High-adhesion gas barrier vapor-deposited film

Abstract

To provide a high interlaminar adhesive gas barrier vapor-deposited film which is excellent in production suitability, and is excellent in gas barrier property while having a simple layer constitution, a laminate using the same, a packaging material, and a package.SOLUTION: A high interlaminar adhesive gas barrier vapor-deposited film has a base material layer and a gas barrier layer, wherein the base material layer has a layer composed of a biaxially stretched resin film containing a polypropylene-based resin, and a PVA-based resin layer, the gas barrier layer has an aluminum oxide vapor-deposited layer, the aluminum oxide vapor-deposited layer is stacked on the PVA-based resin layer in contact therewith by vapor deposition by a CVD method, and interlayer adhesion strength between the aluminum oxide vapor-deposited layer and the PVA-based resin layer is 2 N / 15 mm or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a highly interlayer-adherent gas barrier vapor-deposited film having a base layer made of an organic resin layer and a gas barrier layer made of a metal oxide vapor-deposited layer, and to a gas barrier laminate, gas barrier packaging material, and gas barrier packaging made using the highly interlayer-adherent gas barrier vapor-deposited film. The highly interlayer-adherent gas barrier vapor-deposited film according to the present invention can be applied to products in various fields requiring high barrier properties, and is particularly suitable for use as a packaging material. For example, it can be used in applications such as pharmaceuticals, cosmetics, chemicals, and food and beverages. [Background technology]

[0002] In packaging materials, there is a demand for barrier laminated films that can stably exhibit higher barrier properties unaffected by temperature, humidity, etc., in order to prevent deterioration of the contents and maintain their function and properties. Multilayer barrier laminated films have also been developed, in which a barrier layer consisting of a thin film of vapor-deposited silicon dioxide or aluminum oxide and a barrier coating layer are laminated on a resin substrate. For example, Patent Document 1 discloses a laminate comprising a substrate made of a plastic material, a first vapor-deposited thin film layer provided on the substrate, a gas barrier intermediate layer provided on the first vapor-deposited thin film layer and formed by applying a coating agent containing at least a water-soluble polymer, and a second vapor-deposited thin film layer provided on the intermediate layer, and further comprising a primer layer consisting of a polyol, an isocyanate compound, and a silane coupling agent between the substrate and the first vapor-deposited thin film layer. Patent Document 2 discloses a sheet with high barrier properties comprising a synthetic resin base film, a planarization layer laminated on at least one surface of the base film, a gas barrier layer formed from an inorganic oxide or inorganic nitride laminated on the outer surface of this planarization layer, and a planarization layer formed by a sol-gel method using a composition containing other metal alkoxides and / or hydrolysates thereof, laminated on the outer surface of this gas barrier layer.

[0003] However, the multilayer barrier laminated films described above require not only increased costs due to the extra steps in the manufacturing process, such as higher raw material and equipment operating costs, but also complex tasks such as quality checks for each layer, quality control adjustments based on those checks, and history management. Therefore, there is a need for a barrier film with excellent barrier properties that can solve the manufacturing problems mentioned above without causing a decrease in productivity. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] WO2002 / 083408 publication [Patent Document 2] Japanese Patent Publication No. 2005-324469 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to solve the above-mentioned problems and provide a highly interlayer-adherent gas barrier vapor-deposited film that is easy to manufacture, has a simple layer structure, and exhibits excellent interlayer adhesion and gas barrier properties, as well as laminates, packaging materials, and packaging bodies using the same. [Means for solving the problem]

[0006] As a result of various studies, the inventors have found a specific gas barrier layer comprising a substrate layer consisting of a specific resin and layer configuration, and a metal oxide vapor-deposited layer consisting of a specific vapor deposition method and a specific composition. We found that a highly interlayered, adhesive gas barrier vapor-deposited film consisting of multiple layers achieves the above objective.

[0007] In other words, the present invention is characterized by the following: 1. A highly interlayer-adherent gas barrier vapor-deposited film having a substrate layer and a gas barrier layer, The base layer comprises a layer made of a biaxially oriented resin film containing a polypropylene resin and a PVA resin layer. The gas barrier layer has an aluminum oxide vapor-deposited layer, A highly interlayer-adherent gas barrier vapor-deposited film characterized in that the aluminum oxide vapor-deposited layer is laminated in contact with the PVA-based resin layer. 2. A highly interlayer-adherent gas barrier vapor-deposited film having a substrate layer and a gas barrier layer, The base layer comprises a layer made of a biaxially oriented resin film containing a polypropylene resin and a PVA resin layer. The gas barrier layer has an aluminum oxide vapor-deposited layer, The aluminum oxide vapor-deposited layer is laminated in contact with the PVA-based resin layer by CVD vapor deposition. A highly interlayer-adherent gas barrier vapor-deposited film characterized in that the interlayer adhesion strength between the aluminum oxide vapor-deposited layer and the PVA-based resin layer is 2N / 15mm or more. 3. The gas barrier layer further comprises a barrier protective layer. The above-described high-interlayer adhesion gas barrier vapor-deposited film is characterized in that the barrier protective layer is a layer formed from a resin composition containing silicon alkoxide and a hydroxyl group-containing water-soluble resin, and is laminated in contact with the aluminum oxide vapor-deposited layer. 4. A highly interlayer-adherent gas barrier laminate having a layer made of a highly interlayer-adherent gas barrier vapor-deposited film as described in 1 or 2 above, and a sealant layer containing a polypropylene resin, wherein the sealant layer is laminated on the surface of the highly interlayer-adherent gas barrier vapor-deposited film opposite to the substrate layer. 5. The above-described high-interlayer adhesion gas barrier laminate, characterized in that the sealant layer is a layer made of an unoriented polypropylene resin film. 6. The above-mentioned high-layer inter-layer adhesive gas barrier laminate, characterized in that the content of polypropylene resin in the high-layer inter-layer adhesive gas barrier laminate is 50% by mass or more. 7. A high interlayer adhesion gas barrier packaging material, characterized in that it is produced from the above high interlayer adhesion gas barrier laminate. 8. A high interlayer adhesion gas barrier package, characterized in that it is produced from the above high interlayer adhesion gas barrier packaging material. 9. A high interlayer adhesion gas barrier packaging bag, characterized in that it is produced from the above high interlayer adhesion gas barrier packaging material.

