WO2023021852A1 - ガスバリア積層体及び容器 - Google Patents

ガスバリア積層体及び容器 Download PDF

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Publication number
WO2023021852A1
WO2023021852A1 PCT/JP2022/025824 JP2022025824W WO2023021852A1 WO 2023021852 A1 WO2023021852 A1 WO 2023021852A1 JP 2022025824 W JP2022025824 W JP 2022025824W WO 2023021852 A1 WO2023021852 A1 WO 2023021852A1
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Prior art keywords
layer
gas barrier
resin
laminate
based resin
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Ceased
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PCT/JP2022/025824
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English (en)
French (fr)
Japanese (ja)
Inventor
淑希子 今泉
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Toppan Inc
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Toppan Inc
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Publication date
Application filed by Toppan Inc filed Critical Toppan Inc
Priority to CN202280039593.5A priority Critical patent/CN117412865A/zh
Priority to EP22858175.7A priority patent/EP4368390B1/en
Priority to JP2023542247A priority patent/JPWO2023021852A1/ja
Publication of WO2023021852A1 publication Critical patent/WO2023021852A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical 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
    • 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
    • B32B27/10—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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    • 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
    • B32B7/02—Physical, chemical or physicochemical 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 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
    • B32B2250/44—Number of layers variable across the laminate
    • 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
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/58—Cuttability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B65D2231/00—Means for facilitating the complete expelling of the contents
    • B65D2231/02—Precut holes or weakened zones
    • B65D2231/022—Precut holes or weakened zones for permitting the insertion of a tubular contents-removing device, e.g. a drinking straw
    • 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
    • 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
    • B65D5/00—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/02—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper by folding or erecting a single blank to form a tubular body with or without subsequent folding operations, or the addition of separate elements, to close the ends of the body
    • B65D5/06—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper by folding or erecting a single blank to form a tubular body with or without subsequent folding operations, or the addition of separate elements, to close the ends of the body with end-closing or contents-supporting elements formed by folding inwardly a wall extending from, and continuously around, an end of the tubular body
    • B65D5/064—Rectangular containers having a body with gusset-flaps folded outwardly or adhered to the side or the top of the container
    • 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 laminates and containers.
  • Patent Document 1 discloses a liquid paper container formed by forming a packaging material comprising a paper substrate, a specific barrier layer, an adhesive resin layer having a specific thickness, and a heat-sealable resin layer. ing.
  • a paper container may be formed with a straw piercing opening for sucking out the contained contents with a straw.
  • the piercing opening of the straw is formed by forming a hole penetrating the paper substrate.
  • the present disclosure provides a gas barrier laminate with excellent straw piercing properties, and a container obtained using the same.
  • a gas barrier laminate has a laminate structure including a paper substrate, an adhesive resin layer, a gas barrier layer, and a sealant layer in this order, and the sealant layer comprises a polyethylene resin and At least one of the polypropylene-based resins and a cyclic olefin-based resin are included, and when the tensile elastic modulus of the gas barrier layer is TA and the tensile elastic modulus of the sealant layer is TB , TA and TB are represented by the following formula ( 1) is satisfied. ⁇ 0.26 ⁇ (T B ⁇ T A )/T A ⁇ 0.30 Expression (1)
  • the gas barrier laminate according to one aspect of the present disclosure has excellent straw piercing properties. Such an effect is presumed to be produced by the following mechanism. That is, the straw piercing opening formed in the gas barrier laminate is formed with a hole penetrating the paper substrate, and comprises an adhesive resin layer, a gas barrier layer and a sealant layer in this order. Since the adhesive resin layer is on the outer layer side and the sealant layer is on the inner layer side, when a straw is pierced into the piercing port, the impact from the straw is gradually applied as the straw penetrates the adhesive resin layer and the gas barrier layer.
  • the sealant layer contains at least one of a polyethylene-based resin and a polypropylene-based resin and a cyclic olefin-based resin, and the tensile elastic modulus of the gas barrier layer and the sealant layer satisfies the above formula (1).
  • the sealant layer is easily broken together with the gas barrier layer.
  • the gas barrier laminate has excellent straw piercing properties.
