WO2022220200A1 - ガスバリアフィルム、包装材及び包装袋 - Google Patents

ガスバリアフィルム、包装材及び包装袋 Download PDF

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Publication number
WO2022220200A1
WO2022220200A1 PCT/JP2022/017406 JP2022017406W WO2022220200A1 WO 2022220200 A1 WO2022220200 A1 WO 2022220200A1 JP 2022017406 W JP2022017406 W JP 2022017406W WO 2022220200 A1 WO2022220200 A1 WO 2022220200A1
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Prior art keywords
layer
gas barrier
resin
group
barrier film
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Ceased
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PCT/JP2022/017406
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English (en)
French (fr)
Japanese (ja)
Inventor
健 西川
歩実 田中
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Toppan Inc
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Toppan Inc
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Priority to JP2023514633A priority Critical patent/JPWO2022220200A1/ja
Priority to EP22788125.7A priority patent/EP4324644A4/en
Publication of WO2022220200A1 publication Critical patent/WO2022220200A1/ja
Priority to US18/377,676 priority patent/US20240034037A1/en
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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • 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
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2255/26—Polymeric 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
    • B32B2307/70—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • 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
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/387—Materials used as gas barriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present disclosure relates to gas barrier films, packaging materials, and packaging bags. Specifically, the present disclosure relates to material recyclable gas barrier films, packaging materials, and packaging bags.
  • a resin substrate As a gas barrier film used as a packaging material for foods, pharmaceuticals, etc., a resin substrate, a vacuum film formation layer, and a coating layer provided on the opposite side of the vacuum film formation layer to the resin substrate are used.
  • a film comprising such a film is known (for example, Patent Literature 1).
  • Patent Document 1 Based on the disclosure of Patent Document 1, when trying to realize an all-polyolefin monomaterial package with good recyclability, it is difficult to achieve both simplification of the layer structure and maintenance of gas barrier properties. In order to solve various problems in the realization of mono-material packages, it is necessary to develop a gas barrier film specialized for the solution.
  • the inventors investigated a polyolefin gas barrier film that is material recyclable, has a simple layer structure that can be manufactured in fewer steps than before, and yet has the desired gas barrier properties.
  • the present inventors have found that the above object can be achieved by forming a vacuum deposition layer after providing a specific underlayer on a resin substrate, and have completed the gas barrier film of the present disclosure.
  • the gas barrier film according to one aspect of the present disclosure includes a resin base material, a base layer, and a vacuum deposition layer, the resin base material containing a polyolefin resin, and the base layer being formed from an acid group-containing polyurethane and a polyamine. Contains polyurethane resin that
  • the gas barrier property is lower than that of a polyester layer such as polyethylene terephthalate. Therefore, an underlying layer and a vacuum deposition layer are formed on a substrate to improve gas barrier properties, but it is still difficult to obtain sufficient gas barrier properties.
  • a predetermined gas barrier property is ensured by forming a base layer and a vacuum deposition layer on a polyolefin base material, and further providing a coating layer thereon.
  • the base layer is formed using a specific material, it is composed of the resin base material, the base layer, and the vacuum deposition layer, that is, the coating layer is not essential. Sufficient gas barrier property can be secured by the structure. It can be said that the gas barrier film of the present disclosure can achieve both simplification of the layer structure and maintenance of gas barrier properties.
  • the resin substrate may include a copolymer layer or a terpolymer layer on the surface on the underlayer side.
  • the polyurethane resin may have an aromatic ring.
  • the vacuum deposition layer may contain at least one selected from the group consisting of metals, oxides, nitrides and oxynitrides of metals.
  • a packaging material according to one aspect of the present disclosure is obtained by laminating the gas barrier film and the heat-sealable polyolefin film via an adhesive layer.
  • a packaging bag according to one aspect of the present disclosure is formed from the above packaging material.
  • the present disclosure it is possible to provide a polyolefin-based gas barrier film that achieves both simplification of the layer structure and maintenance of gas barrier properties. Moreover, according to the present disclosure, it is possible to provide a packaging material and a packaging bag using the gas barrier film.
  • FIG. 1 is a cross-sectional view showing one aspect of the gas barrier film according to the present disclosure.
  • FIG. 2 is a cross-sectional view showing one aspect of the packaging material according to the present disclosure.
  • FIG. 1 is a cross-sectional view showing one aspect of the gas barrier film according to the present disclosure.
  • a gas barrier film 10 of the present disclosure includes a resin substrate 1 , a base layer 2 and a vacuum deposition layer 3 .
  • the gas barrier film 10 may further include a protective layer that protects the vacuum deposition layer 3 .
  • the resin substrate contains polyolefin resin.
  • a resin base material is a base material (polyolefin film) for forming a vacuum deposition layer.
  • Examples of the polyolefin resin that constitutes the resin substrate include polyethylene and polypropylene.
  • high-density polyethylene can be mentioned when considering vapor deposition processing, printing processing, bag-making processing, filling suitability, etc.