Advantages of the Invention

[0008] The high interlayer adhesion gas barrier vapor deposition film of the present invention is excellent in manufacturing suitability, and while having a simple layer structure, it exhibits very excellent gas barrier properties and can exhibit excellent interlayer adhesion strength between the excellent base material layer and the metal oxide vapor deposition layer. In addition, the laminate, packaging material, and package produced from the high interlayer adhesion gas barrier vapor deposition film of the present invention, while having a simple layer structure, can exhibit excellent gas barrier properties derived from the high interlayer adhesion gas barrier vapor deposition film and excellent interlayer adhesion strength between the excellent base material layer and the metal oxide vapor deposition layer.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic cross-sectional view showing an example of the layer structure of the high interlayer adhesion gas barrier vapor deposition film of the present invention. [Figure 2] It is a schematic cross-sectional view showing an example of another aspect of the layer structure of the high interlayer adhesion gas barrier vapor deposition film of the present invention. [Figure 3] It is a schematic cross-sectional view showing an example of the layer structure of the high interlayer adhesion gas barrier laminate of the present invention. [Figure 4] It is a schematic cross-sectional view showing an example of another aspect of the layer structure of the high interlayer adhesion gas barrier laminate of the present invention.

[0010] In each figure, for the sake of clarity, the size and ratio of the members may be changed or exaggerated. Also, for the sake of visibility, parts that are not necessary for explanation and repeated reference numerals may be omitted. Furthermore, in each figure, the concavo-convex portions are illustrated as patterns having distinct corners, but they may also have a rounded shape.

Embodiments for Carrying Out the Invention

[0011] The high interlayer adhesion gas barrier vapor deposition film, high interlayer adhesion gas barrier laminate, high interlayer adhesion gas barrier packaging material, high interlayer adhesion gas barrier package, and high interlayer adhesion gas barrier packaging bag of the present invention will be further described in more detail below. Although the description will be given with specific examples, the present invention is not limited thereto.

[0012] <High Interlayer Adhesion Gas Barrier Vapor Deposition Film> As shown in FIG. 1, the high interlayer adhesion gas barrier vapor deposition film of the present invention has at least a base material layer and a gas barrier layer.

[0013] [Base Material Layer] The base material layer is a layer having at least a layer made of a biaxially stretched resin film containing a polypropylene-based resin and a PVA (polyvinyl alcohol)-based resin layer.

[0014] The polypropylene-based resin is a polymer or copolymer using a propylene monomer raw material, and a known polypropylene-based resin capable of being formed into a biaxially stretched resin film for packaging material applications can be used for the base material layer of the high interlayer adhesion gas barrier vapor deposition film of the present invention. As such a polypropylene-based resin, for example, it is preferable to use a polymer of a propylene monomer or a copolymer of a propylene monomer and an alkene monomer having 2 to 8 carbon atoms, and particularly preferably a copolymer with an α-olefin (an alkene monomer having a carbon-carbon double bond at the α-position at the terminal). By using a compound having a long straight chain such as 1-hexene or 1-octene as a copolymerization raw material monomer for the α-olefin, the crystallinity, flexibility, and toughness can be modified.

[0015] The thickness of the layer made of a biaxially oriented resin film containing polypropylene resin is preferably 10 μm or more and 50 μm or less. If it is thinner than the above range, the rigidity of the base layer may be insufficient, and if it is thicker than the above range, the rigidity may become too strong, making it difficult to handle the high-adhesion gas barrier vapor-deposited film.

[0016] Various surface treatments can be applied to the surface of a layer made of a biaxially oriented resin film containing a polypropylene resin, on which a PVA resin layer is laminated. For example, pretreatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, and oxidation treatment using chemicals can be optionally performed. Alternatively, various coating layers such as a primer coating layer, undercoat layer, anchor coating layer, adhesive layer, and vapor-deposited anchor coating layer can be arbitrarily formed on the surface to create a surface treatment layer. For the various coating layers described above, resin compositions can be used in which the vehicle's main component is, for example, polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenolic resin, (meth)acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene or its copolymer or modified resin, cellulose resin, etc.