  • a gas barrier laminate has a laminate structure comprising a paper substrate, an adhesive resin layer, a gas barrier layer, and a sealant layer in this order, and the adhesive resin layer At least one of a polyethylene-based resin and a polypropylene-based resin and a cyclic olefin-based resin are included, and when the tensile elastic modulus of the gas barrier layer is TA and the tensile elastic modulus of the adhesive resin layer is TC , TA and TC satisfies the following formula (2). ⁇ 0.26 ⁇ (T C ⁇ T A )/T A ⁇ 0.30 Expression (2)
  • a gas barrier laminate according to another aspect of the present disclosure has excellent straw piercing properties. Such an effect is presumed to be produced by the following mechanism. That is, when a straw is pierced into the straw piercing opening, the impact applied from the straw causes the straw to penetrate the adhesive resin layer and reach the gas barrier layer.
  • the adhesive resin layer contains at least one of a polyethylene-based resin and a polypropylene-based resin and a cyclic olefin-based resin, and the tensile elastic moduli of the adhesive resin layer and the gas barrier layer satisfy the above formula (2). Since the straw easily reaches the gas barrier layer due to the shock applied from the straw, the gas barrier layer is easily broken together with the adhesive resin layer.
  • the gas barrier layer is torn together with the adhesive resin layer, the impact from the straw is transmitted to the sealant layer outside the gas barrier layer, and the sealant layer is easily torn. As a result, the gas barrier laminate has excellent straw piercing properties.
  • the gas barrier layer includes a polyolefin film as a film base material because the container has excellent recyclability and is even more excellent in straw piercing properties, and the sealant layer and the polyolefin film are in direct contact.
  • the laminate strength with the film may be 1 N/15 mm or more.
  • the gas barrier layer may have a vapor deposition layer containing an inorganic oxide, since the container has excellent water resistance.
  • a container according to still another aspect of the present disclosure is configured by the gas barrier laminate. This container has excellent straw piercing properties.
  • a gas barrier laminate that can provide a container with excellent straw pierceability, and a container obtained using the same are provided.
  • FIG. 1 is an end view schematically showing a gas barrier laminate according to one embodiment of the present disclosure.
  • FIG. 2 is a perspective view schematically showing a container according to one embodiment of the present disclosure;
  • FIG. 1 is an end view schematically showing a laminate according to one embodiment.
  • the laminate 10 according to this embodiment has a laminate structure comprising a paper substrate 1, an adhesive resin layer 2, a gas barrier layer 3, and a sealant layer 4 in this order.
  • the paper base material 1 is formed with a hole 1a passing through the paper base material 1 as a straw piercing opening.
  • a protective layer 5 is arranged on the surface of the paper substrate 1 opposite to the surface in contact with the adhesive resin layer 2 .
  • the gas barrier layer 3 consists of a vapor deposition layer 3a and a film substrate 3b.
  • Paper substrate As the paper substrate 1, for example, paper having shapeability, bending resistance, rigidity, stiffness, strength, and the like can be used. As such paper, for example, strong sizing bleached or unbleached paper, pure white roll paper, kraft paper, cardboard and processed paper can be used.
  • the basis weight of the paper base material 1 is preferably 80 to 600 g/m 2 , more preferably 200 to 450 g/m 2 , since the obtained container has better gas barrier properties.
  • Desired printed patterns such as characters, figures, patterns and symbols can be arbitrarily formed on the paper substrate 1 by a normal printing method.
  • the adhesive resin layer 2 contains at least one of a polyethylene-based resin and a polypropylene-based resin, and a cyclic olefin-based resin.
  • Polyethylene-based resins include low-density polyethylene, high-density polyethylene, copolymer resins of polyethylene and polyvinyl acetate, and acid anhydride-modified polyethylene represented by terpolymers such as ethylene/ethyl acrylate/maleic anhydride. and epoxy compound-modified polyethylene such as ethylene-glycidyl methacrylate copolymer.
  • the polyethylene-based resin is preferably low-density polyethylene because it improves the piercing property.
  • Low density polyethylene includes linear low density polyethylene and branched low density polyethylene, preferably branched low density polyethylene.
  • the branched low-density polyethylene is preferably obtained by high-pressure radical polymerization, more preferably by homopolymerizing ethylene by high-pressure radical polymerization.
  • Such low-density polyethylene has low mechanical strength and is brittle compared to other polyolefins, so it has good puncture resistance.
  • Polyethylene-based resins may be used singly or in combination of two or more.
