WO2025134926A1 - ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料 - Google Patents

ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料 Download PDF

Info

Publication number
WO2025134926A1
WO2025134926A1 PCT/JP2024/044078 JP2024044078W WO2025134926A1 WO 2025134926 A1 WO2025134926 A1 WO 2025134926A1 JP 2024044078 W JP2024044078 W JP 2024044078W WO 2025134926 A1 WO2025134926 A1 WO 2025134926A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas barrier
barrier film
layer
active energy
acrylic compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/044078
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
洋平 西川
周平 岸澤
天平 渡邉
達郎 古田
順二 臼杵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Holdings Inc
Original Assignee
Toppan Holdings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Holdings Inc filed Critical Toppan Holdings Inc
Priority to JP2025530607A priority Critical patent/JP7800782B2/ja
Publication of WO2025134926A1 publication Critical patent/WO2025134926A1/ja
Priority to JP2025265465A priority patent/JP2026065651A/ja
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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 a method for producing a gas barrier film, a gas barrier film produced by the method, a packaging film including the gas barrier film, and a packaging material produced by forming a bag from the packaging film.
  • Packaging materials used for food, medicines, electronic parts, machine parts, etc. are required to have the property of preventing the intrusion of gases (water vapor, oxygen, etc.) that denature the contents, in order to prevent deterioration or spoilage of the contents and to maintain their functionality and quality. In other words, they are required to have gas barrier properties. For this reason, film materials with gas barrier properties (gas barrier films) are used for these packaging materials.
  • Patent Document 1 proposes a laminated material manufactured by mixing a polyurethane resin, nitrocellulose, a silane coupling agent, and a filler with a solvent and diluent to prepare a polyurethane resin composition, providing a thin inorganic oxide film consisting mainly of a silicon oxide vapor deposition film formed by plasma chemical vapor deposition on one side of a flexible plastic substrate, and then using the polyurethane resin composition to coat the surface of the inorganic oxide thin film provided on one side of the flexible plastic substrate to form a thin coating film of the polyurethane resin composition.
  • the surface of the thin coating film of the polyurethane resin composition is coated with an adhesive consisting of a two-component curing polyurethane resin that is formed by a curing reaction between a polyester polyol or polyether polyol and an isocyanate, and then laminating at least a heat-sealable resin layer via the adhesive layer.
  • an adhesive consisting of a two-component curing polyurethane resin that is formed by a curing reaction between a polyester polyol or polyether polyol and an isocyanate
  • a gas barrier film is produced by providing a gas barrier layer made of a material having gas barrier properties on the surface of a resin substrate.
  • a thin coating film made of a polyurethane resin composition corresponds to the gas barrier layer.
  • the thin coating film is formed by applying the polyurethane resin composition to the target by a wet coating method such as roll coating, and then drying with hot air to remove the solvent.
  • the present disclosure has been made in consideration of the above circumstances, and has an object to provide a method for producing a gas barrier film that can exhibit excellent gas barrier properties regardless of the heat resistance of a base film. Another object of the present disclosure is to provide a gas barrier film produced by the production method, a packaging film including the gas barrier film, and a packaging material produced by making a bag from the packaging film.
  • one aspect of the present disclosure provides the following invention.
  • a step of forming an inorganic oxide layer on a substrate layer A step of applying an active energy ray-curable resin composition onto the inorganic oxide layer to form a coating film; and curing the coating film by irradiating it with active energy rays to form an overcoat layer.
  • the active energy ray-curable resin composition contains two or more types of the acrylic compound having an isocyanurate skeleton.