  • high-density polyethylene HDPE
  • MDPE medium-density polyethylene
  • LDPE low-density polyethylene
  • MDPE medium-density polyethylene
  • a multi-layer construction film such as high density polyethylene (HDPE) may be used as the resin substrate.
  • Polypropylene includes oriented polypropylene (OPP). When used as a base film for packaging, homopolymer polypropylene is preferred.
  • OPP oriented polypropylene
  • the resin substrate includes an ethylene-based or propylene-based copolymer or terpolymer layer as a skin layer on the surface of a polyethylene or polypropylene layer (homopolymer layer) as a core layer.
  • the resin substrate may comprise a propylene and ethylene copolymer layer on a polypropylene surface, a terpolymer layer of propylene, ethylene and butene, and the like.
  • the copolymer layer and terpolymer layer tend to improve the adhesion and sealability between the layers that make up the packaging material.
  • These layers also contain a polyolefin resin, and from the viewpoint of sufficiently improving adhesion and sealing properties as a skin layer, the content of monomer units based on olefins is It is preferably more than 50% by mass, more preferably 75% by mass or more, and even more preferably 90% by mass or more.
  • copolymer examples include ethylene-based resins such as ethylene-vinyl acetate copolymer (EVA), ethylene- ⁇ -olefin copolymer, ethylene-(meth)acrylic acid copolymer; propylene-ethylene random copolymer, propylene- Copolymers such as polypropylene resins such as ethylene block copolymers and propylene- ⁇ -olefin copolymers are included.
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- ⁇ -olefin copolymer ethylene-(meth)acrylic acid copolymer
  • propylene-ethylene random copolymer propylene- Copolymers
  • polypropylene resins such as ethylene block copolymers and propylene- ⁇ -olefin copolymers are included.
  • the terpolymer may be a copolymer having monomer units based on the monomers constituting the copolymer and monomer units based on monomers other than the monomers.
  • the resin base material when the resin base material includes a core layer and a skin layer, the resin base material can be formed by co-extruding a homopolymer layer as the core layer and a copolymer or terpolymer layer as the skin layer.
  • a homopolymer layer as the core layer
  • a copolymer or terpolymer layer as the skin layer.
  • copolymer or terpolymer OPP may be used as the skin layer from the viewpoint of interlayer adhesion.
  • the polyolefin film that constitutes the resin substrate may be a stretched film or an unstretched film.
  • the polyolefin film may be a stretched film.
  • the packaging material can be more suitably used for hot filling, boiling treatment, retort treatment, and other hot water treatments.
  • the stretching method is not particularly limited, and any method such as inflation stretching, uniaxial stretching, or biaxial stretching may be used as long as a film with stable dimensions can be supplied.
  • the thickness of the resin base material is not particularly limited.
  • the thickness may be 6 to 200 ⁇ m depending on the application, but may be 9 to 50 ⁇ m or 12 to 38 ⁇ m from the viewpoint of obtaining excellent impact resistance and gas barrier properties.
  • the thickness of the skin layer (individual layers if there are more than one layer) can be 0.5 to 3 ⁇ m, even if it is 0.6 to 2.5 ⁇ m. good.
  • the thickness of each layer may be the same or different.
  • the thickness of the core layer may be appropriately adjusted so that the thickness of the resin substrate preferably falls within the above range.
  • pretreatments such as corona treatment, plasma treatment, flame treatment, etc. may be applied to the resin base material to improve the adhesion with the vacuum film formation layer, as long as the barrier performance is not impaired.
  • same treatment may be applied to the resin substrate on the side opposite to the vacuum film formation layer.
  • a base layer (anchor coat layer) containing a predetermined resin is provided on the surface of the resin substrate on which the vacuum deposition layer is to be laminated.
  • the base layer can improve the gas barrier properties, improve the adhesion between the resin substrate and the vacuum deposition layer, and improve the smoothness of the surface of the resin substrate. By improving the smoothness, it becomes easy to form a vacuum film-formed layer uniformly without any defects, and it is easy to develop a high barrier property.
  • the base layer contains polyurethane resin formed from acid group-containing polyurethane and polyamine.
  • a polyurethane resin is obtained by bonding an acid group of an acid group-containing polyurethane with an amino group of a polyamine as a cross-linking agent. That is, it can be said that the polyurethane resin is a reaction product of an acid group-containing polyurethane and a polyamine, or a product obtained by cross-linking an acid group-containing polyurethane with a polyamine.
  • the bond between the acid group of the acid group-containing polyurethane and the amino group of the polyamine may be an ionic bond (e.g., an ionic bond between a carboxyl group and a tertiary amino group) or a covalent bond (e.g., an amide bond).
  • the acid group-containing polyurethane that constitutes the polyurethane resin has an acid group, it has anionic and self-emulsifying properties, and is also called an anionic self-emulsifying polyurethane.
