WO2024252688A1 - 延伸基材、印刷基材、バリア性基材、積層体および包装容器 - Google Patents
延伸基材、印刷基材、バリア性基材、積層体および包装容器 Download PDFInfo
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- WO2024252688A1 WO2024252688A1 PCT/JP2023/035760 JP2023035760W WO2024252688A1 WO 2024252688 A1 WO2024252688 A1 WO 2024252688A1 JP 2023035760 W JP2023035760 W JP 2023035760W WO 2024252688 A1 WO2024252688 A1 WO 2024252688A1
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- Prior art keywords
- polyethylene
- layer
- resin layer
- surface resin
- polyolefin
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/02—Body construction
- B65D35/10—Body construction made by uniting or interconnecting two or more components
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Definitions
- This disclosure relates to stretched substrates, printed substrates, barrier substrates, laminates, and packaging containers.
- Packaging containers are used to store contents such as liquids and powders.
- Packaging containers are made using a laminate that includes a base material and a heat seal layer (see, for example, Patent Document 1).
- a base material for example, oriented polypropylene film is used as the base material because of its excellent strength and heat resistance.
- packaging containers may be required to have gas barrier properties.
- Stretched polypropylene films do not usually have high gas barrier properties.
- One objective of this disclosure is to provide a polyolefin-based stretched substrate with excellent gas barrier properties.
- a polyolefin-based stretched substrate with excellent gas barrier properties can be provided.
- a barrier substrate having a vapor-deposited film on the polyolefin-based stretched substrate has even better gas barrier properties.
- the stretched substrate and the barrier substrate are useful, for example, as substrates in packaging materials for producing packaging containers with excellent gas barrier properties.
- FIG. 3B is a schematic cross-sectional view showing one embodiment of a barrier substrate.
- FIG. 3C is a schematic cross-sectional view showing one embodiment of a barrier substrate.
- FIG. 3D is a schematic cross-sectional view showing one embodiment of a barrier substrate.
- FIG. 3E is a schematic cross-sectional view showing one embodiment of a barrier substrate.
- FIG. 4A is a schematic cross-sectional view showing one embodiment of a laminate.
- FIG. 4B is a schematic cross-sectional view showing one embodiment of a laminate.
- FIG. 5A is a schematic cross-sectional view showing one embodiment of a laminate.
- FIG. 5B is a schematic cross-sectional view showing one embodiment of a laminate.
- FIG. 6A is a schematic cross-sectional view showing one embodiment of a laminate.
- the numerical range of parameter B may be A1 or more and A4 or less, A1 or more and A5 or less, A1 or more and A6 or less, A2 or more and A4 or less, A2 or more and A5 or less, A2 or more and A6 or less, A3 or more and A4 or less, A3 or more and A5 or less, or A3 or more and A6 or less.
- polypropylene refers to a propylene homopolymer or a polymer in which the content of propylene-derived structural units in all repeating structural units is greater than the content of structural units derived from any comonomer.
- the content of propylene-derived structural units in all repeating structural units may be, for example, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol% or more. The above content is measured by NMR.
- ⁇ -olefins examples include ⁇ -olefins having 2 to 20 carbon atoms other than propylene, specifically ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene, with ethylene, 1-butene, 1-pentene, and 1-hexene being preferred.
- polyethylene refers to a polymer in which the content of ethylene-derived structural units in all repeating structural units exceeds 50 mol%.
- the content of ethylene-derived structural units is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
- the above content is measured by the NMR method.
- the density of polyethylene is as follows:
- the density of the high-density polyethylene is preferably greater than 0.945 g/cm 3.
- the upper limit of the density of the high-density polyethylene is, for example, 0.965 g/cm 3 , preferably 0.960 g/cm 3.
- the density of the medium-density polyethylene is preferably greater than 0.930 g/cm 3 and 0.945 g/cm 3 or less.
- the density of the low-density polyethylene is preferably 0.860 g/cm 3 or more and 0.930 g/cm 3 or less, more preferably 0.900 g/cm 3 or more and 0.930 g/cm 3 or less.
- the first and second aspects provide a polyolefin-based stretched substrate with excellent gas barrier properties.
- a barrier substrate having a vapor-deposited film on the polyolefin-based stretched substrate has even better gas barrier properties.
- the stretched substrate and the barrier substrate are useful, for example, as substrates in packaging materials for producing packaging containers with excellent gas barrier properties.
- a polyolefin-based stretched substrate can be provided that can be suitably used to produce a barrier substrate with excellent gas barrier properties.
- a barrier substrate having a vapor-deposited film on the polyolefin-based stretched substrate has excellent gas barrier properties.
- the stretched substrate and the barrier substrate are useful, for example, as a substrate in a packaging material for producing a packaging container with excellent gas barrier properties.
- the stretched substrate of the fourth aspect in one embodiment, comprises: A first surface resin layer containing polyethylene as a main component; one or more polyethylene intermediate layers containing polyethylene as a main component; a second surface resin layer containing a gas barrier resin as a main component or containing polyethylene and an adhesive resin; in this order, and the polyethylene in at least one layer selected from the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, or has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- biaxially oriented polyethylene films are made using low-density polyethylene to ensure good biaxial orientation.
- the heat resistance of such biaxially oriented polyethylene films tends to be insufficient.
- a biaxially oriented polyethylene film with excellent heat resistance can be provided.
- the biaxially oriented polyethylene film is useful, for example, as a base material in packaging materials for producing packaging containers.
- the stretched substrate has a first surface and a second surface opposite to the first surface.
- the first surface resin layer constitutes the first surface
- the second surface resin layer constitutes the second surface.
- the stretched substrate has a multilayer structure of three or more layers.
- the number of layers in the stretched substrate is three or more, preferably nine or less, and more preferably seven or less, for example, three or more and nine or less layers.
- the number of layers in the stretched substrate is specifically three, five, seven, or nine layers.
- the stretched substrate having a multilayer structure has an excellent balance of, for example, gas barrier properties, strength, rigidity, heat resistance, transparency, and printability.
- the stretched substrate of each embodiment may have two or more polyolefin intermediate layers.
- the stretched substrate of the first embodiment may further comprise a first adhesive resin layer between the first surface resin layer and the polyolefin intermediate layer.
- the stretched substrate of the first embodiment may further comprise a second adhesive resin layer between the polyolefin intermediate layer and the second surface resin layer.
- the stretched substrate of the first embodiment may comprise, in this order, a first surface resin layer, a first adhesive resin layer, a polyolefin intermediate layer, a second adhesive resin layer, and a second surface resin layer.
- the stretched substrate of the second embodiment may further include an adhesive resin layer between the polyolefin intermediate layer and the second surface resin layer.
- the stretched substrate of the second embodiment may include a first surface resin layer, a polyolefin intermediate layer, an adhesive resin layer, and a second surface resin layer in this order.
- the stretched substrate of the second embodiment may comprise, in this order, a first surface resin layer, a first polyolefin layer, a second polyolefin layer, an adhesive resin layer, and a second surface resin layer.
- the stretched polypropylene substrate of the second embodiment may comprise, in this order, a first surface resin layer, a first polypropylene layer, a second polypropylene layer, an adhesive resin layer, and a second surface resin layer.
- the stretched polyethylene substrate of the second embodiment may comprise, in this order, a first surface resin layer, a first polyethylene layer, a second polyethylene layer, an adhesive resin layer, and a second surface resin layer.
- the compositions of the first and second polyolefin layers may be the same or different from each other.
- the thicknesses of the first and second polyolefin layers may be the same or different from each other.
- the stretched substrate of embodiment 4A may further include an adhesive resin layer between the polyolefin intermediate layer and the second surface resin layer.
- the stretched substrate of embodiment 4A may include a first surface resin layer, a polyolefin intermediate layer, an adhesive resin layer, and a second surface resin layer in this order.
- the stretched substrate of embodiment 4B may include, in this order, a first surface resin layer, a first polyolefin layer, a second polyolefin layer, a third polyolefin layer, and a second surface resin layer.
- the polypropylene-based stretched substrate of embodiment 4B may include, in this order, a first surface resin layer, a first polypropylene layer, a second polypropylene layer, a third polypropylene layer, and a second surface resin layer.
- the polyethylene-based stretched substrate of embodiment 4B may include, in this order, a first surface resin layer, a first polyethylene layer, a second polyethylene layer, a third polyethylene layer, and a second surface resin layer.
- the compositions of the first to third polyolefin layers may be the same as or different from each other.
- the thicknesses of the first to third polyolefin layers may be the same as or different from each other.
- the ratio of the thickness of the second surface resin layer to the thickness of the first surface resin layer is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, even more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1, from the viewpoint of symmetry of the stretched substrate and suppression of curling.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the stretched substrate is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 85% by mass or more or 90% by mass or more.
- a laminate (or packaging container) having such a stretched substrate has, for example, excellent recyclability.
- the stretched substrate is, for example, a biaxially stretched substrate, specifically, a substrate that is biaxially stretched in the MD direction and the TD direction.
- the stretched substrate is, for example, a uniaxially stretched substrate, specifically, a substrate that is uniaxially stretched in the MD direction.
- the biaxially stretched polyethylene film is, specifically, a polyethylene film that is biaxially stretched in the MD direction and the TD direction.
- the thickness of the stretched substrate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less, for example, 5 ⁇ m or more and 200 ⁇ m or less.
- a stretched substrate having a thickness equal to or greater than the lower limit has, for example, excellent strength, rigidity, and heat resistance.
- a stretched substrate having a thickness equal to or less than the upper limit has, for example, excellent processability.
- the thickness of the substrate and each layer is the average value of the thicknesses at 10 points measured based on a scanning electron microscope (SEM) image obtained by observing a cross section perpendicular to the substrate surface with SEM.
- SEM scanning electron microscope
- the stretched substrate can be produced, for example, by forming the materials constituting each layer into a single-layer film or a laminated film, and then stretching the film.
- film-forming methods include the T-die casting method and the inflation method, and from the viewpoint of productivity, the T-die casting method is preferred.
- the above film can be obtained by supplying the materials for forming each layer to each extruder and performing co-extrusion T-die casting.
- the stretched substrate is a stretched film of a coextruded resin film.
- the biaxially stretched polyethylene film is a biaxially stretched film of a coextruded resin film.
- the stretched substrate is a resin film obtained by co-extrusion of a material constituting the first surface resin layer, a material constituting the polyolefin intermediate layer, and, if the stretched substrate has an adhesive resin layer, a material constituting the adhesive resin layer and a material constituting the second surface resin layer to produce a laminated film, and then stretching the laminated film.
- the biaxially stretched polyethylene film is a resin film obtained by co-extrusion of a material constituting the first surface resin layer, a material constituting the polyethylene intermediate layer, and a material constituting the second surface resin layer to produce a laminated film, and then biaxially stretching the laminated film.
- co-extrusion T-die casting method One embodiment of the co-extrusion T-die casting method is described below.
- the materials for forming each layer are fed to each extruder, and a laminated film is obtained by co-extrusion T-die casting.
- the extrusion temperature for the surface resin layer containing ethylene-vinyl alcohol copolymer is set to 220°C or more and 240°C or less
- the extrusion temperature for the adhesive resin layer is set to 250°C or more and 270°C or less
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or more and 280°C or less.
- the extrusion temperature for the surface resin layer containing polyamide, the extrusion temperature for the adhesive resin layer, and the extrusion temperature for the polypropylene intermediate layer are each set to 260°C or more and 280°C or less.
- the extrusion temperature for the surface resin layer containing ethylene-vinyl alcohol copolymer, the extrusion temperature for the adhesive resin layer, and the extrusion temperature for the polyethylene intermediate layer are each set to 220°C or higher and 240°C or lower.
- the extrusion temperature for the surface resin layer containing polyamide is set to 260°C or higher and 280°C or lower
- the extrusion temperature for the adhesive resin layer is set to 220°C or higher and 270°C or lower
- the extrusion temperature for the polyethylene intermediate layer is set to 220°C or higher and 270°C or lower.
- the extrusion temperature for the first surface resin layer is set to 240°C or more and 260°C or less
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the adhesive resin layer is set to 250°C or more and 270°C or less
- the extrusion temperature for the second surface resin layer containing an ethylene-vinyl alcohol copolymer is set to 220°C or more and 240°C or less.
- the extrusion temperature for the first surface resin layer, the extrusion temperature for the polyethylene intermediate layer, the extrusion temperature for the adhesive resin layer, and the extrusion temperature for the second surface resin layer containing an ethylene-vinyl alcohol copolymer are each set to 220°C or higher and 240°C or lower.
- the extrusion temperature for the first surface resin layer is set to 220°C or higher and 240°C or lower
- the extrusion temperature for the polyethylene intermediate layer is set to 220°C or higher and 260°C or lower
- the extrusion temperature for the adhesive resin layer is set to 220°C or higher and 270°C or lower
- the extrusion temperature for the second surface resin layer containing polyamide is set to 260°C or higher and 280°C or lower.
- the extrusion temperature for the surface resin layer is set to 240°C or higher and 260°C or lower
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or higher and 280°C or lower.
- the extrusion temperature for the surface resin layer and the extrusion temperature for the polyethylene intermediate layer are each set to 220°C or higher and 240°C or lower.
- the extrusion temperature for the first surface resin layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the adhesive resin layer is set to 250°C or more and 270°C or less
- the extrusion temperature for the second surface resin layer containing an ethylene-vinyl alcohol copolymer is set to 220°C or more and 240°C or less.
- the extrusion temperature for the first surface resin layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the adhesive resin layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the second surface resin layer containing polyamide is set to 260°C or more and 280°C or less.
- the extrusion temperature for the first surface resin layer, the extrusion temperature for the polyethylene intermediate layer, the extrusion temperature for the adhesive resin layer, and the extrusion temperature for the second surface resin layer containing an ethylene-vinyl alcohol copolymer are each set to 220°C or higher and 240°C or lower.
- the extrusion temperature for the first surface resin layer is set to 220°C or higher and 260°C or lower
- the extrusion temperature for the polyethylene intermediate layer is set to 220°C or higher and 260°C or lower
- the extrusion temperature for the adhesive resin layer is set to 220°C or higher and 270°C or lower
- the extrusion temperature for the second surface resin layer containing polyamide is set to 260°C or higher and 280°C or lower.
- the extrusion temperature for the first surface resin layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the polypropylene intermediate layer is set to 260°C or more and 280°C or less
- the extrusion temperature for the second surface resin layer containing polypropylene and adhesive resin is set to 240°C or more and 260°C or less.
- the extrusion temperature for the first surface resin layer, the extrusion temperature for the polyethylene intermediate layer, and the extrusion temperature for the second surface resin layer containing polyethylene and adhesive resin are each set to 220°C or more and 240°C or less. It should be noted that these extrusion temperatures in the extruder are merely examples and can be changed as appropriate.
- the stretched substrate and the printing substrate and barrier substrate described below may be subjected to a surface treatment.
- Such stretched substrates, printing substrates and barrier substrates have, for example, excellent adhesion to other layers.
- the surface treatment method include physical treatment and chemical treatment.
- the physical treatment include corona treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, and glow discharge treatment.
- the chemical treatment include oxidation treatment using chemicals.
- a printing layer may be provided on at least one surface of the stretched substrate. That is, the printing substrate comprises a stretched substrate and a printing layer provided on at least one surface of the stretched substrate.
- the printing substrate comprises a stretched substrate and a printing layer provided on the surface of at least one layer selected from the first surface resin layer and the second surface resin layer of the stretched substrate.
- the polyolefin intermediate layer contains polyolefin as a main component.
- polyolefin include polypropylene, polyethylene, polybutene, and polymethylpentene. Among these, polypropylene and polyethylene are preferred.
- the polyolefin intermediate layer include a polypropylene layer containing polypropylene as a main component and a polyethylene layer containing polyethylene as a main component.
- the polyolefin (e.g., polypropylene or polyethylene) content in the polyolefin intermediate layer is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the polyolefin intermediate layer may contain a resin material other than polyolefin.
- resin materials include polyester, polyamide, (meth)acrylic resin, vinyl resin, cellulose resin, and ionomer resin.
- the polyolefin intermediate layer may contain additives.
- additives include crosslinkers, antioxidants, UV absorbers, light stabilizers, antiblocking agents, slip agents, fillers, reinforcing agents, antistatic agents, compatibilizers, pigments, and modifying resins.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the first embodiment is preferably 4 ⁇ m or more, more preferably 6 ⁇ m or more, even more preferably 8 ⁇ m or more, and is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 20 ⁇ m or less, for example, 4 ⁇ m or more and 60 ⁇ m or less.
- the above "thickness" means the total thickness of each polyolefin intermediate layer.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the first embodiment is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, for example, 40% or more and 90% or less, relative to the thickness of the stretched substrate.
