WO2024101161A1 - ガスバリアフィルム、包装フィルム、包装袋、及び包装製品 - Google Patents

ガスバリアフィルム、包装フィルム、包装袋、及び包装製品 Download PDF

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Publication number
WO2024101161A1
WO2024101161A1 PCT/JP2023/038572 JP2023038572W WO2024101161A1 WO 2024101161 A1 WO2024101161 A1 WO 2024101161A1 JP 2023038572 W JP2023038572 W JP 2023038572W WO 2024101161 A1 WO2024101161 A1 WO 2024101161A1
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Prior art keywords
gas barrier
layer
coating layer
barrier film
barrier coating
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English (en)
French (fr)
Japanese (ja)
Inventor
美季 福上
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Toppan Holdings Inc
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Toppan Holdings Inc
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Priority to JP2024557311A priority Critical patent/JPWO2024101161A1/ja
Publication of WO2024101161A1 publication Critical patent/WO2024101161A1/ja
Priority to US19/195,498 priority patent/US20250270015A1/en
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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins

Definitions

  • the present invention relates to gas barrier films, packaging films, packaging bags, and packaging products.
  • Gas barrier films are widely used as packaging materials for food and pharmaceutical products that undergo heat sterilization processes such as boiling and retort processing.
  • heat sterilization processes such as boiling and retort processing.
  • gas barrier films suitable for such applications have traditionally been made using a polyolefin film base material that is heat resistant and has a low oxygen permeability.
  • Patent Document 1 discloses that a gas barrier laminate comprises a substrate layer containing polyolefin, a metal oxide layer, and a gas barrier coating layer in this order, and that the gas barrier coating layer contains silicon alkoxide or a hydrolyzate thereof, and a water-soluble polymer, and that the content ratio a/b of the silicon atom content (a parts by mass) in the silicon alkoxide or a hydrolyzate thereof to the content (b parts by mass) of the water-soluble polymer is 3/97 or more and 45/55 or less in mass ratio, thereby providing excellent gas barrier properties after retort sterilization and abuse testing.
  • One aspect of the present invention aims to provide a gas barrier film that has low oxygen permeability and excellent adhesion even after heat sterilization (e.g., retort treatment at 130°C for 60 minutes).
  • Another aspect of the present invention aims to provide a packaging film, packaging bag, and packaging product that use the gas barrier film.
  • One aspect of the present invention relates to, for example, the following [1] to [12].
  • the gas barrier film according to [1] which has an oxygen permeability of 5.0 cm 3 /(m 2 ⁇ day ⁇ atm) or less and a lamination strength of 1.5 N/15 mm or more.
  • a packaging film comprising the gas barrier film according to any one of [1] to [9] and a sealant layer.
  • a packaging bag comprising the packaging film according to [10].
  • a packaging product comprising the packaging bag according to [11] and contents contained in the packaging bag.
  • the present invention can provide a gas barrier film that has low oxygen permeability and excellent adhesion even after heat sterilization (e.g., retort treatment at 130°C for 60 minutes).
  • the present invention can also provide packaging films, packaging bags, and packaging products that use the gas barrier film.
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to one embodiment of the present invention.
  • Fig. 1 is a schematic cross-sectional view showing a gas barrier film according to one embodiment of the present invention.
  • the gas barrier film 10 includes a base layer 1, an anchor coat layer 2, a deposition layer 3, and a gas barrier coating layer 4, in this order.
  • the gas barrier film according to one embodiment has low oxygen permeability and excellent adhesion even after heat sterilization.
  • the oxygen permeability of the gas barrier film after heat sterilization may be, for example, 5.0 cm 3 /(m 2 ⁇ day ⁇ atm) or less, 4.0 cm 3 /(m 2 ⁇ day ⁇ atm) or less, or 3.5 cm 3 /(m 2 ⁇ day ⁇ atm) or less.
  • the laminate strength of the gas barrier film after heat sterilization may be 1.5 N/15 mm or more, 2.0 N/15 mm or more, 2.5 N/15 mm or more, 3.0 N/15 mm or more, or 3.5 N/15 mm or more.
  • heat sterilization refers to the treatment described in the examples below
  • the terms "oxygen permeability" and “lamination strength” refer to values measured by the methods described in the examples below.