  • the acid group of the acid group-containing polyurethane can bond with the amino group (primary amino group, secondary amino group, tertiary amino group, etc.) of the polyamine constituting the polyurethane resin.
  • a carboxyl group, a sulfonic acid group, etc. are mentioned as an acid group.
  • An acid group can usually be neutralized with a neutralizing agent (base), and may form a salt with a base.
  • the acid group may be located at the end of the acid-group-containing polyurethane or may be located in a side chain, but is preferably located at least in the side chain.
  • the acid value of the acid-group-containing polyurethane can be selected within a range in which the acid-group-containing polyurethane is water-dispersible, and may be 5 to 100 mgKOH/g, may be 10 to 70 mgKOH/g, or may be 15 to 60 mgKOH/g. g.
  • the acid value of the acid group-containing polyurethane is at least the lower limit of the above range, the acid group-containing polyurethane can easily be dispersed in water, and the uniform dispersibility between the polyurethane resin and other materials and the dispersion stability of the coating agent can be improved. easy to secure.
  • the acid value of the acid group-containing polyurethane is measured by a method according to JIS K 0070.
  • the total urethane group concentration and urea group (urea group) concentration of the acid group-containing polyurethane can be 15% by mass or more, and may be 20 to 60% by mass, from the viewpoint of gas barrier properties.
  • the sum of the urethane group concentration and the urea group concentration is equal to or higher than the above lower limit, the gas barrier properties of the underlying layer tend to be good.
  • the sum of the urethane group concentration and the urea group concentration is equal to or less than the upper limit of the above range, it is easy to prevent the base layer from becoming rigid and brittle.
  • the urethane group concentration means the ratio of the molecular weight (59 g/equivalent) of the urethane group to the molecular weight of the constituent units of the polyurethane resin.
  • the urea group concentration means the ratio of the molecular weight of the urea group (primary amino group (amino group): 58 g/equivalent, secondary amino group (imino group): 57 g/equivalent) to the molecular weight of the structural unit of the polyurethane resin. .
  • the urethane group concentration and the urea group concentration can be calculated based on the amount of reaction components charged, that is, the proportion of each component used.
  • the acid-group-containing polyurethane can have at least rigid units (units composed of hydrocarbon rings) and short-chain units (eg, units composed of hydrocarbon chains).
  • the constituent units of the acid group-containing polyurethane are derived from polyisocyanate components, polyhydroxy acid components, polyol components and chain extender components (especially at least polyisocyanate components), and are composed of hydrocarbon rings (aromatic and non-aromatic hydrocarbon at least one of the rings).
  • the polyurethane resin may contain an aromatic ring, and therefore the constitutional unit of the acid group-containing polyurethane may contain an aromatic hydrocarbon ring as the hydrocarbon ring.
  • the proportion of units composed of hydrocarbon rings in the constituent units of the acid group-containing polyurethane may be 10 to 70% by mass, and may be 15 to 65% by mass, based on the total of all constituent units. It may be 20 to 60% by mass.
  • the ratio of the unit composed of a hydrocarbon ring is equal to or higher than the lower limit of the above range, the gas barrier properties of the underlying layer tend to be good.
  • the ratio of the unit composed of a hydrocarbon ring is equal to or less than the upper limit of the above range, it is easy to prevent the underlayer from becoming rigid and brittle.
  • the number average molecular weight of the acid group-containing polyurethane can be selected as appropriate, but it can be 800 to 1,000,000, may be 800 to 200,000, or may be 800 to 100,000. When the number average molecular weight of the acid group-containing polyurethane is equal to or less than the upper limit of the above range, the appropriate viscosity of the coating agent can be easily obtained. When the number-average molecular weight of the acid group-containing polyurethane is at least the lower limit of the above range, the gas barrier properties of the underlying layer tend to be good.
  • the number average molecular weight of the acid group-containing polyurethane is a value converted to standard polystyrene measured by gel permeation chromatography (GPC).
  • the acid group-containing polyurethane may be crystalline in order to improve gas barrier properties.
  • the glass transition temperature of the acid group-containing polyurethane can be 100° C. or higher, may be 110° C. or higher, or may be 120° C. or higher.
  • the glass transition temperature of the acid group-containing polyurethane can be 200° C. or lower, can be 180° C. or lower, or can be 150° C. or lower. Therefore, the glass transition temperature of the acid group-containing polyurethane can be 100 to 200°C, may be 110 to 180°C, or may be 120 to 150°C.
  • the glass transition temperature of acid group-containing polyurethanes is measured by differential scanning calorimetry (DSC).
  • the polyamine that constitutes the polyurethane resin is a compound having two or more basic nitrogen atoms.
  • the basic nitrogen atom is a nitrogen atom that can bond with the acid group of the acid group-containing polyurethane, and examples thereof include nitrogen atoms in amino groups such as primary amino groups, secondary amino groups, and tertiary amino groups. be done.
