WO2024150748A1 - ガスバリア性積層体、包装容器及び包装製品 - Google Patents

ガスバリア性積層体、包装容器及び包装製品 Download PDF

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Publication number
WO2024150748A1
WO2024150748A1 PCT/JP2024/000204 JP2024000204W WO2024150748A1 WO 2024150748 A1 WO2024150748 A1 WO 2024150748A1 JP 2024000204 W JP2024000204 W JP 2024000204W WO 2024150748 A1 WO2024150748 A1 WO 2024150748A1
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Prior art keywords
gas barrier
layer
barrier laminate
coating layer
barrier coating
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Ceased
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PCT/JP2024/000204
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English (en)
French (fr)
Japanese (ja)
Inventor
歩実 田中
美季 福上
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Toppan Holdings Inc
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Toppan Holdings Inc
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Priority to JP2024570192A priority Critical patent/JPWO2024150748A1/ja
Priority to EP24741521.9A priority patent/EP4650167A4/en
Publication of WO2024150748A1 publication Critical patent/WO2024150748A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • This disclosure relates to gas barrier laminates, packaging containers, and packaging products.
  • Packaging containers such as packaging bags used for packaging food, medicines, etc. require gas barrier properties that block the intrusion of water vapor, oxygen, and other gases that can cause deterioration of the contents in order to prevent deterioration or spoilage of the contents and to maintain their functions and properties. For this reason, gas barrier laminates have traditionally been used in these packaging bags.
  • Patent Document 1 discloses a laminate having a first substrate layer, a second substrate layer, and a sealant layer in this order, in which the first substrate layer, the second substrate layer, and the sealant layer all comprise polyolefin films, in which the polyolefin film of the first substrate layer or the second substrate layer has an inorganic oxide layer and a gas barrier coating layer in this order on at least one surface, and in which the thermal shrinkage rate in the running direction (MD direction) of each of the first substrate layer, the second substrate layer, and the sealant layer after heating at 120°C for 15 minutes satisfies a specific relationship.
  • MD direction running direction
  • Patent Document 1 still has room for improvement in terms of durability and gas barrier properties after sterilization at high temperatures of 121°C or higher (hereinafter also referred to as "high retort processing").
  • the present disclosure has been made in consideration of the above problems, and aims to provide a gas barrier laminate, packaging container, and packaging product that have excellent durability and can maintain excellent gas barrier properties even after high-temperature retort processing.
  • the inventors of the present disclosure conducted intensive research to solve the above problems. As a result, they discovered that the above problems can be solved by providing an intermediate layer between the substrate layer and the barrier layer in a laminate including a substrate layer, a barrier layer including a gas barrier coating layer, and a sealant layer, and by constructing the substrate layer, intermediate layer, and sealant layer from resin films, and by making the hardness of the cross section of the gas barrier coating layer measured by nanoindentation less than a specific value, which led to the present disclosure.
  • one aspect of the present disclosure provides a gas barrier laminate comprising a base layer, an intermediate layer, a barrier layer and a sealant layer in this order, the base layer, the intermediate layer and the sealant layer being made of resin films, the barrier layer having a gas barrier coating layer, and the hardness of the cross section of the gas barrier coating layer measured by nanoindentation is less than 0.75 GPa.
  • the gas barrier laminate has excellent durability and can maintain excellent gas barrier properties even after high-temperature retort processing.
  • the inventors of the present disclosure speculate that it is due to the following reasons. That is, when a packaging container is formed using the gas barrier laminate, the sealant layer is disposed on the inside and the substrate layer is disposed on the outside. At this time, when the packaging container is subjected to high retort processing or deformation, a large stress is likely to be applied to the substrate layer.
  • the barrier layer is not directly provided on the substrate layer but is provided indirectly via an intermediate layer, the stress applied to the substrate layer is relaxed by the intermediate layer and applied to the gas barrier coating layer of the barrier layer.
  • the hardness of the gas barrier coating layer in the cross section is less than 0.75 GPa, flexibility is imparted to the gas barrier coating layer, so that even if the stress applied from the substrate layer to the gas barrier coating layer via the intermediate layer is excessive, the excessive stress is relaxed by the gas barrier coating layer. Therefore, cracks are less likely to form in the gas barrier coating layer.
  • the gas barrier coating layer is likely to be disposed in a position close to the stress center (a portion where stress is likely to concentrate) near the center of the laminate (a portion equidistant from both sides), and the hardness of the gas barrier coating layer in the cross section is less than 0.75 GPa, so that the stress applied to the gas barrier laminate is effectively alleviated. From the above, the inventors of the present disclosure speculate that the above effects can be obtained by the gas barrier laminate.
  • the hardness of the cross section of the gas barrier coating layer may be 0.1 GPa or more as measured by nanoindentation method.
  • the cross-sectional hardness of the gas barrier coating layer is 0.1 GPa or more, the heat shock resistance of the gas barrier coating layer is improved, and the gas barrier coating layer is less likely to deteriorate due to high-temperature retort treatment or the like.
  • the resin film may contain a polypropylene-based resin
  • the resin films constituting the base layer and the intermediate layer among the base layer, the intermediate layer and the sealant layer may be stretched films.
  • the resin films constituting the base layer, intermediate layer and sealant layer contain polypropylene-based resins, the recyclability of the gas barrier laminate is further improved.
  • the strength of the gas barrier laminate is further improved, so that when the gas barrier laminate is subjected to high retort treatment as a part of a packaging container or is deformed as a part of a packaging container, the stress applied to the gas barrier coating layer is alleviated, making it difficult for cracks to form in the gas barrier coating layer, and the barrier property of the gas barrier laminate is further improved.
  • the atomic ratio of silicon atoms to carbon atoms (Si/C) on the surface of the gas barrier coating layer as measured by X-ray photoelectron spectroscopy (XPS) may be less than 0.80. In this case, the durability of the gas barrier laminate can be further improved.
  • the atomic ratio of silicon atoms to carbon atoms (Si/C) on the surface of the gas barrier coating layer as measured by X-ray photoelectron spectroscopy (XPS) may be less than 0.50. In this case, the durability of the gas barrier laminate can be effectively improved.
  • the gas barrier coating layer is formed using a composition for forming a gas barrier coating layer containing a first silicon compound and a water-soluble polymer
  • the first silicon compound may be composed of at least one of a silicon alkoxide represented by the following general formula (1) and a hydrolyzate thereof: Si(OR 1 ) 4 ...(1) (In the general formula (1), R1 represents an alkyl group.)
  • the composition for forming a gas barrier coating layer further contains a second silicon compound
  • the second silicon compound may be composed of at least one of a silane coupling agent represented by the following general formula (2) and a hydrolyzate thereof: ( R2Si ( OR3 ) 3 ) n ...(2)
  • R2 represents a monovalent organic group
  • OR3 represents an alkyl group or -C2H4OCH3
  • n represents an integer of 1 or more.