  • the polypropylene content in the gas barrier film may be 90% by mass or more, 95% by mass or more, or 98% by mass or more, from the viewpoint of realizing mono-materialization and improving recyclability.
  • the substrate layer is a film (base film) that serves as a support, and contains a thermoplastic resin.
  • the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the thermoplastic resin may be polypropylene from the viewpoint of realizing mono-materialization and improving recyclability.
  • the thermoplastic resin is PET, it is easier to achieve lower oxygen permeability and better adhesion even after heat sterilization treatment, compared to when the thermoplastic resin is polypropylene.
  • the polypropylene may be a homopolypropylene or a propylene copolymer.
  • the propylene copolymer include polypropylene-based copolymers such as propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene- ⁇ -olefin copolymers.
  • the polypropylene may be recycled polypropylene, or may be polypropylene obtained by polymerizing raw materials derived from biomass such as plants. These polypropylenes may be used alone, or may be mixed with polypropylene polymerized from fossil fuels.
  • the substrate layer may be a stretched film or an unstretched film.
  • the substrate layer may be a stretched film from the viewpoint of reducing oxygen permeability.
  • examples of the stretched film include uniaxially stretched films and biaxially stretched films.
  • the stretched film may be a biaxially stretched film from the viewpoint of improving heat resistance.
  • the substrate layer may contain known additives.
  • the additives may be, for example, organic additives such as antioxidants, stabilizers, lubricants such as calcium stearate, fatty acid amides, and erucic acid amide, and antistatic agents; or inorganic additives such as particulate lubricants such as silica, zeolite, syloid, hydrotalcite, and silicon particles.
  • the polypropylene content in the base layer may be 90% by mass or more, 95% by mass or more, or 98% by mass or more, from the viewpoint of realizing mono-materialization and improving recyclability.
  • the polypropylene content in the base layer may be substantially 100% by mass (an embodiment in which the base layer is made of polypropylene).
  • the thickness of the substrate layer may be, for example, 3 ⁇ m or more, 6 ⁇ m or more, or 10 ⁇ m or more, and may be 200 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less.
  • the gas barrier film may or may not further include an anchor coat layer between the base layer and the deposition layer.
  • an anchor coat layer in the gas barrier film, low oxygen permeability and excellent adhesion can be more easily achieved even after heat sterilization treatment.
  • the anchor coat layer can be formed, for example, by applying an anchor coat layer-forming composition (anchor coat agent) onto the substrate layer and then drying.
  • anchor coat agents include solutions containing acrylic resin, epoxy resin, acrylic urethane resin, polyester polyurethane resin, polyether polyurethane resin, etc.
  • the anchor coat layer may contain at least one resin selected from the group consisting of acrylic urethane resin and polyester polyurethane resin.
  • the thickness of the anchor coat layer may be 0.05 ⁇ m or more, 0.08 ⁇ m or more, or 0.1 ⁇ m or more, from the viewpoint of further improving the adhesion between the substrate layer and the deposition layer.
  • the thickness of the anchor coat layer may be 2 ⁇ m or less, 1.5 ⁇ m or less, or 1 ⁇ m or less, from the viewpoint of easily imparting flexibility to the anchor coat layer and easily maintaining low oxygen permeability even when external factors such as bending or pulling are applied after the layer is formed.
  • the vapor-deposited layer is a layer provided on the base layer from the viewpoint of reducing oxygen permeability.
  • the vapor-deposited layer preferably has transparency.
  • the vapor deposition layer may contain an inorganic oxide.
  • inorganic oxides include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, and mixtures thereof. From the viewpoint of having better heat resistance during heat sterilization treatment, the vapor deposition layer may contain at least one selected from the group consisting of aluminum oxide and silicon oxide.
  • the deposition layer may be formed by vacuum deposition, which has excellent productivity.
  • the deposition layer may also be formed by other thin film formation methods than vacuum deposition, such as sputtering, ion plating, and plasma chemical vapor deposition (CVD).
  • the heating means for the vacuum deposition method can be any of the following: electron beam heating, resistance heating, and induction heating.
  • the heating means for the vacuum deposition method can be electron beam heating, since it has a wide range of evaporation materials to choose from.