[0017] PVA-based resins are resins consisting of polymers or copolymers having a repeating unit represented by the structural formula -CH2CH(OH)- as the main backbone. There are no particular restrictions as long as the resin has the above repeating unit as the main backbone, and it may have various functional groups. For example, polyvinyl alcohol obtained by saponifying polyvinyl acetate, or ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate, can be used. The degree of saponification of PVA-based resins is preferably 80-100 mol%, more preferably 85-100 mol%, and particularly preferably 90-100 mol%. Higher degrees of saponification tend to result in higher gas barrier properties.

[0018] The thickness of the PVA resin layer is preferably 0.3 μm or more and 1.5 μm or less. If it is thinner than the above range, the effect of providing the PVA resin layer will be difficult to achieve, and if it is thicker than the above range, it will be difficult to make the thickness of the PVA resin layer uniform, and the rigidity will become too strong, making it difficult to handle the high-adhesion gas barrier vapor-deposited film.

[0019] While PVA-based resin layers can be formed by known methods, it is preferable to prepare a PVA-based resin layer with a thin and uniform thickness by applying and drying a resin composition for PVA-based resin layers onto the surface of a substrate layer.

[0020] [Gas barrier layer] The gas barrier layer is a layer having at least a metal oxide vapor deposition layer, and as shown in Figure 2, a barrier protective layer may further be provided on the surface of the metal oxide vapor deposition layer.

[0021] (Silicon oxide vapor deposition layer) Preferably, the silicon oxide vapor-deposited layer is laminated in contact with the PVA-based resin layer of the substrate layer. By laminating the silicon oxide vapor-deposited layer in contact with the PVA-based resin layer, the gas barrier properties of the gas barrier vapor-deposited film can be enhanced, and furthermore, the interlayer adhesion strength between the silicon oxide vapor-deposited layer and the PVA-based resin layer is increased, enhancing the gas barrier properties of the highly interlayer-adherent gas barrier vapor-deposited film and making delamination between the silicon oxide vapor-deposited layer and the PVA-based resin layer less likely to occur. The silicon oxide vapor deposition layer may include a vapor deposition layer made of known silicon oxide, which is used in packaging materials and is produced by a known vapor deposition method. However, the vapor deposition method is preferably CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition). In particular, it is preferable to include a silicon oxide vapor-deposited layer deposited by the CVD method. These silicon oxide vapor-deposited layers may be a single layer of one type, a multilayer structure of two or more layers, or a multilayer structure of two or more types. Furthermore, the term "silicon oxide vapor-deposited layer" above means that it contains silicon oxide as its main component, but it may also contain trace amounts of other metal components, metal oxide components, metal nitride components, metal carbides, etc. Furthermore, in the present invention, the aluminum oxide vapor-deposited layer may be laminated in contact with the PVA-based resin layer by PVD vapor deposition.

[0022] Examples of CVD methods include plasma CVD, plasma polymerization, thermal CVD, and optical CVD. Examples of CVD methods include Method D and catalytic CVD methods. Among these CVD methods, the plasma CVD method, which allows for the formation of a silicon oxide vapor-deposited layer at relatively low temperatures, is preferred. Even when the substrate layer contains a polyolefin resin with relatively low heat resistance, the deterioration of the substrate layer can be suppressed and the silicon oxide vapor-deposited layer can be formed.

[0023] Examples of PVD methods include vacuum deposition, sputtering, ion plating, ion beam-assisted deposition, and cluster ion beam deposition, but sputtering is preferred because it facilitates the vaporization of the plasma raw material.

[0024] (Barrier protective layer) The barrier protective layer is a layer laminated in contact with the silicon oxide vapor deposition layer, which physically and chemically protects and stabilizes the silicon oxide vapor deposition layer, and can also enhance the barrier properties of the high-layer adhesion gas barrier vapor deposition film. The barrier protective layer preferably has a chemical structure formed by a hydrolysis condensation reaction using a sol-gel method, in which a barrier protective resin composition containing a silicon alkoxide and a hydroxyl group-containing water-soluble resin is carried out. The barrier protective resin composition may also contain a solvent. In the present invention, a hydrolysis reaction is a chemical reaction in which water molecules react with the alkoxy group or phenoxy group of a silicon alkoxide to produce silicon hydroxide, alcohols, phenols, and hydrogen molecules. A condensation reaction is a chemical reaction in which silicon hydroxides, sometimes including hydroxyl-containing water-soluble resins, combine through a dehydration reaction to form polymers. Furthermore, a hydrolysis-condensation reaction is a chemical reaction in which the above-mentioned hydrolysis and condensation proceed in succession.

[0025] The barrier protective layer is formed by applying a barrier protective resin composition to the metal oxide vapor deposition layer, drying by heating, and, if necessary, aging by heating. Here, drying primarily aims to remove the solvent from the barrier protective resin composition, and the barrier protective resin composition can be dried at low temperatures and in a short time. The drying temperature requires the temperature at which the solvent evaporates, so it is preferably 70°C or higher and 120°C or lower, and more preferably 80°C or higher and 110°C or lower. If the temperature is lower than the above range, the drying process will be slow, and if it is higher than the above range, the barrier protective layer tends to become brittle. The drying time depends on the composition of the barrier protective resin composition, but within the above temperature range, it is preferably 5 seconds or more and 30 minutes or lower, and more preferably 10 seconds or more and 10 minutes or lower.