  • the thickness of the gas barrier coating layer is preferably more than 50 nm and less than 700 nm. In this case, the gas barrier laminate has superior durability and can have superior gas barrier properties even after high-temperature retort treatment.
  • the barrier layer may further include an inorganic oxide layer between the intermediate layer and the gas barrier coating layer.
  • the gas barrier laminate can have an improved gas barrier property by having an inorganic oxide layer.
  • the inorganic oxide layer preferably has a thickness of more than 5 nm and less than 80 nm.
  • the gas barrier laminate has superior durability and can have superior gas barrier properties even after high-temperature retort treatment, compared with a case in which the thickness of the inorganic oxide layer is outside the above range.
  • the gas barrier laminate preferably further comprises an anchor coat layer between the intermediate layer and the inorganic oxide layer.
  • an anchor coat layer between the intermediate layer and the inorganic oxide layer.
  • the thickness of the anchor coat layer is preferably more than 50 nm and less than 300 nm.
  • the gas barrier property can be improved even after high retort treatment, compared to when the thickness of the anchor coat layer is 50 nm or less.
  • the durability of the gas barrier laminate can be improved.
  • the thickness of the anchor coat layer is less than 300 nm, the durability of the gas barrier laminate can be improved, compared to when the thickness of the anchor coat layer is 300 nm or more, and the gas barrier property can be improved even after high retort treatment.
  • Another aspect of the present disclosure provides a packaging container including the gas barrier laminate described above. Since the packaging container includes the gas barrier laminate, it has excellent durability and can have excellent gas barrier properties even after high-temperature retort treatment. Therefore, when the contents are contained in the packaging container and sealed, deterioration of the quality of the contents due to oxygen contamination can be suppressed for a long period of time. In addition, even if the packaging container is deformed into various shapes, deterioration of the gas barrier properties can be suppressed.
  • Another aspect of the present disclosure provides a packaging product comprising a packaging container as described above and a content sealed within the packaging container. Since the packaging product includes the gas barrier laminate, it has excellent durability and can maintain excellent gas barrier properties even after high-temperature retort treatment. Therefore, deterioration of the quality of the contents due to oxygen contamination can be suppressed for a long period of time. In addition, even if the packaging container of the packaging product is deformed into various shapes, deterioration of the gas barrier properties can be suppressed.
  • the present disclosure provides a gas barrier laminate, packaging container, and packaging product that has excellent durability and excellent gas barrier properties even after high-temperature retort processing.
  • FIG. 1 is a cross-sectional view showing an embodiment of a gas barrier laminate according to one aspect of the present disclosure.
  • 1 is a cross-sectional view illustrating another embodiment of a packaged product according to an aspect of the present disclosure.
  • FIG. 2 is a cross-sectional view of an embodiment of a packaging product according to another aspect of the present disclosure.
  • FIG. 1 is a cross-sectional view showing one embodiment of a gas barrier laminate according to one aspect of the present disclosure
  • Figure 2 is a cross-sectional view showing another embodiment of a gas barrier laminate according to one aspect of the present disclosure.
  • the gas barrier laminate 20 shown in FIG. 1 includes a base layer 1, an intermediate layer 2, a barrier layer 5, and a sealant layer 21 in this order.
  • the base layer 1, the intermediate layer 2, and the sealant layer 21 are made of resin films.
  • the barrier layer 5 includes, from the intermediate layer 2 side, an inorganic oxide layer 3 and a gas barrier coating layer 4.
  • the hardness of the cross section of the gas barrier coating layer 4 measured by a nanoindentation method is less than 0.75 GPa.
  • the barrier layer 5 may further include an anchor coat layer 6 between the intermediate layer 2 and the inorganic oxide layer 3, as in the gas barrier laminate 20 shown in FIG. 2.
  • the gas barrier laminate 20 may further include an adhesive layer 22 between the barrier layer 5 and the sealant layer 21.
  • This gas barrier laminate 20 has excellent durability and can maintain excellent gas barrier properties even after high-temperature retort processing.
  • the substrate layer 1, intermediate layer 2, anchor coat layer 6, inorganic oxide layer 3, gas barrier coating layer 4, adhesive layer 22 and sealant layer 21 are described in detail below.
  • the substrate layer 1 is made of a resin film and serves as a support for the gas barrier coating layer 4.
  • the resin contained in the resin film include thermoplastic resins such as polyolefin resins and polyester resins.
  • polyolefin resins include polyethylene-based resins and polypropylene-based resins.
  • polyethylene-based resins include low-density polyethylene resins (LDPE), medium-density polyethylene resins (MDPE), linear low-density polyethylene resins (LLDPE), ethylene-vinyl acetate copolymers (EVA), ethylene- ⁇ -olefin copolymers, and ethylene-(meth)acrylic acid copolymers.
  • polypropylene-based resins include homopolypropylene and propylene copolymers.
  • propylene copolymers include propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -olefin copolymers.
  • Polyester resins include polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyethylene naphthalate resin (PEN), polybutylene naphthalate resin (PBN), etc.
  • PET include virgin PET newly synthesized from raw materials such as petroleum, and recycled PET, which is regenerated PET.
  • recycled PET include PET regenerated by mechanical recycling and PET regenerated by chemical recycling. Part of the terephthalic acid in PET may be modified to phthalic acid.
  • the resin content in the resin film may be 99.5% by mass or more based on the total amount of the base material layer 1 .
  • the base layer 1 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, etc. as minor components.
  • the base layer 1 may be subjected to a surface treatment such as a plasma treatment in order to improve adhesion to a layer to be laminated thereon.
  • the substrate layer 1 may be a stretched film or a non-stretched film, but from the viewpoint of gas barrier properties, it is preferable that it is a stretched film.
  • stretched films include uniaxially stretched films and biaxially stretched films, but biaxially stretched films are preferable because they improve the heat resistance of the gas barrier laminate 20.
  • the thickness of the substrate layer 1 is not particularly limited, but may be, for example, 0.1 mm or less.
  • the thickness of the substrate layer 1 is preferably 40 ⁇ m or less, more preferably 35 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the thickness of the substrate layer 1 is 0.1 mm or less, the flexibility of the gas barrier laminate 20 is further improved, and the durability of the gas barrier laminate 20 can be further improved, compared to when the thickness of the substrate layer 1 exceeds 0.1 mm.
  • the thickness of the substrate layer 1 is preferably 10 ⁇ m or more, and more preferably 12 ⁇ m or more.
  • the intermediate layer 2 is made of a resin film.
  • the resin film constituting the intermediate layer 2 may be the same as or different from the resin film contained in the base layer 1.
  • the resin contained in the resin film include thermoplastic resins such as polyolefin resins and polyester resins.
  • polyolefin resins include polyethylene-based resins and polypropylene-based resins.