- the above “thickness” refers to the sum of the thicknesses of the polyolefin intermediate layers.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the second embodiment and the fourth A embodiment is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, even more preferably 10 ⁇ m or more, and is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, even more preferably 60 ⁇ m or less, even more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less, for example, 5 ⁇ m or more and 100 ⁇ m or less.
- the above "thickness" means the sum of the thicknesses of the polyolefin intermediate layers.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the second embodiment and the fourth A embodiment is preferably 45% or more, more preferably 55% or more, even more preferably 65% or more, and is preferably 95% or less, more preferably 90% or less, even more preferably 85% or less, for example 45% or more and 95% or less, relative to the thickness of the stretched substrate.
- the above "thickness" refers to the sum of the thicknesses of the polyolefin intermediate layers.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the third embodiment and the fourth B embodiment is preferably 6 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 14 ⁇ m or more, and is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, even more preferably 60 ⁇ m or less, even more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less, for example, 6 ⁇ m or more and 100 ⁇ m or less.
- the above "thickness" means the sum of the thicknesses of the polyolefin intermediate layers.
- the thickness of the polyolefin intermediate layer in the stretched substrate of the third embodiment and the fourth embodiment is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, particularly preferably 84% or more, and is preferably 98% or less, more preferably 96% or less, even more preferably 92% or less, for example, 60% or more and 98% or less, relative to the thickness of the stretched substrate.
- the above "thickness" refers to the sum of the thicknesses of the polyolefin intermediate layers.
- a stretched substrate having a polyolefin intermediate layer whose thickness is equal to or greater than the above-mentioned lower limit has, for example, excellent strength, rigidity, heat resistance, and recyclability.
- a stretched substrate having a polyolefin intermediate layer whose thickness is equal to or less than the above-mentioned upper limit has, for example, excellent processability.
- the stretched substrate may have one polyolefin intermediate layer, or two or more layers.
- the stretched substrate of the second and fourth A aspects may include a first surface resin layer, a first polyolefin layer, a second polyolefin layer, an adhesive resin layer, and a second surface resin layer in this order.
- the polyolefin layer may be, for example, a polyethylene layer or a polypropylene layer.
- the thickness of the second polyolefin layer is preferably 4 ⁇ m or more, more preferably 6 ⁇ m or more, even more preferably 8 ⁇ m or more, and is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 20 ⁇ m or less, for example, 4 ⁇ m or more and 60 ⁇ m or less.
- the thickness of the second polyolefin layer is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, for example, 40% or more and 90% or less, of the thickness of the stretched substrate.
- the thickness of the first polyolefin layer is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, even more preferably 1 ⁇ m or more, and is preferably 18 ⁇ m or less, more preferably 13 ⁇ m or less, even more preferably 8 ⁇ m or less, and particularly preferably 5 ⁇ m or less, for example, 0.5 ⁇ m or more and 18 ⁇ m or less.
- the thickness of the first polyolefin layer is preferably 2% or more, more preferably 4% or more, even more preferably 6% or more, and is preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, and particularly preferably 10% or less, for example, 2% or more and 25% or less, relative to the thickness of the stretched substrate.
- the ratio of the thickness of the first polyolefin layer to the thickness of the adhesive resin layer is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, even more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1, from the viewpoints of symmetry of the stretched substrate and suppression of curling.
- the stretched substrate of the third and fourth B aspects may include a first surface resin layer, a first polyolefin layer, a second polyolefin layer, a third polyolefin layer, and a second surface resin layer in this order.
- the polyolefin layer may be, for example, a polyethylene layer or a polypropylene layer.
- the thickness of the second polyolefin layer is preferably 4 ⁇ m or more, more preferably 6 ⁇ m or more, even more preferably 8 ⁇ m or more, and is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 20 ⁇ m or less, for example, 4 ⁇ m or more and 60 ⁇ m or less.
- the thickness of the second polyolefin layer is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, for example, 40% or more and 90% or less, of the thickness of the stretched substrate.
- the thickness of the first and third polyolefin layers is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, even more preferably 1 ⁇ m or more, and is preferably 18 ⁇ m or less, more preferably 13 ⁇ m or less, even more preferably 8 ⁇ m or less, and particularly preferably 5 ⁇ m or less, for example, 0.5 ⁇ m or more and 18 ⁇ m or less.
- the thickness of the first and third polyolefin layers is preferably at least 2%, more preferably at least 4%, even more preferably at least 6%, and is preferably at most 25%, more preferably at most 20%, even more preferably at most 15%, and particularly preferably at most 10%, for example at least 2% and at most 25%, relative to the thickness of the stretched substrate.
- the ratio of the thickness of the first polyolefin layer to the thickness of the third polyolefin layer is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, even more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1, from the viewpoints of symmetry of the stretched substrate and suppression of curling.
- the polyolefin intermediate layer may further contain a compatibilizer.
- a compatibilizer in the polyolefin intermediate layer, the mixability between the gas barrier resin and the polyolefin can be improved when the stretched substrate and the barrier substrate are heated and melted for recycling. This effectively prevents the physical properties of the polyolefin from decreasing after recycling, and also effectively prevents the transparency of the polyolefin from decreasing.
- the stretched substrate has two or more polyolefin intermediate layers, at least one of the polyolefin intermediate layers may contain a compatibilizer.
- the content of the compatibilizer in the polyolefin intermediate layer is preferably 25 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the gas barrier resin in the stretched substrate.
- the content of the compatibilizer in the polyolefin intermediate layer is preferably 100 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the ethylene-vinyl alcohol copolymer in the stretched substrate.
- the content of the compatibilizer in the polyolefin intermediate layer is preferably 25 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polyamide in the stretched substrate.
- the compatibilizer may be, for example, an acid-modified polyolefin, with acid-modified polyethylene and acid-modified polypropylene being preferred from the viewpoint of recyclability.
- the acid-modified polyolefin may be, for example, a polyolefin modified with an unsaturated carboxylic acid such as maleic acid or fumaric acid, or an acid anhydride, ester, or metal salt thereof, particularly a graft-modified polyolefin.
- the compatibilizer may be, for example, an unsaturated carboxylic acid compound-modified polyethylene or an unsaturated carboxylic acid compound-modified polypropylene, with maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene being more preferred.
- the polyolefin intermediate layer may further contain a compatibilizer.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the polyolefin intermediate layer is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 65% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more or 80% by mass or more.
- the content of polyolefin (e.g., polypropylene or polyethylene) is 100% by mass or less, may be 99% by mass or less, may be 97% by mass or less, may be 95% by mass or less, or may be 90% by mass or less.
- the content of the compatibilizer in the polyolefin intermediate layer is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less or 20% by mass or less.
- the second polyolefin layer may further contain a compatibilizer.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the second polyolefin layer is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 65% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more or 80% by mass or more.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the second polyolefin layer is 100% by mass or less, may be 99% by mass or less, may be 97% by mass or less, or may be 95% by mass or less.
- the content of the compatibilizer in the second polyolefin layer is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less or 20% by mass or less.
- the polypropylene intermediate layer contains polypropylene as a main component.
- polypropylene include homopolypropylene, random polypropylene, and block polypropylene. Among these, homopolypropylene is preferred from the viewpoint of the heat resistance of the stretched substrate.
- the polypropylene may be isotactic polypropylene, syndiotactic polypropylene, or atactic polypropylene. From the viewpoint of the heat resistance of the stretched substrate, isotactic polypropylene and syndiotactic polypropylene are preferred as polypropylene, and isotactic polypropylene is more preferred.
- the melting point (Tm) of the polypropylene in the polypropylene intermediate layer is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, particularly preferably 165°C or higher, and preferably 175°C or lower, for example, 130°C or higher and 175°C or lower, from the viewpoint of the strength and heat resistance of the stretched substrate.
- the Tm of various materials is the melting peak temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012 (using test pieces after conditioning according to 3.(2) (however, a cooling rate of 10°C/min)).
- the polyethylene intermediate layer contains polyethylene as a main component.
- polyethylene for example, high density polyethylene, medium density polyethylene, low density polyethylene and linear low density polyethylene are preferable. From the viewpoint of strength and heat resistance of the stretched substrate, high density polyethylene and medium density polyethylene are preferable. From the viewpoint of film formability and processability of the stretched substrate, linear low density polyethylene and medium density polyethylene are preferable.
- Linear low density polyethylene includes, for example, ethylene-1-butene copolymer (C4-LLDPE) in which the comonomer is at least 1-butene, ethylene-1-hexene copolymer (C6-LLDPE) in which the comonomer is at least 1-hexene, and ethylene-1-octene copolymer (C8-LLDPE) in which the comonomer is at least 1-octene.
- the comonomers are not limited to the above-mentioned ones, and further comonomers may be used.
- linear low density polyethylene produced using a metallocene catalyst is preferred.
- the melting point (Tm) of the polyethylene in the polyethylene intermediate layer is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, and particularly preferably 115°C or higher, and is preferably 140°C or lower, for example, 100°C or higher and 140°C or lower, from the viewpoint of the strength and heat resistance of the stretched substrate.
- the polyethylene intermediate layer is a polyethylene layer (1) described below that contains at least one polyethylene selected from high density polyethylene and medium density polyethylene, or a polyethylene layer (2) described below that is a layer containing polyethylene as a main component and in which the polyethylene contained in the layer has a density of more than 0.930 g/cm 3 and not more than 0.960 g/cm 3.
- the polyethylene layers (1) and (2) will be described in detail later, and description thereof will be omitted in this section.
- the surface resin layer (G) containing a gas barrier resin as a main component will be described below.
- the first and second surface resin layers in the stretched substrate of the first embodiment each independently contain a gas barrier resin as a main component.
- the second surface resin layer in the stretched substrate of the second embodiment contains a gas barrier resin as a main component.
- the second surface resin layer in the stretched substrate of the fourth embodiment contains a gas barrier resin as a main component.
- Such a surface resin layer (G) tends to have excellent surface smoothness, and the vapor deposition film provided on the surface of the surface resin layer (G) tends to have excellent adhesion to the surface resin layer (G) and to exhibit good gas barrier properties.
- the stretched substrate having a surface resin layer (G) containing a gas barrier resin as a main component has superior gas barrier properties (particularly oxygen barrier properties), heat resistance, and rigidity compared to conventional stretched polyolefin films, for example.
- Gas barrier resins are resins that have the function of suppressing gas permeation.
- gas barrier resins include ethylene-vinyl alcohol copolymers, polyvinyl alcohol, polyamides, polyvinylidene chloride, polyesters, polyether polyols, polyester polyols, polyurethanes, polyacrylonitrile, and (meth)acrylic resins.
- ethylene-vinyl alcohol copolymers, polyvinyl alcohol, and polyamides are preferred, ethylene-vinyl alcohol copolymers and polyamides are more preferred, and from the viewpoint of gas barrier properties, ethylene-vinyl alcohol copolymers are even more preferred.
- the surface resin layer (G) contains at least polyamide as a gas barrier resin.
- Ethylene-vinyl alcohol copolymer can be obtained, for example, by copolymerizing ethylene with a vinyl ester monomer and then saponifying the copolymer.
- the copolymerization of ethylene with a vinyl ester monomer can be carried out by any known polymerization method, such as solution polymerization, suspension polymerization, or emulsion polymerization.
- EVOH may be modified by known methods, such as urethanization, acetalization, cyanoethylation, or oxyalkylenation.
- Vinyl acetate is generally used as the vinyl ester monomer, but other vinyl ester monomers may also be used.
- examples of other vinyl ester monomers include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate, as well as aromatic vinyl esters such as vinyl benzoate.
- the content of ethylene-derived structural units in EVOH is preferably 20 mol% or more, more preferably 25 mol% or more, of all repeating structural units from the viewpoint of processability of the stretched substrate, and is even more preferably 30 mol% or more, even more preferably 35 mol% or more, and particularly preferably 40 mol% or more or 45 mol% or more, of all repeating structural units from the viewpoint of excellent surface smoothness and stretchability, especially biaxial stretchability.
- the ethylene content in EVOH is preferably 60 mol% or less, more preferably 55 mol% or less, of all repeating structural units from the viewpoint of heat resistance, oxygen barrier property, and water vapor barrier property of the stretched substrate.
- the ethylene content is, for example, 20 mol% or more and 60 mol% or less.
- the ethylene content is measured by NMR.
- the average degree of saponification of EVOH is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.
- the average degree of saponification is measured in accordance with JIS K6726:1994 (wherein EVOH is dissolved uniformly in a water/methanol solvent).
- the melting point (Tm) of EVOH is preferably 130°C or higher, more preferably 135°C or higher, even more preferably 140°C or higher, and is preferably 200°C or lower, more preferably 190°C or lower, even more preferably 180°C or lower, even more preferably 170°C or lower, and particularly preferably 165°C or lower, for example, 130°C or higher and 200°C or lower.
- the MFR of EVOH is preferably 0.1 g/10 min or more, more preferably 1 g/10 min or more, even more preferably 1.5 g/10 min or more, and is preferably 50 g/10 min or less, more preferably 30 g/10 min or less, even more preferably 10 g/10 min or less, for example, 0.1 g/10 min or more and 50 g/10 min or less.
- the MFR of EVOH is measured by Method A at a temperature of 190°C and a load of 2.16 kg in accordance with JIS K7210-1:2014. The measurement temperature may be 210°C depending on the melting point of EVOH.
- the average degree of saponification in polyvinyl alcohol (PVA) is preferably 70 mol% or more, more preferably 75 mol% or more, even more preferably 80 mol% or more, and particularly preferably 85 mol% or more.
- the average degree of saponification is measured in accordance with JIS K6726:1994.
- polyamide examples include aliphatic polyamide and aromatic polyamide.
- the surface resin layer (G) contains at least aromatic polyamide as a gas barrier resin.
- Such a stretched substrate has, for example, excellent rigidity and gas barrier properties.
- polyamide will also be referred to as "PA.”
- aliphatic polyamides examples include aliphatic homopolyamides and aliphatic copolymer polyamides.
- aliphatic homopolyamides include polycaprolactam or poly(6-aminocaproic acid) (PA6), polyenantholactam or poly(7-aminoenanthic acid) (PA7), polyundecane lactam or poly(11-aminoundecanoic acid) (PA11), polylauryllactam or poly(12-aminolauric acid) (PA12), polyhexamethylene adipamide (PA66), polytetramethylene dodecamide (PA412), polypentamethylene azelamide (PA59), polypentamethylene sebacamide (PA510), polypentamethylene dodecamide (PA512), polyhexamethylene azelamide (PA69), polyhex ...
- Examples include bacamide (PA610), polyhexamethylene dodecamide (PA612), polynonamethylene adipamide (PA96), polynonamethylene azelamide (PA99), polynonamethylene sebacamide (PA910), polynonamethylene dodecamide (PA912), polydecamethylene adipamide (PA106), polydecamethylene azelamide (PA109), polydecamethylene decamamide (PA1010), polydecamethylene dodecamide (PA1012), polydodecamethylene adipamide (PA126), polydodecamethylene azelamide (PA129), polydodecamethylene sebacamide (PA1210) and polydodecamethylene dodecamide (PA1212).
- PA610 polyhexamethylene dodecamide
- PA96 polynonamethylene adipamide
- PA99 polynonamethylene sebacamide
- PA91010 polynonamethylene dodecamide
- PA1012 polydecamethylene adipamide
- PA126 polydo
- aliphatic copolymer polyamides include caprolactam/hexamethylenediaminoadipic acid copolymer (PA6/66), caprolactam/hexamethylenediaminoazelaic acid copolymer (PA6/69), caprolactam/hexamethylenediaminosebacic acid copolymer (PA6/610), caprolactam/hexamethylenediaminoundecanoic acid copolymer (PA6/611), caprolactam/hexamethylenediaminododecanoic acid copolymer (PA6/612), caprolactam/amino Examples of such copolymers include undecanoic acid copolymer (PA6/11), caprolactam/lauryllactam copolymer (PA6/12), caprolactam/hexamethylenediaminoadipic acid/lauryllactam copolymer (PA6/66/12), caprolactam/hexamethylenediaminoadipic acid
- a crystalline aliphatic polyamide is preferable.
- the crystalline aliphatic polyamide include PA6, PA11, PA12, PA66, PA610, PA612, PA6/66, and PA6/66/12.
- the melting point (Tm) of the crystalline aliphatic polyamide is preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher, and is preferably 300°C or lower, more preferably 270°C or lower, and even more preferably 240°C or lower, for example, 180°C or higher and 300°C or lower.
- Aromatic polyamides include semi-aromatic polyamides and fully aromatic polyamides, with semi-aromatic polyamides being preferred.
