravure coater so that the thickness after drying was 0.20 μm, thereby laminating a primer layer.

[0123] (3) Lamination process of vapor-deposited film layers A material was prepared by mixing metal silicon powder and silicon dioxide powder so that the element ratio O / Si was 1.5, and a vapor deposition film layer 0.05 μm thick was laminated on top of the primer layer using a vacuum deposition machine to produce gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8, each having a resin substrate / primer layer / vapor deposition film layer configuration.

[0124] (4) Preparation of gas barrier coating layer solution A solution of tetraethoxysilane hydrolyzed with 0.02 mol / L hydrochloric acid was added to a 5% aqueous solution of PVA with a saponification degree of 99% and a polymerization degree of 2400 in a ratio of SiO2 / PVA = 60 / 40 to prepare a gas barrier coating layer solution.

[0125] (5) Gas barrier coating solution coating process The gas barrier coating layer solution was applied using a gravure coater onto the vapor-deposited film layer of each of the gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8, which was produced in step (3), to form a gas barrier coating layer having a thickness of 0.40 μm after drying, thereby producing the gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8.

[0126] (6) Laminating resin layer onto gas barrier laminate film The gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8, on both sides of which the gas barrier coating layer was laminated in step (5), were coated with 5 g / m 2A 50 μm thick hydrolysis-resistant PET film (X10S, manufactured by Toray Advanced Film Co., Ltd.) was laminated on the film by dry lamination via the polyurethane adhesive to prepare gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8.

[0127] <Evaluation of gas barrier laminated film> (1) Measurement of water vapor permeability The gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8 prepared in step (3) were measured for water vapor permeability (g / m) under an atmosphere of 40°C and 90% RH using a water vapor permeability meter (MOCON PERMATRAN-W 3 / 31) manufactured by Modern Controls. 2 / day) were measured. The results are shown in Table 3.

[0128] (2) High-temperature testing The gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8 produced in step (6) were cut into 10 mm widths and subjected to a high temperature test under the temperature and time conditions of the heat resistance test specified in JISC 8917.

[0129] (3) Light resistance test After the high temperature test, a light resistance test was carried out on the gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8. The light resistance test was carried out under the conditions of a light irradiation test according to JISC 8917, with an irradiation time of 120 hours.

[0130] (4) Measurement of adhesion strength The gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8, which were subjected only to the high-temperature test, and the gas barrier laminate films of Examples 1 to 11 and Comparative Examples 1 to 8, which were subjected to both the high-temperature test and the light resistance test, were subjected to adhesion strength measurements using a Tensilon universal testing machine. Specifically, the T-peel test and the 180-degree peel test, which are test methods of JIS K 6854, were performed to measure the laminate strength (N / 10 mm width). In both the T-peel test and the 180-degree peel test, a laminate strength (adhesion strength) of 1 N / 10 mm width or greater was evaluated as "good," and a laminate strength of less than 1 N / 10 mm width was evaluated as "bad." The results are shown in Table 3.

[0131] [Table 3]

[0132] In all of the gas barrier laminate films of Examples 1 to 11, the polyol forming the primer layer 12 contained a repeating unit (a) having a partial structure represented by general formula (I) or (II), and therefore had an adhesion strength of 1 N / 10 mm width or more even after the high-temperature test. However, in all of the gas barrier laminate films of Comparative Examples 1 to 8, the polyol forming the primer layer 12 did not contain a repeating unit (a), and therefore the adhesion strength after the high-temperature test was less than 1 N / 10 mm width.

[0133] Furthermore, the gas barrier laminate film of Example 2 failed the test due to a decrease in adhesion strength after the light resistance test, whereas the gas barrier laminate film of Example 3, which was prepared under the same conditions except for the addition of a light stabilizer when preparing the primer layer solution, maintained an acceptable adhesion strength even after the light resistance test. Similarly, when comparing Examples 6 and 7, only Example 7, which used a light stabilizer, maintained an acceptable adhesion strength even after the light resistance test. However, even Comparative Example 4, which also used a light stabilizer, did not contain the repeating unit (a) in the polyol forming the primer layer 12, and therefore failed the test at high temperatures. This is because the use of a polyol containing the repeating unit (a) prevented the thermal degradation of the light stabilizer additive.

[0134] From the above, it can be said that the polyol forming the primer layer containing the repeating unit (a) is useful for improving the adhesion of the gas barrier laminate film.

[0135] The present invention is not limited to the above-described embodiments, and various modifications can be made in the implementation stage without departing from the spirit of the invention. Furthermore, the above-described embodiments include various inventions, and various inventions can be extracted by selecting and combining the multiple constituent elements disclosed. For example, if the problem can be solved and the effect can be obtained even if some constituent elements are deleted from all the constituent elements shown in the embodiments, the configuration from which these constituent elements are deleted can be extracted as an invention. [Industrial Applicability]

[0136] The gas barrier film laminate of the present invention is expected to be suitably used in the fields of packaging foods, daily necessities, medicines, etc., and electronic equipment-related materials, particularly when high durability is required. [Explanation of symbols]

[0137] 11. Resin substrate 12 Primer layer 13...Vapor deposited film layer 21 Gas barrier coating layer 31...Adhesive layer 32 Laminated resin layer 10, 20, 30... Gas barrier laminated film

Claims

1. A gas barrier laminate film comprising a resin substrate, a primer layer, and a vapor-deposited film layer, the primer layer is laminated directly on the corona-treated surface of the resin substrate that has been subjected to corona treatment so as to have a film thickness of 30 nm or more and 300 nm or less; the vapor-deposited layer is directly laminated on the primer layer, the primer layer is formed from a composite of a polyol and an isocyanate compound, The gas barrier laminate film is characterized in that the polyol contains a repeating unit having a partial structure represented by the following general formula (I) or (II), and a repeating unit having a partial structure represented by the following general formula (III). 【Chemical 1】 In formula (I), Q Ａ represents the ester bond shown in the formula, and R Ａ represents a substituent, n1 represents an integer of 1 to 5, * represents the bonding site to the rest of the repeating unit, and ** represents the bonding site to the phenyl group in the formula. 【Chemistry 2】 In formula (II), Q Ｂ is Q in formula (I) Ａ represents a single bond or a linking group other than an ester bond represented by Ｂ represents a substituent, n2 represents an integer of 1 to 5, and * represents a bonding site with the rest of the repeating unit. Ｂ represents a hydroxyl group. 【Chemistry 3】

2. 2. The gas barrier laminate film according to claim 1, wherein the content of the repeating unit in the polyol is 2 mol % or more and 50 mol % or less based on all repeating units in the polyol.

3. 3. The gas barrier laminate film according to claim 1, wherein the repeating unit is any one of a repeating unit derived from a (meth)acrylate monomer, a repeating unit derived from a (meth)acrylamide monomer, and a repeating unit derived from an N-substituted maleimide monomer.

4. The gas barrier laminate film according to claim 1 , wherein the primer layer further contains an organic additive.

5. A gas barrier coating layer is provided on the surface of the vapor-deposited film layer, which is a thin, dried film made of a coating liquid containing a water-soluble polymer and an alkoxysilane or a hydrolysis product thereof. The gas barrier laminate film according to claim 1 ,

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