  • polyethylene-based resins examples include low-density polyethylene resins (LDPE), medium-density polyethylene resins (MDPE), linear low-density polyethylene resins (LLDPE), ethylene-vinyl acetate copolymers (EVA), ethylene- ⁇ -olefin copolymers, and ethylene-(meth)acrylic acid copolymers.
  • LDPE low-density polyethylene resins
  • MDPE medium-density polyethylene resins
  • LLDPE linear low-density polyethylene resins
  • EVA ethylene-vinyl acetate copolymers
  • ethylene- ⁇ -olefin copolymers examples include ethylene-(meth)acrylic acid copolymers.
  • polypropylene-based resins examples include homopolypropylene and propylene copolymers.
  • propylene copolymers examples include propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -
  • Polyester resins include polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polyethylene naphthalate resin (PEN), polybutylene naphthalate resin (PBN), etc.
  • PET include virgin PET newly synthesized from raw materials such as petroleum, and recycled PET, which is regenerated PET.
  • recycled PET include PET regenerated by mechanical recycling and PET regenerated by chemical recycling. Part of the terephthalic acid in PET may be modified to phthalic acid.
  • the resin content in the resin film may be 99.5% by mass or more based on the total amount of the intermediate layer 2 .
  • the intermediate layer 2 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, etc. as minor components.
  • the intermediate layer 2 may be subjected to a surface treatment such as a plasma treatment in order to improve adhesion to the layer to be laminated thereon.
  • the intermediate layer 2 may be a stretched film or a non-stretched film, but from the viewpoint of gas barrier properties, it is preferable that it is a stretched film.
  • stretched films include uniaxially stretched films and biaxially stretched films, but biaxially stretched films are preferable because they improve the heat resistance of the gas barrier laminate 20.
  • the intermediate layer 2 is also a stretched film.
  • the strength of the gas barrier laminate 20 is further improved, and when the gas barrier laminate 20 is subjected to high-temperature sterilization treatment as part of a packaging container or is deformed as part of a packaging container, the stress applied to the gas barrier coating layer 4 is alleviated, making it difficult for cracks to form in the gas barrier coating layer 4, and further improving the barrier properties of the gas barrier laminate 20.
  • the thickness of the intermediate layer 2 is not particularly limited, but may be, for example, 0.1 mm or less.
  • the thickness of the intermediate layer 2 is preferably 40 ⁇ m or less, more preferably 35 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the thickness of the intermediate layer 2 is 0.1 mm or less, the flexibility of the gas barrier laminate 20 is further improved, and the durability of the gas barrier laminate 20 can be further improved, compared to when the thickness of the intermediate layer 2 exceeds 0.1 mm.
  • the thickness of the intermediate layer 2 is preferably 10 ⁇ m or more, and more preferably 12 ⁇ m or more.
  • the anchor coat layer 6 is a layer for further improving the adhesion between the intermediate layer 2 and the inorganic oxide layer 3, and is provided between the intermediate layer 2 and the inorganic oxide layer 3.
  • the material constituting the anchor coat layer 6 is not particularly limited as long as it can improve the adhesion between the intermediate layer 2 and the inorganic oxide layer 3, but such materials include a reaction product of an organosilane or an organometallic compound, a polyol compound, and an isocyanate compound.
  • the anchor coat layer 6 can also be said to be a urethane-based adhesive layer.
  • the organosilane is, for example, a trifunctional organosilane or a hydrolyzate of a trifunctional organosilane.
  • the organometallic compound is, for example, a metal alkoxide or a hydrolyzate of a metal alkoxide.
  • the metal element contained in the organometallic compound is, for example, Al, Ti, Zr, etc.
  • the organosilane hydrolyzate and the metal alkoxide hydrolyzate each only need to have at least one hydroxyl group.
  • the polyol compound is preferably an acrylic polyol.
  • the isocyanate compound mainly functions as a crosslinking agent or a curing agent.
  • the polyol compound and the isocyanate compound may be a monomer or a polymer.
  • the thickness of the anchor coat layer 6 is not particularly limited as long as it is capable of improving the adhesion between the intermediate layer 2 and the inorganic oxide layer 3, but is preferably greater than 50 nm. In this case, the gas barrier property can be improved even after high retort treatment, compared to when the thickness of the anchor coat layer 6 is 50 nm or less. In addition, the durability of the gas barrier laminate 20 can be improved.
  • the thickness of the anchor coat layer 6 is more preferably 70 nm or more, and even more preferably 80 nm or more. By increasing the thickness of the anchor coat layer 6, the deterioration of the water vapor barrier property when an external force such as stretching is applied can be further suppressed.
  • the thickness of the anchor coat layer 6 is preferably less than 300 nm.
  • the durability of the gas barrier laminate 20 can be improved and the gas barrier property can be improved even after high retort treatment, compared to when the thickness of the anchor coat layer 6 is 300 nm or more.
  • the thickness of the anchor coat layer 6 is more preferably 200 nm or less.
  • the thickness of the anchor coat layer 6 may be 180 nm or less or 160 nm or less.
  • the inorganic oxide layer 3 is a layer containing an inorganic oxide. By including the inorganic oxide layer 3, the gas barrier laminate 20 can further improve the gas barrier property.
  • the inorganic substance constituting the inorganic oxide may be at least one atom selected from the group consisting of Si, Al, Mg, Sn, Ti, and In.
  • SiOx or AlOx silicon oxide or aluminum oxide
  • SiOx is preferable from the viewpoint of water vapor barrier property.
  • SiOx is preferable.
  • the inorganic oxide layer 3 may be composed of a single layer or multiple layers.
  • the thickness of the inorganic oxide layer 3 is not particularly limited, but is preferably greater than 5 nm. In this case, the gas barrier properties of the gas barrier laminate 20 can be improved even after high retort processing, compared to when the thickness of the inorganic oxide layer 3 is 5 nm or less. The durability of the gas barrier laminate 20 can also be improved.
  • the thickness of the inorganic oxide layer 3 is more preferably 8 nm or more, and particularly preferably 10 nm or more.
  • the thickness of the inorganic oxide layer 3 is less than 80 nm.
  • the gas barrier properties of the gas barrier laminate 20 after high retort treatment can be further improved compared to when the thickness of the inorganic oxide layer 3 is 80 nm or more. It is also possible to further improve the durability of the gas barrier laminate 20. It is more preferable that the thickness of the inorganic oxide layer 3 is 70 nm or less, and particularly preferable that it is 60 nm or less. From the viewpoint of improving the durability of the gas barrier laminate 20, the thickness of the inorganic oxide layer 3 may be 50 nm or less, 40 nm or less, 30 nm or less, 28 nm or less, or 25 nm or less.
  • the gas barrier coating layer 4 is formed from a cured product of a composition for forming a gas barrier coating layer.
  • the hardness of the gas barrier coating layer 4 in the cross section measured by nanoindentation is less than 0.75 GPa.
  • the gas barrier laminate 20 has better durability than when the hardness of the gas barrier coating layer 4 in the cross section is 0.75 GPa or more, and can have excellent gas barrier properties even after high retort treatment.