- Semi-aromatic polyamides are polyamides having constituent units derived from aromatic diamines and constituent units derived from aliphatic dicarboxylic acids, or polyamides having constituent units derived from aliphatic diamines and constituent units derived from aromatic dicarboxylic acids. Examples include polyamides composed of aromatic diamines and aliphatic dicarboxylic acids, and polyamides composed of aliphatic diamines and aromatic dicarboxylic acids.
- Semi-aromatic polyamides include, for example, polyhexamethylene terephthalamide (PA6T), polyhexamethylene isophthalamide (PA6I), polynonamethylene terephthalamide (PA9T), polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer (PA66/6T), polyhexamethylene adipamide/polyhexamethylene isophthalamide copolymer (PA66/6I), polyhexamethylene terephthalamide/polycaproamide copolymer (PA6T/6), polyhexamethylene isophthalamide/polycaproamide copolymer (PA6I/6), polyhexamethylene tere ...
- PA6T polyhexamethylene terephthalamide
- PA6I polyhexamethylene isophthalamide
- PA9T polynonamethylene terephthalamide
- PA66/6T polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer
- copolymers examples include lydodecamide copolymer (PA6T/12), polyhexamethylene isophthalamide/polyhexamethylene terephthalamide copolymer (PA6I/6T), polyhexamethylene terephthalamide/poly(2-methylpentamethylene terephthalamide) copolymer (PA6T/M5T), polyhexamethylene adipamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (PA66/6T/6I), polyhexamethylene adipamide/polycaproamide/polyhexamethylene isophthalamide copolymer (PA66/6/6I), and polymetaxylylene adipamide (PAMXD6). Among these, polymetaxylylene adipamide (PAMXD6) is preferred.
- the semi-aromatic polyamide a crystalline semi-aromatic polyamide is preferred.
- the melting point (Tm) of the crystalline semi-aromatic polyamide is preferably 190°C or higher, more preferably 200°C or higher, even more preferably 210°C or higher, and is preferably 310°C or lower, more preferably 280°C or lower, even more preferably 250°C or lower, for example, 190°C or higher and 310°C or lower.
- the melt volume rate (MVR) of the semi-aromatic polyamide is preferably 5 cm3 /10 min or more, more preferably 10 cm3 /10 min or more, and preferably 200 cm3 /10 min or less, more preferably 100 cm3 /10 min or less, for example, 5 cm3 /10 min or more and 200 cm3 /10 min or less.
- the MVR is measured in accordance with JIS K7210-1:2014 at a temperature of 275°C and a load of 5.00 kg.
- the relative viscosity of polyamides such as aliphatic polyamides is preferably 1.5 or more, more preferably 2.0 or more, even more preferably 2.5 or more, and is preferably 5.0 or less, more preferably 4.5 or less, even more preferably 4.0 or less, for example, 1.5 or more and 5.0 or less.
- the relative viscosity of polyamides is measured in accordance with JIS K6920-2:2009 by dissolving 1 g of polyamide in 100 mL of 96% concentrated sulfuric acid at 25°C.
- the MFR of polyamide is preferably 0.1 g/10 min or more, more preferably 0.3 g/10 min or more, even more preferably 0.5 g/10 min or more, even more preferably 1 g/10 min or more, particularly preferably 1.5 g/10 min or more, and is preferably 50 g/10 min or less, more preferably 30 g/10 min or less, even more preferably 10 g/10 min or less, for example, 0.1 g/10 min or more and 50 g/10 min or less.
- the MFR of polyamide is measured by Method A at a temperature of 235°C and a load of 2.16 kg in accordance with JIS K7210-1:2014. An appropriate measurement temperature can be adopted depending on the melting point of the polyamide.
- the content of the gas barrier resin in the surface resin layer (G) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, from the viewpoint of the above-mentioned physical properties such as gas barrier properties.
- the surface resin layer (G) may contain an aliphatic polyamide as a main component.
- the content of the aliphatic polyamide in the surface resin layer (G) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, from the viewpoint of the above-mentioned physical properties such as the processability of the stretched substrate.
- the surface resin layer (G) may contain aromatic polyamide as a main component.
- the content of aromatic polyamide in the surface resin layer (G) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, from the viewpoint of the above-mentioned physical properties such as the rigidity and gas barrier properties of the stretched substrate.
- the surface resin layer (G) may contain aromatic polyamide and aliphatic polyamide.
- Aromatic polyamides tend to be more excellent in gas barrier properties and rigidity. Aliphatic polyamides tend to be more excellent in processability.
- the content ratio of aromatic polyamide is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, even more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 40% by mass or more and 60% by mass or less
- the content ratio of aliphatic polyamide is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, even more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 40% by mass or more and 60% by mass or less.
- the surface resin layer (G) may contain the above-mentioned resin materials other than the above-mentioned components.
- the surface resin layer (G) may contain the above-mentioned additives.
- each surface resin layer (G) is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.8 ⁇ m or more, from the viewpoint of the above-mentioned physical properties such as gas barrier properties.
- the thickness of each surface resin layer (G) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less, from the viewpoint of recyclability of the stretched substrate and the barrier substrate.
- the thickness of each surface resin layer (G) is, for example, 0.3 ⁇ m or more and 15 ⁇ m or less. When the surface resin layer has convex portions due to particles described later, it is preferable that the thickness of each layer is measured in an area where convex portions due to the particles are not formed. The same applies to other embodiments.
- each surface resin layer (G) is preferably 1% or more, more preferably 2% or more, even more preferably 4% or more, and is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less, and particularly preferably 8% or less, for example, 1% or more and 20% or less, relative to the thickness of the stretched substrate.
- the surface resin layer (AH) containing a polyolefin and an adhesive resin will be described below.
- the first surface resin layer in the stretched substrate of the second embodiment contains a polyolefin and an adhesive resin.
- the first and second surface resin layers in the stretched substrate of the third embodiment each independently contain a polyolefin and an adhesive resin.
- the second surface resin layer in the stretched substrate of the fourth embodiment contains a polyolefin and an adhesive resin.
- the vapor deposition film provided on the surface of such a surface resin layer (AH) tends to have excellent adhesion to the surface resin layer (AH) and to exhibit good gas barrier properties.
- polyolefins examples include polypropylene, polyethylene, polybutene, and polymethylpentene. Among these, polypropylene and polyethylene are preferred.
- polypropylene examples include homopolypropylene, random polypropylene, and block polypropylene.
- random polypropylene and homopolypropylene are preferred, and random polypropylene is more preferred, from the viewpoints of the surface smoothness of the stretched substrate, adhesion between the surface resin layer (AH) and the vapor deposition film, and heat resistance of the stretched substrate. If the stretched substrate contains a high proportion of random polypropylene, the heat resistance may be insufficient. In such cases, the main component of the polypropylene intermediate layer described above may be homopolypropylene.
- the melting point (Tm) of the polypropylene in the surface resin layer (AH) is preferably 120°C or higher, more preferably 125°C or higher, even more preferably 130°C or higher, from the viewpoints of the strength and heat resistance of the stretched substrate and the adhesion between the surface resin layer (AH) and the vapor deposition film, and is preferably 175°C or lower, more preferably 170°C or lower, even more preferably 165°C or lower, even more preferably 160°C or lower, particularly preferably 155°C or lower or 150°C or lower, for example, 120°C or higher and 175°C or lower.
- polyethylene examples include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene. From the viewpoint of the surface smoothness of the stretched substrate and the adhesion between the surface resin layer (AH) and the vapor-deposited film, linear low-density polyethylene is more preferable. Examples of linear low-density polyethylene include C4-LLDPE, C6-LLDPE, and C8-LLDPE.
- the melting point (Tm) of the polyethylene in the surface resin layer (AH) is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, and particularly preferably 115°C or higher, and is preferably 140°C or lower, for example, 100°C or higher and 140°C or lower, from the viewpoints of the strength and heat resistance of the stretched substrate, and the adhesion between the surface resin layer (AH) and the vapor deposition film.
- Adhesive resins include, for example, acid-modified resins, silicone resins, epoxy resins, and phenolic resins, and acid-modified resins are preferred.
- Acid-modified resins include, for example, acid-modified polyolefins and acid-modified vinyl resins. Among these, acid-modified polyolefins are preferred from the viewpoint of recyclability and adhesion, and acid-modified polypropylene and acid-modified polyethylene are more preferred.
- acid-modified polypropylene is even more preferred, and in the viewpoint of heat resistance and adhesion, acid-modified random polypropylene and acid-modified homopolypropylene are even more preferred, and acid-modified random polypropylene is particularly preferred.
- the surface resin layer (AH) containing acid-modified random polypropylene tends to have better adhesion to the vapor deposition film.
- acid-modified polyethylene is even more preferred, and acid-modified linear low-density polyethylene is even more preferred.
- the surface resin layer (AH) containing acid-modified linear low-density polyethylene tends to have better adhesion to the vapor deposition film.
- the polyolefin in the first surface resin layer comprises polypropylene
- the adhesive resin comprises acid-modified polypropylene
- the polyolefin intermediate layer comprises polypropylene as a main component.
- the polyolefin in the first surface resin layer comprises random polypropylene
- the adhesive resin comprises acid-modified random polypropylene
- the polyolefin intermediate layer comprises homopolypropylene as a main component.
- the polyolefin in the first surface resin layer comprises polyethylene
- the adhesive resin comprises acid-modified polyethylene
- the polyolefin intermediate layer contains polyethylene as a main component.
- acid-modified polyolefins include polyolefins (such as polypropylene and polyethylene) modified with an acid-modifying component, particularly graft-modified polyolefins with an acid-modifying component.
- acid-modified components include unsaturated carboxylic acids such as maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, or acid anhydrides, esters, or metal salts thereof.
- Preferred acid-modified polyolefins are maleic acid-modified polyolefins and maleic anhydride-modified polyolefins, and more preferred are maleic acid-modified polypropylene, maleic anhydride-modified polypropylene, maleic acid-modified polyethylene, and maleic anhydride-modified polyethylene.
- the content of the structural units derived from the acid-modified component in the acid-modified polyolefin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of adhesion between the surface resin layer (AH) and the vapor deposition film.
- the content of the structural units derived from the acid-modified component in the acid-modified polyolefin is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of adhesion between the surface resin layer (AH) and the polyolefin intermediate layer.
- the above content is, for example, 0.01% by mass or more and 10% by mass or less.
- the content of the structural units derived from the acid-modified component is measured by infrared spectroscopy.
- the MFR of the acid-modified polyolefin is preferably 0.1 g/10 min or more, more preferably 1 g/10 min or more, even more preferably 1.5 g/10 min or more, and is preferably 50 g/10 min or less, more preferably 30 g/10 min or less, even more preferably 10 g/10 min or less, for example, 0.1 g/10 min or more and 50 g/10 min or less.
- the MFR of the acid-modified polyolefin is measured by Method A under a load of 2.16 kg in accordance with JIS K7210-1:2014.
- the measurement temperature for the MFR is set according to the melting point of the acid-modified polyolefin, and is 230°C for acid-modified polypropylene and 190°C for acid-modified polyethylene.
- the density of the acid-modified polypropylene is, for example, 0.88 g/cm3 or more and 0.92 g/cm3 or less.
- the density of the acid-modified polypropylene is measured in accordance with JIS K7112:1999 D method (density gradient tube method, 23°C).
- the density of the acid-modified polyethylene may be in the same range as that of the polyethylene described above.
- the melting point (Tm) of the acid-modified polypropylene is preferably 120°C or higher, more preferably 125°C or higher, even more preferably 130°C or higher, from the viewpoints of the strength and heat resistance of the stretched substrate, and the adhesion between the surface resin layer (AH) and the vapor-deposited film, and is preferably 175°C or lower, more preferably 170°C or lower, even more preferably 165°C or lower, even more preferably 160°C or lower, particularly preferably 155°C or lower or 150°C or lower, for example, 120°C or higher and 175°C or lower.
- the melting point (Tm) of the acid-modified polyethylene is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, and particularly preferably 115°C or higher, and is preferably 140°C or lower, for example, from the viewpoints of the strength and heat resistance of the stretched substrate, and the adhesion between the surface resin layer (AH) and the vapor-deposited film.
- the polyolefin content is preferably 60% by mass or more and 95% by mass or less, and the adhesive resin content is preferably 5% by mass or more and 40% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and the adhesive resin content is more preferably 5% by mass or more and 30% by mass or less, even more preferably 80% by mass or more and 95% by mass or less, and the adhesive resin content is more preferably 5% by mass or more and 20% by mass or less, and particularly preferably 85% by mass or more and 95% by mass or less, and the adhesive resin content is more preferably 5% by mass or more and 15% by mass or less.
- the surface resin layer (AH) of such an embodiment tends to have better surface smoothness, adhesion to the vapor deposition film, and adhesion to the polyolefin intermediate layer. If the adhesive resin content is equal to or less than the upper limit, for example, it is possible to suppress the film from adhering more than necessary to a roll or the like during the production of a stretched substrate.
- the above polyolefin is, for example, polyethylene or polypropylene.
- the surface resin layer (AH) may contain linear low-density polyethylene as a main component from the viewpoints of biaxial stretchability and surface smoothness. Details of linear low-density polyethylene are described later in the section on polyethylene layer (1), and a description of this will be omitted here.
- the surface resin layer (AH) contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, and preferably contains high density polyethylene. Therefore, a stretched substrate having such a surface resin layer has, for example, high heat resistance, specifically, excellent resistance to drying during printing and heating during heat sealing, and excellent resistance to deposition when deposition is performed on the film. In addition, the surface resin layer has, for example, high rigidity, and can increase the film transport speed when deposition is performed on the film, thereby increasing productivity.
- high density polyethylene and medium density polyethylene are described below in the section on polyethylene layer (1), and will not be described here.
- the high density polyethylene and medium density polyethylene the ethylene- ⁇ -olefin copolymers described below are each preferred.
- the content of linear low-density polyethylene in the 100% by mass of polyethylene contained in the surface resin layer (AH) may be 60% by mass or more, 65% by mass or more, 70% by mass or more, 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less, for example, 60% by mass or more and 100% by mass or less.
- the total content of high density polyethylene and medium density polyethylene in the 100% by mass of polyethylene contained in the surface resin layer (AH) may be 0% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 40% by mass or less, 35% by mass or less, or 30% by mass or less, for example, 0% by mass or more and 40% by mass or less.
- the polyethylene contained in the surface resin layer (AH) may have a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 , and the density is preferably 0.931 g/cm3 or more and 0.955 g/ cm3 or less, more preferably 0.931 g/cm3 or more and 0.950 g/cm3 or less .
- the density of the polyethylene means the density of a mixture of two or more types of polyethylene.
- the surface resin layer (AH) may contain the above-mentioned resin materials other than the above-mentioned components.
- the surface resin layer (AH) may contain the above-mentioned additives.
- each surface resin layer (AH) is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 0.8 ⁇ m or more, and is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less, for example, 0.3 ⁇ m or more and 15 ⁇ m or less.
- each surface resin layer (AH) is preferably 1% or more, more preferably 2% or more, even more preferably 4% or more, and is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less, and particularly preferably 8% or less, for example, 1% or more and 20% or less, relative to the thickness of the stretched substrate.
- the surface resin layer (PO) containing polyolefin as a main component contains polyolefin as a main component.
- polyolefin include polypropylene, polyethylene, polybutene, and polymethylpentene. Among these, polypropylene and polyethylene are preferred.
- the surface resin layer (PO) include a layer containing polypropylene as a main component and a layer containing polyethylene as a main component.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the surface resin layer (PO) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- An example of a layer in the surface resin layer (PO) that contains polypropylene as a main component is a layer similar to the (polypropylene intermediate layer) in the above-mentioned ⁇ polyolefin intermediate layer>.
- the layer in the surface resin layer (PO) containing polypropylene as a main component may contain homopolypropylene and random polypropylene, for example, from the viewpoint of adhesion with other layers provided on the surface resin layer (PO) in the laminate described below.
- the homopolypropylene content is 50% by mass or more and 95% by mass or less, and the random polypropylene content is 5% by mass or more and 50% by mass or less, it is more preferable that the homopolypropylene content is 60% by mass or more and 90% by mass or less, and the random polypropylene content is 10% by mass or more and 40% by mass or less, and it is even more preferable that the homopolypropylene content is 70% by mass or more and 85% by mass or less, and the random polypropylene content is 15% by mass or more and 30% by mass or less.
- the surface resin layer (PO) may be, for example, a layer similar to the (polyethylene intermediate layer) of the above-mentioned ⁇ polyolefin intermediate layer>.
- the surface resin layer (PO) may be, for example, the polyethylene layer (1) or (2) described below.