[0026] Furthermore, aging (baking) aims to advance the hydrolysis condensation reaction described above. There are no particular restrictions on the aging conditions; aging can be performed at temperatures below 60°C using a general coating machine and simple heating equipment. However, the reaction proceeds faster at higher temperatures, allowing for shorter aging times. The aging temperature is preferably 20°C or higher and 200°C or lower, more preferably 30°C or higher and 180°C or lower, and particularly preferably 40°C or higher and 120°C or lower. In the present invention, since the base material layer is a low heat-resistant material having a layer made of a biaxially oriented resin film containing a polyolefin resin and a PVA resin layer, a relatively low temperature, between 40°C and 60°C, is particularly preferred. If the aging period is lower than the above range, the aging process will be slow, and if it is higher than the above range, the barrier protective layer tends to become brittle. The aging period is preferably between 1 day and 70 days, and more preferably between 1 day and 5 days. In addition, water is produced as a byproduct during aging, but the amount produced is small so it does not pose a problem.

[0027] The thickness of the barrier protective layer is preferably 0.01 μm or more and 1 μm or less, and preferably 0.05 μm or more. A thickness of 0.7 μm or less is more preferable, and a thickness of 0.1 μm or more and 0.5 μm or less is particularly preferable. If the thickness is thinner than the above range, the effect of forming a barrier protective layer tends to be less effective, and if the thickness is greater than the above range, flexibility tends to be inferior. Furthermore, the barrier protective layer may consist of a single layer or multiple layers of the same or different compositions. By distributing the desired function among multiple layers, it is possible to achieve barrier properties against various gases and balance various other properties.

[0028] The formation of the barrier protective layer is preferably carried out in line, continuously with the formation of the silicon oxide deposition layer, and without exposure to the outside air. By carrying out the process continuously in line, contamination and degradation of the silicon oxide deposition layer surface are suppressed, the interlayer adhesion between the silicon oxide deposition layer and the barrier protective layer is strengthened, and the protective effect of the barrier protective layer can be enhanced.

[0029] (solvent) The solvent contained in the barrier protective resin composition may be any solvent capable of uniformly dissolving or dispersing silicon alkoxide and its hydrolysates, hydrolyzed condensate oligomers, and hydroxyl group-containing water-soluble resins. It may be water or an organic solvent, and one or more may be used. Furthermore, the solvent is preferably water-soluble, and has an octanol / water partition coefficient Log P ow However, it is preferable that it be 0.5 or less. Specific solvents include water and methanol (Log P ow :-0.77), Ethanol (Log P ow:-0.30), 1-propanol (Log P ow :0.25), 2-propanol (Log P ow Examples include 0.05), and mixtures thereof.

[0030] (Silicon alkoxide) In the present invention, the silicon alkoxide is a compound having a silicon atom and an alkoxy group bonded to the silicon atom, capable of producing silicon hydroxide after hydrolysis, preferably having two or more hydroxyl groups, and may be a monomer or an oligomer. It may also already have hydroxyl groups. Having two or more hydroxyl groups allows for the formation of a barrier protective layer by generating a continuous hydrolysis condensate via the sol-gel method.

[0031] It is also possible to use metal alkoxides other than silicon alkoxides in combination. Specific examples of metal elements include aluminum, titanium, zirconium, tin, lead, and borane. These metal elements can be used individually or in combination of two or more.

[0032] Specific examples of alkoxy groups include aliphatic alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and 3-(meth)acryloxy groups; aromatic phenoxy groups, etc., but aliphatic alkoxy groups are preferred, and among them, methoxy and ethoxy groups are more preferred. These alkoxy groups can be used individually or in combination of two or more. Silicon alkoxides or metal alkoxides may further have various functional groups, including epoxy groups, (meth)acrylic groups, amino groups, vinyl groups, and the like.

[0033] Specific examples of silicon alkoxides include trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Examples include silanes, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, or various alkoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and phenoxysilanes. Among these, tetraethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferred. The above silicon alkoxides may be used individually or as a mixture of two or more.

[0034] The content of silicon atoms derived from silicon alkoxide in the barrier protective layer is preferably 20% by mass or more and 50% by mass or less, particularly preferably 25% by mass or more and 45% by mass or less, and most preferably 30% by mass or more and 40% by mass or less. If the content is greater than the above range, the barrier protective layer tends to become brittle and the protective effect tends to be insufficient, and if the content is less than the above range, the gas barrier properties tend to decrease. Furthermore, the content of silicon atoms derived from silicon alkoxide in the total non-solvent components of the barrier protective resin composition before hydrolysis is preferably 70% by mass or more and 99% by mass or less, particularly preferably 80% by mass or more and 97% by mass or less, and most preferably 85% by mass or more and 95% by mass or less. If the content is greater than the above range, the coating properties of the barrier protective resin composition tend to be poor and the barrier protective layer tends to become brittle, and if the content is less than the above range, the protective effect tends to be weakened and the gas barrier properties tend to decrease.