  • FIG. 1 is a schematic cross-sectional view of a gas barrier film according to a first embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view of a gas barrier film according to a second embodiment of the present disclosure.
  • FIG. 1 is a schematic cross-sectional view of a gas barrier film according to a first embodiment of the present disclosure.
  • the gas barrier film 100 includes a base layer 10, an undercoat layer 30, an inorganic oxide layer 40, and an overcoat layer 20, in this order.
  • Examples of the resin constituting the base layer 10 include olefin-based resins such as polyethylene, polypropylene, polymers of olefins having 2 to 10 carbon atoms, and propylene-ethylene copolymers; polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide-based resins such as aliphatic polyamides such as nylon 6 and nylon 66, and aromatic polyamides such as polymetaxylylene adipamide; vinyl-based resins such as polystyrene, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer; acrylic-based resins such as homopolymers or copolymers of acrylic monomers such as polymethyl methacrylate and polyacrylonitrile; cellophane; and engineering plastics such as polycarbonate and polyimide.
  • olefin-based resins such as polyethylene, polypropy
  • the substrate layer 10 may be a single-layer film made of a single resin, or a single-layer or laminate film made of multiple resins.
  • the substrate layer 10 may be a film in which the above-mentioned various resins are laminated onto another substrate (metal, wood, paper, ceramics, etc.).
  • the film constituting the base layer 10 may be an unstretched film or a stretched film, such as a uniaxially stretched or biaxially stretched film. From the viewpoint of excellent water vapor barrier properties, an oriented polypropylene (OPP) film is particularly preferred as the base layer 10.
  • OPP film may be one layer or two or more layers.
  • the OPP film may be at least one type of polymer selected from homopolymer, random copolymer, and block copolymer processed into a film shape.
  • a homopolymer is a polypropylene consisting of only propylene monomer.
  • a random copolymer is a polypropylene in which the main monomer propylene and a small amount of a comonomer different from propylene are randomly copolymerized to form a homogeneous phase.
  • a block copolymer is a polypropylene in which the main monomer propylene and the above comonomer are copolymerized in a block form or polymerized in a rubber form to form a heterogeneous phase.
  • the surface of the substrate layer 10 on which the undercoat layer 30 or inorganic oxide layer 40 is formed may be subjected to a surface treatment such as chemical treatment, solvent treatment, corona treatment, low-temperature plasma treatment, or ozone treatment. This can improve the adhesion between the substrate layer and the undercoat layer or inorganic oxide layer.
  • a surface treatment such as chemical treatment, solvent treatment, corona treatment, low-temperature plasma treatment, or ozone treatment. This can improve the adhesion between the substrate layer and the undercoat layer or inorganic oxide layer.
  • the film constituting the base layer 10 may contain additives such as fillers, antiblocking agents, antistatic agents, plasticizers, lubricants, and antioxidants. These additives may be used alone or in combination of two or more.
  • the thickness of the base layer 10 is preferably 3 to 200 ⁇ m, more preferably 5 to 120 ⁇ m, even more preferably 6 to 100 ⁇ m, and particularly preferably 10 to 30 ⁇ m.
  • the underlayer 30 contains an organic polymer.
  • the content of the organic polymer in the underlayer 30 may be, for example, 70% by mass or more, or 80% by mass or more.
  • the organic polymer include polyacrylic resin, polyester resin, polycarbonate resin, polyol resin, polyurethane resin, polyamide resin, polyolefin resin, polyimide resin, melamine resin, and phenol resin.
  • the underlayer 30 contains at least one of a polyacrylic resin, a polyol resin, a polyurethane resin, a polyamide resin, or a reaction product of these organic polymers.
  • the base layer 30 may contain a silane coupling agent, an organic titanate, a modified silicone oil, etc.