- the surface resin layer (PO) may contain the above-mentioned resin materials other than polyolefin.
- the surface resin layer (PO) may contain the above-mentioned additives.
- the thickness of the surface resin layer (PO) is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 0.8 ⁇ m or more, and is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less, for example, 0.3 ⁇ m or more and 15 ⁇ m or less.
- the thickness of the surface resin layer (PO) is preferably 1% or more, more preferably 2% or more, even more preferably 4% or more, and is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less, and particularly preferably 8% or less, for example, 1% or more and 20% or less, relative to the thickness of the stretched substrate.
- the first surface resin layer and/or the second surface resin layer in the stretched substrate of each of the above-mentioned embodiments may further contain particles.
- the surface resin layer contains particles, for example, the anti-blocking property or slip property of the stretched substrate can be improved. Details of the particles are explained in the section ⁇ Layer structure of film>, and explanations thereof will be omitted here.
- the absolute value of the difference between the density of the polyethylene constituting layer (i) and the density of the polyethylene constituting layer (ii) is preferably 0.030 g/ cm3 or less, more preferably 0.025 g/cm3 or less , even more preferably 0.020 g/cm3 or less, and particularly preferably 0.010 g/ cm3 or less.
- Such a film has excellent interlayer adhesion, for example, excellent drop resistance.
- the density of the polyethylene in the polyethylene intermediate layer is higher than the density of the polyethylene in the first surface resin layer, and optionally the density of the polyethylene in the second surface resin layer is lower than the density of the polyethylene in the polyethylene intermediate layer.
- a stretched substrate tends to have an excellent balance of surface smoothness, transparency, printability, vapor deposition adhesion, and heat resistance.
- the polyethylene intermediate layer is thicker than the surface resin layer, the polyethylene intermediate layer provides high heat resistance.
- the density difference between the polyethylene in the polyethylene intermediate layer and the above surface resin layer may be, for example, 0.003 g/cm 3 or more.
- the total content ratio of the high density polyethylene and the medium density polyethylene is hereinafter referred to as "content ratio A.”
- content ratio A the total content ratio of the high density polyethylene and the medium density polyethylene
- the content ratio A in the polyethylene intermediate layer is greater than the content ratio A in the first surface resin layer, and optionally the content ratio A in the second surface resin layer is smaller than the content ratio A in the polyethylene intermediate layer.
- Such a stretched substrate tends to have an excellent balance of surface smoothness, transparency, printability, vapor deposition adhesion, and heat resistance.
- the difference in content ratio A between the polyethylene intermediate layer and the surface resin layer may be, for example, 10% by mass or more, 50% by mass or less, 40% by mass or less, or 30% by mass or less.
- the density of the polyethylene in the polyethylene intermediate layer is lower than the density of the polyethylene in the first surface resin layer, and, if desired, the density of the polyethylene in the second surface resin layer is higher than the density of the polyethylene in the polyethylene intermediate layer.
- Such a stretched substrate tends to have a good balance between biaxial stretchability and heat resistance.
- the polyethylene intermediate layer is thicker than the surface resin layer, the polyethylene intermediate layer provides high biaxial stretchability.
- the density difference between the polyethylene in the surface resin layer and the polyethylene intermediate layer may be, for example, 0.003 g/cm 3 or more.
- the content ratio A in the polyethylene intermediate layer is smaller than the content ratio A in the first surface resin layer, and if desired, the content ratio A in the second surface resin layer is larger than the content ratio A in the polyethylene intermediate layer.
- Such a stretched substrate tends to have an excellent balance between biaxial stretchability and heat resistance.
- the difference in content ratio A between the surface resin layer and the polyethylene intermediate layer may be, for example, 10% by mass or more, 50% by mass or less, 40% by mass or less, or 30% by mass or less.
- the first surface resin layer, the polyethylene intermediate layer, and the optional second surface resin layer each have a substantially equal density of polyethylene, for example, the difference in density between the layer with the highest polyethylene density and the layer with the lowest polyethylene density among the first surface resin layer, the polyethylene intermediate layer, and the optional second surface resin layer is less than 0.003 g/ cm3 .
- the first surface resin layer, the polyethylene intermediate layer, and the optional second surface resin layer each have approximately the same content ratio A.
- the difference in content ratio A between the layer having the highest content ratio A and the layer having the lowest content ratio A among the first surface resin layer, the polyethylene intermediate layer, and the optional second surface resin layer is less than 10% by mass.
- the density of the polyethylene refers to the density of a mixture of two or more types of polyethylene. The method of measuring and calculating the density is as described above.
- the stretched substrate of the first embodiment may further comprise a first adhesive resin layer between the first surface resin layer and the polyolefin intermediate layer.
- the stretched substrate of the first embodiment may further comprise a second adhesive resin layer between the polyolefin intermediate layer and the second surface resin layer.
- the stretched substrate of the second embodiment and the fourth A embodiment may further comprise an adhesive resin layer between the polyolefin intermediate layer and the second surface resin layer.
- Such a stretched substrate has, for example, excellent adhesion between the polyolefin intermediate layer and the surface resin layer.
- the adhesive resin layer contains an adhesive resin as a main component.
- the adhesive resin include acid-modified resin, silicone resin, epoxy resin, and phenol resin, and acid-modified resin is preferred.
- the acid-modified resin include acid-modified polyolefin and acid-modified vinyl resin. Among these, acid-modified polyolefin is preferred, and acid-modified polypropylene and acid-modified polyethylene are more preferred.
- acid-modified polypropylene is more preferred from the viewpoint of recyclability and adhesion to both the polypropylene layer and the surface resin layer, and acid-modified random polypropylene and acid-modified homopolypropylene are more preferred from the viewpoint of heat resistance and adhesion, and acid-modified random polypropylene is particularly preferred.
- acid-modified polyethylene is more preferred from the viewpoint of recyclability and adhesion to both the polyethylene layer and the surface resin layer, and acid-modified linear low-density polyethylene is more preferred. Details of the acid-modified polyolefin (structure, physical properties such as MFR, density, and Tm) are as explained in the section on the surface resin layer (AH), and explanations in this section are omitted.
- the content of the structural units derived from the acid-modified component in the acid-modified polyolefin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of adhesion between the surface resin layer and the polyolefin intermediate layer.
- the content of the structural units derived from the acid-modified component in the acid-modified polyolefin is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of adhesion between the surface resin layer and the polyolefin intermediate layer.
- the above content is, for example, 0.01% by mass or more and 10% by mass or less.
- the content of the structural units derived from the acid-modified component is measured by infrared spectroscopy.
- the adhesive resin content in the adhesive resin layer is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the adhesive resin layer may contain the above additives.
- the thickness of each adhesive resin layer is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and even more preferably 1 ⁇ m or more. From the viewpoint of recyclability of the stretched substrate and the barrier substrate, the thickness of each adhesive resin layer is preferably 18 ⁇ m or less, more preferably 13 ⁇ m or less, even more preferably 8 ⁇ m or less, and particularly preferably 5 ⁇ m or less. The thickness of each adhesive resin layer is, for example, 0.5 ⁇ m or more and 18 ⁇ m or less.
- each adhesive resin layer is preferably 2% or more, more preferably 4% or more, even more preferably 6% or more, and is preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, and particularly preferably 10% or less, for example, 2% or more and 25% or less, relative to the thickness of the stretched substrate.
- the stretched substrate of the first embodiment may comprise, in this order, a first surface resin layer, a first adhesive resin layer, a polyolefin intermediate layer, a second adhesive resin layer, and a second surface resin layer.
- a stretched substrate comprising, in this order, a first surface resin layer, a first adhesive resin layer, a polyolefin intermediate layer, a second adhesive resin layer, and a second surface resin layer
- the ratio of the thickness of the first adhesive resin layer to the thickness of the second adhesive resin layer is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, even more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1, from the viewpoints of symmetry of the stretched substrate and suppression of curling.
- the stretched substrate of the fifth embodiment comprises a polyethylene layer (1).
- the polyethylene layer (1) contains at least one polyethylene selected from high density polyethylene and medium density polyethylene, and preferably contains high density polyethylene. Therefore, the stretched substrate having the polyethylene layer (1) has high heat resistance, for example, and specifically, excellent resistance to drying during printing and heating during heat sealing, and excellent resistance to deposition when deposition is performed on the film.
- the polyethylene layer (1) has high rigidity, for example, and can increase the film conveying speed when deposition is performed on the film, thereby increasing productivity.
- High-density polyethylene includes, for example, ethylene homopolymers and ethylene- ⁇ -olefin copolymers.
- ⁇ -olefins include, for example, the above-mentioned ⁇ -olefins having 3 to 20 carbon atoms, with ⁇ -olefins having 3 to 8 carbon atoms being preferred, and ⁇ -olefins having 4 to 8 carbon atoms being more preferred.
- Ethylene- ⁇ -olefin copolymers include, for example, ethylene-1-butene copolymers (C4-HDPE) in which the comonomer is at least 1-butene, ethylene-1-hexene copolymers (C6-HDPE) in which the comonomer is at least 1-hexene, and ethylene-1-octene copolymers (C8-HDPE) in which the comonomer is at least 1-octene.
- the comonomers are not limited to the above, and further comonomers may be used.
- high-density polyethylenes produced using a metallocene catalyst are preferred.
- the medium density polyethylene may be, for example, an ethylene homopolymer or an ethylene- ⁇ -olefin copolymer.
- the ⁇ -olefin may be, for example, the above-mentioned ⁇ -olefin having 3 to 20 carbon atoms, with ⁇ -olefins having 3 to 8 carbon atoms being preferred, and ⁇ -olefins having 4 to 8 carbon atoms being more preferred.
- the ethylene- ⁇ -olefin copolymer may be, for example, an ethylene-1-butene copolymer (C4-MDPE) in which the comonomer is at least 1-butene, an ethylene-1-hexene copolymer (C6-MDPE) in which the comonomer is at least 1-hexene, and an ethylene-1-octene copolymer (C8-MDPE) in which the comonomer is at least 1-octene.
- the comonomers are not limited to the above-mentioned ones, and further comonomers may be used.
- a medium density polyethylene produced using a metallocene catalyst is preferred.
- the high density polyethylene and medium density polyethylene are preferably the above-mentioned ethylene- ⁇ -olefin copolymers.
- Films containing such high density polyethylene and/or medium density polyethylene have, for example, excellent biaxial stretchability, particularly excellent stretchability in the width direction. This is presumably because the side chains derived from the ⁇ -olefins prevent the film from tearing during stretching.
- the above-mentioned ethylene- ⁇ -olefin copolymers are preferably polyethylenes obtained by polymerizing ethylene and a small amount of ⁇ -olefins by a polymerization method using, for example, a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst, and more preferably polyethylenes produced using a metallocene catalyst.
- a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst
- the density of the high-density polyethylene is preferably more than 0.945 g/cm 3 and not more than 0.960 g/cm 3.
- the density of the medium-density polyethylene is preferably more than 0.930 g/cm 3 and not more than 0.945 g/cm 3.
- the density can be adjusted, for example, by the amount of constitutional units derived from an ⁇ -olefin, which is a comonomer in the ethylene- ⁇ -olefin copolymer, introduced.
- the melting point (Tm) of the polyethylene is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, and particularly preferably 115°C or higher, and is preferably 140°C or lower, for example, 100°C or higher and 140°C or lower, from the viewpoint of the strength and heat resistance of the biaxially stretched polyethylene film.
- the polyethylene layer (1) may, for example, contain high density polyethylene as a main component, may contain medium density polyethylene as a main component, or may contain a mixture of high density polyethylene and medium density polyethylene as a main component.
- the polyethylene layer (1) may, for example, contain as a main component a mixture of high-density polyethylene and another polyethylene, may contain as a main component a mixture of medium-density polyethylene and another polyethylene, or may contain as a main component a mixture of high-density polyethylene, medium-density polyethylene, and another polyethylene.
- the main component being the above mixture means that the content of the above mixture in the polyethylene layer (1) is more than 50% by mass, and the above content is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
- the high-density polyethylene may be, for example, an ethylene homopolymer, an ethylene- ⁇ -olefin copolymer, or a mixture thereof.
- the medium-density polyethylene may be, for example, an ethylene homopolymer, an ethylene- ⁇ -olefin copolymer, or a mixture thereof.
- the other polyethylene may be, for example, at least one selected from linear low-density polyethylene and high-pressure low-density polyethylene, and may be linear low-density polyethylene, high-pressure low-density polyethylene, or a mixture of linear low-density polyethylene and high-pressure low-density polyethylene.
- the total content of the high-density polyethylene and the medium-density polyethylene in the polyethylene layer (1) is, from the viewpoint of heat resistance, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and may be 30% by mass or more, 35% by mass or more, or 40% by mass or more.
- the total content of high-density polyethylene and medium-density polyethylene in the polyethylene layer (1) is 100% by mass or less, and from the viewpoint of biaxial stretchability, is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, may be 70% by mass or less, 65% by mass or less, or 60% by mass or less.
- the total content of high density polyethylene and medium density polyethylene in the polyethylene layer (1) is, for example, 10% by mass or more and 100% by mass or less, and preferably 20% by mass or more and 60% by mass or less.
- the polyethylene layer (1) is the surface resin layer of the film
- a small total content ratio tends to improve the adhesion between the surface resin layer and a printed layer or a vapor deposition film, etc., by the above-mentioned surface treatment.
- high-density polyethylene is highly crystalline and may not be able to sufficiently introduce polar groups into the polyethylene layer by surface treatment such as corona treatment
- a small total content ratio allows sufficient introduction of polar groups into the polyethylene layer by surface treatment such as corona treatment.
- a small total content ratio tends to provide the film with excellent appearance, surface smoothness, and transparency.
- the polyethylene layer (1) preferably contains linear low-density polyethylene in addition to at least one type of polyethylene selected from high-density polyethylene and medium-density polyethylene, and more preferably contains linear low-density polyethylene in addition to high-density polyethylene.
- linear low density polyethylene examples include ethylene- ⁇ -olefin copolymers.
- ⁇ -olefins include the above-mentioned ⁇ -olefins having 3 to 20 carbon atoms, with ⁇ -olefins having 3 to 8 carbon atoms being preferred, and ⁇ -olefins having 4 to 8 carbon atoms being more preferred.
- linear low density polyethylene examples include ethylene-1-butene copolymers (C4-LLDPE) in which the comonomer is at least 1-butene, ethylene-1-hexene copolymers (C6-LLDPE) in which the comonomer is at least 1-hexene, and ethylene-1-octene copolymers (C8-LLDPE) in which the comonomer is at least 1-octene.
- the comonomers are not limited to the above-mentioned comonomers, and further comonomers may be used.
- linear low density polyethylenes produced using a metallocene catalyst are preferred.
- the density of the linear low density polyethylene is preferably 0.900 g/cm 3 or more and 0.930 g/cm 3 or less.
- the content of the linear low-density polyethylene in the polyethylene layer (1) is, from the viewpoint of biaxial stretchability, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and may be 30% by mass or more, 35% by mass or more, or 40% by mass or more.
- the content of the linear low-density polyethylene in the polyethylene layer (1) is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, and may be 70% by mass or less, 65% by mass or less, or 60% by mass or less.
- the content of the linear low density polyethylene in the polyethylene layer (1) is, for example, from 10% by mass to 90% by mass, and preferably from 40% by mass to 80% by mass.
- the polyethylene layer (1) contains polyethylene as a main component.
- the content of polyethylene in the polyethylene layer (1) is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the polyethylene layer (1) may contain polyethylene other than high density polyethylene, medium density polyethylene, and linear low density polyethylene, or a resin material other than polyethylene.
- resin materials other than polyethylene include polyolefins other than polyethylene, polyesters, polyamides, (meth)acrylic resins, vinyl resins, cellulose resins, and ionomer resins.
- the polyethylene layer (1) may contain additives.
- additives include crosslinking agents, antioxidants, UV absorbers, light stabilizers, antiblocking agents, slip agents, fillers, reinforcing agents, antistatic agents, compatibilizers, pigments, and modifying resins.
- the stretched substrate of the sixth embodiment comprises a polyethylene layer (2).
- the polyethylene layer (2) contains polyethylene as a main component, and the polyethylene has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- the density of the polyethylene in the polyethylene layer (2) is preferably 0.931 g/ cm3 or more and 0.955 g/cm3 or less, more preferably 0.931 g/cm3 or more and 0.950 g/ cm3 or less.
- the density of the polyethylene means the density of a mixture of two or more polyethylenes.
- the density is measured for polyethylene sampled from the layer in accordance with JIS K7112:1999, Method D (density gradient tube method, 23°C).
- Method D density gradient tube method, 23°C.