[0035] (Hydroxy group-containing water-soluble resin) Hydroxyl group-containing water-soluble resins provide excellent coating properties to barrier protective resin compositions, making them less prone to cracking in the barrier protective layer and stabilizing gas barrier properties. Hydroxyl group-containing water-soluble resins exhibit excellent water solubility and good affinity with silicon alkoxides due to the presence of hydroxyl groups. In some cases, they can become part of the crosslinking matrix in the barrier protective layer, resulting in excellent film-forming properties and the ability to obtain a homogeneous barrier protective layer. The hydroxyl groups in the hydroxyl-containing water-soluble resin may be either phenolic or alcoholic hydroxyl groups, but alcoholic hydroxyl groups are preferred. The main chain structure of the molecular skeleton of the hydroxyl-containing water-soluble resin may be either an aromatic or aliphatic main chain, but aliphatic main chains are preferred because they offer superior flexibility.

[0036] The content of the hydroxyl group-containing water-soluble resin in the barrier protective layer is preferably 5% by mass or more and 35% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and most preferably 15% by mass or more and 25% by mass or less. If the value is less than the range mentioned above, the barrier protective layer tends to become brittle, and if it is more than the range mentioned above, the gas barrier properties tend to decrease. Furthermore, the content of hydroxyl group-containing water-soluble resin in the total non-solvent components of the barrier protective resin composition before hydrolysis is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 15% by mass or less. If the amount is less than the above range, the coating properties of the barrier protective resin composition tend to be poor, and the obtained The barrier protective layer tends to become brittle, and if the amount exceeds the range mentioned above, the gas barrier properties tend to decrease.

[0037] The degree of polymerization of the hydroxyl group-containing water-soluble resin is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less, and particularly preferably 1500 or more and 3000 or less. The molecular weight of the hydroxyl group-containing water-soluble resin is preferably 20,000 or more and 230,000 or less, more preferably 40,000 or more and 180,000 or less, and particularly preferably 60,000 or more and 140,000 or less. If the degree of polymerization and / or molecular weight of the hydroxyl group-containing water-soluble resin is within the above range, the coating properties of the barrier protective resin composition tend to be good, the barrier protective layer tends to have appropriate flexibility, and the protective effect tends to be high.

[0038] The average number of hydroxyl groups in one molecule of the hydroxyl group-containing water-soluble resin is preferably 2 or more, and more preferably 400 or more and 5000 or less. Specific examples of hydroxyl group-containing water-soluble resins include polyacrylic acid, polyacrylamide, polyvinyl alcohol, poly-2-hydroxymethyl methacrylate, poly-2-hydroxyethyl methacrylate, polyethylene glycol, and the like. Here, these are names of polymers of a single monomer, but copolymers in which other monomers are used in combination for modification may also be used. Furthermore, examples include linear polymers formed by the polymerization of two or more components, such as polymers of difunctional phenol compounds and difunctional epoxy compounds, and ethylene-vinyl alcohol copolymers. These may be used individually or in combination of two or more.

[0039] Among these, polyvinyl alcohol and ethylene-vinyl alcohol copolymers are preferred due to their excellent flexibility and affinity. In particular, those with a degree of saponification of 90 mol% or more and 100 mol% or less are preferred, those with a degree of saponification of 95 mol% or more and 100 mol% or less are more preferred, and those with a degree of saponification of 99 mol% or more and 100 mol% or less are most preferred. If the degree of saponification is lower than the above range, the hardness of the barrier coating layer tends to decrease. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate, and ethylene-vinyl alcohol copolymer can be obtained by saponifying ethylene-vinyl acetate copolymer.

[0040] <High-rise inter-floor adhesive gas barrier laminate> The high-adhesion gas barrier laminate of the present invention is a laminate having a layer made of the high-adhesion gas barrier vapor-deposited film of the present invention and a sealant layer containing a heat-sealable resin. The sealant layer is laminated on the surface of the high-adhesion gas barrier vapor-deposited film, on the side opposite to the substrate layer.

[0041] [Sealant layer] The heat-sealable resin contained in the sealant layer can be a known thermoplastic resin used in the sealant layer of packaging materials. Specific examples of heat-sealable resins include polyethylene-based resins such as LLDPE and LDPE; and polypropylene-based resins, but polypropylene-based resins are preferred. Polypropylene resins are obtained by polymerizing propylene monomers alone. Even if it is a mopolymer, it may be a copolymer such as a random copolymer or block copolymer obtained by copolymerizing propylene with monomers such as ethylene or butene, or a mixture thereof. Propylene homopolymers offer excellent rigidity, heat resistance, and oil resistance; random copolymers have a lower melting point than homopolymers, resulting in superior low-temperature sealing properties; and block copolymers exhibit excellent impact strength at low temperatures. Polypropylene resins offer excellent heat-sealing properties, higher heat resistance than ethylene resins, and greater resistance to retort processing. Furthermore, unstretched polypropylene films are preferred for sealant layers.

[0042] The sealant layer may be a layer laminated by extrusion coating the above-mentioned heat-sealable resin onto another layer, or it may be a layer formed by laminating the above-mentioned heat-sealable resin, which has been first made into a resin film, via an adhesive layer or the like, but it is preferable that the layer is formed after it has been first made into an unstretched resin film. In other words, it is more preferable that the sealant layer is a layer formed from an unoriented polypropylene resin film that has heat-sealing properties.