  • the organic polymer used in the undercoat layer 30 is preferably an organic polymer having a urethane bond formed by the reaction of a polyol having two or more hydroxyl groups at the molecular end or in the molecular chain with an isocyanate compound, or an organic polymer containing a reaction product of a polyol having two or more hydroxyl groups at the molecular end or in the molecular chain with an organic silane compound such as a silane coupling agent or its hydrolysate. Either one of these may be used, or both may be used.
  • the polyols may be, for example, at least one selected from acrylic polyol, polyvinyl acetal, polystyrene polyol, polyurethane polyol, etc.
  • the acrylic polyol may be obtained by polymerizing an acrylic acid derivative monomer, or may be obtained by copolymerizing an acrylic acid derivative monomer with another monomer.
  • the acrylic acid derivative monomer include ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
  • Examples of the monomer to be copolymerized with the acrylic acid derivative monomer include styrene, etc.
  • the isocyanate compound reacts with the polyol to form a urethane bond, which acts to increase the adhesion between the base layer 10 and the inorganic oxide layer 40 or the overcoat layer 20. That is, the isocyanate compound functions as a crosslinking agent or a curing agent.
  • isocyanate compounds include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aromatic aliphatic xylene diisocyanate (XDI), aliphatic hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), a mixture of 1-methylcyclohexane-2,4-diisocyanate and 1-methylcyclohexane-2,6-diisocyanate (HTDI, hydrogenated TDI), and cyclohexylmethane diisocyanate (HMDI, hydrogenated MDI), as well as other monomers, polymers thereof, and derivatives thereof.
  • the above-mentioned isocyanate compounds may be used alone or in combination of two or more.
  • Silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropylmethyldimethoxysilane.
  • the organic silane compound may be a hydrolyzate of these silane coupling agents.
  • the organic silane compound may contain one of the above-mentioned silane coupling agents and their hydrolyzates, either alone or in combination of two or more of them.
  • the undercoat layer 30 can be formed using a mixture of the above-mentioned components in an organic solvent in any ratio.
  • the mixture may contain, for example, a curing accelerator such as a tertiary amine, an imidazole derivative, a metal salt compound of a carboxylic acid, a quaternary ammonium salt, or a quaternary phosphonium salt; an antioxidant such as a phenol-based, sulfur-based, or phosphite-based antioxidant; a leveling agent; a flow regulator; a catalyst; a crosslinking reaction accelerator; a filler, etc.
  • a curing accelerator such as a tertiary amine, an imidazole derivative, a metal salt compound of a carboxylic acid, a quaternary ammonium salt, or a quaternary phosphonium salt
  • an antioxidant such as a phenol-based, sulfur-based, or phosphite-based antioxidant
  • a leveling agent such as
  • the thickness of the undercoat layer 30 there is no particular limit to the thickness of the undercoat layer 30, and it can be, for example, 0.005 to 5 ⁇ m. The thickness can be appropriately determined depending on the application or the desired characteristics.
  • the thickness of the undercoat layer 30 is preferably 0.01 to 1 ⁇ m, and more preferably 0.01 to 0.5 ⁇ m. If the thickness of the undercoat layer 30 is 0.01 ⁇ m or more, sufficient adhesion strength between the base layer 10 and the inorganic oxide layer 40 or the overcoat layer 20 is obtained, and the gas barrier properties are also good. If the thickness of the undercoat layer 30 is 1 ⁇ m or less, it becomes easier to form a uniform coating surface, and the drying load and manufacturing costs can be suppressed.
  • inorganic oxide layer examples of inorganic oxides constituting the inorganic oxide layer 40 include aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, tin oxide, zinc oxide, indium oxide, etc.
  • aluminum oxide or silicon oxide is preferable because it has excellent productivity and excellent oxygen barrier properties and water vapor barrier properties under high temperature and high humidity conditions.
  • the inorganic oxide layer 40 may be formed of one type of inorganic oxide, or may be formed of two or more types of inorganic oxides selected appropriately.