- the average density Dav calculated according to the following formula may be used as the density of the polyethylene constituting the layer.
- ⁇ means taking the sum of W i ⁇ D i from 1 to n (n types of polyethylene are present), n is an integer of 2 or more, W i represents the mass fraction of the i-th polyethylene, and D i represents the density (g/cm 3 ) of the i-th polyethylene.
- the density of the polyethylene layer (2) can be adjusted, for example, based on the composition described for the polyethylene layer (1) above. That is, the polyethylene layer (2) can have the composition described for the polyethylene layer (1).
- the polyethylene layer (2) may contain the above-mentioned resin materials other than polyethylene.
- the polyethylene layer (2) may contain the above-mentioned additives.
- the stretched substrate (biaxially oriented polyethylene film) of the fifth aspect is a monolayer film consisting of a polyethylene layer (1).
- the stretched substrate (biaxially oriented polyethylene film) of the fifth aspect has two or more polyethylene layers, at least one of which is the polyethylene layer (1), and preferably all of which are the polyethylene layers (1).
- the stretched substrate (biaxially stretched polyethylene film) of the sixth aspect is a monolayer film consisting of a polyethylene layer (2). In one embodiment, the stretched substrate (biaxially stretched polyethylene film) of the sixth aspect has two or more polyethylene layers, at least one of which is a polyethylene layer (2), and preferably all of which are polyethylene layers (2).
- the polyethylene layer contains polyethylene as a main component.
- polyethylene for example, high density polyethylene, medium density polyethylene, low density polyethylene and linear low density polyethylene are preferable.
- the content of polyethylene in the polyethylene layer is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the polyethylene layer may contain the above-mentioned resin materials other than polyethylene.
- the polyethylene layer may contain the additives described above.
- the biaxially oriented polyethylene film has a multilayer structure of two or more layers.
- the number of layers of the film is preferably two or more, more preferably three or more, and preferably nine or less, more preferably seven or less, for example, two or more and nine or less.
- the number of layers of the biaxially oriented polyethylene film is specifically three, five, seven, or nine.
- the biaxially oriented polyethylene film substrate having a multilayer structure has an excellent balance of, for example, strength, rigidity, heat resistance, transparency, and printability.
- the biaxially oriented polyethylene film comprises: A first surface resin layer containing polyethylene as a main component; A polyethylene intermediate layer containing polyethylene as a main component; a second surface resin layer containing polyethylene as a main component; in this order in the thickness direction, and at least one layer selected from the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer is a polyethylene layer (1) or a polyethylene layer (2). From the viewpoint of heat resistance, it is preferable that the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer are all the polyethylene layer (1) or the polyethylene layer (2).
- the biaxially oriented polyethylene film may comprise two or more polyethylene intermediate layers.
- the biaxially oriented polyethylene film may comprise a first surface resin layer, a first polyethylene layer, a second polyethylene layer, a third polyethylene layer, and a second surface resin layer, in this order. At least one layer selected from the first surface resin layer, the first polyethylene layer, the second polyethylene layer, the third polyethylene layer, and the second surface resin layer is a polyethylene layer (1) or a polyethylene layer (2), and from the viewpoint of heat resistance, it is preferable that all of the above layers are polyethylene layers (1) or polyethylene layers (2).
- compositions of the first and second surface resin layers may be the same or different.
- the thicknesses of the first and second surface resin layers may be the same or different.
- the compositions of the first to third polyethylene layers may be the same or different.
- the thicknesses of the first to third polyethylene layers may be the same or different.
- the absolute value of the difference between the density of the polyethylene constituting layer (i) and the density of the polyethylene constituting layer (ii) is preferably 0.030 g/cm or less , more preferably 0.025 g/cm or less, even more preferably 0.020 g/cm or less, and particularly preferably 0.010 g/cm or less.
- Such a film has excellent interlayer adhesion, for example, excellent drop resistance.
- the density of the polyethylene in the polyethylene intermediate layer is higher than the density of the polyethylene in the first surface resin layer, and the density of the polyethylene in the second surface resin layer is lower than the density of the polyethylene in the polyethylene intermediate layer.
- Such a film tends to have an excellent balance of surface smoothness, transparency, printability, vapor deposition adhesion, and heat resistance.
- the polyethylene intermediate layer is thicker than the surface resin layer, the polyethylene intermediate layer provides high heat resistance.
- the density difference between the polyethylene in the polyethylene intermediate layer and the above surface resin layer may be, for example, 0.003 g/ cm3 or more.
- the total content ratio of the high density polyethylene and the medium density polyethylene is hereinafter referred to as "content ratio A.”
- content ratio A The total content ratio of the high density polyethylene and the medium density polyethylene is hereinafter referred to as "content ratio A.”
- content ratio A in the polyethylene intermediate layer is greater than the content ratio A in the first surface resin layer, and the content ratio A in the second surface resin layer is smaller than the content ratio A in the polyethylene intermediate layer.
- Such a film tends to have an excellent balance of surface smoothness, transparency, printability, vapor deposition adhesion, and heat resistance.
- the difference in content ratio A between the polyethylene intermediate layer and the surface resin layer may be, for example, 10% by mass or more, or 30% by mass or less.
- the density of the polyethylene in the polyethylene intermediate layer is lower than the density of the polyethylene in the first surface resin layer, and the density of the polyethylene in the second surface resin layer is higher than the density of the polyethylene in the polyethylene intermediate layer.
- Such a film tends to have an excellent balance between biaxial stretchability and heat resistance.
- the polyethylene intermediate layer is thicker than the surface resin layer, the polyethylene intermediate layer provides high biaxial stretchability.
- the density difference between the polyethylene in the surface resin layer and the polyethylene intermediate layer may be, for example, 0.003 g/ cm3 or more.
- the content ratio A in the polyethylene intermediate layer is smaller than the content ratio A in the first surface resin layer, and the content ratio A in the second surface resin layer is larger than the content ratio A in the polyethylene intermediate layer.
- Such a film tends to have an excellent balance between biaxial stretchability and heat resistance.
- the difference in content ratio A between the surface resin layer and the polyethylene intermediate layer may be, for example, 10% by mass or more, or 30% by mass or less.
- the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer each have a substantially equal density of polyethylene, for example, the difference in density between the layer with the highest polyethylene density and the layer with the lowest polyethylene density among the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer is less than 0.003 g/ cm3 .
- the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer each have approximately the same content ratio A.
- the difference in content ratio A between the layer having the largest content ratio A and the layer having the smallest content ratio A among the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer is less than 10 mass %.
- the density of the polyethylene refers to the density of a mixture of two or more types of polyethylene. The method of measuring and calculating the density is as described above.
- first and second surface resin layers may further contain particles.
- the surface resin layer contains particles, for example, the antiblocking property or slipperiness of the biaxially oriented polyethylene film can be improved.
- the following description of particles can also be applied to the oriented substrates of the first to fourth embodiments.
- the particles include inorganic compound-based antiblocking agents and resin particle-based antiblocking agents.
- inorganic compound-based antiblocking agents include oxides such as silica, aluminum oxide, magnesium oxide, calcium oxide, titanium oxide, and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; carbonates such as magnesium carbonate and calcium carbonate; sulfates such as calcium sulfate and barium sulfate; silicates such as magnesium silicate, aluminum silicate, calcium silicate, and aluminosilicate; and others, kaolin, talc, and diatomaceous earth.
- the resin particles include resin particles composed of resin components such as polymethyl methacrylate (PMMA), polystyrene, methyl methacrylate-styrene copolymer, polyester, polyamide, polytetrafluoroethylene, epoxy resin, urea resin, and phenol resin.
- the resin particles may be crosslinked or non-crosslinked.
- the particles may be an inorganic compound-based antiblocking agent.
- the particles may be a resin particle-based antiblocking agent. This reduces the possibility that the particles will damage the vapor-deposited film when the substrate is stored in a roll shape, for example, in the case of a barrier substrate having one surface resin layer containing a resin particle-based antiblocking agent and the other surface resin layer having a vapor-deposited film, as described below. This is because the resin particle-based antiblocking agent is usually smaller in unevenness and softer than the inorganic compound-based antiblocking agent.
- the average particle size of the particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, even more preferably 2 ⁇ m or more, and is preferably 6 ⁇ m or less, more preferably 5.5 ⁇ m or less, even more preferably 5 ⁇ m or less, for example, 0.5 ⁇ m or more and 6 ⁇ m or less.
- the average particle size of the particles refers to the average particle size (arithmetic mean diameter) measured for non-aggregates of 100 randomly selected particles when the cross section in the thickness direction of each layer is observed with a scanning electron microscope (SEM).
- the particle content is preferably 100 ppm or more, more preferably 500 ppm or more, even more preferably 1,000 ppm or more, based on the mass of the first surface resin layer, and is preferably 10,000 ppm or less, more preferably 8,000 ppm or less, even more preferably 5,000 ppm or less, for example 100 ppm or more and 10,000 ppm or less.
- the particle content is preferably 100 ppm or more, more preferably 500 ppm or more, even more preferably 1,000 ppm or more, based on the mass of the second surface resin layer, and is preferably 10,000 ppm or less, more preferably 8,000 ppm or less, even more preferably 5,000 ppm or less, for example 100 ppm or more and 10,000 ppm or less.
- the surface resin layer on which the vapor deposition film is provided does not contain particles, from the viewpoint of formability of the vapor deposition film.
- the ratio of the average particle size of the particles to the thickness of the surface resin layer is preferably 0.5 to 5.0, more preferably 0.8 to 4.0, and even more preferably 1.0 to 3.5.
- the surface resin layer here may be the first surface resin layer, the second surface resin layer, or both.
- the thickness of the first and second surface resin layers is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 0.8 ⁇ m or more, and is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less, for example, 0.3 ⁇ m or more and 15 ⁇ m or less. If the surface resin layer has convex portions due to particles, it is preferable that the thickness of each layer is measured in an area where convex portions due to the particles are not formed.
- the thickness of the first and second surface resin layers is preferably at least 1%, more preferably at least 2%, even more preferably at least 4%, and is preferably at most 20%, more preferably at most 15%, even more preferably at most 10%, and particularly preferably at most 8%, for example at least 1% and at most 20%, relative to the thickness of the biaxially oriented polyethylene film.
- the thickness of the polyethylene intermediate layer is preferably 6 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 14 ⁇ m or more, and preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, even more preferably 60 ⁇ m or less, even more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less, for example, 6 ⁇ m or more and 100 ⁇ m or less.
- a biaxially oriented polyethylene film having a polyethylene intermediate layer whose thickness is equal to or greater than the lower limit has, for example, excellent strength, rigidity, heat resistance, and recyclability.
- a biaxially oriented polyethylene film having a polyethylene intermediate layer whose thickness is equal to or less than the upper limit has, for example, excellent processability.
- the above "thickness” means the sum of the thicknesses of the polyethylene intermediate layers.
- the thickness of the polyethylene intermediate layer is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, particularly preferably 84% or more, and is preferably 98% or less, more preferably 96% or less, even more preferably 92% or less, for example, 60% or more and 98% or less, relative to the thickness of the biaxially oriented polyethylene film.
- the above "thickness" refers to the sum of the thicknesses of the individual polyethylene intermediate layers.
- the biaxially oriented polyethylene film may have one or more polyethylene intermediate layers.
- the biaxially oriented polyethylene film may have a first surface resin layer, a first polyethylene layer, a second polyethylene layer, a third polyethylene layer, and a second surface resin layer, in this order.
- the thickness of the second polyethylene layer is preferably 4 ⁇ m or more, more preferably 6 ⁇ m or more, even more preferably 8 ⁇ m or more, and is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 20 ⁇ m or less, for example, 4 ⁇ m or more and 60 ⁇ m or less.
- the thickness of the second polyethylene layer is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and is preferably 94% or less, more preferably 90% or less, even more preferably 86% or less, for example, 50% or more and 94% or less, of the thickness of the polyethylene intermediate layer.
- the thickness of the first and third polyethylene layers is, independently of each other, preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, even more preferably 1 ⁇ m or more, and is preferably 18 ⁇ m or less, more preferably 13 ⁇ m or less, even more preferably 8 ⁇ m or less, and particularly preferably 5 ⁇ m or less, for example, 0.5 ⁇ m or more and 18 ⁇ m or less.
- the thickness of the first and third polyethylene layers is, independently of each other, preferably 3% or more, more preferably 5% or more, even more preferably 7% or more, and preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, for example 3% or more and 25% or less, relative to the thickness of the polyethylene intermediate layer.
- the ratio of the thickness of the second surface resin layer to the thickness of the first surface resin layer is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, even more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1, from the viewpoint of film symmetry and suppression of curling.
- a layer containing a gas barrier resin as a main component, or a layer containing polyethylene and an adhesive resin may be provided between the polyethylene layer and the vapor-deposited film.
- the surface resin layer in the biaxially oriented polyethylene film may be a layer containing a gas barrier resin as a main component, or a layer containing polyethylene and an adhesive resin, and the vapor-deposited film may be provided on the layer.
- a layer containing a gas barrier resin as a main component for example, a coating layer, an extruded resin layer
- a layer containing polyethylene and an adhesive resin for example, a coating layer, an extruded resin layer
- the vapor-deposited film tends to have excellent adhesion to the biaxially oriented polyethylene film and to exhibit good gas barrier properties.
- the thickness of the layer containing a gas barrier resin as a main component, or the layer containing polyethylene and an adhesive resin is not particularly limited, but may be independently 0.3 ⁇ m or more, 0.5 ⁇ m or more, 0.8 ⁇ m or more, 15 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less, for example, 0.3 ⁇ m or more and 15 ⁇ m or less.
- Gas barrier resins are resins that have the function of suppressing the permeation of gas.
- gas barrier resins include ethylene-vinyl alcohol copolymers, polyvinyl alcohol, polyamides, polyvinylidene chloride, polyesters, polyether polyols, polyester polyols, polyurethanes, polyacrylonitrile, and (meth)acrylic resins.
- ethylene-vinyl alcohol copolymers, polyvinyl alcohol, and polyamides are preferred from the standpoint of gas barrier properties (particularly oxygen barrier properties), heat resistance, and rigidity, with ethylene-vinyl alcohol copolymers and polyamides being more preferred.
- Adhesive resins include, for example, acid-modified resins, silicone resins, epoxy resins, and phenolic resins, with acid-modified resins being preferred.
- Acid-modified resins include, for example, acid-modified polyolefins and acid-modified vinyl resins. Among these, acid-modified polyolefins are preferred from the viewpoint of recyclability and adhesion, with acid-modified polypropylene and acid-modified polyethylene being more preferred, and acid-modified polyethylene being even more preferred.
- Acid-modified polyolefins include, for example, polyolefins (e.g., polypropylene and polyethylene) modified with an acid-modifying component, and in particular, graft-modified polyolefins with an acid-modifying component.
- Acid-modified components include, for example, unsaturated carboxylic acids such as maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, or their acid anhydrides, esters, or metal salts.
- Acid-modified polyolefins include, for example, maleic acid-modified polyolefins and maleic anhydride-modified polyolefins, with maleic acid-modified polypropylene, maleic anhydride-modified polypropylene, maleic acid-modified polyethylene, and maleic anhydride-modified polyethylene being more preferred.
- the polyethylene content is 60% by mass or more and 95% by mass or less, and the adhesive resin content is 5% by mass or more and 40% by mass or less, it is more preferable that the polyethylene content is 70% by mass or more and 95% by mass or less, and the adhesive resin content is 5% by mass or more and 30% by mass or less, it is even more preferable that the polyethylene content is 80% by mass or more and 95% by mass or less, and the adhesive resin content is 5% by mass or more and 20% by mass or less, it is particularly preferable that the polyethylene content is 85% by mass or more and 95% by mass or less, and the adhesive resin content is 5% by mass or more and 15% by mass or less.
- the biaxially oriented polyethylene film 1A shown in FIG. 10 comprises a first surface resin layer 20, a polyethylene layer 10 (polyethylene intermediate layer), and a second surface resin layer 22, in this order.
- the biaxially oriented polyethylene film 1A shown in FIG. 11 comprises, in this order, a first surface resin layer 20, a first polyethylene layer 11, a second polyethylene layer 12, a third polyethylene layer 13, and a second surface resin layer 22.
- the oxygen permeability (unit: cc/( m2 ⁇ day ⁇ atm)) of the stretched substrate of the present disclosure may be, for example, less than 30, less than 25, less than 18, less than 10, or less than 5.0.
- the oxygen permeability is measured in accordance with JIS K7126-2:2006 in an environment at a temperature of 23° C. and a humidity of 90% RH.
- the water vapor permeability (unit: g/( m2 ⁇ day)) of the stretched substrate of the present disclosure may be, for example, less than 20, less than 15, less than 10, less than 8.0, or less than 5.0.