[0043] The thickness of the sealant layer is preferably 20 μm or more and 150 μm or less, more preferably 30 μm or more and 100 μm or less, and particularly preferably 30 μm or more and 80 μm or less. If it is thinner than the above range, the heat sealability tends to be poor, and if it is thicker than the above range, the flexibility tends to be poor. Furthermore, the sealant layer can consist of two or more layers of the same or different composition, allowing for a balance between barrier properties against various gases and other characteristics by dividing the intended functions among them.

[0044] Furthermore, it is preferable that the heat-sealable resin contained in the sealant layer is a resin with the same basic structure as the polyolefin resin contained in the layer made of a biaxially oriented resin film that constitutes the base layer. For example, it is preferable that both the heat-sealable resin contained in the sealant layer and the polyolefin resin contained in the layer made of a biaxially oriented resin film that constitutes the base layer contain a polypropylene resin.

[0045] Furthermore, it is more preferable that the content of the polypropylene resin of the basic framework in the high-strand-adhesion gas barrier laminate is 50% by mass or more. There is no particular upper limit, and ideally it is 100% by mass. By including the resin of the basic framework within the above range, the effect of making the high-strand-adhesion gas barrier laminate and the packaging materials and packaging bodies made therefrom easier to recycle can be obtained. Here, a resin with the same basic structure refers to a resin that has been (co)polymerized using the same raw material monomer as its main component. The copolymer components may be different, the molecular weight and softening point of the resin may be different, and the lamination method may be different. For example, the biaxially oriented resin film constituting the base layer is a non-heat-sealable biaxially oriented polypropylene resin film, and the sealant layer is a layer formed from a heat-sealable unoriented polypropylene resin film, or a heat-sealable layer laminated with polypropylene resin by extrusion coating or the like.

[0046] <Gas barrier packaging materials> The gas barrier packaging material of the present invention is a packaging material made from the gas barrier laminate of the present invention. Gas barrier packaging materials can also have intermediate layers with various functions laminated between the base layer and the sealant layer, or on the outside of the base layer, as needed.

[0047] <High-level inter-layer gas barrier packaging> The high-layer inter-layer gas barrier packaging of the present invention is a packaging made from the high-layer inter-layer gas barrier packaging material of the present invention. For example, by heat sealing, which involves heat-fusing the sealant layer of a highly interlayered gas barrier packaging material made of multilayer films, highly interlayered gas barrier packaging bodies in forms such as pillow bags, three-sided seals, four-sided seals, and gusset types can be manufactured.

[0048] <High-level inter-layer gas barrier packaging bags> The high-layer inter-layer gas barrier packaging bag of the present invention is one embodiment of the high-layer inter-layer gas barrier packaging body described above, and is a packaging bag made from the high-layer inter-layer gas barrier packaging material of the present invention. The present invention is further characterized by the following: 1. A highly interlayer-adherent gas barrier vapor-deposited film having a substrate layer and a gas barrier layer, The base layer comprises a layer made of a biaxially oriented resin film containing a polypropylene resin and a PVA resin layer. The gas barrier layer has a silicon oxide vapor-deposited layer, The silicon oxide vapor-deposited layer is laminated in contact with the PVA-based resin layer by CVD vapor deposition. A highly interlayer-adherent gas barrier vapor-deposited film characterized in that the interlayer adhesion strength between the silicon oxide vapor-deposited layer and the PVA-based resin layer is 3N / 15mm or more. 2. The CVD deposition method is characterized in that it is a plasma CVD method. The high-layer interlayer adhesion gas barrier vapor-deposited film described in item 1 above. 3. The gas barrier layer further comprises a barrier protective layer. The barrier protective layer is a layer formed from a resin composition containing silicon alkoxide and a hydroxyl group-containing water-soluble resin, and is characterized by being laminated in contact with the silicon oxide vapor-deposited layer. A highly interlayer-adherent gas barrier vapor-deposited film as described in 1 or 2 above. 4. A highly adhesive gas barrier laminate having a layer made of a highly adhesive gas barrier vapor-deposited film as described in any of 1 to 3 above, and a sealant layer containing a polypropylene resin, The sealant layer is characterized by being laminated on the surface of the high-layer-adhesion gas barrier vapor-deposited film on the side opposite to the substrate layer. High-rise inter-layer adhesive gas barrier laminate. 5. The sealant layer is characterized in that it is a layer made of an unoriented polypropylene resin film. The high-rise inter-layer gas barrier laminate described in item 4 above. 6. The polypropylene resin content in the high-layer inter-layer adhesive gas barrier laminate is 50% by mass or more. Characterized by, A high-layer inter-layer adhesive gas barrier laminate as described in 4 or 5 above. 7. A high-layer gas barrier packaging material characterized by being made from a high-layer gas barrier laminate described in any of 4 to 6 above. 8. A gas barrier packaging body characterized by being made from the gas barrier packaging material with high interlayer adhesion as described in item 7 above. 9. A gas barrier packaging bag characterized by being made from the gas barrier packaging material with high interlayer adhesion as described in item 7 above. [Examples]