  • the thickness of the inorganic oxide layer 40 can be 1 to 200 nm. If the thickness is 1 nm or more, it is easy to obtain excellent oxygen barrier properties and water vapor barrier properties. If the thickness is 200 nm or less, it is possible to keep manufacturing costs low, and cracks caused by external forces such as bending or pulling are less likely to occur, making it easier to prevent deterioration of the gas barrier properties.
  • the inorganic oxide layer 40 can be formed by a known film formation method such as vacuum deposition, sputtering, ion plating, or plasma chemical vapor deposition (CVD).
  • a known film formation method such as vacuum deposition, sputtering, ion plating, or plasma chemical vapor deposition (CVD).
  • the overcoat layer 20 is a cured coating film containing an acrylic compound (a compound having an acryloyl group), and is, for example, an organic polymer film obtained by applying a solvent-free coating liquid containing a monomer and an oligomer of an acrylic compound, i.e., an active energy ray curable resin composition, and curing the coating film by irradiating the active energy ray such as EB (electron beam) or UV (ultraviolet ray).
  • the overcoat layer is a cured product of an active energy ray curable resin composition having a crosslinked structure.
  • the active energy ray curable resin composition contains at least a monomer (or oligomer) of an acrylic compound, and may further contain additives such as a methacrylic compound (a compound having a methacryloyl group), a photoradical generator, a silane coupling agent, etc. Note that by using EB, the above composition can be cured even if it does not contain a photoradical generator. From the viewpoint of hygiene, the above composition does not need to contain a photoradical generator.
  • Acrylic compounds are generally low-cost active energy ray-curable compounds that have superior EB curing speed and UV curing speed compared to methacrylic compounds.
  • the active energy ray-curable resin composition may contain one or more acrylic compounds.
  • the active energy ray curable resin composition contains an acrylic compound having a molecular weight of 300 or more.
  • a coating film formed from an acrylic compound tends to have poor gas barrier properties, particularly poor oxygen barrier properties, but by using an acrylic compound having a molecular weight of 300 or more, it is possible to develop excellent gas barrier properties compared to the case of using an acrylic compound having a molecular weight of less than 300.
  • the molecular weight is preferably 350 or more.
  • the upper limit of the molecular weight can be 1900 or less, but from the viewpoint of coatability, the molecular weight may be 1000 or less, 700 or less, or 500 or less.
  • the molecular weight is preferably 300 or more and 1,900 or less, 300 or more and 1,000 or less, 350 or more and 1,000 or less, 350 or more and 700 or less, or 350 or more and 500 or less.
  • Acrylic compounds with a molecular weight of 300 or more include, for example, stearyl acrylate, methoxy PEG #400 acrylate, methoxy PEG #600 acrylate, methoxy PEG #1000 acrylate, methoxy-polyethylene glycol acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, PEG #200 diacrylate, PEG #400 diacrylate, PEG #600 diacrylate, PEG #1000 diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, bisphenol A ethylene glycol diether diacrylate, Acrylate, bisphenol A polyethylene glycol diether diacrylate, bisacrylate 1,6-hexanediylbis(oxy)bis(2-hydroxy-3,1-propanediyl
  • epoxy acrylate, urethane acrylate, polyester acrylate, etc. which have a molecular weight of 300 or more, can also be used.
  • acrylic compounds having an isocyanurate skeleton can be used.
  • acrylic compounds having an isocyanurate skeleton such as tris(2-hydroxyethyl)isocyanuric acid diacrylate and tris(2-hydroxyethyl)isocyanuric acid triacrylate are preferably used.
  • the active energy ray-curable resin composition may contain two or more types of acrylic compounds having an isocyanurate skeleton from the viewpoint of adjusting the coatability of the composition.
  • the gas barrier properties of organic polymers depend on the free volume and cohesive energy. Free volume is the gap between polymers, and the smaller the free volume, the higher the gas barrier properties. To suppress the thermal motion of the molecules, it is preferable to use a resin with a high glass transition temperature and increase the crosslink density. Many acrylic resins have a relatively low glass transition temperature.