  • the density of the low-density polyethylene is preferably 0.900 g/cm 3 to 0.935 g/cm 3 , more preferably 0.915 g/cm 3 to 0.930 g/cm 3 . If the density is within the above range, the low-density polyethylene has appropriate rigidity, so that the adhesive resin layer 2 has improved film formability and extrusion suitability.
  • the melting point of the polyethylene resin is preferably lower than the glass transition point (Tg) of the cyclic olefin resin, preferably 60 to 130°C, more preferably 70 to 120°C. If the melting point is within this range, coextrusion workability and compatibility are improved.
  • Tg glass transition point
  • Polypropylene-based resins include, for example, propylene homopolymers, propylene/ ⁇ -olefin random copolymers, acid anhydride-modified polypropylenes represented by terpolymers such as propylene/ethyl acrylate/maleic anhydride, and Epoxy compound-modified polypropylene such as propylene/glycidyl methacrylate copolymer can be used.
  • propylene/ ⁇ -olefin random copolymers include propylene-ethylene copolymers, propylene-butene-1 copolymers and propylene-ethylene-butene-1 copolymers.
  • the polypropylene-based resin may be synthesized using a metallocene catalyst.
  • the polypropylene-based resin is preferably a propylene- ⁇ -olefin random copolymer, more preferably a propylene/ ⁇ -olefin random copolymer polymerized using a metallocene catalyst.
  • the heat resistance of the adhesive resin layer 2 can be improved and the softening temperature can be increased.
  • the laminate 10 can be suitably used for boiling or hot filling at 100° C. or lower, or steam heating such as retort sterilization at 100° C. or higher, or sterilization by high-pressure heating.
  • Polypropylene-based resins may be used singly or in combination of two or more.
  • the melting point of the polypropylene resin is preferably 110-165°C, more preferably 115-160°C.
  • the melting point of the polypropylene-based resin can be appropriately changed according to the glass transition point (Tg) of the cyclic olefin-based resin.
  • Cyclic olefin-based resins are not particularly limited, but examples thereof include ring-opening polymers (COP) of norbornene-based monomers, norbornene-based polymers (COC), vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. be done. Among these, norbornene-based polymers are preferable from the viewpoint of compatibility with polyethylene-based resins.
  • Examples of commercial products of ring-opening polymers of norbornene-based monomers include ZEONOR (trade name) manufactured by Nippon Zeon Co., Ltd.
  • Examples of commercially available norbornene-based polymers include APEL (trade name) manufactured by Mitsui Chemicals, Inc. and TOPAS (trade name) manufactured by Polyplastics Co., Ltd.
  • the density of the cyclic olefin resin is preferably 0.99 g/cm 3 to 1.05 g/cm 3 and more preferably 1.00 g/cm 3 to 1.03 g/cm 3 . If the density is within the above range, the film formability and extrusion suitability of the adhesive resin layer 2 are improved.
  • the glass transition point (Tg) of the cyclic olefin resin is preferably 60°C to 180°C, more preferably 70°C to 150°C. If the Tg is within the above range, the film formability and extrusion suitability of the adhesive resin layer 2 are improved.
  • the mass ratio of the total mass of the polyethylene-based resin and polypropylene-based resin to the mass of the cyclic olefin-based resin in the adhesive resin layer 2 is 70. /30 or more, more preferably 80/20 or more, preferably 95/5 or less, more preferably 90/10 or less.
  • the total mass of the polyethylene-based resin and polypropylene-based resin in the adhesive resin layer 2 and the mass of the cyclic olefin-based resin is 80% by mass or more, 90% by mass or more, or 95% by mass, based on the total amount of the adhesive resin layer 2. % by mass or more.
  • the thickness of the adhesive resin layer 2 is, for example, preferably 1 to 40 ⁇ m, more preferably 10 to 40 ⁇ m, even more preferably 15 to 25 ⁇ m.
  • the adhesive resin layer 2 may or may not be uniaxially stretched.
  • the sealant layer 4 contains at least one of a polyethylene-based resin and a polypropylene-based resin, and a cyclic olefin-based resin.
  • a polyethylene-based resin As the polyethylene-based resin, the polypropylene-based resin, and the cyclic olefin-based resin, the same ones as those exemplified for the adhesive resin layer 2 can be used.