  • the deposition layer may be formed by a plasma-assisted method or an ion-beam-assisted method in order to improve adhesion to the base layer and the density of the deposition layer.
  • the deposition layer may be formed by reactive deposition in which various gases such as oxygen are blown in during deposition in order to improve the transparency of the deposition layer.
  • the thickness of the deposition layer may be 5 nm or more, 15 nm or more, or 20 nm or more, from the viewpoint of making it easier to make the thickness of the deposition layer uniform and to more easily ensure the function as a gas barrier film.
  • the thickness of the deposition layer may be 300 nm, 150 nm or less, or 100 nm or less, from the viewpoint of making it easier to impart flexibility to the deposition layer and making it less likely to crack even if external factors such as bending or pulling are applied after the layer is formed.
  • the gas barrier coating layer is provided for the purpose of protecting the deposition layer and reducing the oxygen permeability of the gas barrier film.
  • the gas barrier coating layer may be made of a cured product of a composition containing a water-soluble polymer having a hydroxyl group, a metal alkoxide or a hydrolysate thereof, and a silane coupling agent or a hydrolysate thereof.
  • the gas barrier coating layer may be made of a cured product of a composition containing a water-soluble polymer having a hydroxyl group, a metal alkoxide or a hydrolysate thereof, and a silane coupling agent or a hydrolysate thereof, from the viewpoint of easily realizing a lower oxygen permeability and a better adhesion even after heat sterilization treatment, the gas barrier coating layer may be made of a cured product of a composition containing a water-soluble polymer having a hydroxyl group, a metal alkoxide or a hydrolysate thereof, and a silane coupling agent or a hydrolysate thereof.
  • the content of the water-soluble polymer having a hydroxyl group in the composition is made smaller than the content of the metal alkoxide, so that it is easier to realize a lower oxygen permeability and a better adhesion even after heat sterilization treatment.
  • water-soluble polymers having hydroxyl groups examples include polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, etc. From the viewpoint of lowering oxygen permeability even after heat sterilization treatment, the water-soluble polymer having hydroxyl groups may be polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the metal alkoxide may be a compound represented by the following general formula (1).
  • R 11 is a monovalent organic group having 1 to 8 carbon atoms, and may be an alkyl group such as a methyl group or an ethyl group (OR 11 is a hydrolyzable group).
  • R 12 is a monovalent organic group having 1 to 8 carbon atoms, and may be an alkyl group such as a methyl group or an ethyl group.
  • M represents an n-valent metal atom such as Si, Ti, Al, or Zr.
  • m is an integer from 1 to n.
  • metal alkoxides include tetraethoxysilane [Si(OC 2 H 5 ) 4 ] and triisopropoxyaluminum [Al(O-2′-C 3 H 7 ) 3 ].
  • Tetraethoxysilane (TEOS) and triisopropoxyaluminum are preferred because they are relatively stable in aqueous solvents after hydrolysis.
  • the metal alkoxide may be tetraethoxysilane, which is likely to achieve lower oxygen permeability and better adhesion even after heat sterilization.
  • the silane coupling agent includes a compound represented by the following general formula (2). Si(OR 21 ) p (R 22 ) 3-p R 23 ... (2)
  • R 21 represents an alkyl group such as a methyl group or an ethyl group
  • R 22 represents a monovalent organic group such as an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group
  • R 23 represents a monovalent organic functional group
  • p represents an integer of 1 to 3.
  • the R 21s or the R 22s may be the same or different.
  • Examples of the monovalent organic functional group represented by R 23 include a monovalent organic functional group containing a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, an alkyl group substituted with a halogen atom, or an isocyanate group.
  • a monovalent organic functional group containing a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, an alkyl group substituted with a halogen atom, or an isocyanate group may also be used.
  • silane coupling agents include vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, and 1,3,5-tris(3-methoxysilylpropyl)isocyanurate.
  • the silane coupling agent may be 1,3,5-tris(3-methoxysilylpropyl)isocyanurate, which is more likely to achieve lower oxygen permeability and better adhesion even after heat sterilization.
  • the gas barrier coating layer contains, for example, hydrogen atoms, carbon atoms, oxygen atoms, and metal atoms.