  • the polyamine is not particularly limited as long as it can bond with the acid group of the acid group-containing polyurethane to improve gas barrier properties, and various compounds having two or more basic nitrogen atoms can be used.
  • As the polyamine a polyamine having two or more at least one amino group selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups can be used.
  • polyamines examples include alkylenediamines, polyalkylenepolyamines, and silicon compounds having a plurality of basic nitrogen atoms.
  • alkylenediamines examples include alkylenediamines having 2 to 10 carbon atoms such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine and 1,6-hexamethylenediamine. be done.
  • Polyalkylenepolyamines include, for example, tetraalkylenepolyamine.
  • Silicon compounds having a plurality of basic nitrogen atoms include, for example, 2-[N-(2-aminoethyl)amino]ethyltrimethoxysilane, 3-[N-(2- Examples thereof include silane coupling agents having a plurality of basic nitrogen atoms, such as aminoethyl)amino]propyltriethoxysilane.
  • the amine value of the polyamine may be 100 to 1900 mgKOH/g, may be 150 to 1900 mgKOH/g, may be 200 to 1900 mgKOH/g, may be 200 to 1700 mgKOH/g, It may be from 300 to 1500 mgKOH/g. If the amine value of the polyamine is at least the lower limit of the above range, the gas barrier properties of the underlying layer tend to be good. If the amine value of the polyamine is equal to or less than the upper limit of the above range, the water dispersion stability of the polyurethane resin tends to be good.
  • the amine value of polyamine is measured by the following method. Accurately weigh 0.5 to 2 g of the sample (sample amount Sg). 30 g of ethanol is added to the precisely weighed sample to dissolve it. Bromophenol blue is added to the resulting solution as an indicator, and titration is performed with a 0.2 mol/L ethanolic hydrochloric acid solution (potency f). The point at which the color of the solution changes from green to yellow is defined as the end point, and the titration amount (AmL) at this time is used to obtain the amine value using the following formula 1.
  • Amine value A x f x 0.2 x 56.108/S [mgKOH/g]
  • the molar ratio (acid group/basic nitrogen atom) between the acid group of the acid group-containing polyurethane and the basic nitrogen atom of the polyamine can be 10/1 to 0.1/1. , 5/1 to 0.2/1. If the acid group/basic nitrogen atoms are within the above range, the underlying layer is likely to exhibit excellent oxygen barrier properties.
  • the polyurethane resin can be obtained in a state of being dispersed in an aqueous medium (aqueous dispersion form). That is, the polyurethane resin can be called an aqueous polyurethane resin.
  • Aqueous media include water, water-soluble or hydrophilic organic solvents, or mixtures thereof. Examples of water-soluble or hydrophilic organic solvents include alcohols such as methanol, ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; cellosolves; is mentioned.
  • the aqueous medium may be water or one containing water as a main component.
  • the water content in the aqueous medium can be 70% by mass or more, and may be 80% by mass or more.
  • the aqueous medium may or may not contain a neutralizing agent (base) that neutralizes the acid groups of the acid group-containing polyurethane.
  • the average particle size of dispersed particles is not particularly limited, and may be 20 to 500 nm, may be 25 to 300 nm, or may be 30 to 200 nm. good too.
  • the average particle diameter of the dispersed particles is equal to or less than the upper limit of the above range, it is easy to ensure uniform dispersibility of the dispersed particles and other materials and dispersion stability of the coating agent, and the gas barrier of the underlayer formed from the coating agent. properties tend to be good.
  • the average particle size should be measured with a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., FPAR-10) after being diluted with water so that the solid content concentration is 0.03 to 0.3% by mass. can be done.
  • polyurethane resin a commercially available polyurethane resin may be used, or a polyurethane resin produced by a known production method may be used.
  • polyurethane resins formed from acid group-containing polyurethanes and polyamines include Takelac WPB-341 (manufactured by Mitsui Chemicals, Inc.).
  • the method for producing the polyurethane resin is not particularly limited, and includes ordinary water-based polyurethane resin techniques such as the acetone method and the prepolymer method.
  • urethanization catalysts such as amine-based catalysts, tin-based catalysts and lead-based catalysts may be used as necessary.
  • a polyisocyanate compound for example, in an inert organic solvent such as ketones such as acetone, ethers such as tetrahydrofuran, and nitriles such as acetonitrile, a polyisocyanate compound, a polyhydroxy acid, and, if necessary, a polyol component and a chain extender component
  • the acid group-containing polyurethane can be prepared by reacting with at least one of More specifically, a polyisocyanate compound, a polyhydroxy acid, and a polyol component are reacted in an inert organic solvent (particularly, a hydrophilic or water-soluble organic solvent) to form a prepolymer having an isocyanate group at the end.
  • a polyurethane resin in the form of an aqueous dispersion can be prepared by adding a polyamine to the aqueous dispersion of the acid group-containing polyurethane thus obtained and heating if necessary. When heating, the heating temperature can be 30 to 60°C.