  • the mass ratio and total mass of the polyethylene-based resin, the polypropylene-based resin and the cyclic olefin-based resin in the sealant layer 4 are the same as those of the adhesive resin layer 2 .
  • the thickness of the sealant layer 4 is not particularly limited, it is preferably 20 ⁇ m to 50 ⁇ m considering suitability as a packaging material and workability when laminating another film or forming a vapor deposition layer.
  • sealant layer 4 components such as antifog agents, antistatic agents, heat stabilizers, nucleating agents, antioxidants, lubricants, antiblocking agents, mold release agents, ultraviolet absorbers and colorants are added as necessary. can be added as long as the object of the present disclosure is not impaired.
  • the lamination method of the sealant layer 4 may be, for example, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, and a co-extrusion inflation method.
  • the deposited layer 3a is a layer in which silicon oxide (SiO x ) is deposited. Thereby, the laminate 10 becomes excellent in water resistance.
  • the thickness of the deposited layer 3a may be appropriately set according to the intended use, but is preferably 1 to 300 nm, more preferably 10 to 300 nm, and still more preferably 30 to 100 nm. When the thickness of the vapor deposition layer 3a is 1 nm or more, the continuity of the vapor deposition layer 3a can be easily made sufficient, and when the thickness is 300 nm or less, the occurrence of curling and cracking can be sufficiently suppressed, and sufficient gas barrier performance and flexibility can be obtained. easy to achieve.
  • the deposited layer 3a may be a layer deposited with an inorganic oxide other than silicon oxide (SiO x ) or a metal.
  • the deposited layer 3a may be obtained by, for example, depositing aluminum, or may contain aluminum oxide (AlO x ).
  • Film formation means include known methods such as a vacuum deposition method, a sputtering method, and a chemical vapor deposition method (CVD method), but the vacuum deposition method is preferred because of its high film formation speed and high productivity.
  • vacuum evaporation methods electron beam heating is particularly effective because the film formation rate can be easily controlled by adjusting the irradiation area and electron beam current, and the temperature of the vapor deposition material can be raised and lowered in a short period of time. be.
  • Film substrate examples of materials for the film substrate 3b include polyolefin films, polyethylene terephthalate films, and nylon films.
  • the film substrate 3b is preferably a polyolefin film. By using the polyolefin film, it becomes possible to recycle the adhesive resin layer 2 and the sealant layer 4 together with the olefin plastic material.
  • Polyolefin films include, for example, polypropylene films and polyethylene films.
  • the film substrate 3b may be a uniaxially stretched film or a biaxially stretched film.
  • the lamination strength between the film base material 3b and the sealant layer 4 is preferably 1 N/15 mm or more, preferably 1.5 N/15 mm, because it is more excellent in puncture resistance. It is more preferably 2 N/15 mm or more, and more preferably 2 N/15 mm or more. Laminate strength is measured according to JIS Z-1707.
  • the wettability of the surface of the film substrate 3b in contact with the polyolefin film that achieves such lamination strength may be 34 dynes or more when the lamination strength is 1 N/15 mm or more, and may be 1.5 N/15 mm or more. In some cases, it may be 36 dynes or more, and in cases of 2 N/15 mm or more, it may be 38 dynes or more. Wettability is measured according to JIS K6768:1999. The wettability of the surface of the film substrate 3b can be adjusted, for example, by subjecting the film substrate 3b to corona treatment.
  • the thickness of the film substrate 3b is preferably 15 to 30 ⁇ m, more preferably 18 to 20 ⁇ m, from the viewpoint of ease of processing such as lamination.
  • the material of the protective layer 5 may be polyethylene resin, for example. Since the protective layer 5 is made of polyethylene resin, the obtained container is excellent in recyclability.
  • the polyethylene resin is preferably medium-density polyethylene or high-density polyethylene, since the polyethylene resin has high physical strength and the resulting container has even more excellent gas barrier properties.
  • the thickness of the protective layer 5 is preferably from 10 to 30 ⁇ m, more preferably from 15 to 20 ⁇ m, since the obtained container has a more excellent gas barrier property.
  • (T B ⁇ T A )/T A is preferably ⁇ 0.20 or more, more preferably ⁇ 0.10 or more, because the puncture resistance is further improved. From the same viewpoint, (T B -T A )/T A is preferably 0.25 or less, more preferably 0.10 or less, and even more preferably 0.05 or less.