  • the hydrogen atoms and carbon atoms are mainly derived from a water-soluble polymer having a hydroxyl group, a metal alkoxide, a silane coupling agent, etc.
  • the oxygen atoms are mainly derived from a metal alkoxide and a silane coupling agent.
  • the metal atoms are mainly derived from a metal alkoxide and a silane coupling agent.
  • the metal atoms may be silicon atoms.
  • the proportion of nitrogen atoms in the gas barrier coating layer may be 2.0 atomic % or less.
  • the gas barrier coating layer contains atoms such as hydrogen atoms, carbon atoms, oxygen atoms, and metal atoms can be confirmed by performing a surface analysis of the gas barrier coating layer using Rutherford backscattering spectroscopy (RBS) and hydrogen forward scattering spectroscopy (HFS).
  • RBS Rutherford backscattering spectroscopy
  • HFS hydrogen forward scattering spectroscopy
  • the number of these atoms can also be measured using Rutherford backscattering spectroscopy and hydrogen forward scattering spectroscopy, and specifically, can be measured using the method described in the Examples below.
  • the atomic density of the gas barrier coating layer is 10.5 ⁇ 10 22 to 13.0 ⁇ 10 22 atoms/cm 3.
  • the gas barrier coating layer is prevented from becoming too hard, is less likely to crack, and is likely to have a low oxygen permeability even after heat sterilization.
  • the atomic density of the gas barrier coating layer is 13.0 ⁇ 10 22 atoms/cm 3 or less, the heat resistance is excellent, and the oxygen permeability is low even after heat sterilization, making it easy to achieve excellent adhesion.
  • the atomic density of the gas barrier coating layer can be calculated by the method described in the examples below.
  • the atomic density may be 10.55 ⁇ 10 22 atoms/cm 3 or more, or 10.6 ⁇ 10 22 atoms/cm 3 or more, from the viewpoint of preventing the gas barrier coating layer from becoming too hard and becoming less likely to crack, and of making it easier to lower the oxygen permeability even after heat sterilization treatment.
  • the atomic density may be 12.5 ⁇ 10 22 atoms/cm 3 or less, 12.0 ⁇ 10 22 atoms/cm 3 or less, or 11.7 ⁇ 10 22 atoms/cm 3 or less , from the viewpoint of improving heat resistance and making it easier to lower the oxygen permeability and realize better adhesion even after heat sterilization treatment.
  • the atomic density of the gas barrier coating layer can be adjusted, for example, by adjusting the type and amount of components contained in the gas barrier coating layer (water-soluble polymers having hydroxyl groups, metal alkoxides, silane coupling agents, etc.) and the drying temperature of the gas barrier coating layer.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the lowering the drying temperature of the gas barrier coating layer the atomic density of the gas barrier coating layer tends to increase.
  • the density of the gas barrier coating layer is 1.6 to 2.1 g/cm 3.
  • the density of the gas barrier coating layer is 1.6 g/cm 3 or more, the heat resistance is excellent, and the oxygen permeability is reduced even after heat sterilization, making it easier to realize excellent adhesion.
  • the density of the gas barrier coating layer is 2.1 g/cm 3 or less, the gas barrier coating layer is prevented from becoming too hard, is less likely to crack, and makes it easier to reduce the oxygen permeability even after heat sterilization.
  • the density of the gas barrier coating layer can be calculated by the method described in the examples below.
  • Conventional gas barrier coating layers have a density of less than 1.6 g/cm 3 , whereas the gas barrier coating layer in the gas barrier film according to one embodiment has a density of 1.6 to 2.1 g/cm 3 , making it easier to realize a gas barrier film having low oxygen permeability and excellent adhesion even after heat sterilization.
  • the density may be 1.65 g/ cm3 or more, or 1.7 g/cm3 or more, from the viewpoints of more excellent heat resistance, lowering oxygen permeability even after heat sterilization, and making it easier to realize better adhesion.
  • the density may be 2.05 g/cm3 or less, or 2.0 g/ cm3 or less , from the viewpoints of more suppressing the gas barrier coating layer from becoming too hard, making it less likely to crack, and making it easier to make the oxygen permeability lower even after heat sterilization.