- the water vapor permeability is measured in accordance with JIS K7129-2:2019 at a temperature of 40° C. and a humidity of 90% RH.
- the barrier substrate according to the first to third aspects of the present disclosure comprises: A stretched substrate according to any one of the first to third aspects described above; a vapor-deposited film provided on a surface of at least one layer selected from the first surface resin layer and the second surface resin layer of the stretched substrate; Equipped with.
- the barrier substrate according to the fourth aspect of the present disclosure comprises: The stretched substrate according to the fourth aspect described above, a vapor-deposited film provided on a surface of the second surface resin layer of the stretched substrate; Equipped with.
- the barrier substrate according to the fifth and sixth aspects of the present disclosure comprises: A stretched substrate according to any one of the fifth and sixth aspects described above; A vapor-deposited film provided on at least one surface of the stretched substrate (for example, a vapor-deposited film provided on the surface of at least one layer selected from the first surface resin layer and the second surface resin layer); Equipped with.
- the vapor deposition film may be provided only on the surface of the first surface resin layer of the stretched substrate, may be provided only on the surface of the second surface resin layer, or may be provided on the surface of the first surface resin layer and the surface of the second surface resin layer. In the barrier substrate of the fourth embodiment, the vapor deposition film may also be provided on the surface of the first surface resin layer of the stretched substrate.
- the vapor deposition film may be provided only on one side of the stretched substrate (biaxially stretched polyethylene film), only on the other side, or on both sides. In the barrier substrate of the fifth to sixth embodiments, the vapor deposition film may be provided only on the surface of the first surface resin layer of the stretched substrate (biaxially stretched polyethylene film), only on the surface of the second surface resin layer, or on the surface of the first surface resin layer and the surface of the second surface resin layer.
- the barrier substrate of the fifth to sixth aspects may have, as described above, a layer containing, for example, a gas barrier resin as a main component, or a layer containing polyethylene and an adhesive resin, between the polyethylene layer and the vapor deposition film.
- the surface resin layer of the biaxially oriented polyethylene film may be a layer containing a gas barrier resin as a main component, or a layer containing polyethylene and an adhesive resin, and the vapor deposition film may be provided on the layer.
- the barrier substrate may have, between the biaxially oriented polyethylene film and the vapor deposition film, a layer containing a gas barrier resin as a main component (e.g., a coating layer, an extruded resin layer), or a layer containing polyethylene and an adhesive resin (e.g., a coating layer, an extruded resin layer).
- a layer containing a gas barrier resin as a main component e.g., a coating layer, an extruded resin layer
- an adhesive resin e.g., a coating layer, an extruded resin layer
- barrier substrate When describing matters common to the barrier substrates of the first to sixth embodiments, or when there is no particular distinction to be made between the barrier substrates of the first to sixth embodiments, they will also be referred to simply as "barrier substrate.”
- the barrier substrate of the present disclosure comprises: A first vapor-deposited film; The stretched substrate described above; A second deposited film; In the thickness direction, at least
- the stretched substrate has a first surface and a second surface opposite to the first surface.
- the first surface resin layer constitutes the first surface
- the second surface resin layer constitutes the second surface.
- the first vapor deposition film is provided on the first surface of the stretched substrate.
- the first vapor deposition film is provided, for example, on the surface of the first surface resin layer of the stretched substrate.
- the second vapor deposition film is provided, for example, on the surface of the second surface resin layer of the stretched substrate.
- the barrier substrate may further include a printing layer, which will be described later.
- the barrier substrate of the present disclosure has a vapor deposition film and is excellent in gas barrier properties. Therefore, a packaging container produced using such a barrier substrate has excellent gas barrier properties.
- the barrier substrate of the present disclosure has a first vapor deposition film and a second vapor deposition film and is more excellent in gas barrier properties. Since such a barrier substrate has vapor deposition films on both sides of the stretched substrate, it is possible to suppress the deterioration of gas barrier properties due to pinholes.
- the vapor deposition film is composed of, for example, a metal and/or an inorganic oxide.
- the vapor deposition film may be a metal vapor deposition film composed of one or more metals, or an inorganic oxide vapor deposition film composed of one or more inorganic oxides.
- the inorganic oxide vapor deposition film may be a transparent vapor deposition film.
- metals include aluminum, chromium, tin, nickel, copper, silver, gold, and platinum.
- inorganic oxides include aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon carbide oxide (carbon-containing silicon oxide).
- the vapor deposition films aluminum vapor deposition films, aluminum oxide (alumina) vapor deposition films, silicon oxide (silica) vapor deposition films, and silicon carbide oxide vapor deposition films are preferred, and the first vapor deposition film and the second vapor deposition film are each preferably independently an aluminum vapor deposition film, an aluminum oxide (alumina) vapor deposition film, a silicon oxide (silica) vapor deposition film, or a silicon carbide oxide vapor deposition film.
- the combination of the first and second evaporated films is not particularly limited.
- the first vapor-deposited film may be a metal vapor-deposited film and the second vapor-deposited film may be a metal vapor-deposited film, and the two may be the same or different.
- One of the first vapor-deposited film and the second vapor-deposited film may be a metal vapor-deposited film and the other may be an inorganic oxide vapor-deposited film or a transparent vapor-deposited film.
- the first vapor-deposited film may be an inorganic oxide vapor-deposited film or a transparent vapor-deposited film
- the second vapor-deposited film may be an inorganic oxide vapor-deposited film or a transparent vapor-deposited film, and the two may be the same or different.
- the first vapor-deposited film is a metal vapor-deposited film
- the second vapor-deposited film is a metal vapor-deposited film.
- the two may be the same or different.
- Such a barrier substrate has particularly excellent gas barrier properties.
- the metal vapor deposition film may oxidize to become a metal oxide, causing discoloration, corrosion, or volume expansion, reducing the laminate strength, and causing problems such as lifting or peeling of layers.
- At least one of the first and second vapor deposition films is an inorganic oxide vapor deposition film.
- a packaging container with excellent resistance to contents can be produced.
- a laminate including a barrier substrate and a heat seal layer is prepared.
- the laminate includes a barrier substrate in which the inorganic oxide vapor deposition film faces the heat seal layer side (inside of the packaging container) and the other vapor deposition film faces the outside (outside of the packaging container).
- the orientation of the barrier substrate is not particularly limited.
- the first vapor-deposited film is an inorganic oxide vapor-deposited film
- the second vapor-deposited film is a metal vapor-deposited film.
- the first vapor-deposited film is a metal vapor-deposited film
- the second vapor-deposited film is an inorganic oxide vapor-deposited film.
- the inorganic oxide vapor-deposited film may be a transparent vapor-deposited film.
- the first vapor deposition film is an inorganic oxide vapor deposition film
- the second vapor deposition film is an inorganic oxide vapor deposition film.
- the inorganic oxide vapor deposition film may be a transparent vapor deposition film.
- Such a barrier substrate can avoid the problem of oxidation deterioration when the vapor deposition film is a metal vapor deposition film, for example, and can also suppress corrosion of the vapor deposition film from the end face of the barrier substrate.
- a barrier substrate has excellent transparency, it is possible to produce a packaging container with excellent visibility of the contents, for example, a packaging container that can be used in a microwave oven and a packaging container that can pass through a metal detector.
- a packaging container equipped with such a barrier substrate can be clearly understood by, for example, a consumer that does not contain an aluminum vapor deposition film, making it easy to separate, and further, it is possible to suppress the inclusion of foreign matter such as black spots (metallic color) that may occur due to the aluminum vapor deposition film during recycling processing.
- the first and second vapor-deposited films may both be aluminum vapor-deposited films, and they may be the same or different.
- One of the first and second vapor-deposited films may be an alumina vapor-deposited film, a silica vapor-deposited film, or a silicon carbide oxide vapor-deposited film, and the other may be an aluminum vapor-deposited film.
- the first vapor-deposited film may be an alumina vapor-deposited film, a silica vapor-deposited film, or a silicon carbide oxide vapor-deposited film
- the second vapor-deposited film may be an alumina vapor-deposited film, a silica vapor-deposited film, or a silicon carbide oxide vapor-deposited film, and they may be the same or different.
- the barrier substrate of the present disclosure has a vapor deposition film only on one surface of the stretched substrate. In one embodiment, the barrier substrate of the present disclosure has a vapor deposition film only on the surface of the second surface resin layer of the stretched substrate, and does not have a vapor deposition film on the surface of the first surface resin layer.
- a packaging container with excellent content resistance can be produced. For example, a laminate having a barrier substrate and a heat seal layer is prepared. The laminate has a barrier substrate arranged so that the stretched substrate faces the heat seal layer side (inside of the packaging container) and the vapor deposition film faces the outside (outside of the packaging container).
- the vapor deposition film can be arranged on the outside, so that discoloration, corrosion, or deterioration of the vapor deposition film, and lifting or peeling of the layer can be suppressed even when corrosive contents are filled in the packaging container.
- the thickness of the vapor-deposited film is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. From the viewpoint of suppressing the occurrence of cracks in the vapor-deposited film and the recyclability of the packaging container, the thickness of the vapor-deposited film is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 80 nm or less. The thickness of the vapor-deposited film is, for example, 1 nm or more and 150 nm or less. It is preferable that the thicknesses of the first vapor-deposited film and the second vapor-deposited film are each independently within the above range.
- the optical density (OD value) of the aluminum vapor deposition film is preferably 2.0 or more and 3.5 or less, more preferably 2.2 or more and 3.5 or less, even more preferably 2.7 or more and 3.5 or less, and particularly preferably 3.0 or more and 3.5 or less. This makes it possible, for example, to improve the oxygen barrier property and water vapor barrier property while maintaining the productivity of the barrier substrate.
- one vapor deposition film in the barrier substrate of the present disclosure is a transparent vapor deposition film, there is a tendency that the other vapor deposition film has a stable OD value and is an aluminum vapor deposition film with excellent thickness uniformity.
- the OD value can be measured in accordance with JIS K7361-1:1997.
- the barrier substrate may have two or more vapor-deposited films on the first surface (or the surface of the first surface resin layer) of the stretched substrate.
- the barrier substrate may have two or more vapor-deposited films on the second surface (or the surface of the second surface resin layer) of the stretched substrate.
- Such a barrier substrate has, for example, better gas barrier properties.
- the barrier substrate may have at least a stretched substrate, a third vapor-deposited film, and a fourth vapor-deposited film in this order, or may have at least a sixth vapor-deposited film, a fifth vapor-deposited film, a stretched substrate, a third vapor-deposited film, and a fourth vapor-deposited film in this order, or may have further vapor-deposited films.
- a barrier coat layer may be provided on the fourth vapor-deposited film.
- a barrier coat layer may be provided on the sixth vapor-deposited film.
- the fourth vapor deposition film may be in contact with the third vapor deposition film.
- the third vapor deposition film and the fourth vapor deposition film may be vapor deposition films constituting a multi-stage vapor deposition film.
- the sixth vapor deposition film may be in contact with the fifth vapor deposition film.
- the fifth vapor deposition film and the sixth vapor deposition film may be vapor deposition films constituting a multi-stage vapor deposition film.
- the thickness and/or composition of each vapor deposition film may be the same as or different from each other.
- a barrier coat layer may be provided on the multi-stage vapor deposition film.
- the surface of the deposited film is preferably subjected to the above-mentioned surface treatment.
- Such a deposited film has, for example, excellent adhesion to adjacent layers.
- Methods for forming the vapor deposition film include, for example, physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating, as well as chemical vapor deposition methods (CVD methods) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.
- PVD methods physical vapor deposition methods
- CVD methods chemical vapor deposition methods
- the vapor deposition film may be a composite film containing two or more layers of different types of vapor deposition films, formed by using both physical vapor deposition and chemical vapor deposition in combination.
- the degree of vacuum in the deposition chamber is preferably about 10 -2 to 10 -8 mbar before oxygen is introduced, and about 10 -1 to 10 -6 mbar after oxygen is introduced.
- the amount of oxygen introduced varies depending on the size of the deposition machine.
- an inert gas such as argon gas, helium gas, or nitrogen gas may be used as a carrier gas to the extent that no problems occur.
- the transport speed of the target film on which the deposition film is formed is, for example, 10 m/min or more and 800 m/min or less.
- the vapor-deposited film may be a single layer formed by a single vapor deposition process, or may be a multilayer formed by multiple vapor deposition processes.
- each layer may be composed of the same components or different components.
- Each layer may be formed by the same method or different methods.
- the stretched substrate comprises a first surface resin layer constituting the first surface and a second surface resin layer constituting the second surface, a first vapor deposition film is provided on the surface of the first surface resin layer, and a second vapor deposition film is provided on the surface of the second surface resin layer.
- a stretched substrate has, for example, excellent vapor deposition film formability, smoothness, and adhesion
- the resulting barrier substrate has, for example, excellent gas barrier properties, specifically, oxygen barrier properties and water vapor barrier properties, and also has excellent brightness when the vapor deposition film is a metal vapor deposition film.
- the stretched substrate comprises a first surface resin layer constituting the first surface and a second surface resin layer constituting the second surface, and a vapor deposition film is provided on the surface of the second surface resin layer.
- a stretched substrate has, for example, excellent vapor deposition film formability, smoothness, and adhesion
- the resulting barrier substrate has, for example, excellent gas barrier properties, specifically, oxygen barrier properties and water vapor barrier properties, and also has excellent brightness when the vapor deposition film is a metal vapor deposition film.
- the barrier substrate of the present disclosure may further include a barrier coat layer on the vapor-deposited film. That is, the barrier substrate may further include a barrier coat layer on the surface of the vapor-deposited film opposite to the surface on the stretched substrate side.
- a barrier substrate has, for example, excellent oxygen barrier properties and water vapor barrier properties, and can effectively suppress the occurrence of cracks in the vapor-deposited film when the vapor-deposited film is made of an inorganic oxide such as aluminum oxide or silicon oxide.
- the barrier substrate comprises, in this order, a metal vapor-deposited film as a first vapor-deposited film, a first surface resin layer, a polyolefin intermediate layer, a second surface resin layer, an inorganic oxide vapor-deposited film as the second vapor-deposited film, and a barrier coat layer.
- the barrier substrate comprises, in this order, a barrier coat layer, an inorganic oxide vapor-deposited film as a first vapor-deposited film, a first surface resin layer, a polyolefin intermediate layer, a second surface resin layer, and a metal vapor-deposited film as the second vapor-deposited film.
- the barrier substrate comprises, in this order, a first barrier coating layer, an inorganic oxide vapor deposition film as the first vapor deposition film, a first surface resin layer, a polyolefin intermediate layer, a second surface resin layer, an inorganic oxide vapor deposition film as the second vapor deposition film, and a second barrier coating layer.
- the barrier substrate comprises a first surface resin layer, a polyolefin intermediate layer, a second surface resin layer, an inorganic oxide vapor deposition film, and a barrier coat layer, in this order.
- the barrier substrate comprises, in this order, a metal vapor-deposited film as a first vapor-deposited film, a biaxially oriented polyethylene film, an inorganic oxide vapor-deposited film as a second vapor-deposited film, and a barrier coat layer.
- the barrier substrate comprises, in this order, a barrier coat layer, an inorganic oxide vapor-deposited film as a first vapor-deposited film, a biaxially oriented polyethylene film, and a metal vapor-deposited film as a second vapor-deposited film.
- the barrier substrate comprises, in this order, a first barrier coat layer, an inorganic oxide vapor deposition film as a first vapor deposition film, a biaxially oriented polyethylene film, an inorganic oxide vapor deposition film as a second vapor deposition film, and a second barrier coat layer.
- the barrier substrate comprises a biaxially oriented polyethylene film, an inorganic oxide vapor deposition film, and a barrier coat layer in this order.
- the barrier substrate may have two or more laminate films each composed of a vapor-deposited film and a barrier coat layer on the first surface (or the surface of the first surface resin layer) of the stretched substrate.
- the barrier substrate may have two or more laminate films each composed of a vapor-deposited film and a barrier coat layer on the second surface (or the surface of the second surface resin layer) of the stretched substrate.
- Such a barrier substrate has, for example, superior gas barrier properties.
- the barrier substrate may include, in this order, a third vapor-deposited film, a third barrier coat layer, a fourth vapor-deposited film, and a fourth barrier coat layer on a first surface (or a surface of a first surface resin layer) of the stretched substrate.
- the barrier substrate may include, in this order, a third vapor-deposited film, a third barrier coat layer, a fourth vapor-deposited film, and a fourth barrier coat layer on a second surface (or a surface of a second surface resin layer) of the stretched substrate.