  • the hardness of the gas barrier coating layer 4 in the cross section is preferably less than 0.71 GPa, more preferably 0.60 GPa or less, even more preferably less than 0.5 GPa, and particularly preferably less than 0.35 GPa.
  • the gas barrier laminate 20 has excellent durability, and the gas barrier properties of the gas barrier laminate 20 can be further improved even after high retort treatment.
  • the cross-sectional hardness of the gas barrier coating layer 4 is preferably 0.1 GPa or more.
  • the hardness of the gas barrier coating layer 4 is more preferably 0.12 GPa or more, and even more preferably 0.13 GPa or more.
  • the hardness of the gas barrier coating layer 4 in a cross section may be 0.20 GPa or more, 0.25 GPa or more, or 0.30 GPa or more.
  • the hardness of the cross section of the gas barrier coating layer 4 is measured by a nanoindentation method, which is a measurement method in which a quasi-static indentation test is performed on a target measurement object to obtain mechanical properties of the sample.
  • a measurement sample (cross-sectional sample) is prepared as follows. That is, after corona treatment is performed on both sides of the gas barrier laminate 20, it is embedded in a visible light curable resin (Aronix LCR D-800, manufactured by Toagosei Co., Ltd.). Then, the gas barrier laminate 20 is cut perpendicularly to the lamination direction with a diamond knife (Microstar, LH) using an ultramicrotome (Leica, EM UC7).
  • the resulting cross section is finished under conditions of a cutting thickness (Feed) of 100 nm and a cutting speed (Speed) of 1 mm/s to prepare a measurement sample.
  • a cutting thickness (Feed) of 100 nm
  • a cutting speed (Speed) of 1 mm/s
  • a Hysitron TI-Premier product name
  • a Berkovich type diamond indenter manufactured by Bruker Japan Co., Ltd.
  • Measurement condition Temperature: normal temperature (25°C) Mode: Load control mode Pressing and unloading: Pressing was performed up to a load of 15 ⁇ N at a pressing speed of 1.5 ⁇ N/sec, the maximum load was maintained for 5 seconds, and then the load was unloaded at a speed of 1.5 ⁇ N/sec.
  • Measurement points A cross-sectional shape image of the gas barrier coating layer is obtained using the shape measurement function of a measuring device that scans the sample surface with an indenter, and 20 points are specified on the cross-section of the gas barrier coating layer from the shape image at intervals of 1 ⁇ m or more.
  • fused quartz is used as a standard sample to calibrate the relationship between the contact depth and contact projected area of the indenter and sample. After that, the unloading curve in the 60-95% region relative to the maximum load at the time of unloading is analyzed by the Oliver-Pharr method to calculate the hardness.
  • the atomic ratio of silicon atoms to carbon atoms (Si/C) on the surface of the gas barrier coating layer 4 measured by X-ray photoelectron spectroscopy (XPS) may be less than 0.80 or may be less than 0.75. In this case, when Si/C is less than 0.80, the durability of the gas barrier laminate 20 can be further improved.
  • the Si/C ratio on the surface of the gas barrier coating layer 4 is preferably less than 0.50. In this case, the durability of the gas barrier laminate 20 can be effectively improved. From the viewpoint of improving the adhesion between the sealant layer 21 and the gas barrier coating layer 4 , the Si/C ratio on the surface of the gas barrier coating layer 4 is preferably greater than 0.
  • the Si/C ratio at the surface of the gas barrier coating layer 4 may be 0.15 or more, 0.20 or more, 0.30 or more, or 0.40 or more.
  • the Si/C is determined by performing narrow spectrum analysis under the following measurement conditions using the following measuring equipment to obtain narrow spectra of O1s, N1s, C1s, and Si2p orbitals on the surface of the gas barrier coating layer 4, and determining elemental quantitative values (atomic %) from the respective peak areas for O, N, C, and Si elements using relative sensitivity coefficients of 1.00 eV for C1s and 0.9 eV for Si2p, and using the obtained elemental quantitative values.
  • the composition for forming a gas barrier coating layer includes, for example, a first silicon compound and a water-soluble polymer.
  • the first silicon compound is composed of at least one of a silicon alkoxide represented by the following general formula (1) and a hydrolyzate thereof. Si(OR 1 ) 4 ...(1)
  • R 1 represents an alkyl group. Examples of the alkyl group include a methyl group and an ethyl group. Among them, an ethyl group is preferable. In this case, the silicon alkoxide becomes tetraethoxysilane, which becomes relatively stable in an aqueous solvent after hydrolysis.
  • the content of the first silicon compound in the solid content is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 8% by mass or more, calculated as SiO 2.
  • the content of the first silicon compound in the solid content is 8% by mass or more, the adhesion between the gas barrier coating layer 4 and the sealant layer 21 and the inorganic oxide layer 3 after retort is further improved, compared to when the content of the first silicon compound in the solid content is less than 8% by mass.
  • the content of the first silicon compound in the solid content is preferably less than 65% by mass, more preferably 60% by mass or less, even more preferably less than 54% by mass, and particularly preferably less than 39% by mass.
  • the durability of the gas barrier laminate 20 can be further improved compared to when the content of the first silicon compound in the solid content is 65% by mass or more.
  • the gas barrier properties of the gas barrier laminate 20 can be further improved even after high retort treatment.
  • water-soluble polymers examples include polyvinyl alcohol resin, modified products thereof, and polyacrylic acid. These can be used alone or in combination of two or more. Among them, polyvinyl alcohol resin or modified products thereof is preferred as the water-soluble polymer. In this case, this composition can impart better gas barrier properties to the gas barrier laminate 20 by curing. Furthermore, even after curing, this composition can impart better flexibility to the gas barrier laminate 20, and can further improve the gas barrier properties after abuse.
  • the degree of saponification of the water-soluble polymer is not particularly limited, but from the viewpoint of improving the gas barrier properties of the gas barrier laminate 20, it is preferably 95% or more, and may be 100%.
  • the degree of polymerization of the water-soluble polymer is not particularly limited, but from the viewpoint of improving the gas barrier properties of the gas barrier laminate 20, it is preferable that the degree of polymerization is 300 or more.
  • the degree of polymerization of the water-soluble polymer is preferably 450 to 2400.
  • the content of the water-soluble polymer in the solid content is preferably more than 25% by mass, more preferably more than 27% by mass, even more preferably more than 41% by mass, and particularly preferably more than 56% by mass.
  • the durability of the gas barrier laminate 20 can be further improved compared to when the content of the water-soluble polymer in the solid content is 25% by mass or less.
  • the content of the water-soluble polymer in the solid content is preferably 92% by mass or less, more preferably 90% by mass or less, and particularly preferably 88% by mass or less.
  • the interlayer adhesion in the gas barrier laminate 20 after retort treatment can be further improved compared to when the content of the water-soluble polymer in the solid content exceeds 92% by mass.