  • the density of the gas barrier coating layer can be adjusted, for example, by adjusting the type and amount of components contained in the gas barrier coating layer (water-soluble polymers having hydroxyl groups, metal alkoxides, silane coupling agents, etc.) and the drying temperature of the gas barrier coating layer.
  • the density of the gas barrier coating layer tends to decrease.
  • the density of the gas barrier coating layer tends to decrease.
  • the atomic density of the gas barrier coating layer tends to increase.
  • the density of the gas barrier coating layer tends to decrease.
  • the gas barrier coating layer can be formed by coating the vapor deposition layer with a composition for forming the gas barrier coating layer, followed by heating and drying.
  • the composition for forming the gas barrier coating layer can be prepared by dissolving a water-soluble polymer in an aqueous solvent (water, a mixed solvent of water and alcohol, etc.) and mixing it with at least one of a metal alkoxide and a silane coupling agent, or a pre-hydrolyzed version of either of these.
  • This composition (mixed solution) can also contain known additives such as an isocyanate compound, a dispersant, a stabilizer, a viscosity modifier, and a colorant.
  • the amount of PVA in the composition may be 15% by mass or more, 20% by mass or more, or 25% by mass or more based on the total solid content of the composition, from the viewpoint of maintaining the flexibility of the gas barrier coating layer and making it easier to form the gas barrier coating layer.
  • the amount of PVA in the composition may be 70% by mass or less, 60% by mass or less, or 50% by mass or less based on the total solid content of the composition, from the viewpoint of making it easier to maintain low oxygen permeability even after heat sterilization treatment.
  • the amount of TEOS in the composition may be 30% by mass or more, 35% by mass or more, or 40% by mass or more based on the total solid content of the composition, from the viewpoint of easily maintaining low oxygen permeability even after heat sterilization treatment.
  • the amount of TEOS in the composition may be 80% by mass or less, 75% by mass or less, or 70% by mass or less based on the total solid content of the composition, from the viewpoint of maintaining the flexibility of the gas barrier coating layer and making it easier to form the gas barrier coating layer.
  • the amount of TEOS means a value converted to SiO2 .
  • the amount of isocyanurate silane in the composition may be 1 mass% or more, 3 mass% or more, or 5 mass% or more based on the total solid content of the composition, from the viewpoint of easily realizing hot water resistance and easily realizing excellent adhesion even after heat sterilization treatment.
  • the amount of isocyanurate silane in the composition may be 20 mass% or less, 15 mass% or less, or 10 mass% or less based on the total solid content of the composition, from the viewpoint of easily maintaining low oxygen permeability even after heat sterilization treatment without making the amount of other components in the composition too small.
  • the ratio of the content of the metal alkoxide to the content of the water-soluble polymer having a hydroxyl group in the composition may be 0.5 or more, 0.6 or more, 0.7 or more, or 0.8 or more, from the viewpoint of easily achieving better adhesion even after heat sterilization treatment, and may be 5 or less, 4 or less, 3 or less, 2.5 or less, 2 or less, or 1 or less, from the viewpoint of easily achieving lower oxygen permeability even after heat sterilization treatment.
  • the ratio of the content of the silane coupling agent to the content of the water-soluble polymer having a hydroxyl group in the composition may be 0 or more, 0.1 or more, 0.2 or more, or 0.22 or more, from the viewpoint of easily achieving lower oxygen permeability and better adhesion even after heat sterilization treatment, and may be 0.45 or less, 0.4 or less, or 0.35 or less, from the viewpoint of easily achieving lower oxygen permeability even after heat sterilization treatment.
  • the ratio of the content of the silane coupling agent to the content of the metal alkoxide in the composition may be 0 or more, 0.1 or more, 0.2 or more, or 0.22 or more, from the viewpoint of easily achieving lower oxygen permeability and better adhesion even after heat sterilization treatment, and may be 2 or less, 1 or less, 0.8 or less, 0.6 or less, or 0.4 or less, from the viewpoint of easily achieving better adhesion even after heat sterilization treatment.
  • the silicon oxide content in the gas barrier coating layer may be 30% by mass or more, 35% by mass or more, or 40% by mass or more, from the viewpoints of more excellent heat resistance and of lowering oxygen permeability even after heat sterilization treatment, making it easier to achieve better adhesion.