  • the base layer may contain a water-soluble polymer in addition to the polyurethane resin.
  • a water-soluble polymer refers to a polymer that can be dissolved in water.
  • the term "dissolution” as used herein refers to a state in which the solute polymer is dispersed in the solvent water at the molecular chain level to form a homogeneous system. More specifically, it refers to a state in which the intermolecular force with water molecules is stronger than the intermolecular force between polymer chains, the entanglement of the polymer chains is broken, and the particles are evenly dispersed in water. Since the water-soluble polymer improves the flexibility of the underlying layer, deterioration of the gas barrier property due to post-processing can be easily suppressed.
  • water-soluble polymers include polyvinyl alcohol resins such as polyvinyl alcohol polymers and derivatives thereof; vinyl polymers such as polyvinylpyrrolidone, polyhydroxyethyl methacrylate and copolymers thereof; polyacrylic acid, polymethacrylic acid, or their esters, salts and copolymers thereof; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; starches such as oxidized starch, etherified starch and dextrin; copolymers having acid components containing polar groups such as sulfoisophthalic acid polyester; water-soluble urethane-based polymers; and functional group-modified polymers obtained by modifying the functional groups (carboxyl group, etc.) of these various polymers.
  • polyvinyl alcohol resins such as polyvinyl alcohol polymers and derivatives thereof
  • vinyl polymers such as polyvinylpyrrolidone, polyhydroxyethyl methacrylate and copolymers thereof
  • Polyvinyl alcohol polymers include, for example, graft polymers obtained by graft polymerization of monomers to the side chains of polyvinyl alcohol.
  • the degree of polymerization of the water-soluble polymer may be 200 or more.
  • the number of water-soluble polymers contained in the underlayer may be one or two or more.
  • the water-soluble polymer may contain at least one polyvinyl alcohol resin selected from the group consisting of polyvinyl alcohol-based polymers and derivatives thereof, from the viewpoint of achieving both gas barrier properties and flexibility of the underlayer.
  • a polyvinyl alcohol resin having a degree of saponification of 95% or more and a degree of polymerization of 300 or more may be included.
  • the polymerization degree of the polyvinyl alcohol resin can be 300-2400, and may be 450-2000. The higher the degree of saponification or polymerization of the polyvinyl alcohol resin is, the lower the hygroscopic swelling property becomes and the easier it is to exhibit a high gas barrier property.
  • the degree of saponification of the polyvinyl alcohol resin is 95% or more, it is easy to obtain sufficient gas barrier properties.
  • the degree of polymerization of the polyvinyl alcohol resin is 300 or more, the gas barrier property and the cohesive strength of the film are less likely to decrease.
  • the degree of polymerization of the polyvinyl alcohol resin is 2400 or less, the viscosity of the coating agent becomes moderate, and it becomes easy to mix uniformly with other components, and problems such as deterioration of gas barrier properties and adhesion strength are less likely to occur.
  • the underlayer may have a crosslinked structure formed by a silane coupling agent.
  • silane coupling agents can be used, and examples thereof include compounds in which an alkoxy group and an organic reactive group are bonded to a silicon atom.
  • silane coupling agents include compounds represented by RSiX 3 (wherein R is an organic reactive group and X is an alkoxy group).
  • the organic reactive group include those having an amino group, (meth)acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, isocyanurate group and the like.
  • a (meth)acryloyl group denotes both acryloyl and methacryloyl groups.
  • alkoxy groups include methoxy groups and ethoxy groups.
  • vinyl group-containing silane coupling agents include vinyltrimethoxysilane and vinyltriethoxysilane.
  • Silane coupling agents having an epoxy group include 2(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyl. methyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane and the like.
  • Silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
  • Silane coupling agents having a mercapto group include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
  • Silane coupling agents having a (meth)acryloyl group include 3-acryloxypropyltrimethoxysilane.
  • Silane coupling agents having an isocyanate group include 3-isocyanatopropyltriethoxysilane and the like.
  • Examples of silane coupling agents having an isocyanurate group include 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate. Any one of these silane coupling agents may be used alone, or two or more thereof may be used in combination. From the viewpoint of good reactivity with hydroxyl groups of polyurethane resins and water-soluble polymers, silane coupling agents having epoxy groups are preferably used.
  • the undercoat layer may be formed from a liquid composition (hereinafter also referred to as an undercoat agent) containing a polyurethane resin, a water-soluble polymer and a silane coupling agent if necessary, and may be composed of a cured product of the composition. . It can be said that the underlayer is a heat-dried product (heat-cured product) of the composition.
  • an undercoat agent a liquid composition containing a polyurethane resin, a water-soluble polymer and a silane coupling agent if necessary, and may be composed of a cured product of the composition.
  • the underlayer is a heat-dried product (heat-cured product) of the composition.
  • the mass ratio (polyurethane resin/water-soluble polymer) of the solid content of the polyurethane resin and the water-soluble polymer can be 85/15 to 10/90, and 75/25 to 20/ It may be 80, or it may be 70/30 to 25/75.