[0049] <Ingredients> The main raw materials used in this example are as follows. • Base resin film 1: Biaxially oriented polypropylene film with a PVA-based resin layer (approximately 0.7 μm thick), manufactured by Mitsui Chemicals Tohcello Co., Ltd., A-OP-BH. 20 μm thick. • Base resin film 2: Biaxially oriented polypropylene film, U-1, manufactured by Mitsui Chemicals Tohcello Co., Ltd. 20 μm thick, corona treated on the bottom surface. • PVA resin 1: VC-10 manufactured by Nippon Vivaceae Co., Ltd., fully saponified polyvinyl alcohol, degree of polymerization 1000, degree of saponification 99.3 mol% or higher. • Sealant resin film 1: Unstretched polypropylene film manufactured by Toray Film Processing Co., Ltd. M, ZK-207. 70μm thick. • DL Adhesive 1: Dry laminating adhesive manufactured by Rock Paint Co., Ltd., RU-77T / H-7. • Hydroxyl group-containing water-soluble resin 1: Polyvinyl alcohol with a degree of polymerization of 2400 and a degree of saponification of 99 mol% or more.

[0050] [Preparation of base resin film 3] PVA solution 1 was prepared by mixing the following raw materials. PVA resin 1 4.7 parts by mass Water 324 parts by mass Isopropyl alcohol 17 parts by mass The PVA solution 1 obtained above was applied to the corona-treated surface of the base resin film 2, and dried at 80°C and a transport speed of 100 m / min to form a PVA-based resin layer (0.5 μm thick) and obtain the base resin film 3.

[0051] [Preparation of Barrier Protective Resin Composition 1] Solution A was prepared by mixing 7.3 g of 0.5 N hydrochloric acid as a hydrolysis accelerator with a solvent consisting of 300 g of water and 146 g of isopropyl alcohol to adjust the pH to 2.2. To this solution, 175 g of tetraethoxysilane and 9.2 g of γ-glycidoxypropyltrimethoxysilane were added as silicon alkoxides, and the mixture was mixed while cooling to 10°C. Next, solution B was prepared by mixing the following raw materials. Hydroxyl group-containing water-soluble resin 1 4.7 parts by mass Water 324 parts by mass Isopropyl alcohol 17 parts by mass Then, liquid A and liquid B were mixed in a mass ratio of 3.5:6.5 to obtain barrier protective resin composition 1.

[0052] [Reference example 1] A highly interlayer-adherent gas barrier vapor-deposited film was obtained by forming a silicon oxide vapor-deposited layer (20 nm thick) by CVD on the surface of a PVA-based resin layer of a base resin film 1, which serves as the base layer, under the following conditions, as a gas barrier layer. Conditions for forming a silicon oxide vapor-deposited layer • Power supply for cooling electrode drum: 10kW ·Vacuum degree: 5×10 -1 Pa • Conveying speed: 100 m / min • Supply gas: Hexamethyldisiloxane / Oxygen / Helium Next, DL adhesive 1 was applied to the silicon oxide vapor-deposited layer described above, dried, and a sealant resin film 1 was laminated to create a highly interlayer-adherent gas barrier laminate, and various evaluations were performed.

[0053] [Reference example 2] First, a silicon oxide vapor deposition layer was formed on the surface of the PVA-based resin layer of the base resin film 1 by CVD, following the same procedure as in Example 1. Next, barrier protective resin composition 1 was applied to the surface of the silicon oxide vapor-deposited layer, dried at 80°C at a transport speed of 100 m / min, and aged at 55°C for 3 days to obtain a highly interlayer-adherent gas barrier vapor-deposited film with a barrier protective layer (0.3 μm thick). Next, DL adhesive 1 was applied to the barrier protective layer described above, dried, and a sealant resin film 1 was laminated to create a barrier laminate with high interlayer adhesion, and the evaluation was carried out in the same manner.

[0054] [Reference example 3] By using base resin film 2 instead of base resin film 1, the base resin film 2 Except for forming a silicon oxide vapor deposition layer on the Rona-treated surface by CVD, a gas barrier laminate having a sealant layer was fabricated in the same manner as in Example 2, and evaluation was carried out in the same manner.

[0055] [Example 1] A gas barrier laminate having a sealant layer was fabricated and evaluated in the same manner as in Example 2, except that base resin film 3 was used instead of base resin film 1, and an aluminum oxide layer was formed by PVD method instead of silicon oxide deposition layer by CVD method under the following conditions. Conditions for forming an aluminum oxide vapor-deposited layer • Heating method for vacuum deposition: Reactive resistance heating method ·Vacuum degree: 8.1×10 -2 Pa • Conveying speed: 400 m / min • Oxygen gas supply: 8000 sccm

[0056] <Summary of Results> Example 1, which has a base layer consisting of a biaxially oriented resin film containing a polypropylene resin and a PVA resin layer, and a gas barrier layer consisting of an aluminum oxide vapor-deposited layer by PVD, showed good interlayer adhesion strength between the silicon oxide vapor-deposited layer and the base layer (PVA resin layer), and good gas barrier properties. Furthermore, Reference Examples 1 and 2, which have a base layer consisting of a biaxially oriented resin film containing polypropylene resin and a PVA resin layer, and a gas barrier layer consisting of a silicon oxide vapor-deposited layer produced by CVD, showed good interlayer adhesion strength between the silicon oxide vapor-deposited layer and the base layer (PVA resin layer) and good gas barrier properties. However, Reference Example 3, which does not have this layer configuration, showed inferior interlayer adhesion strength and gas barrier properties.