  • (T C -T A )/T A is preferably -0.20 or more, more preferably -0.10 or more, because the puncture resistance is further improved. From the same viewpoint, (T C -T A )/T A is preferably 0.25 or less, more preferably 0.10 or less, and even more preferably 0.05 or less.
  • the tensile elastic modulus TA of the gas barrier layer 3 may be 800 MPa or more and may be 1300 MPa or less.
  • T A , T B and T C are measured according to ISO 527.
  • the laminate 10 is obtained by laminating each layer.
  • Methods for laminating each layer include, for example, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, and a co-extrusion inflation method.
  • the major surface of each layer may be subjected to, for example, corona treatment, plasma treatment and ozone treatment prior to lamination.
  • the laminate 10 having the above configuration has excellent straw piercing properties.
  • Such an effect is presumed to be produced by the following mechanism. That is, when the straw is pierced into the straw piercing opening, the impact applied from the straw is transmitted to the sealant layer while gradually attenuating as the straw penetrates the adhesive resin layer and the gas barrier layer.
  • the adhesive resin layer 2 and the sealant layer 4 contain at least one of a polyethylene-based resin and a polypropylene-based resin, and a cyclic olefin-based resin, and T A , T B and T C are the above formula (1) and the formula (2) is satisfied. Therefore, the impact applied from the straw is easily transmitted to the sealant layer 4, and the adhesive resin layer 2, the gas barrier layer 3 and the sealant layer 4 are easily broken. As a result, the laminate 10 has excellent straw piercing properties.
  • the laminate 10 has excellent piercing properties with a straw. Therefore, even if the material of the straw to be pierced is not plastic, which is generally used, but a material such as paper that is difficult to apply force to, the piercing can be performed satisfactorily.
  • the present disclosure is not limited to the above embodiments.
  • the stacking order of the film substrate 3b and the deposited layer 3a may be changed.
  • the laminate strength between the film substrate 3b and the adhesive resin layer 2 may be the same as the laminate strength between the film substrate 3b and the sealant layer 4 described above.
  • the vapor deposition layer 3a may not be provided.
  • the adhesive resin layer 2 out of the adhesive resin layer 2 and the sealant layer 4 may contain at least one of polyethylene-based resin and polypropylene-based resin, and a cyclic olefin-based resin. In that case, the sealant layer 4 does not have to satisfy the above formula (1).
  • the sealant layer 4 out of the adhesive resin layer 2 and the sealant layer 4 may contain at least one of polyethylene-based resin and polypropylene-based resin, and a cyclic olefin-based resin. In that case, the adhesive resin layer 2 does not have to satisfy the above formula (2).
  • a container 50 shown in FIG. 2 is composed of the laminate 10 .
  • the container 50 can fill and package various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, sundries such as medicines, and various other articles. Since the container 50 has excellent piercing properties and gas barrier properties, it can be used to store dairy products such as sake and milk, juices such as fruit juice beverages, mineral water, liquid seasonings such as soy sauce and sauces, curries, stews and soups. It is particularly suitably used as a packaging container for filling and packaging liquid food and drink.
  • the container 50 is a brick type container.
  • the container 50 includes a rectangular parallelepiped container main body 52 having an upper portion 52a provided with a straw piercing opening 51, a side surface 52b, and a bottom portion 52c.
  • the straw piercing opening 51 is a portion of the laminate 10 where the hole 1a is formed in the paper base material 1 .
  • the container according to the present disclosure is not limited to the above embodiment.
  • the shape of the container is not limited to the shape of the container 50, and may be, for example, a gable top type or a triangular pyramid shape.
  • the shape of the container body may be cylindrical.
  • Cyclic olefin resin A TOPAS 5013F-04 (trade name, norbornene polymer, tensile modulus: 2600 MPa, manufactured by Polyplastics Co., Ltd.)
  • Cyclic olefin resin B ZEONOR 1020R (trade name, ring-opening polymer of norbornene-based monomer, cycloolefin polymer, tensile modulus: 2100 MPa, manufactured by Nippon Zeon Co., Ltd.)
  • Cyclic olefin resin C TOPAS 6015S-04 (trade name, norbornene polymer, tensile modulus of elasticity 3000 MPa, manufactured by Polyplastic Co., Ltd.)