  • the solid content ratio is within the above range, it becomes easy to apply the undercoat agent evenly, and it is easy to form an undercoat layer excellent in gas barrier properties and flexibility.
  • the content (solid content) of the silane coupling agent can be 0.5 to 30% by mass relative to the total solid content in the undercoating agent. , 1 to 25% by mass, or 3 to 20% by mass.
  • the content of the silane coupling agent is within the above range, it is easy to form an underlayer having excellent gas barrier properties and flexibility.
  • Antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and other substances are used in undercoating agents, as long as they do not impair gas barrier properties. and other known additives may be included.
  • any known coating method can be used without any particular limitation, including dipping methods; methods using sprays, coaters, printers, brushes, and the like.
  • the types of coaters and printing machines used in these methods and their coating methods include gravure coaters such as direct gravure, reverse gravure, kiss reverse gravure, and offset gravure, reverse roll coaters, and micro gravure.
  • a coater, a coater combined with a chamber doctor, an air knife coater, a dip coater, a bar coater, a comma coater, a die coater and the like can be used.
  • the method for drying the undercoating agent is not particularly limited, but may be a natural drying method, a method of drying in an oven set at a predetermined temperature, or a dryer attached to the coater (e.g., arch dryer, floating dryer, drum dryer, A method using an infrared drier, etc.) can be mentioned.
  • the drying conditions can be appropriately selected depending on the drying method. For example, in the method of drying in an oven, drying can be performed at 60 to 100° C. for about 1 second to 2 minutes.
  • the thickness of the underlayer may be 10 to 1400 nm, may be 50 to 1000 nm, may be 120 to 800 nm, or may be 150 to 600 nm.
  • the thickness of the underlayer is at least the above lower limit, sufficient gas barrier properties and stretching resistance can be easily obtained. If the thickness of the underlayer is equal to or less than the above upper limit, it is suitable for post-processing such as stretching, and it is easy to suppress the drying load and manufacturing cost.
  • the thickness of the underlayer can be measured, for example, with a scanning electron microscope (SEM).
  • the vacuum deposition layer may contain at least one selected from the group consisting of metals, oxides, nitrides and oxynitrides of metals.
  • metals such as metal aluminum (Al), metal oxides such as silicon oxide (SiOx) and aluminum oxide (AlOx), metal nitrides such as silicon nitride (SiN), silicon oxynitride (SiON) metal oxynitrides such as
  • the constituent material of the barrier layer may be aluminum oxide or silicon oxide, particularly silicon oxide.
  • the thickness of the vacuum deposition layer can be, for example, 5 to 100 nm, and may be 10 to 80 nm.
  • a vacuum film-forming layer can be formed on a resin substrate by, for example, a vacuum deposition method.
  • Heating means for the vacuum deposition method include an electron beam heating method, a resistance heating method, an induction heating method, and the like.
  • vapor deposition can be performed using a plasma assist method or an ion beam assist method.
  • the protective layer imparts superior gas barrier properties to the packaging material and also has a function of protecting the vacuum-coated layer.
  • the protective layer may contain a water-soluble polymer. More specifically, the protective layer may be formed from a liquid composition containing a water-soluble polymer, and may be said to be a heat-dried product of the composition.
  • water-soluble polymers include the compounds exemplified for the base layer.
  • the water-soluble polymer can contain at least one polyvinyl alcohol resin selected from the group consisting of polyvinyl alcohol-based polymers and derivatives thereof, from the viewpoint of achieving both gas barrier properties and flexibility of the protective layer.
  • the water-soluble polymer may be cured with a curing agent.
  • a curing agent is not particularly limited, a metal alkoxide or a silane coupling agent can be used from the viewpoint of maintaining excellent laminate strength even after retorting.
  • metal alkoxides include compounds represented by the following general formula (I).
  • R 1 and R 2 are each independently a monovalent organic group having 1 to 8 carbon atoms, and may be an alkyl group such as methyl or ethyl.
  • M represents an n-valent metal atom such as Si, Ti, Al, Zr.
  • m is an integer from 1 to n.
  • metal alkoxides include tetraethoxysilane [Si(OC 2 H 5 ) 4 ] and aluminum isopropoxide [Al(O-sec-C 3 H 7 ) 3 ]. These metal alkoxides are relatively stable in aqueous solvents after hydrolysis.
  • silane coupling agent examples include the compounds exemplified for the base layer.
  • the protective layer is formed using a liquid composition (hereinafter also referred to as an overcoat agent) obtained by adding a raw material containing a water-soluble polymer and, if necessary, a curing agent, to water or a water/alcohol mixture. be done.
  • a liquid composition hereinafter also referred to as an overcoat agent
  • the amount of the curing agent in the overcoating agent can be 1 to 60% by mass based on the total solid content of the overcoating agent, from the viewpoint of maintaining the adhesion to the vacuum deposition layer and the gas barrier property, and 2 to 60% by mass. It may be 30% by mass, or 4 to 15% by mass.