  • composition for forming the gas barrier coating layer may further contain a second silicon compound as a curing agent.
  • the second silicon compound is not particularly limited, but is preferably composed of at least one of a silane coupling agent represented by the following general formula (2) and a hydrolyzate thereof.
  • a silane coupling agent represented by the following general formula (2)
  • R 2 represents a monovalent organic group
  • R 3 represents an alkyl group or —C 2 H 4 OCH 3 .
  • R2 and R3 may be the same or different.
  • R3s may be the same or different.
  • Examples of the monovalent organic group represented by R2 include a monovalent organic functional group containing a vinyl group, an epoxy group, a mercapto group, an amino group, or an isocyanate group. Among them, the monovalent organic functional group is preferably an isocyanate group. In this case, the composition can have better hot water resistance by curing, and it is possible to impart greater laminate strength to the gas barrier laminate 20 even after retort treatment.
  • Examples of the alkyl group represented by R3 include a methyl group and an ethyl group. Among them, a methyl group is preferable because hydrolysis is rapid.
  • n represents an integer of 1 or more.
  • n 1, the silane coupling agent represents a monomer, whereas when n is 2 or more, the silane coupling agent represents a polymer.
  • n is preferably 3.
  • the hot water resistance of the gas barrier coating layer 4 can be further improved, and it is possible to impart greater laminate strength to the gas barrier laminate 20 even after retort treatment.
  • Silane coupling agents include, for example, silane coupling agents having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; silane coupling agents having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylethyldiethoxysilane; silane coupling agents having a mercapto group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; silane coupling agents having an amino group such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; and silane coupling agents having an isocyanate group such as 3-isocyanatepropyltriethoxysilane and 1,3,5-tris(3-methoxysilylpropy
  • the content of the second silicon compound in the solid content is not particularly limited, but is preferably 1 mass% or more, more preferably 2 mass% or more, and particularly preferably 5 mass% or more.
  • the gas barrier laminate 20 can be given a greater laminate strength by curing even after retort treatment, compared to when the content of the second silicon compound in the solid content is less than 1 mass%.
  • the content of the second silicon compound in the solid content is preferably 20% by mass or less, more preferably 18% by mass or less, particularly preferably 15% by mass or less, and even more preferably less than 10% by mass.
  • the second silicon compound is less likely to bleed out and contaminate the surface, compared with the case where the content of the second silicon compound in the solid content exceeds 20% by mass.
  • the silane coupling agent is represented by the above general formula (2)
  • the content of the second silicon compound in the solid content is calculated by converting the mass of the silane coupling agent and its hydrolyzate into the mass of R 2 Si(OH) 3 .
  • the solid content may further contain known additives such as dispersants, stabilizers, viscosity adjusters, and colorants as necessary, to the extent that the gas barrier properties of the gas barrier coating layer 4 are not impaired.
  • the total content of the first silicon compound, the water-soluble polymer, and the second silicon compound in the solid content is not particularly limited, but is usually 95% by mass or more, preferably 97% by mass or more, and may be 100% by mass.
  • aqueous medium is usually used as the liquid in which the solids are dissolved or dispersed.
  • aqueous media include water, hydrophilic organic solvents, and mixtures of these.
  • hydrophilic organic solvents include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; carbitols; and nitriles such as acetonitrile. These can be used alone or in combination of two or more.
  • the aqueous medium is preferably an aqueous medium consisting of water alone or an aqueous medium containing water as the main component.
  • the water content in the aqueous medium is preferably 70% by mass or more, and more preferably 80% by mass or more.
  • the thickness of the gas barrier coating layer 4 is not particularly limited, but is preferably greater than 50 nm.
  • the gas barrier laminate 20 has better durability and can have better gas barrier properties even after high-temperature retort treatment, compared to when the thickness of the gas barrier coating layer 4 is 50 nm or less.
  • the thickness of the gas barrier coating layer 4 is more preferably 100 nm or more, even more preferably 200 nm or more, and particularly preferably 250 nm or more.
  • the thickness of the gas barrier coating layer 4 is preferably less than 700 nm. Compared with a case where the thickness of the gas barrier coating layer 4 is 700 nm or more, the gas barrier laminate 20 has superior durability and can have superior gas barrier properties even after high-temperature retort treatment.
  • the thickness of the gas barrier coating layer 4 is more preferably 500 nm or less, and particularly preferably 400 nm or less.
  • the adhesive that is the material for forming the adhesive layer 22 may be, for example, an adhesive containing a resin such as a polyester-isocyanate resin, a urethane resin, or a polyether resin.
  • the adhesive may or may not further contain a solvent, but preferably does not contain one.
  • the adhesive does not contain a solvent, when heat sealing the gas barrier laminate 20, the heat conduction from the heat seal bar is improved, making it possible to reduce the sealing time and temperature, and making it possible to suppress the occurrence of wrinkles and the like due to heat sealing. Furthermore, since the adhesive does not contain a solvent, it is possible to reduce the amount of residual solvent in the gas barrier laminate 20.
  • the adhesive when the adhesive contains a solvent, the solvent in the adhesive is not sufficiently removed by evaporation and remains in the gas barrier laminate 20, which may leave an odor due to the residual solvent. In contrast, when the adhesive does not contain a solvent, it is possible to further reduce the amount of residual solvent in the adhesive layer 2, thereby reducing the amount of residual solvent in the gas barrier laminate 20 and suppressing the generation of odor. Furthermore, since the adhesive does not contain a solvent, the working environment can be improved when producing the gas barrier laminate 20 . Furthermore, since the adhesive does not contain a solvent, the adhesive layer 2 can be formed thin. Therefore, the proportion of mono-materials in the gas barrier laminate 20 can be increased. When the gas barrier laminate 20 is used for retort applications, a two-component curing urethane adhesive that is resistant to retort treatment can be preferably used.
  • Methods for forming and laminating the adhesive layer 22 include known methods such as the dry lamination method and the non-solvent lamination method.
  • the sealant layer 21 is made of a resin film.
  • the resin contained in the resin film may be, for example, a thermoplastic resin such as a polyolefin resin.
  • polyolefin resins include polyethylene-based resins and polypropylene-based resins.
  • polyethylene-based resins include low-density polyethylene resins (LDPE), medium-density polyethylene resins (MDPE), linear low-density polyethylene resins (LLDPE), ethylene-vinyl acetate copolymers (EVA), ethylene- ⁇ -olefin copolymers, and ethylene-(meth)acrylic acid copolymers.
  • LDPE low-density polyethylene resins
  • MDPE medium-density polyethylene resins
  • LLDPE linear low-density polyethylene resins
  • EVA ethylene-vinyl acetate copolymers
  • ethylene- ⁇ -olefin copolymers ethylene-(meth)acrylic acid copoly
  • polypropylene-based resins include homopolypropylene and propylene copolymers.
  • propylene copolymers include propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -olefin copolymers.