[0057] <Evaluation Method> [Oxygen permeability] Using an oxygen permeability measuring device (MOCON, OX-TRAN2 / 22), the test specimen was set so that the substrate layer surface faced the oxygen supply side, and the oxygen permeability was measured in accordance with JIS K 7126 under conditions of 23°C and 90% RH relative humidity.

[0058] [Water vapor transmission rate] Using a water vapor transmission rate measuring device (MOCON, PERMATRAN-W3-34G), the test specimen was set so that the substrate layer surface faced the water vapor supply side, and the water vapor transmission rate was measured in accordance with JIS K 7129 under conditions of 40°C and 90% RH relative humidity.

[0059] [Interlayer adhesion strength] The laminate was cut into strips 15 mm wide, and the interlayer adhesion strength (N / 15 mm) between the vapor-deposited film and sealant was measured using a tensile testing machine under the following conditions. Tensile test conditions Tensile speed: 50 mm / min Peeling angle: 90°

[0060] [Heat sealability] The laminate was cut into 10cm x 10cm sections, folded in half with the sealant surfaces overlapping, and a 1cm x 10cm area was heat-sealed using a heat seal tester (Tester Industries Co., Ltd.: TP-701-A) under the following conditions, leaving the ends unheat-sealed and separated into two sections. The laminate was then cut into 15mm wide strips to prepare test specimens. Then, each end of the test piece that was bifurcated was attached to a tensile testing machine, and the tensile strength (N / 15 mm) was measured under the following conditions and evaluated according to the following pass / fail criteria. Heat sealing conditions Temperature: 180 °C Pressure: 1 kgf / cm 2 Time: 1 second Tensile test conditions Tensile speed: 300 mm / min Peeling angle: 90° Pass / fail judgment ○: The tensile strength is 25 N / 15 mm or more, and it is qualified. ×: The tensile strength is less than 25 N / 15 mm, and it is unqualified.

[0061] [Bag-making property] A pouch bag with a size of 150 mm × 210 mm was produced by four-side sealing with a seal width of 10 mm from the laminate under the following conditions and evaluated according to the following pass / fail criteria. Heat sealing conditions Temperature: 180 °C Pressure: 1 kgf / cm 2 Time: 1 second Pass / fail judgment ○: The bag could be made without problems. ×: The bag could not be made.

[0062] [ [Table 1] [Explanation of symbols]

[0063] 1 High-interlayer adhesion gas barrier vapor-deposited film 2 Base material layer <c 2a Biaxially stretched resin film layer 2b PVA-based resin layer 3 Gas barrier layer 3a Silicon oxide vapor-deposited layer 3b Barrier protective layer 4 High-interlayer adhesion gas barrier laminate, high-interlayer adhesion gas barrier packaging material 5 Sealing layer

Claims

1. A highly interlayered gas barrier laminate having a base layer, a gas barrier layer, an adhesive layer, and a sealant layer in this order, The base layer comprises a layer made of a biaxially oriented resin film containing a polypropylene resin and a PVA resin layer. The polypropylene resin is a resin selected from the group consisting of polymers of propylene monomers and copolymers of propylene monomers and alkene monomers having 2 to 8 carbon atoms. The polypropylene resin content in the high-layer inter-layer adhesive gas barrier laminate is 50% by mass or more. The PVA-based resin is a polyvinyl alcohol obtained by saponifying polyvinyl acetate, or an ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate. The degree of saponification of the PVA-based resin is 85 to 100 mol%, The thickness of the layer made of the biaxially oriented resin film is 10 μm or more and 50 μm or less. The thickness of the PVA resin layer is 0.3 μm or more and 1.5 μm or less. The gas barrier layer has an aluminum oxide vapor-deposited layer, The aluminum oxide vapor-deposited layer is laminated in contact with the PVA-based resin layer by PVD vapor deposition. The interlayer adhesion strength between the aluminum oxide vapor-deposited layer and the PVA-based resin layer is 2 N / 15 mm. The gas barrier layer further comprises a barrier protective layer. The barrier protective layer is a layer formed from a resin composition containing silicon alkoxide and a hydroxyl group-containing water-soluble resin, and is laminated in contact with the aluminum oxide vapor-deposited layer. The sealant layer is a layer formed from an unoriented polypropylene resin film that has heat-sealing properties. Measurements were taken in accordance with JIS K7126, under conditions of 23°C and 90% RH relative humidity. Oxygen permeability is 0.6 cc / m³ 2 The humidity is less than or equal to day·atm, and the water vapor transmission rate measured in accordance with JIS K7129 at 40°C and 90% relative humidity is 0.8 g / m³. 2 A highly interlayered, adhesive gas barrier laminate characterized by having a gas barrier property of 1 / day or less. 。

2. It is characterized by being made from a high-layer inter-layer adhesive gas barrier laminate as described in claim 1. High-level inter-layer adhesion gas barrier packaging material.

3. A gas barrier packaging body characterized by being made from the gas barrier packaging material with high interlayer adhesion described in claim 2.

4. A gas barrier packaging bag characterized by being made from the gas barrier packaging material with high interlayer adhesion as described in claim 2.

Images