  • Cohesive energy is the energy related to the magnitude of interaction between functional groups and polar groups and the permeating gas. It is known that chloro groups, fluoro groups, hydroxyl groups, etc. are excellent for oxygen gas, with hydroxyl groups being particularly excellent. Therefore, acrylic compounds with hydroxyl groups (hydroxyl-containing acrylic compounds) can be used to form organic polymer films with excellent gas barrier properties.
  • hydroxyl group-containing acrylic compounds examples include 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 1,6-hexanediylbis(oxy)bis(2-hydroxy-3,1-propanediyl)bisacrylate, bisphenol A diglycidyl ether acrylic acid adduct, glycerin 1,3-diglycerolate diacrylate, tris(2-hydroxyethyl)isocyanuric acid diacrylate, and dipentaerythritol pentaacrylate.
  • N A and N B When the number of acryloyl groups and the number of hydroxyl groups contained in one molecule of the acrylic compound are represented by N A and N B , respectively, and the value of the following formula (1) is calculated using N A and N B , it is preferable that the value of formula (1) is 4 or more. N A ⁇ 2 + N B ⁇ 3 ⁇ 4 ... (1)
  • the value of formula (1) is 4 or more, the crosslinking density due to the acryloyl group is improved compared to when the value is less than 4, and it becomes easier to form a coating with a dense structure. This makes the coating less permeable to oxygen molecules, and makes it easier to exhibit better gas barrier properties. From this perspective, it is preferable that the value of formula (1) is 5 or more, 6 or more, or 7 or more.
  • the upper limit of the value of formula (1) can be, for example, 65, but from the perspective of suppressing embrittlement of the coating due to an internal structure becoming too dense and making it easier to maintain ease of handling (flexibility) as a film, the upper limit of the value of formula (1) may be 30 or less, or 15 or less.
  • N A of acryloyl groups contained in one molecule of the acrylic compound can take a value of 1 to 15.
  • N A may be 2 to 10, 2 to 6, or 3 to 6.
  • the active energy ray-curable resin composition may further contain an acrylic compound having a molecular weight of less than 300 from the viewpoint of the coatability of the composition. That is, the active energy ray-curable resin composition may contain an acrylic compound having a molecular weight of 300 or more and an acrylic compound having a molecular weight of less than 300.
  • Acrylic compounds with a molecular weight of less than 300 include, for example, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, butoxyethyl acrylate, butoxydiethylene glycol acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxyPEG #200 acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2 -Acryl
  • Carboxy group-containing acrylic compounds that can be used include, for example, the above-mentioned 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, etc., as well as 2-carboxyethyl acrylate, ⁇ -carboxycaprolactone monoacrylate, etc.
  • Hydroxyl group-containing methacrylic compounds that can be used include, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-methacryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl-phthalic acid, glycerin dimethacrylate, 1,6-hexanediylbis(oxy)bis(2-hydroxy-3,1-propanediyl)bismethacrylate, bisphenol A diglycidyl ether methacrylic acid adduct, glycerin 1,3-diglycerolate dimethacrylate, tris(2-hydroxyethyl)isocyanuric acid dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, etc
  • the active energy ray-curable resin composition contains a carboxy group-containing acrylic compound having a molecular weight of less than 300
  • the content thereof can be 10 to 600 parts by mass relative to 100 parts by mass of the acrylic compound having a molecular weight of 300 or more.
  • the coatability and adhesion of the composition (coating liquid) are likely to be improved, and when the content is 600 parts by mass or less, good gas barrier properties are likely to be maintained.
  • the content of the carboxy group-containing acrylic compound having a molecular weight of less than 300 is preferably 10 to 600 parts by mass, 10 to 300 parts by mass, 20 to 300 parts by mass, 20 to 200 parts by mass, or 20 to 100 parts by mass per 100 parts by mass of the acrylic compound having a molecular weight of 300 or more.