- the barrier substrate may include at least a sixth barrier coat layer, a sixth vapor-deposited film, a fifth barrier coat layer, a fifth vapor-deposited film, a stretched substrate, a third vapor-deposited film, a third barrier coat layer, a fourth vapor-deposited film, and a fourth barrier coat layer in this order, or may include a further laminated film of the vapor-deposited films and the barrier coat layer.
- each deposited film may be the same as or different from each other.
- the thickness and/or composition of each barrier coat layer may be the same as or different from each other.
- the barrier coat layer contains a gas barrier resin.
- gas barrier resins include ethylene-vinyl alcohol copolymers, polyvinyl alcohol, polyamide, polyvinylidene chloride, polyester, polyether polyol, polyester polyol, polyurethane, polyacrylonitrile, and (meth)acrylic resins.
- the content of the gas barrier resin in the barrier coat layer is preferably more than 50% by mass, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
- Such a barrier coat layer has, for example, excellent gas barrier properties.
- the barrier coat layer may contain the above additives.
- the thickness of the barrier coat layer containing the gas barrier resin is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, from the viewpoint of gas barrier properties.
- the thickness of the barrier coat layer containing the gas barrier resin is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, from the viewpoint of processability of the barrier substrate and recyclability of the packaging container.
- the thickness is, for example, 0.01 ⁇ m or more and 10 ⁇ m or less.
- the barrier coat layer can be formed, for example, by applying a coating liquid obtained by dissolving or dispersing a material such as a gas barrier resin in water or a suitable organic solvent to the vapor deposition film and drying it.
- the barrier coat layer is a gas barrier coating film formed by mixing a metal alkoxide, a water-soluble polymer, and optionally a silane coupling agent, and adding water, an organic solvent, and a sol-gel catalyst as necessary to obtain a gas barrier composition, applying the gas barrier composition to a vapor deposition film, and drying the gas barrier composition.
- the gas barrier coating film contains a hydrolysis polycondensate obtained by hydrolyzing and polycondensing the metal alkoxide and the like by the sol-gel method.
- metal alkoxides include alkoxysilanes, specifically tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
- water-soluble polymers examples include hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Depending on the desired physical properties such as oxygen barrier properties, water vapor barrier properties, water resistance, and weather resistance, either polyvinyl alcohol or ethylene-vinyl alcohol copolymers may be used, or both may be used in combination. Also, a gas barrier coating film obtained using polyvinyl alcohol and a gas barrier coating film obtained using ethylene-vinyl alcohol copolymer may be laminated. The amount of water-soluble polymer used is preferably 5 parts by mass or more and 500 parts by mass or less per 100 parts by mass of the metal alkoxide.
- a known organoalkoxysilane containing an organic reactive group can be used as the silane coupling agent, and an organoalkoxysilane having an epoxy group is preferred, such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
- the amount of the silane coupling agent used is preferably 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the metal alkoxide.
- the gas barrier composition may contain water in an amount of preferably 0.1 mol or more, more preferably 0.5 mol or more, and preferably 100 mol or less, more preferably 60 mol or less per mol of metal alkoxide.
- water content By making the water content equal to or greater than the lower limit, for example, the oxygen barrier property and water vapor barrier property of the barrier substrate can be improved.
- the hydrolysis reaction By making the water content equal to or less than the upper limit, for example, the hydrolysis reaction can be carried out quickly.
- the gas barrier composition may contain an organic solvent.
- organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol.
- an acid or amine compound is preferred.
- Methods for applying the gas barrier composition include, for example, application means such as roll coating using a gravure roll coater or the like, spray coating, spin coating, dipping, brush coating, bar coating, and applicators.
- a gas barrier composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and, if necessary, a silane coupling agent.
- a polycondensation reaction gradually proceeds.
- the composition is applied to the deposition film by a conventional method and dried. This drying causes the polycondensation of the metal alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) to proceed further, forming a composite polymer layer.
- the above operation may be repeated to laminate a plurality of composite polymer layers.
- the applied composition is heated at a temperature of preferably 20° C. or higher, more preferably 50° C. or higher, and even more preferably 70° C. or higher, and preferably at a temperature of 150° C. or lower, more preferably 120° C. or lower, and even more preferably at a temperature of 100° C. or lower, for 1 second to 10 minutes. This allows the formation of a gas barrier coating film.
- the thickness of the gas barrier coating film is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, even more preferably 0.1 ⁇ m or more, and is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 5 ⁇ m or less, even more preferably 2 ⁇ m or less, and particularly preferably 1 ⁇ m or less, for example, 0.01 ⁇ m or more and 100 ⁇ m or less.
- a barrier substrate provided with such a gas barrier coating film has, for example, excellent gas barrier properties, can suppress the occurrence of cracks in a vapor deposition film composed of an inorganic oxide, and also has excellent recyclability and processability of a packaging container.
- the barrier substrate 1 shown in FIG. 1A comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a polyolefin intermediate layer 10, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 1B comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, a second surface resin layer 22, and a vapor deposition film 40.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 2A comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a first adhesive resin layer 30, a polyolefin intermediate layer 10, a second adhesive resin layer 32, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first adhesive resin layer 30, a polyolefin intermediate layer 10, a second adhesive resin layer 32, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 2B comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 2C comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, a second surface resin layer 22, and a vapor deposition film 40.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 2D comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 2E comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, a third polyolefin layer 13, a second surface resin layer 22, and a vapor deposition film 40.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, a third polyolefin layer 13, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 3A comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a first adhesive resin layer 30, a first polyolefin layer 11, a second polyolefin layer 12, a second adhesive resin layer 32, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first adhesive resin layer 30, a first polyolefin layer 11, a second polyolefin layer 12, a second adhesive resin layer 32, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 3B comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, an adhesive resin layer 30, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, an adhesive resin layer 30, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 3C comprises, in this order, a first vapor deposition film 40, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, a third polyolefin layer 13, a second surface resin layer 22, and a second vapor deposition film 42.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, a third polyolefin layer 13, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 3D comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, a second surface resin layer 22, and a vapor deposition film 40.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a polyolefin intermediate layer 10, an adhesive resin layer 30, and a second surface resin layer 22.
- the barrier substrate 1 shown in FIG. 3E comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, an adhesive resin layer 30, a second surface resin layer 22, and a vapor deposition film 40.
- the stretched substrate comprises, in this order, a first surface resin layer 20, a first polyolefin layer 11, a second polyolefin layer 12, an adhesive resin layer 30, and a second surface resin layer 22.
- the barrier substrate 1 may further include a barrier coat layer (not shown) on the first vapor deposition film 40. In Figs. 1 to 3, the barrier substrate 1 may further include a barrier coat layer (not shown) on the second vapor deposition film 42. In Figs. 1 to 3, a vapor deposition film may be provided only on one surface of the stretched substrate. In Figs. 1 to 3, the barrier substrate 1 may further include a barrier coat layer (not shown) on the vapor deposition film 40.
- the oxygen permeability (unit: cc/( m2 ⁇ day ⁇ atm)) of the barrier substrate of the present disclosure may be, for example, less than 30, less than 20, less than 10, less than 5.0, less than 4.0, less than 3.0, less than 2.0, less than 1.5, less than 1.0, less than 0.8, less than 0.5, less than 0.3, or less than 0.2.
- the lower limit of the oxygen permeability may be, for example, 0.01.
- the oxygen permeability is measured in accordance with JIS K7126-2:2006 in an environment at a temperature of 23° C. and a humidity of 90% RH.
- the water vapor permeability (unit: g/( m2 ⁇ day)) of the barrier substrate of the present disclosure may be, for example, less than 10, less than 8.0, less than 5.0, less than 4.0, less than 3.0, less than 2.0, less than 1.5, less than 1.0, less than 0.8, less than 0.5, less than 0.3, or less than 0.2.
- the lower limit of the water vapor permeability may be, for example, 0.01.
- the water vapor permeability is measured in accordance with JIS K7129-2:2019 in an environment at a temperature of 40° C. and a humidity of 90% RH.
- the laminate of the present disclosure comprises at least the above-mentioned stretched substrate, printed substrate or barrier substrate, and a heat seal layer.
- the laminate of the first aspect of the present disclosure comprises at least the stretched substrate, the printed substrate or the barrier substrate of the first aspect of the present disclosure and a heat seal layer.
- the laminate of the second aspect of the present disclosure comprises at least the stretched substrate, the printed substrate or the barrier substrate of the second aspect of the present disclosure and a heat seal layer.
- the laminate of the third aspect of the present disclosure comprises at least the stretched substrate, the printed substrate or the barrier substrate of the third aspect of the present disclosure and a heat seal layer.
- the laminate of the fourth aspect of the present disclosure comprises at least the stretched substrate, the printed substrate or the barrier substrate of the fourth aspect of the present disclosure and a heat seal layer.
- the laminate of the fifth or sixth aspect of the present disclosure comprises at least the stretched substrate, the printed substrate or the barrier substrate of the fifth or sixth aspect of the present disclosure and a heat seal layer.
- laminates When describing matters common to the laminates of the first to sixth embodiments, or when there is no particular distinction to be made between the laminates of the first to sixth embodiments, they will also be referred to simply as "laminates.”
- the laminate of the present disclosure can be suitably used as a packaging material.
- the total thickness of the laminate of the present disclosure may be 40 ⁇ m or more, 60 ⁇ m or more, 80 ⁇ m or more, 100 ⁇ m or more, 120 ⁇ m or more, 140 ⁇ m or more, 400 ⁇ m or less, 350 ⁇ m or less, or 300 ⁇ m or less, for example, 40 ⁇ m or more and 400 ⁇ m or less.
- the total thickness of the laminate can be appropriately changed depending on, for example, the use or shape of the packaging container.
- the laminate of the present disclosure includes the stretched substrate, the printed substrate, or the barrier substrate of the present disclosure.
- the laminate of the present disclosure may include two or more stretched substrates.
- the laminate of the present disclosure may include two or more printed substrates.
- the laminate of the present disclosure may include two or more barrier substrates. Details of the stretched substrate, the printed substrate, and the barrier substrate are as described above, and detailed description will be omitted in this section.
- the orientation of the barrier substrate is not particularly limited.
- the barrier substrate is preferably arranged so that the first vapor deposition film faces the heat seal layer side (inside of the packaging container) and the second vapor deposition film faces the opposite side to the heat seal layer (outside of the packaging container). That is, the laminate preferably includes the second vapor deposition film, the second surface resin layer, the polyolefin intermediate layer, the first surface resin layer, the first vapor deposition film, and the heat seal layer in this order.
- the barrier substrate is preferably arranged so that the first surface resin layer faces the heat seal layer side (inside of the packaging container) and the vapor deposition film faces the opposite side to the heat seal layer (outside of the packaging container). That is, the laminate preferably includes the vapor deposition film, the second surface resin layer, the polyolefin intermediate layer, the first surface resin layer, and the heat seal layer in this order.
- the orientation of the stretched or printed substrate is not particularly limited.
- the stretched and printed substrates are preferably arranged so that the first surface resin layer faces the heat seal layer (the inside of the packaging container) and the second surface resin layer faces the opposite side to the heat seal layer (the outside of the packaging container).
- the laminate preferably comprises the second surface resin layer, the polyolefin intermediate layer, the first surface resin layer, and the heat seal layer in this order.
- the orientation of the biaxially oriented polyethylene film is not particularly limited.
- the orientation of the printing substrate is not particularly limited.
- the orientation of the barrier substrate is not particularly limited.
- the laminate of the present disclosure does not include aluminum foil.
- Such a laminate of the present disclosure and a packaging container including the laminate have excellent recyclability.
- the laminate of the present disclosure may further include a polyolefin oriented substrate containing polyolefin as a main component.
- polyolefin examples include polypropylene, polyethylene, polybutene, and polymethylpentene. Among these, polypropylene and polyethylene are preferred.
- the polyolefin oriented substrate examples include a polypropylene oriented substrate containing polypropylene as a main component, and a polyethylene oriented substrate containing polyethylene as a main component.
- the polyolefin oriented substrate is a polyolefin substrate that has been subjected to a stretching process. Details of the stretching process are as described above, and will not be described here.
- the polyolefin oriented substrate is, for example, a uniaxially stretched substrate or a biaxially stretched substrate.
- the thickness of the oriented polyolefin substrate is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and even more preferably 10 ⁇ m or more, from the viewpoint of the strength and heat resistance of the laminate, and is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less, from the viewpoint of the processability of the laminate, for example, 5 ⁇ m or more and 300 ⁇ m or less.
- the oriented polyolefin substrate may be subjected to the above-mentioned surface treatment.
- Such an oriented polyolefin substrate has, for example, excellent adhesion to a layer adjacent to the substrate.
- an anchor coat layer may be formed on the surface of the oriented polyolefin substrate using a conventionally known anchor coat agent.
- a laminate further comprising a stretched polyolefin substrate may, for example, comprise, in this order, a stretched polyolefin substrate, a stretched substrate of the present disclosure, a printed substrate or a barrier substrate, and a heat seal layer, or may comprise, in this order, a stretched polyolefin substrate, a printed substrate or a barrier substrate of the present disclosure, a stretched polyolefin substrate, and a heat seal layer.
- the laminate of the present disclosure may include a printed layer on one or both sides of the substrate such as the above-mentioned stretched substrate, barrier substrate, and stretched polyolefin substrate.
- the laminate of the present disclosure may include a printed layer on the second heat seal layer described below.
- the printing layer includes an image.
- images include characters, figures, patterns, symbols, and combinations of these.
- the image may include text information such as the product name, the name of the item in the packaging container, the manufacturer, and the names of ingredients.
- the image may be a single, plain color (a so-called solid image).
- the printed layer can be formed, for example, using an ink composition.
- Methods for forming the printed layer include, for example, gravure printing, offset printing, flexographic printing, screen printing, letterpress printing, and transfer printing. From the viewpoint of reducing the environmental load, the printed layer may be formed by flexographic printing. From the viewpoint of reducing the environmental load, the printed layer may be formed using ink derived from biomass.
- the thickness of the printing layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, even more preferably 0.3 ⁇ m or more, and is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, even more preferably 3 ⁇ m or less, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
- the laminate of the present disclosure may have a surface protective layer on the printed layer provided on the second heat seal layer described later in order to improve the scratch resistance and weather resistance of the printed layer.
- the laminate of the present disclosure preferably has a surface protective layer that covers the entire area of the printed layer. From the viewpoint of visibility of the printed layer, the surface protective layer is preferably transparent in the visible light region, and more preferably colorless and transparent.
- the surface protective layer contains, for example, a thermoplastic resin, a cured product of a thermosetting resin, or a cured product of an energy ray curable compound.
- the surface protective layer preferably contains a cured product of a thermosetting resin or a cured product of an energy ray curable compound, and more preferably contains a cured product of an energy ray curable compound.
- the proportion of the above cured product in the total resin components of the surface protective layer is preferably 80 mass% or more, more preferably 90 mass% or more.
- printing methods for the surface protective layer include letterpress printing, flexographic printing, gravure printing, offset printing, screen printing, inkjet printing, and thermal transfer printing.
- the thickness of the surface protective layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, for example, 0.5 ⁇ m or more and 15 ⁇ m or less.
- a laminate having such a surface protective layer has excellent scratch resistance and weather resistance.
- the laminate of the present disclosure comprises a heat seal layer.
- the heat seal layer contains, as a main component, a heat-fusible resin that can be melted by heat and fused to each other.
- the heat-fusible resin include polyolefins such as polyethylene, polypropylene, and polymethylpentene, cyclic polyolefins, cyclic olefin copolymers, ionomer resins, acid-modified polyolefins, and terpolymers of ethylene-(meth)acrylic acid ester-unsaturated carboxylic acid.
- polyethylene examples include linear low-density polyethylene, high-pressure low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, and ethylene-(meth)acrylic acid ester copolymers.
- acid-modified polyolefins include resins obtained by modifying polyolefins such as polyethylene and polypropylene with unsaturated carboxylic acid compounds such as (meth)acrylic acid and maleic anhydride.
- the base material and the heat seal layer are each made of the same type of resin material (mono-material).
- the heat seal layer contains a polyolefin such as polyethylene or polypropylene as a main component. This allows the packaging container to be made mono-material.
- Such packaging containers have excellent recyclability, and for example, after collecting used packaging containers, there is no need to separate the base material and the heat seal layer.
- the heat seal layer preferably contains polypropylene as a main component.
- the heat seal layer preferably contains polyethylene as a main component.
- the content of polyolefin (e.g., polypropylene or polyethylene) in the entire laminate of the present disclosure is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- polyolefin e.g., polypropylene or polyethylene
- the laminate may be used to produce a mono-material packaging container, improving the recyclability of the packaging container.
- the heat seal layer may contain the above additives.