  • Cyclic olefin resin D TOPAS 9506F-500 (trade name, norbornene polymer, tensile modulus 1800 MPa, manufactured by Polyplastic Co., Ltd.)
  • the tensile elastic moduli of cyclic olefin resins and polyethylene resins are values measured according to ISO 527.
  • Example 1 A laminate according to this example was obtained through the following steps. That is, as resins for forming the sealant layer and the adhesive resin layer, a polyethylene resin A and a cyclic olefin resin A were mixed by dry blending to obtain a resin mixture. The mass ratio of the polyethylene-based resin and the cyclic olefin-based resin (mass of the polyethylene-based resin/mass of the cyclic olefin-based resin) was set to 80/20.
  • a gas barrier film was prepared in which a vapor deposition layer containing silica as a main component (silica vapor deposition layer, thickness: 50 nm) was formed on one surface of a film substrate (material: polypropylene resin, thickness: 18 ⁇ m).
  • the surface of the film substrate opposite to the surface on which the deposited layer was formed was subjected to corona treatment so that the wettability of the surface was 40 dynes.
  • a sealant layer (thickness: 30 ⁇ m) was formed on the corona-treated surface of the film substrate by extrusion lamination of the resin mixture to obtain an inner layer material.
  • the wettability of the surface of the film substrate was measured according to JIS K6768:1999 using a wet tension test mixture (manufactured by Kanto Kagaku Co., Ltd.).
  • a protective layer material: polyethylene-based resin, thickness: 20 ⁇ m
  • a paper base material basic weight: 260 g/m 2
  • An outer layer material containing a paper substrate was obtained.
  • a laminated body was obtained by bonding the inner layer material and the outer layer material together with a resin mixture (adhesive resin layer) by extrusion lamination so that the vapor-deposited layer of the inner layer material and the paper base material of the outer layer material faced each other.
  • the thickness of the adhesive resin layer was 15 ⁇ m.
  • Example 2 A laminate was obtained in the same manner as in Example 1, except that the cyclic olefin resin B was used instead of the cyclic olefin resin A.
  • Example 3 A laminate was obtained in the same manner as in Example 1, except that the cyclic olefin resin C was used instead of the cyclic olefin resin A.
  • Example 4 A laminate was obtained in the same manner as in Example 1, except that the cyclic olefin resin C was used instead of the cyclic olefin resin A, and the mass ratio of the polyethylene resin and the cyclic olefin resin was set to 85/15. rice field.
  • Example 5 A laminate according to this example was obtained through the following steps. That is, a resin mixture was obtained in the same manner as in Example 1, except that the polyethylene resin B was used instead of the polyethylene resin A. Next, a gas barrier film was prepared in the same manner as in Example 1 and subjected to corona treatment. A sealant layer (thickness: 30 ⁇ m) was formed by co-extrusion laminating the resin mixture and polyethylene resin A on the corona-treated surface of the film substrate to obtain an inner layer material. By coextrusion lamination, a layer of the resin mixture was formed on the corona-treated surface of the film substrate, and a layer of the polyethylene resin A was formed on the layer of the resin mixture. A laminate was obtained in the same manner as in Example 1 using the obtained inner layer material.
  • Example 6 A laminate was obtained in the same manner as in Example 5, except that the mass ratio of the polyethylene resin and the cyclic olefin resin was 95/5.
  • Example 7 A laminate was obtained in the same manner as in Example 1, except that polyethylene-based resin A was used instead of the resin mixture as the resin for bonding the inner layer material and the outer layer material.
  • Example 1 A laminate was obtained in the same manner as in Example 1, except that the mass ratio of the polyethylene resin and the cyclic olefin resin was 97/3.
  • Example 3 A laminate was obtained in the same manner as in Example 1, except that the mass ratio of the polyethylene resin and the cyclic olefin resin was 50/50.
  • the lamination strength between the sealant layer and the gas barrier film was measured for the laminate obtained in each example and comparative example. The measurement was performed according to JIS Z-1707. Specifically, the laminate was cut into strips having a width of 15 mm. The sealant layer of the laminate cut into strips is measured using a Tensilon tensile tester (product name "Tensilon RTC-1250", manufactured by Orientec) so that the sealant layer and the gas barrier film face the opposite side ( That is, the film was peeled off from the gas barrier film at a peeling rate of 300 mm/min so that the peeling angle was T-shaped, and the strength required for peeling (unit: N/15 mm) was measured as the lamination strength. Table 1 shows the results.