  • the silicon oxide content in the gas barrier coating layer may be 80% by mass or less, 75% by mass or less, or 70% by mass or less, from the viewpoints of more preventing the gas barrier coating layer from becoming too hard, making it less likely to crack, and of easier to achieve lower oxygen permeability even after heat sterilization treatment.
  • the drying temperature when forming the gas barrier coating layer may be 40°C or higher, 50°C or higher, 60°C or higher, or 90°C or higher, from the viewpoint of easily achieving lower oxygen permeability and better adhesion even after heat sterilization treatment, and may be 140°C or lower, 130°C or lower, or 120°C or lower, from the viewpoint of easily achieving lower oxygen permeability and better adhesion even after heat sterilization treatment.
  • the thickness of the gas barrier coating layer may be 80 nm or more, 90 nm or more, or 100 nm or more. If the thickness of the gas barrier coating layer is 80 nm or more, it is easy to maintain low oxygen permeability even after heat sterilization treatment.
  • the thickness of the gas barrier coating layer may be 1000 nm or less, 700 nm or less, 500 nm or less, or 400 nm or less. If the thickness of the gas barrier coating layer is 1000 nm or less, it is possible to suppress a decrease in gas barrier properties due to the occurrence of cracks in the layer during coating. From this perspective, the thickness of the gas barrier coating layer may be 80 to 1000 nm.
  • ⁇ Packaging film> Another embodiment of the present invention is a packaging film comprising the above gas barrier film and a sealant layer.
  • the sealant layer may be provided on the gas barrier coating layer side of the gas barrier film via an adhesive layer.
  • the adhesive layer is for bonding the films together.
  • adhesives constituting the adhesive layer include polyurethane resins in which a bifunctional or higher isocyanate compound is reacted with a base material such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol.
  • the various polyols may be used alone or in combination of two or more.
  • the adhesive layer may be composed of a two-liquid curing urethane adhesive from the viewpoint of heat resistance during heat sterilization treatment.
  • the polyurethane resin may be blended with a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, or the like.
  • the adhesive used may be one whose polymer component is derived from biomass or has biodegradability.
  • the adhesive may be an adhesive with gas barrier properties.
  • the amount of adhesive applied may be, for example, 0.5 to 10 g/ m2 from the viewpoint of obtaining the desired adhesive strength, followability, processability, and the like.
  • the sealant layer includes a thermoplastic resin, for example, a polyolefin resin.
  • the polyolefin resin include ethylene resins such as low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), linear low-density polyethylene resin (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene- ⁇ -olefin copolymer, and ethylene-(meth)acrylic acid copolymer, and polypropylene resins such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene- ⁇ -olefin copolymer, and mixtures thereof.
  • the material of the sealant layer can be appropriately selected from the above-mentioned thermoplastic resins depending on the intended use and temperature conditions such as boiling and retorting.
  • thermoplastic resin constituting the sealant layer may or may not be stretched.
  • the sealant layer does not have to be stretched in order to lower the melting point and facilitate heat sealing.
  • the thickness of the sealant layer is not particularly limited, but may be, for example, 15 ⁇ m or more, 30 ⁇ m or more, or 50 ⁇ m or more, and may be 200 ⁇ m or less, 150 ⁇ m or less, or 100 ⁇ m or less.
  • the packaging bag is formed by making the packaging film described above. That is, another embodiment of the present invention is a packaging bag including the packaging film.
  • the packaging bag can accommodate contents such as food, medicine, etc.
  • another embodiment of the present invention is a packaging product including the packaging bag and the contents accommodated in the packaging bag.
  • the packaging bag may be one in which a sheet of packaging film is folded in half with the sealant layers facing each other, and then three sides are heat-sealed to form a bag shape, or two sheets of packaging material are stacked together with the sealant layers facing each other, and then four sides are heat-sealed to form a bag shape.
  • the packaging bag may also have a shape that has a bent portion (folded portion) such as a standing pouch.
  • the packaging bag according to this embodiment can maintain excellent gas barrier properties even when it has a shape that has a bent portion.