  • the resin content in the resin film may be 99.5 mass % or more based on the total amount of the sealant layer 21 .
  • the sealant layer 21 may contain additives such as antistatic agents, ultraviolet absorbers, plasticizers, lubricants, etc. as minor components.
  • the intermediate layer 2 may be subjected to a surface treatment such as a plasma treatment in order to improve adhesion to the layer to be laminated thereon.
  • the material of the sealant layer 21 can be appropriately selected from the above-mentioned thermoplastic resins depending on the intended use and temperature conditions such as boiling and retort treatment.
  • the resin films constituting the base layer 1 and intermediate layer 2 contain a polypropylene-based resin
  • the resin film constituting the sealant layer 21 also contains a polypropylene-based resin.
  • the resin films constituting the base layer 1, intermediate layer 2, and sealant layer 21 contain a polypropylene-based resin, the recyclability of the gas barrier laminate 20 is further improved.
  • the resin film that constitutes the sealant layer 21 may be a stretched film or a non-stretched film, but a non-stretched film (e.g., CPP) is preferred from the viewpoint of lowering the melting point and making heat sealing easier.
  • a non-stretched film e.g., CPP
  • the thickness of the sealant layer 21 is determined appropriately depending on the mass of the contents and the shape of the packaging bag, and is not particularly limited, but is preferably 30 to 150 ⁇ m from the viewpoint of the flexibility and adhesiveness of the gas barrier laminate 20.
  • the intermediate layer 2 is prepared.
  • an anchor coat layer 6 is formed on one surface of the intermediate layer 2 to obtain a first laminate.
  • the anchor coat layer 6 is formed by applying an anchor coat layer forming composition for forming the anchor coat layer 6 onto one surface of the intermediate layer 2, and then heating and drying the composition.
  • the heating temperature is, for example, 50 to 120° C.
  • the heating time is, for example, about 10 seconds to 10 minutes.
  • the inorganic oxide layer 3 is formed on the anchor coat layer 6 to obtain a second laminate.
  • the inorganic oxide layer 3 can be formed by a vacuum film formation method.
  • the vacuum film formation method include physical vapor deposition and chemical vapor deposition.
  • the physical vapor deposition method include vacuum deposition, sputter deposition, and ion plating.
  • the vacuum deposition method is particularly preferably used.
  • the vacuum deposition method include resistance heating vacuum deposition, EB (Electron Beam) heating vacuum deposition, and induction heating vacuum deposition.
  • Examples of the chemical vapor deposition method include thermal CVD, plasma CVD, and photo CVD.
  • a gas barrier coating layer 4 is formed on the inorganic oxide layer 3 of the second laminate.
  • the gas barrier coating layer 4 can be formed, for example, by applying a composition for forming a gas barrier coating layer onto the inorganic oxide layer 3 and curing the resulting coating film.
  • curing the coating film specifically means curing the solid content contained in the coating film. Curing of the solid content means that the first silicon compound and the water-soluble polymer, or the first silicon compound, the water-soluble polymer, and the second silicon compound in the solid content react with each other to be integrated.
  • a known method can be used to apply the composition for forming a gas barrier coating layer.
  • Specific examples of the application method include wet film formation methods such as gravure coating, dip coating, reverse coating, wire bar coating, and die coating.
  • the gas barrier coating layer 4 can be obtained, for example, by carrying out a first drying step in which the coating film is heated and dried by infrared rays, and then carrying out a second drying step in which the coating film is heated, cured, and dried in an oven.
  • the reason for drying the coating film by infrared rays before heating it in the oven is mainly to prevent surface roughening, and also to apply a uniform amount of heat to the entire coating film in advance so that the entire coating film dries uniformly.
  • drying in an oven is an excellent means for drying and curing a coating film, drying starts from the surface of the coating film, so that a concentration gradient of the solvent is likely to occur in the thickness direction of the coating film.
  • infrared drying can dry the coating film uniformly in its thickness direction by infrared rays, and therefore, by drying the coating film by infrared rays prior to drying in an oven, the above-mentioned skinning is less likely to occur, heating spots are less likely to occur, and the hardness of the cross section of the gas barrier coating layer 4 is more likely to be reduced.
  • Drying with infrared rays can be carried out using an infrared dryer such as an infrared heater (far-infrared heater).
  • the conditions for the infrared heater can be, for example, a central wavelength of 3 to 10 ⁇ m (far-infrared region), a ceramic temperature of 180 to 250° C., and an emissivity of 0.90 to 0.98. Any of far-infrared, mid-infrared, and near-infrared rays can be used as the infrared rays, but far-infrared rays are preferred from the viewpoint of applying a uniform amount of heat to the coating film.
  • the drying temperature by infrared rays can be 40° C. or higher, and preferably 50° C. or higher, from the viewpoint of providing a sufficient amount of heat to the entire coating film.
  • the drying temperature can be 70° C. or lower, and preferably 60° C. or lower, from the viewpoint of suppressing shrinkage of the gas barrier coating layer 4.
  • the drying temperature is the temperature of the coating film measured using a temperature indicating material (heat label manufactured by Micron Corporation). From the same viewpoint as above, the drying time can be set to 3 seconds or more, and is preferably 5 seconds or more, and can be set to 15 seconds or less, and is preferably 10 seconds or less.
  • the heating temperature and heating time in the oven are set so as to suppress deformation (e.g., thermal shrinkage) of the substrate layer 1 and to simultaneously harden the solid content in the composition for forming a gas barrier coating layer and remove the liquid such as the aqueous medium.
  • the heating temperature is 50° C. or higher, preferably 60° C. or higher, and more preferably 80° C. or higher, from the viewpoint of hardening the solid content in the composition for forming a gas barrier coating layer and removing the liquid such as the aqueous medium.
  • the heating temperature is 120° C. or lower, from the viewpoint of suppressing deformation (e.g., thermal shrinkage) of the substrate layer 1, but is preferably 110° C. or lower.
  • the heating time is preferably 3 seconds or more, more preferably 5 seconds or more, and even more preferably 10 seconds or more, and is preferably 10 minutes or less, more preferably 5 minutes or less, and even more preferably 3 minutes or less.
  • a barrier layer 5 consisting of an anchor coat layer 6, an inorganic oxide layer 3, and a gas barrier coating layer 4 is formed on the intermediate layer 2, and a third laminate is obtained.
  • the base material layer 1 is prepared. Then, this base material layer 1 is attached to the surface of the intermediate layer 2 of the third laminate on which the barrier layer 5 is not formed, for example, by a dry lamination method. In this way, a fourth laminate is obtained.
  • a sealant layer 21 is attached to the surface of the gas barrier coating layer 4 of the fourth laminate, for example, using an adhesive layer forming composition.
  • the base layer 1 may be bonded to the intermediate layer 2 in advance before the anchor coat layer 6 is formed on the intermediate layer 2 .