  • the content of the hydroxyl group-containing acrylic compound having an isocyanurate skeleton can be 30 mass% or more, 50 mass% or more, or 70 mass% or more based on the total amount of the acrylic compounds having an isocyanurate skeleton.
  • the content is 30 mass% or more, the gas barrier properties are more likely to be improved compared to when the content is less than 30 mass%.
  • the upper limit of the content is not particularly limited, but can be 100 mass%.
  • the active energy ray-curable resin composition may contain 50% by mass or more of an acrylic compound, 70% by mass or more, or 80% by mass or more.
  • the upper limit of the content is not particularly limited, but may be 100% by mass.
  • the active energy ray curable resin composition may contain a photoradical generator as necessary.
  • Any photoradical generator capable of generating radicals upon irradiation with EB or UV can be used.
  • the photoradical generator is not particularly limited, but examples thereof include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, and diphenyl disulfide.
  • the active energy ray curable resin composition may contain a silane coupling agent as necessary.
  • a silane coupling agent having an acryloyl group or a methacryloyl group is preferred.
  • silane coupling agents include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane.
  • the undercoat layer 30 and the inorganic oxide layer 40 or only the inorganic oxide layer 40 are formed on the substrate layer 10.
  • the overcoat layer 20 formed as described above is a cured product of a coating agent (active energy ray curable resin composition) having a crosslinked structure.
  • a coating agent active energy ray curable resin composition
  • having a crosslinked structure means that the molecular chains of the reactive compound, including the acrylic compound, form a three-dimensional mesh-like structure.
  • the presence of a crosslinked structure can be confirmed by various analyses, including Fourier transform infrared spectroscopy, solid-state NMR, X-ray photoelectron spectroscopy, dynamic viscoelasticity, and gel fraction measurement.
  • the gas barrier film may further include a printing layer, a protective layer, a light-shielding layer, an adhesive layer, a heat-sealable heat-fusion layer, and other functional layers, as necessary.
  • the heat-sealing layer is CPP (non-oriented polypropylene).
  • the heat-sealing layer can be laminated onto the base layer by known methods such as dry lamination and extrusion lamination using known adhesives such as polyurethane, polyester, and polyether.
  • both the base layer and the heat-sealing layer from polypropylene
  • the polypropylene content in the packaging film and packaging material can be increased to 90% by mass or more. This makes the packaging film and packaging material a so-called mono-material material with excellent recyclability.
  • the gas barrier film of the present disclosure will be further explained using examples and comparative examples.
  • the present disclosure is not limited in any way by the specific contents of the examples and comparative examples.
  • Inorganic oxide layer formation A mixed material containing two or more of metallic silicon, silicon monoxide, and silicon dioxide was evaporated using a vacuum deposition apparatus using an electron beam heating method to form an inorganic oxide layer 40 (silicon oxide vapor deposition layer) made of silicon oxide and having a thickness of 30 nm on the corona-treated surface of the substrate layer 10.
  • Example 2 to 6 and Comparative Examples 1 to 3 A gas barrier film was obtained in the same manner as in Example 1, except that the acrylic compounds shown in Table 1 were used.
  • the molecular weight of each compound, the value of the above formula (1), and the presence or absence of an isocyanurate skeleton are also shown in Table 1.
  • Example 4 A gas barrier film was obtained in the same manner as in Example 1, except that no overcoat layer was formed.