  • the puncture strength of the laminate was measured. Specifically, a needle was pierced using a tension/compression tester (manufactured by Shimadzu Corporation) from the protective layer side of the straw piercing opening of the laminate. A hemispherical needle with a hemispherical tip (diameter: 0.5 mm) was used as the needle. The needle piercing speed was 50 mm/min. The puncture strength measurement was taken as the peak value measured during needle puncture.
  • the laminate obtained in each example exhibited good puncture resistance.
  • the laminates obtained in Comparative Examples 1 and 2 stretched when pierced with a straw.
  • the laminate obtained in Comparative Example 3 was caught when pierced with a straw.
  • the gist of the present disclosure resides in the following [1] to [6].
  • a paper substrate an adhesive resin layer; a gas barrier layer; a sealant layer; in this order,
  • the sealant layer contains at least one of a polyethylene-based resin and a polypropylene-based resin, and a cyclic olefin-based resin,
  • a gas barrier laminate wherein TA and TB satisfy the following formula (1), where TA is the tensile modulus of elasticity of the gas barrier layer and TB is the tensile modulus of elasticity of the sealant layer.
  • the gas barrier layer comprises a polyolefin film as a film substrate, The sealant layer and the polyolefin film are in direct contact, The gas barrier laminate according to [1] or [2], wherein the laminate strength between the sealant layer and the polyolefin film is 1 N/15 mm or more.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2022/025824 2021-08-18 2022-06-28 ガスバリア積層体及び容器 Ceased WO2023021852A1 (ja)

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EP22858175.7A EP4368390B1 (en) 2021-08-18 2022-06-28 GAS BARRIER LAMINATE AND CONTAINER
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JP2001171649A (ja) 1999-12-13 2001-06-26 Dainippon Printing Co Ltd 液体紙容器
JP2006256293A (ja) * 2005-02-15 2006-09-28 Nippon Paper-Pak Co Ltd 液体紙容器用ポリオレフィンフィルム、それを用いた液体紙容器材料及びアセプティック液体紙容器
JP2008273546A (ja) * 2007-04-26 2008-11-13 Toppan Printing Co Ltd 蓋材
JP2014196143A (ja) * 2013-03-04 2014-10-16 株式会社細川洋行 ポリスチレン容器用の易剥離蓋材
JP2021054078A (ja) * 2019-09-30 2021-04-08 大日本印刷株式会社 バリア性積層体、該バリア性積層体を備える包装容器

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CA2856513C (en) * 2011-12-22 2019-08-20 Fujimori Kogyo Co., Ltd. Resin composition for sealant, laminated film, and packaging bag
EP2940717A4 (en) * 2012-12-28 2016-08-10 Lintec Corp CUTTING FOIL SUBSTRATE FILM AND CUTTING FOIL
JP6903879B2 (ja) * 2016-07-29 2021-07-14 大日本印刷株式会社 酸素バリア性を有する積層体および該積層体からなる包装材料
WO2018034350A1 (ja) * 2016-08-18 2018-02-22 凸版印刷株式会社 液体用紙容器の製造方法及び液体用紙容器

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Publication number Priority date Publication date Assignee Title
JP2001171649A (ja) 1999-12-13 2001-06-26 Dainippon Printing Co Ltd 液体紙容器
JP2006256293A (ja) * 2005-02-15 2006-09-28 Nippon Paper-Pak Co Ltd 液体紙容器用ポリオレフィンフィルム、それを用いた液体紙容器材料及びアセプティック液体紙容器
JP2008273546A (ja) * 2007-04-26 2008-11-13 Toppan Printing Co Ltd 蓋材
JP2014196143A (ja) * 2013-03-04 2014-10-16 株式会社細川洋行 ポリスチレン容器用の易剥離蓋材
JP2021054078A (ja) * 2019-09-30 2021-04-08 大日本印刷株式会社 バリア性積層体、該バリア性積層体を備える包装容器

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Title
See also references of EP4368390A4

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EP4368390A1 (en) 2024-05-15
EP4368390A4 (en) 2024-10-30

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