  • Fig. 3 is a cross-sectional view showing one embodiment of the packaging product of the present disclosure.
  • a packaged product 40 includes a packaging container 30 and a content C sealed in the packaging container 30.
  • the packaging container 30 shown in Fig. 3 is obtained by using a pair of gas barrier laminates 20 and heat-sealing the peripheral portions of the gas barrier laminates 20 with the sealant layers 21 facing each other. Note that the adhesive layer 22 of the gas barrier laminates 20 is omitted in Fig. 3.
  • This packaging product 40 includes a packaging container 30, has excellent durability, and is capable of maintaining excellent gas barrier properties even after high-temperature retort processing. This makes it possible to prevent deterioration of the quality of the contents C due to oxygen contamination over a long period of time. In addition, even if the packaging container 30 of the packaging product 40 is deformed into various shapes, deterioration of the gas barrier properties can be prevented.
  • the packaging container 30 can also be obtained by folding one gas barrier laminate 20 and heat sealing the periphery of the gas barrier laminate 20 with the sealant layers 21 facing each other.
  • Examples of the packaging container 30 include packaging bags, laminated tube containers, and liquid paper containers.
  • Contents C are not particularly limited, and examples of contents C include food, liquids, medicines, electronic parts, etc.
  • a gas barrier laminate comprising a base layer, an intermediate layer, a gas barrier coating layer, and a sealant layer in this order, wherein the base layer, the intermediate layer, and the sealant layer are made of resin films, and the hardness of the cross section of the gas barrier coating layer, as measured by a nanoindentation method, is less than 0.75 GPa.
  • the hardness of the cross section of the gas barrier coating layer is 0.1 GPa or more as measured by a nanoindentation method.
  • the gas barrier laminate according to [11], wherein the thickness of the anchor coat layer is more than 50 nm and less than 300 nm.
  • a packaging container comprising the gas barrier laminate according to any one of [1] to [12].
  • a packaging product comprising the packaging container according to [13] and a content sealed in the packaging container.
  • Coating solutions 1 to 5 serving as compositions for forming gas barrier coating layers used in the examples and comparative examples were prepared as follows.
  • Coating Liquid 1 The following solutions A to C were mixed to obtain coating solution 1.
  • Coating solution 1 was prepared so that the mass ratio of tetraethoxysilane (also referred to as "TEOS”, calculated as SiO2 ), polyvinyl alcohol (also referred to as "PVA”), and isocyanurate silane (calculated as R2Si (OH) 3 ) was 68/27/5, assuming that the solid content was 100.
  • TEOS tetraethoxysilane
  • PVA polyvinyl alcohol
  • isocyanurate silane calculated as R2Si (OH) 3
  • Solution A 17.9 g of TEOS (product name: KBE04, solid content: 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) as a first silicon compound, 10 g of methanol (manufactured by Kanto Chemical Co., Ltd.), and 72.1 g of 0.1 N hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) were mixed, and the resulting mixture was stirred for 30 minutes to hydrolyze TEOS (5 mass% ( SiO2 equivalent) hydrolyzed solution of TEOS).
  • Solution B a 5% by mass aqueous solution of PVA (product name: Kuraray Poval 60-98, manufactured by Kuraray Co., Ltd.).
  • SC agent silane coupling agent
  • Coating liquid 2 The above-mentioned solutions A to C were mixed to obtain coating solution 2.
  • Coating solution 2 was prepared so that the mass ratio of TEOS ( SiO2 equivalent value), PVA, and isocyanurate silane ( R2Si (OH) 3 equivalent value) was 54/41/5 when the solid content was 100.
  • Coating liquid 3 (Coating liquid 3) The above-mentioned solutions A to C were mixed to obtain coating solution 3. Coating solution 3 was prepared so that the mass ratio of TEOS ( SiO2 equivalent value), PVA, and isocyanurate silane ( R2Si (OH) 3 equivalent value) was 39/56/5 when the solid content was 100.
  • Coating liquid 4 The above-mentioned solutions A to C were mixed to obtain coating solution 4.
  • Coating solution 4 was prepared so that the mass ratio of TEOS ( SiO2 equivalent value), PVA, and isocyanurate silane ( R2Si (OH) 3 equivalent value) was 8/87/5 when the solid content was 100.
  • Coating Liquid 5 Coating Liquid 5
  • Coating solution 5 was prepared so that the mass ratio of TEOS ( SiO2 equivalent value), PVA, and isocyanurate silane ( R2Si (OH) 3 equivalent value) was 65/25/10 when the solid content was taken as 100.
  • the composition for forming the anchor coat layer was prepared as follows. Acrylic polyol and tolylene diisocyanate were mixed so that the number of NCO groups in tolylene diisocyanate was equal to the number of OH groups in the acrylic polyol, and the mixture was diluted with ethyl acetate so that the solid content (total amount of acrylic polyol and tolylene diisocyanate) was 5 mass%.
  • ⁇ -(3,4 epoxycyclohexyl)trimethoxysilane was further added to the diluted mixture so that the amount was 5 parts by mass relative to 100 parts by mass of the total amount of acrylic polyol and tolylene diisocyanate, and these were mixed to prepare a composition for forming an anchor coat layer (anchor coating agent).
  • Example 1 a polypropylene resin film having a thickness of 20 ⁇ m (product name "U-1", biaxially oriented film: OPP, manufactured by Mitsui Chemicals Tocello Co., Ltd.) was prepared as an intermediate layer. Next, the composition for forming the anchor coat layer prepared as described above was applied to one side of the polypropylene resin film by gravure coating to form a coating film. The coating film was then heated at 120°C for 10 seconds and dried to form an anchor coat layer (AC layer) having a thickness of 150 nm.
  • AC layer anchor coat layer having a thickness of 150 nm.
  • a SiOx film (inorganic oxide layer) was formed to a thickness of 20 nm on the anchor coat layer of the first laminate obtained as described above.
  • the SiOx film was formed by evaporating silicon dioxide by electron beam heating using an electron beam heating vacuum deposition device.
  • the coating liquid 1 was applied onto the SiOx film to form a coating film.
  • the coating film thus formed was dried (IR dried) by far-infrared (IR) heating using a far-infrared heater (manufactured by Yamato Scientific Co., Ltd., product name: DIR631) at a set temperature of 60°C for 10 seconds.
  • the conditions of the far-infrared heater were a central wavelength of 6 ⁇ m, a ceramic temperature of 203°C, and an emissivity of 0.93.
  • the coating film dried by IR drying was further heated and dried in an oven at 100°C for 30 seconds to form a gas barrier coating layer having a thickness of 300 nm.
  • a barrier layer consisting of an anchor coat layer, an inorganic oxide layer and a gas barrier coating layer was formed on the intermediate layer to obtain a first laminate.
  • the heating was performed so that the TEOS, PVA and isocyanurate silane constituting the solid content in the coating liquid 1 were cured to form a cured body, while the liquid in the coating liquid 1 was removed.