  • the following anchor coating agent was applied by gravure coating onto a 20 ⁇ m thick polypropylene film (manufactured by Mitsui Chemicals Tohcello, Inc., product name: ME-1), and dried to form an anchor coating layer with a thickness of 0.1 ⁇ m.
  • a vapor deposition layer made of silicon oxide with a thickness of 25 nm was formed on the anchor coating layer using a vacuum deposition device with electron beam heating.
  • Acrylic polyol and tolylene diisocyanate were mixed so that the number of NCO groups in tolylene diisocyanate was equal to the number of OH groups in the acrylic polyol, and then the mixture was diluted with ethyl acetate so that the total solid content (total amount of acrylic polyol and tolylene diisocyanate) was 5 mass%. 5 mass parts of ⁇ -(3,4-epoxycyclohexyl)trimethoxysilane were added to the diluted mixture per 100 mass parts of the total amount of acrylic polyol and tolylene diisocyanate, and these were mixed to prepare an anchor coating agent.
  • the following coating liquid was applied onto the deposition layer and dried at 80° C. for 1 minute to form a gas barrier coating layer with a thickness of 320 nm. This resulted in a laminate (gas barrier film) in which the substrate layer/anchor coat layer/deposition layer/gas barrier coating layer were laminated in this order.
  • the polypropylene resin content in the resulting gas barrier film was 90% by mass or more.
  • Coating liquid The following A liquid, B liquid, and C liquid were mixed so that the mass ratio of polyvinyl alcohol (PVA) of A liquid, SiO2 of B liquid, and silane coupling agent (SC agent) of C liquid was 45:45:10 to prepare a coating liquid.
  • Solution A an aqueous solution containing 5% by mass of PVA (manufactured by Kuraray Co., Ltd., product name: Kuraray Bobal 60-98).
  • Solution B Tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE04), methanol (manufactured by Kanto Chemical Co., Ltd.), and 0.1 N hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) were mixed in a mass ratio of 17:10:73 to prepare a hydrolysis solution having a solid content of 5 mass% ( SiO2 equivalent).
  • Liquid C A hydrolysis solution prepared by dissolving 1,3,5-tris(3-methoxysilylpropyl)isocyanurate in a solution with a mass ratio of water and IPA (isopropyl alcohol) of 1:1 so that the solid content was 5 mass % (calculated as R 2 Si(OH) 3 ).
  • Examples 2 to 8, Comparative Examples 1 to 5 Gas barrier films were obtained in the same manner as in Example 1, except that the mixing ratio of the liquids A, B, and C, the thickness of the gas barrier coating layer, the drying temperature, and the drying time were changed as shown in Table 1.
  • the polypropylene resin content in each of the obtained gas barrier films was 90% by mass or more.
  • Example 9 Gas barrier films were obtained in the same manner as in Example 1, except that a 12 ⁇ m-thick PET film (manufactured by Futamura Chemical Co., Ltd., product name: FE2001) was used as the substrate, and the drying temperature and drying time were changed as shown in Table 1.
  • the polypropylene resin content in each of the obtained gas barrier films was 90 mass % or more.
  • ⁇ Preparation of packaging film> A 60 ⁇ m-thick unstretched polypropylene film (manufactured by Toray Industries, Inc., product name: Torayfan ZK207) was laminated on the gas barrier coating layer side of the prepared gas barrier film by dry lamination via a two-component curing urethane adhesive (manufactured by Mitsui Chemicals SKC Polyurethanes, Inc., product name: A525/A52). This produced a packaging film.
  • the density of each atom in the gas barrier coating layer was calculated from the composition and surface density of each atom on the surface of the gas barrier coating layer using the following formula (2), and the density of the gas barrier coating layer was calculated by adding up the densities of each atom.
  • the calculation results of the atomic number density and density of the gas barrier coating layer are shown in Table 1.
  • the proportion of nitrogen atoms in the gas barrier coating layer was 2.0 atomic % or less.
  • Atomic density surface density / thickness ...
  • Density of each atom surface density ⁇ atomic composition ⁇ atomic weight of each atom / Avogadro's constant / thickness ...
  • the oxygen transmission rate of the sealed pouch after retort treatment was measured.
  • the measurement was performed using an oxygen transmission rate measuring device (OXTRAN 2/20, manufactured by Modern Control) under conditions of a temperature of 30°C and a relative humidity of 70%.