  • the amount of the metal alkoxide in the overcoating agent can be 10 to 60% by mass based on the total solid content of the overcoating agent, from the viewpoint of maintaining adhesion to the vacuum deposition layer and gas barrier properties. It may be 50% by mass, or 20 to 40% by mass.
  • the amount of the silane coupling agent in the overcoating agent can be 1 to 30% by mass based on the total solid content of the overcoating agent, from the viewpoint of maintaining adhesion to the vacuum film-forming layer and gas barrier properties. It may be from 2 to 25% by mass, and may be from 4 to 15% by mass.
  • the overcoat agent may contain known additives such as dispersants, stabilizers, viscosity modifiers, colorants, and metal oxide particles within the range that does not impair gas barrier properties.
  • the overcoat agent can be applied by, for example, a dipping method, a roll coating method, a gravure coating method, a reverse gravure coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, or a gravure offset method. can be done.
  • a coating film formed by applying an overcoating agent can be dried by, for example, a hot air drying method, a hot roll drying method, a high frequency irradiation method, an infrared irradiation method, a UV irradiation method, or a combination thereof.
  • the temperature for drying the coating film can be, for example, 50 to 150°C, and may be 70 to 100°C. By setting the drying temperature within the above range, it is easy to suppress the occurrence of cracks in the vacuum deposition layer and the protective layer, and excellent barrier properties can be exhibited.
  • the thickness of the protective layer is preferably 50-1000 nm, more preferably 100-500 nm.
  • the thickness of the protective layer is 50 nm or more, there is a tendency that sufficient gas barrier properties can be obtained while protecting the vacuum deposition layer, and when it is 1000 nm or less, there is a tendency that sufficient flexibility can be maintained. .
  • FIG. 2 is a cross-sectional view showing one aspect of the packaging material according to the present disclosure.
  • the packaging material 100 of the present disclosure is obtained by laminating the gas barrier film 10 and the heat-sealable polyolefin film 12 with an adhesive layer 11 interposed therebetween.
  • the heat-sealable polyolefin film is composed of a resin having a lower melting point than the polyolefin resin that constitutes the resin substrate. Therefore, the heat-sealable polyolefin film can also be called a sealant layer.
  • the heat-sealable polyolefin film may be an unstretched film (eg, CPP).
  • the resin base material and the heat-sealable polyolefin film may be made of different materials, but may be made of the same material from the viewpoint of ease of re-forming after the resin material is melted.
  • "made of the same material” means, for example, that both layers are made of polyethylene or both layers are made of polypropylene.
  • LLDPE linear low-density polyethylene
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • low density polyethylene resin LDPE
  • medium density polyethylene resin MDPE
  • linear low density polyethylene resin LLDPE
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- ⁇ -olefin copolymer ethylene-(meth)acrylic acid copolymer and other ethylene-based resins
  • blended resin of polyethylene and polybutene homopolypropylene resin (PP)
  • propylene-ethylene random copolymer propylene -Polypropylene-based resins such as ethylene block copolymers and propylene- ⁇ -olefin copolymers
  • PP homopolypropylene resin
  • PP propylene-ethylene random copolymer
  • propylene -Polypropylene-based resins such as ethylene block copolymers and propylene- ⁇ -olefin copolymers
  • additives such as flame retardants, slip agents, anti-blocking agents, antioxidants, light stabilizers, and tackifiers may be added to the heat-fusible polyolefin film.
  • the thickness of the heat-sealable polyolefin film is determined by the mass of the contents, the shape of the packaging bag, etc., and can be, for example, 30 to 150 ⁇ m.
  • the gas barrier film and the heat-sealable polyolefin film are laminated via an adhesive layer.
  • Means for laminating the two include a dry lamination method in which adhesives such as one-component curing or two-component curing urethane adhesives are used, a non-solvent dry lamination method in which non-solvent adhesives are used, polyethylene and polypropylene.
  • a known lamination method such as an extrusion lamination method in which a polyolefin resin such as polyolefin resin is heated and melted, extruded in a curtain shape, and laminated together can be employed.
  • the films (resin base material and heat-sealable polyolefin film) that make up the packaging material can all be polyolefin films.
  • a packaging material can be said to be a (mono-material) material made of a single material with excellent recyclability.
  • the total mass of components other than the polyolefin component can be 10% by mass or less with respect to the total mass of the packaging material. , 7.5% by mass or less, and may be 5.0% by mass or less.
  • the packaging bag can be obtained by heat-sealing the heat-sealable polyolefin films of the packaging material thus obtained.
  • a package can be obtained by filling the contents into the packaging bag thus obtained and sealing the bag.
  • [Invention 1] comprising a resin base material, a base layer, and a vacuum deposition layer,
  • the resin base material contains a polyolefin resin
  • the gas barrier film, wherein the base layer contains a polyurethane resin formed from an acid group-containing polyurethane and a polyamine.