  • the Si/C ratio was determined for the surface of the gas barrier coating layer of the first laminate obtained in this manner by the method described below. The results are shown in Table 1.
  • a polypropylene resin film having a thickness of 20 ⁇ m (product name "U-1", biaxially oriented film: OPP, manufactured by Mitsui Chemicals Tocello Co., Ltd.) was prepared as a substrate layer. Then, this polypropylene resin film was bonded by dry lamination using a two-component curing urethane adhesive (product name "A525/A52") to the side of the intermediate layer of the first laminate on which the barrier layer was not formed, to obtain a second laminate.
  • a 60 ⁇ m-thick unstretched polypropylene film (product name "Torayfan ZK207", manufactured by Toray Industries, Inc.) was attached as a sealant layer to the gas barrier coating layer of the second laminate by dry lamination using a two-component curing urethane adhesive (product name "A525/A52").
  • Examples 2 to 11 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer, the thickness of the inorganic oxide layer, the type of coating liquid used to form the gas barrier coating layer, the hardness of the gas barrier coating layer, the Si/C ratio of the gas barrier coating layer, and the thickness of the gas barrier coating layer were as shown in Table 1.
  • Example 12 A gas barrier laminate was obtained in the same manner as in Example 1, except that an AlO x film (inorganic oxide layer) was formed on the anchor coat layer, and the type of coating liquid used to form the gas barrier coating layer, the hardness of the gas barrier coating layer, and the Si/C ratio of the gas barrier coating layer were as shown in Table 2.
  • the AlO x film was formed by introducing oxygen to a pressure of 1.2 ⁇ 10 ⁇ 2 Pa while evaporating an aluminum ingot by electron beam heating using an electron beam heating type vacuum deposition apparatus.
  • Example 13 A gas barrier laminate was obtained in the same manner as in Example 1, except that a solventless adhesive was used as the adhesive for bonding the gas barrier coating layer and the sealant layer.
  • Example 14 A gas barrier laminate was obtained in the same manner as in Example 3, except that a solventless adhesive was used as the adhesive for bonding the gas barrier coating layer and the sealant layer.
  • Example 15 A gas barrier laminate was obtained in the same manner as in Example 3, except that the thickness of the inorganic oxide layer was as shown in Table 2.
  • a first laminate was prepared in the same manner as in Example 1, except that the thickness of the anchor coat layer, the type of coating liquid used to form the gas barrier coating layer, the hardness of the gas barrier coating layer, and the Si/C of the gas barrier coating layer were as shown in Table 2.
  • a polypropylene resin film having a thickness of 20 ⁇ m (product name "U-1", biaxially oriented film: OPP, manufactured by Mitsui Chemicals Tocello Co., Ltd.) was prepared as a substrate layer. Then, this polypropylene resin film was attached to the surface of the gas barrier coating layer of the first laminate by dry lamination using a two-component curing urethane adhesive (product name "A525/A52").
  • a 60 ⁇ m-thick unstretched polypropylene film (product name "Torayfan ZK207", manufactured by Toray Industries, Inc.) was attached as a sealant layer to the surface of the intermediate layer on which the barrier layer was not formed, using a dry lamination method with a two-component curing urethane adhesive (product name "A525/A52") interposed therebetween.
  • Example 2 A gas barrier laminate was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer, the type of coating liquid used to form the gas barrier coating layer, the hardness of the gas barrier coating layer, and the Si/C of the gas barrier coating layer were as shown in Table 2.
  • Example 5 A gas barrier laminate was obtained in the same manner as in Example 1, except that when forming the gas barrier coating layer, the coating film of Coating Liquid 1 was not IR dried, but was only heated and dried in an oven, and the hardness and Si/C of the gas barrier coating layer were as shown in Table 2.
  • Comparative Example 6 A gas barrier laminate was obtained in the same manner as in Comparative Example 4, except that a solventless adhesive was used as the adhesive for bonding the gas barrier coating layer and the sealant layer.
  • the Si/C ratio on the surface of the gas barrier coating layer of the first laminate obtained in the Examples or Comparative Examples was determined as follows. That is, the Si/C ratio was determined by narrow analysis using the following measuring equipment under the following measuring conditions. Specifically, narrow spectra of O1s, N1s, C1s, and Si2p orbitals were obtained from the surface of the gas barrier coating layer of the first laminate, and quantitative elemental values (atomic %) were calculated from the peak areas of O, N, C, and Si using relative sensitivity coefficients of 2.28 eV for O1s, 1.61 eV for N1s, 1.00 eV for C1s, and 0.9 eV for Si2p.
  • the Si/C ratio on the surface of the gas barrier coating layer was determined.
  • ⁇ Measurement conditions (spectrum collection conditions)> Incident X-ray: MgK ⁇ (monochromatic X-ray, h ⁇ 1253.6eV)
  • the hardness of the cross section of the gas barrier coating layer of the gas barrier laminate obtained in the Examples or Comparative Examples was measured by the nanoindentation method as follows. Measurement samples (cross-sectional samples) were prepared as follows. That is, after corona treatment was performed on both sides of the gas barrier laminate, it was embedded in a visible light curable resin (Aronix LCR D-800, manufactured by Toagosei Co., Ltd.). Then, the gas barrier laminate was cut perpendicular to the lamination direction with a diamond knife (Microstar, LH) using an ultramicrotome (Leica, EM UC7).
  • a visible light curable resin Aronix LCR D-800, manufactured by Toagosei Co., Ltd.
  • the resulting cross section was finished under the conditions of a cutting thickness (Feed) of 200 nm and a cutting speed (Speed) of 1 mm/s to prepare a measurement sample.
  • a cutting thickness (Feed) of 200 nm
  • a cutting speed (Speed) of 1 mm/s
  • a Hysitron TI-Premier product name
  • a Berkovich type diamond indenter manufactured by Bruker Japan Co., Ltd. was used as the indenter.
  • the measurement conditions were as follows.
  • Measurement condition Temperature: normal temperature (25°C) Mode: Load control mode
  • Indentation and unloading Indentation was performed up to a load of 15 ⁇ N at an indentation speed of 1.5 ⁇ N/sec, and then the maximum load was maintained for 5 seconds, after which unloading was performed at a speed of 1.5 ⁇ N/sec.
  • Measurement points A shape image of the cross section of the gas barrier coating layer was obtained using the shape measurement function of the measuring device that scans the sample surface with an indenter, and 20 points were specified on the cross section of the gas barrier coating layer at intervals of 1 ⁇ m or more from the shape image.
  • the cylinder was then bent by repeatedly gripping both ends of the cylinder, twisting it by 440 degrees with an initial gripping distance of 175 mm and a stroke of 87.5 mm, and repeating this reciprocating motion 10 times at a speed of 40 times/min.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2024/000204 2023-01-11 2024-01-09 ガスバリア性積層体、包装容器及び包装製品 Ceased WO2024150748A1 (ja)

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