  • acrylic compounds used are as follows: ⁇ 1,6-Hexanediylbis(oxy)bis(2-hydroxy-3,1-propanediyl)bisacrylate (Product name: KAYARAD R-167, manufactured by Nippon Kayaku Co., Ltd.) 2-Acryloyloxyethyl-2-hydroxyethyl-phthalic acid (product name: Light Acrylate HOA-MPE(N), manufactured by Kyoeisha Chemical) Bisphenol A diglycidyl ether acrylic acid adduct (product name: Epoxy Ester 3000A, manufactured by Kyoeisha Chemical) Tris(2-hydroxyethyl)isocyanuric acid triacrylate (product name: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) Tris(2-hydroxyethyl)isocyanuric acid diacrylate (product name: M-215, manufactured by Toagosei) -Butyl acrylate (product name: Butyl Acrylate, manufactured by
  • the gas barrier films obtained in each example were evaluated as follows. The results are shown in Table 2.
  • the curing property of the overcoat layer of the gas barrier film was confirmed by the tackiness when the overcoat layer was rubbed with a latex glove. If the overcoat layer did not have any rubbing marks and was not sticky, it was rated as ⁇ , and if it was sticky, it was rated as ⁇ .
  • the oxygen permeability (cc/(m2 ⁇ day ⁇ atm)) of the gas barrier film obtained in each example was measured in an atmosphere of 30° C. and 70% RH (relative humidity) using an oxygen permeability measuring device (product name: OXTRAN- 2 /20, manufactured by MOCON Corporation). For examples in which the curability was rated as ⁇ , handling was difficult due to the stickiness of the overcoat layer surface, so the oxygen barrier property was not evaluated.
  • Example 2 where the value of formula (1) is 5 or more, better oxygen barrier properties were exhibited than in Example 1. This is thought to be because, when the value of formula (1) is 5 or more, the balance between the improvement in crosslink density due to the acryloyl groups and the interaction inside the coating due to the hydroxyl groups is better balanced, and the coating structure becomes denser, making it less permeable to oxygen molecules.
  • Examples 5 and 6 which used an acrylic compound with an isocyanurate skeleton, even better oxygen barrier properties were observed. This is thought to be because the acrylic compound with an isocyanurate skeleton has a relatively high glass transition temperature among acrylic compounds, suppressing the thermal movement of the internal structure of the coating, increasing density, and making it more difficult for oxygen molecules to pass through.
  • Example 8 A gas barrier film was obtained in the same manner as in Example 7, except that the mass ratio of A and B was changed as shown in Table 3.
  • Examples 8 to 10 in which the amount of hydroxyl group-containing compound (B) was 30 mass% or more, showed oxygen barrier properties superior to those of Example 7. This is believed to be because the diffusion of oxygen molecules was further suppressed by the presence of hydroxyl groups, which have a high affinity for oxygen molecules, in the coating having an isocyanurate skeleton in its structure.
  • the viscosities shown in Table 4 are the viscosities of the coating liquid at a shear rate of 100 (1/s) when the coating liquid viscosity was continuously measured at a shear rate of 1 (1/s) to 1000 (1/s) using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) at a temperature of 23° C. and a cone plate (diameter 60 mm, cone angle 1°).
  • Example 12 A gas barrier film was obtained in the same manner as in Example 11, except that the mass ratio of C and D was changed as shown in Table 4.
  • Example 16 to 18 A gas barrier film was obtained in the same manner as in Example 15, except that the mass ratio of C and E was changed as shown in Table 4.
  • Example 20 2-Acryloyloxyethylhexahydrophthalic acid (product name: Light Acrylate HOA-HH (N), manufactured by Kyoeisha Chemical, molecular weight 270) (H) was used in place of G.
  • a gas barrier film was obtained in the same manner as in Example 19 except for this.
  • Example 21 2-Acryloyloxyethyl phthalic acid (product name: M-5400, manufactured by Toagosei, molecular weight 264) (I) was used instead of G. Other than this, a gas barrier film was obtained in the same manner as in Example 19.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
PCT/JP2024/044078 2023-12-21 2024-12-12 ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料 Pending WO2025134926A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2025530607A JP7800782B2 (ja) 2023-12-21 2024-12-12 ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料
JP2025265465A JP2026065651A (ja) 2023-12-21 2025-12-18 ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023216068 2023-12-21
JP2023-216068 2023-12-21