  • the gas barrier film according to invention 1 wherein the resin substrate includes a copolymer layer or a terpolymer layer on the surface of the underlayer.
  • [Invention 3] The gas barrier film according to invention 1 or 2, wherein the polyurethane resin has an aromatic ring.
  • invention 4 The gas barrier film according to any one of Inventions 1 to 3, wherein the vacuum deposition layer contains at least one selected from the group consisting of a metal and oxides, nitrides and oxynitrides of the metal.
  • invention 5 A packaging material in which the gas barrier film according to any one of inventions 1 to 4 and a heat-sealable polyolefin film are laminated via an adhesive layer.
  • invention 6 A packaging bag formed from the packaging material according to invention 5.
  • OPP film A Mitsui Chemicals Tohcello Co., Ltd., ME-1, thickness 20 ⁇ m (core layer: OPP (19 ⁇ m), skin layer: OPP (ethylene-containing copolymer, 1 ⁇ m))
  • OPP film B AJ PLAST, PJ201, thickness 20 ⁇ m (core layer: OPP (19 ⁇ m), skin layer: OPP (ethylene/butene-containing terpolymer, 1 ⁇ m))
  • OPP film C Mitsui Chemicals Tohcello Co., Ltd., M-1, thickness 20 ⁇ m PE film: Tokyo Ink Co., Ltd., SMUQ, thickness 30 ⁇ m
  • a base layer (thickness: 0.15 to 0.2 ⁇ m) made of the following barrier urethane or PVA was formed on the resin substrate (or on the skin layer, if any).
  • Barrier urethane A Takelac WPB-341 (manufactured by Mitsui Chemicals, Inc., an aqueous dispersion of a polyurethane resin formed from an acid group-containing polyurethane and a polyamine. The polyurethane resin has an aromatic ring) was prepared. By coating this on a resin base material and drying it, a base layer was formed.
  • Barrier urethane B A coating liquid was prepared by mixing Takelac WPB-341 and isocyanate silane KBE-9007N (manufactured by Shin-Etsu Chemical Co., Ltd.) at a solid content ratio of 9:1. By coating this on a resin base material and drying it, a base layer was formed.
  • Barrier urethane C A coating liquid was prepared by mixing Takelac WPB-341 and an aqueous solution of Kuraray Poval PVA-124 (manufactured by Kuraray Co., Ltd., completely saponified PVA) at a solid content ratio of 7:3. By coating this on a resin base material and drying it, a base layer was formed.
  • PVA An aqueous solution of Kuraray Poval PVA-124 (manufactured by Kuraray Co., Ltd., completely saponified PVA) was applied onto a resin substrate and dried to form an underlayer.
  • Silicon oxide deposited layer SiOx layer, thickness 30 nm
  • a SiO material was deposited using an electron beam heating vacuum deposition apparatus.
  • Aluminum oxide deposition layer AlOx layer, thickness 14 nm: Using an electron beam heating type vacuum deposition apparatus, metal aluminum was deposited while adding oxygen.
  • protective layer The following protective layer 1 or 2 was formed on the vacuum deposition layer.
  • Protective layer 1 PVA/TEOS layer: A coating solution was prepared by mixing a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of Kuraray Poval PVA-124 at a solid content ratio of 6:4. A protective layer having a thickness of 0.3 ⁇ m was formed by coating this on the vacuum film formation layer by a gravure coating method and drying it.
  • Protective layer 2 Hydrolyzed solution of tetraethoxysilane (TEOS), Kuraray Poval PVA-124 aqueous solution, and 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate at a solid content ratio of 65/25/10.
  • a coating solution was prepared by mixing as follows.
  • a protective layer having a thickness of 0.3 ⁇ m was formed by coating this on the vacuum film formation layer by a gravure coating method and drying it.
  • the water vapor transmission rate (WVTR) of the gas barrier film obtained in each example was measured using a water vapor transmission rate measuring device (manufactured by MOCON, trade name: PERMATRAN) under the conditions of a temperature of 40 ° C. and a relative humidity of 90% according to JIS K. -Measured according to 7126-2. Table 1 shows the results.
  • the unit of water vapor permeability is [g/m 2 ⁇ day].
  • the base layer was formed using a specific material, it was possible to ensure sufficient gas barrier properties with the configuration of the resin base material, base layer, and vacuum film formation layer.
  • the gas barrier films of Examples do not require the formation of a protective layer, that is, it can be said that both the simplification of the layer structure and the maintenance of gas barrier properties can be achieved.
  • a packaging material equipped with a gas barrier film according to the present disclosure can have a polyolefin content of 90% by mass or more in the total amount of the packaging material, and material recycling is possible.
  • Resin base material 1... Resin base material, 2... Base layer, 3... Vacuum film formation layer, 10... Gas barrier film, 11... Adhesive layer, 12... Heat-sealable polyolefin film, 100... Packaging material.

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