  • the measurement method was in accordance with JIS K-7126, Method B (isobaric method), and ASTM D3985-81, and the measured value was expressed in units of [ cm3 / m2 ⁇ day ⁇ atm]. The results are shown in Table 1.
  • Example 1 shows that lowering the drying temperature tends to increase the atomic number density and decrease the density. Also, a comparison between Example 1 and Example 3 shows that increasing the drying temperature can achieve lower oxygen permeability and better adhesion even after heat sterilization.
  • Example 1 shows that by increasing the amount of water-soluble polymer having hydroxyl groups while keeping the amount of silane coupling agent constant, the atomic number density tends to increase and the density tends to decrease. Furthermore, a comparison between Example 1 and Example 4 shows that by decreasing the amount of water-soluble polymer having hydroxyl groups while keeping the amount of silane coupling agent constant, lower oxygen permeability and better adhesion can be achieved even after heat sterilization treatment.
  • Example 1 and Example 8 show that by increasing the amount of silane coupling agent while keeping the amount of water-soluble polymer having hydroxyl groups constant, the atomic number density increases and there is a tendency for the density to also increase. Furthermore, a comparison between Example 1 and Example 8 shows that by increasing the amount of silane coupling agent while keeping the amount of water-soluble polymer having hydroxyl groups constant, lower oxygen permeability and better adhesion can be achieved even after heat sterilization treatment.
  • Comparing Example 2 with Comparative Example 2 it can be seen that by increasing the amount of water-soluble polymer having hydroxyl groups while keeping the amount of metal alkoxide constant, the atomic number density tends to increase and the density tends to decrease. Also, comparing Example 2 with Comparative Example 2, it can be seen that by increasing the amount of water-soluble polymer having hydroxyl groups while keeping the amount of metal alkoxide constant, a lower oxygen permeability can be achieved even after heat sterilization treatment.
  • Reference Signs List 1 substrate layer, 2: anchor coat layer, 3: vapor deposition layer, 4: gas barrier coating layer, 10: gas barrier film.

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PCT/JP2023/038572 2022-11-08 2023-10-25 ガスバリアフィルム、包装フィルム、包装袋、及び包装製品 Ceased WO2024101161A1 (ja)

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Publication number Priority date Publication date Assignee Title
WO2026029000A1 (ja) * 2024-08-02 2026-02-05 Ｔｏｐｐａｎホールディングス株式会社 積層体及び包装材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048081A1 (ja) * 2002-11-22 2004-06-10 Toppan Printing Co., Ltd. ガスバリア積層フィルム
WO2016158794A1 (ja) * 2015-03-27 2016-10-06 凸版印刷株式会社 積層フィルム、及び包装袋
JP2018001631A (ja) * 2016-07-04 2018-01-11 三井化学東セロ株式会社 バリア性積層フィルムおよび食品用包装体
JP2019119132A (ja) * 2018-01-05 2019-07-22 凸版印刷株式会社 ラミネートフィルムおよび成形品
WO2021220977A1 (ja) * 2020-04-27 2021-11-04 凸版印刷株式会社 ガスバリア積層体及び包装袋

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048081A1 (ja) * 2002-11-22 2004-06-10 Toppan Printing Co., Ltd. ガスバリア積層フィルム
WO2016158794A1 (ja) * 2015-03-27 2016-10-06 凸版印刷株式会社 積層フィルム、及び包装袋
JP2018001631A (ja) * 2016-07-04 2018-01-11 三井化学東セロ株式会社 バリア性積層フィルムおよび食品用包装体
JP2019119132A (ja) * 2018-01-05 2019-07-22 凸版印刷株式会社 ラミネートフィルムおよび成形品
WO2021220977A1 (ja) * 2020-04-27 2021-11-04 凸版印刷株式会社 ガスバリア積層体及び包装袋

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026029000A1 (ja) * 2024-08-02 2026-02-05 Ｔｏｐｐａｎホールディングス株式会社 積層体及び包装材料
JP7838723B1 (ja) * 2024-08-02 2026-04-01 Ｔｏｐｐａｎホールディングス株式会社 積層体及び包装材料

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