Publications (1)

Publication Number Publication Date
WO2025134926A1 true WO2025134926A1 (ja) 2025-06-26

Family

ID=96136974

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/044078 Pending WO2025134926A1 (ja) 2023-12-21 2024-12-12 ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料

Country Status (2)

Country Link
JP (2) JP7800782B2 (https=)
WO (1) WO2025134926A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003213159A (ja) * 2002-01-18 2003-07-30 Toagosei Co Ltd 活性エネルギー線硬化型被覆用組成物
WO2016143461A1 (ja) * 2015-03-10 2016-09-15 東洋紡株式会社 透明バリアフィルムの製造法
WO2017217522A1 (ja) * 2016-06-17 2017-12-21 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びこれを用いてなるコーティング剤
JP2019119059A (ja) * 2017-12-28 2019-07-22 大日本印刷株式会社 ガスバリアフィルム
JP2020142430A (ja) * 2019-03-06 2020-09-10 凸版印刷株式会社 積層体

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019108464A (ja) 2017-12-18 2019-07-04 東洋インキＳｃホールディングス株式会社 バリア性積層体用光硬化性組成物、バリア性積層体、バリアフィルム、およびそれを用いたデバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003213159A (ja) * 2002-01-18 2003-07-30 Toagosei Co Ltd 活性エネルギー線硬化型被覆用組成物
WO2016143461A1 (ja) * 2015-03-10 2016-09-15 東洋紡株式会社 透明バリアフィルムの製造法
WO2017217522A1 (ja) * 2016-06-17 2017-12-21 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びこれを用いてなるコーティング剤
JP2019119059A (ja) * 2017-12-28 2019-07-22 大日本印刷株式会社 ガスバリアフィルム
JP2020142430A (ja) * 2019-03-06 2020-09-10 凸版印刷株式会社 積層体

Also Published As

Publication number Publication date
JP2026065651A (ja) 2026-04-15
JPWO2025134926A1 (https=) 2025-06-26
JP7800782B2 (ja) 2026-01-16

Similar Documents

Publication Publication Date Title
US5565501A (en) Active-energy-ray-curable coating composition
EP3492258A1 (en) Laminate having oxygen barrier properties and packaging material comprising laminate
JP5743149B2 (ja) 無溶剤型接着剤用樹脂組成物、及び接着剤
KR20110021777A (ko) 유기 디바이스용 가스 배리어성 적층 필름
JP6760270B2 (ja) ガスバリア性皮膜形成用コーティング剤およびガスバリア性フィルム
TW201605990A (zh) 活性能量線硬化型樹脂組成物、塗料、塗膜、及積層薄膜
JP6260412B2 (ja) ガスバリア性フィルム
JP2014069389A (ja) ガスバリア積層フィルム
JP7596882B2 (ja) 印刷面保護フィルム及び多層体、並びに包装体及び包装物品
JP4941149B2 (ja) ガスバリア性積層フィルム
KR102432490B1 (ko) 투명증착 나일론을 이용한 즉석밥용 포장재 제조방법
JP2025182023A (ja) 積層フィルム、積層体および包装材料
JP7800782B2 (ja) ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料
JP7816472B2 (ja) 積層フィルム
JP7841664B2 (ja) ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料
JP6807668B2 (ja) バリア性積層フィルムおよびレトルト食品用包装体
JP6578473B2 (ja) 活性エネルギー線硬化型樹脂組成物、塗料、塗膜、及び積層フィルム
WO2023248610A1 (ja) ガスバリア性フィルム、積層体、および包装材料
JP7783424B2 (ja) セラミックグリーンシート製造用剥離フィルム
JP2021169163A (ja) 積層フィルムロール、それを用いたフィルム積層体ロール
WO2025164314A1 (ja) ガスバリア性フィルムの製造方法、ガスバリア性フィルム、包装材フィルム、及び包装材料
JP2020163857A (ja) 保護フィルム、それを用いたフィルム積層体およびその製造方法
JP5818234B2 (ja) ハードコートフィルム
JP2021138066A (ja) 積層フィルム、それを用いたフィルム積層体
JP4548073B2 (ja) ガスバリア性透明積層体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2025530607

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025530607

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24907311

Country of ref document: EP

Kind code of ref document: A1