- the laminate of the present disclosure may include at least a first heat seal layer as the heat seal layer, a stretched substrate, a printed substrate or a barrier substrate of the present disclosure, and a second heat seal layer as the heat seal layer, in this order.
- the first heat seal layer and the second heat seal layer can be melted by heating and fused to each other.
- Such a laminate can be suitably used, for example, as a packaging material for forming the body of a tube container body.
- the second heat seal layer is a sealant layer on the outer surface side of the body
- the first heat seal layer is a sealant layer on the inner surface side of the body.
- the body includes, from the outside to the inside of the body, the second heat seal layer, the stretched substrate, the printed substrate or a barrier substrate, and the first heat seal layer, in this order.
- the first heat seal layer and the second heat seal layer contain polyolefins such as polypropylene and polyethylene as main components.
- the orientation of the barrier substrate is not particularly limited.
- the barrier substrate is preferably arranged such that the first vapor-deposited film faces the first heat-seal layer and the second vapor-deposited film faces the second heat-seal layer, i.e., the laminate preferably includes, in this order, the second heat-seal layer, the second vapor-deposited film, the second surface resin layer, the polyolefin intermediate layer, the first surface resin layer, the first vapor-deposited film, and the first heat-seal layer.
- an unstretched resin film corresponding to the heat seal layer may be laminated onto a stretched substrate, a printed substrate, or a barrier substrate, if necessary, via an adhesive layer, or a heat seal layer may be formed by melt-extruding a heat-fusible resin or a resin composition thereof onto a stretched substrate, a printed substrate, or a barrier substrate.
- an adhesive layer may not be provided. Examples of adhesive layers include the adhesive layers described below.
- the laminate of the present disclosure may, for example, comprise the stretched substrate, printed substrate or barrier substrate of the present disclosure, an adhesive layer and a heat seal layer in this order; the laminate may comprise the stretched polyolefin substrate, a second adhesive layer, the stretched substrate, printed substrate or barrier substrate of the present disclosure, a first adhesive layer and a heat seal layer in this order; or the laminate may comprise the stretched substrate, printed substrate or barrier substrate of the present disclosure, a second adhesive layer, a stretched polyolefin substrate, a first adhesive layer and a heat seal layer in this order.
- the laminate of the present disclosure may, for example, comprise the second heat seal layer, a second adhesive layer, the stretched substrate, printed substrate or barrier substrate of the present disclosure, a first adhesive layer and a first heat seal layer in this order.
- the adhesive layer may be an adhesive layer made of an adhesive.
- the adhesive may be a one-component curing adhesive, a two-component curing adhesive, or a non-curing adhesive.
- the adhesive may be a solventless adhesive or a solvent-based adhesive.
- solvent-free adhesives i.e., non-solvent laminate adhesives
- solvent-free adhesives include polyether-based adhesives, polyester-based adhesives, silicone-based adhesives, epoxy-based adhesives, and urethane-based adhesives.
- urethane-based adhesives are preferred, and two-component curing urethane-based adhesives are more preferred.
- Solvent-based adhesives include, for example, rubber-based adhesives, vinyl-based adhesives, olefin-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and urethane-based adhesives. Among these, urethane-based adhesives are preferred, and two-component curing urethane-based adhesives are more preferred.
- the laminate of the present disclosure may be produced by bonding the stretched substrate, printed substrate, or barrier substrate of the present disclosure, and optionally a stretched polyolefin substrate and a resin film corresponding to the heat seal layer by a non-solvent lamination method using a solvent-free adhesive, or by a dry lamination method using a solvent-based adhesive.
- the adhesive layer can be formed by applying and drying an adhesive to a stretched substrate, a printed substrate, or a barrier substrate, for example, by a method such as direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, Fontaine method, or transfer roll coating.
- the thickness of the adhesive layer may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.5 ⁇ m or more, 10 ⁇ m or less, 8 ⁇ m or less, or 6 ⁇ m or less, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
- the thickness of the adhesive layer may be 2 ⁇ m or less.
- the adhesive layer may be an adhesive resin layer containing a thermoplastic resin, or an extruded resin layer containing a thermoplastic resin.
- the thermoplastic resin include the above-mentioned heat-sealable resins.
- the thermoplastic resin may be a material derived from fossil fuels, a material derived from biomass, or both of these may be used.
- the thickness of the extruded resin layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of interlayer adhesion, and is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, from the viewpoint of reducing the production cost of the laminate and improving its productivity, for example, 5 ⁇ m or more and 30 ⁇ m or less.
- 4A comprises, in this order, a barrier substrate 1, an adhesive layer 60, and a heat seal layer 80, and more specifically, in this order, a second vapor-deposited film 42, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, a first vapor-deposited film 40, an adhesive layer 60, and a heat seal layer 80.
- the laminate 2 may further comprise a printed layer (not shown), and may further comprise a printed layer on, for example, the first vapor-deposited film 40 or the second vapor-deposited film 42 of the barrier substrate 1.
- the laminate 2 shown in FIG. 4B comprises a barrier substrate 1, an adhesive layer 60, and a heat seal layer 80 in this order, and more specifically, a vapor deposition film 40, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, an adhesive layer 60, and a heat seal layer 80 in this order.
- the laminate 2 may further comprise a printed layer (not shown), for example, on the vapor deposition film 40 or on the first surface resin layer 20 of the barrier substrate 1.
- the laminate 2 shown in FIG. 5A includes a polyolefin stretched substrate 70, a second adhesive layer 62, a barrier substrate 1, a first adhesive layer 60, and a heat seal layer 80 in this order, specifically, a polyolefin stretched substrate 70, a second adhesive layer 62, a second vapor deposition film 42, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, a first vapor deposition film 40, a first adhesive layer 60, and a heat seal layer 80 in this order.
- the laminate 2 may further include a printed layer (not shown), for example, a printed layer may further be included on the surface of the polyolefin stretched substrate 70 facing the barrier substrate 1.
- a laminate having such a configuration is suitable as a packaging material for forming a standing pouch, for example.
- the laminate 2 shown in FIG. 5B comprises, in this order, a polyolefin oriented substrate 70, a second adhesive layer 62, a barrier substrate 1, a first adhesive layer 60, and a heat seal layer 80.
- the laminate 2 comprises, in this order, a polyolefin oriented substrate 70, a second adhesive layer 62, a vapor deposition film 40, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, a first adhesive layer 60, and a heat seal layer 80.
- the laminate 2 may further comprise a printed layer (not shown), for example, on the surface of the polyolefin oriented substrate 70 facing the barrier substrate 1.
- a laminate having such a configuration is suitable, for example, as a packaging material for forming a standing pouch.
- the laminate 2 shown in FIG. 6A includes a second heat seal layer 82, a second adhesive layer 62, a barrier substrate 1, a first adhesive layer 60, and a first heat seal layer 80 in this order, specifically, a second heat seal layer 82, a second adhesive layer 62, a second vapor deposition film 42, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, a first vapor deposition film 40, a first adhesive layer 60, and a first heat seal layer 80 in this order.
- the laminate 2 may further include a printed layer (not shown), for example, a printed layer on the surface of the second heat seal layer 82.
- a laminate having such a configuration is suitable as a packaging material for forming the body of a tube container body, for example.
- the laminate 2 shown in FIG. 6B includes, in this order, a second heat seal layer 82, a second adhesive layer 62, a barrier substrate 1, a first adhesive layer 60, and a first heat seal layer 80.
- the laminate 2 includes, in this order, a second heat seal layer 82, a second adhesive layer 62, a vapor deposition film 40, a second surface resin layer 22, a polyolefin intermediate layer 10, a first surface resin layer 20, a first adhesive layer 60, and a first heat seal layer 80.
- the laminate 2 may further include a printed layer (not shown), for example, on the surface of the second heat seal layer 82.
- a laminate having such a configuration is suitable, for example, as a packaging material for forming the body of a tube container body.
- the polyolefin intermediate layer 10 is, for example, a polyethylene intermediate layer or a polypropylene intermediate layer.
- the barrier substrate 1 may further include a barrier coat layer (not shown) on the first vapor deposition film 40.
- the barrier substrate 1 may further include a barrier coat layer (not shown) on the second vapor deposition film 42.
- the orientation of the barrier substrate 1 may be reversed.
- the laminate 2 may include a stretched substrate or a printed substrate instead of the barrier substrate 1, or may include a barrier substrate having a vapor deposition film on only one surface of the stretched substrate or the printed substrate.
- the barrier substrate 1 may further include a barrier coating layer (not shown) on the vapor deposition film 40.
- the orientation of the barrier substrate 1 may be reversed.
- the laminate 2 may include a stretched substrate or a printed substrate instead of the barrier substrate 1.
- the laminate of the present disclosure can be suitably used for packaging material applications.
- the packaging material is used to produce a packaging container.
- a packaging container having excellent gas barrier properties can be produced.
- packaging containers include packaging bags, tube containers, and containers with lids.
- the packaging bag may be of various shapes, such as a standing pouch type, a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a grooving seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and a gusset type.
- the packaging bag may be, for example, a small bag or a zipper bag.
- the packaging bag may be a refill pouch, particularly a standing pouch, that contains contents such as liquids and powders and is refilled into containers such as bottles.
- the packaging bag may be, for example, a soft packaging bag.
- the packaging bag of the present disclosure comprises the laminate of the present disclosure.
- the packaging bag of the present disclosure is, for example, one or more laminates of the present disclosure; a seal portion where the heat seal layers of the laminate are joined together; A storage section for storing contents; has.
- the seal portion includes an inner edge that defines the receiving portion.
- Methods for forming the sealed portion include, for example, heat sealing, which melts the heat-sealed layers of the laminate by heating or the like and fuses the heat-sealed layers together, and specific examples include bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, and ultrasonic sealing.
- heat sealing which melts the heat-sealed layers of the laminate by heating or the like and fuses the heat-sealed layers together
- specific examples include bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, and ultrasonic sealing.
- the packaging bag may have an easy-to-open portion.
- easy-to-open portions include a notch portion that serves as the starting point for tearing the packaging bag, and a half-cut line formed by laser processing or a cutter as a path for tearing the packaging bag.
- the laminate of the present disclosure is used as a lid material in a lidded container.
- the lidded container comprises a container body having a storage section, and a lid material joined (heat sealed) to the container body so as to seal the storage section.
- the lid material i.e., the heat seal layer of the laminate
- the container body are heat sealed.
- the shape of the container body include a cup shape and a cylindrical shape with a bottom.
- the container body is made of, for example, polystyrene, polypropylene, polyethylene, or paper.
- Contents contained in the packaging container include, for example, liquids, solids, powders, and gels.
- the contents may be food or beverages, or non-food or beverages such as chemicals, cosmetics, medicines, metal parts, and electronic parts.
- Contents include, for example, shampoo, rinse, conditioner, hand soap, body soap, air fresheners, deodorants, insect repellents, fabric softeners, detergents; sauces, soy sauce, dressings, edible oils, mayonnaise, ketchup, syrups, cooking alcohol, and other liquid or viscous seasonings; fruit juices; spices; liquid beverages, jelly-like beverages, liquid soups, powdered soups, instant foods, other food and beverages; creams; toothpaste; metal parts, and electronic parts.
- toothpaste is a preferred content for tube containers.
- a packaging bag can be produced by folding and stacking the laminate of the present disclosure in half so that the stretched substrate, printed substrate, or barrier substrate is on the outside and the heat seal layer is on the inside, and then heat sealing the ends, etc.
- a packaging bag can be produced by stacking multiple laminates of the present disclosure so that the heat seal layers face each other, and then heat sealing the ends, etc.
- the entire packaging bag may be composed of the above-mentioned laminate, or only a portion of the packaging bag may be composed of the above-mentioned laminate.
- the standing pouch comprises a body portion composed of side sheets and a bottom portion composed of a bottom sheet.
- the bottom sheet retains the shape of the side sheets, thereby imparting self-supporting properties to the pouch, making it possible to form a standing pouch.
- a storage section for storing contents is formed within the area surrounded by the side sheets and the bottom sheet.
- only the side sheets may be the laminate of the present disclosure, only the bottom sheet may be the laminate of the present disclosure, or both the side sheets and the bottom sheet may be the laminate of the present disclosure.
- the side sheet can be formed by making a bag so that the heat seal layer of the laminate of the present disclosure is the innermost layer.
- the side sheet can be formed by preparing two laminates of the present disclosure, stacking them together so that the heat seal layers face each other, and heat sealing the side edges on both sides to make a bag.
- the head is formed from a resin composition containing a thermoplastic resin.
- thermoplastic resin include polyolefins such as polyethylene and polypropylene, polyesters, cellulose resins, and vinyl resins.
- the resin composition may contain the additives described above.
- a stretched substrate comprising, in this order, at least a first surface resin layer containing a polyolefin and an adhesive resin, a polyolefin intermediate layer containing a polyolefin as a main component, and a second surface resin layer containing a polyolefin and an adhesive resin.
- the content ratio of the polyolefin is 60% by mass or more and 95% by mass or less
- the content ratio of the adhesive resin is 5% by mass or more and 40% by mass or less, respectively.
- a stretched substrate comprising, in this order, at least a first surface resin layer containing a polyolefin as a main component, a polyolefin intermediate layer containing a polyolefin as a main component, and a second surface resin layer containing a gas barrier resin as a main component.
- the stretched substrate according to [7], wherein the polypropylene in the polyolefin intermediate layer and the first surface resin layer each independently comprises a homopolypropylene.
- the thickness of the first surface resin layer is 0.3 ⁇ m or more and 15 ⁇ m or less
- the thickness of the polyolefin intermediate layer is 5 ⁇ m or more and 100 ⁇ m or less
- the thickness of the second surface resin layer is 0.3 ⁇ m or more and 15 ⁇ m or less.
- a barrier substrate comprising the stretched substrate according to any one of [1] to [15] above, and a vapor-deposited film provided on a surface of the second surface resin layer of the stretched substrate.
- a stretched substrate comprising at least a first surface resin layer containing a polyolefin and an adhesive resin, a polyolefin intermediate layer containing a polyolefin as a main component, and a second surface resin layer containing a gas barrier resin as a main component, in this order, wherein the gas barrier resin in the second surface resin layer contains an aromatic polyamide.
- the content of the polyolefin in the first surface resin layer is 60% by mass or more and 95% by mass or less
- the content of the adhesive resin is 5% by mass or more and 40% by mass or less.
- a stretched substrate comprising at least a first surface resin layer containing a polyolefin as a main component, a polyolefin intermediate layer containing a polyolefin as a main component, and a second surface resin layer containing a gas barrier resin as a main component, in this order, wherein the gas barrier resin in the second surface resin layer contains an aromatic polyamide.
- a barrier substrate comprising: the stretched substrate according to any one of [1] to [7] and [11] to [13] above; and a vapor-deposited film provided on a surface of at least one layer selected from the first surface resin layer and the second surface resin layer of the stretched substrate; or the stretched substrate according to any one of [8] to [13] above; and a vapor-deposited film provided on a surface of the second surface resin layer of the stretched substrate.
- a barrier substrate comprising at least a first vapor-deposited film, the stretched substrate according to any one of [1] to [13] above, and a second vapor-deposited film, in this order, wherein the first vapor-deposited film is provided on a surface of the first surface resin layer, and the second vapor-deposited film is provided on a surface of the second surface resin layer.
- a stretched substrate comprising at least a first surface resin layer containing a gas barrier resin as a main component, one or more polyethylene intermediate layers containing polyethylene as a main component, and a second surface resin layer containing a gas barrier resin as a main component, in this order, wherein the polyethylene in at least one of the polyethylene intermediate layers contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, or has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- a stretched substrate comprising, in this order, at least a first surface resin layer containing polyethylene and an adhesive resin, one or more polyethylene intermediate layers containing polyethylene as a main component, and a second surface resin layer containing a gas barrier resin as a main component, wherein the polyethylene in at least one layer selected from the first surface resin layer and the polyethylene intermediate layer contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, or has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- the gas barrier resin in the second surface resin layer contains an aromatic polyamide.
- a stretched substrate comprising at least a first surface resin layer containing polyethylene and an adhesive resin, one or more polyethylene intermediate layers containing polyethylene as a main component, and a second surface resin layer containing polyethylene and an adhesive resin, in this order, wherein the polyethylene in at least one layer selected from the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, or has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- the content ratio of the polyethylene is 60% by mass or more and 95% by mass or less, and the content ratio of the adhesive resin is 5% by mass or more and 40% by mass or less, respectively.
- a stretched substrate comprising, in this order, at least a first surface resin layer containing polyethylene as a main component, one or more polyethylene intermediate layers containing polyethylene as a main component, and a second surface resin layer containing a gas barrier resin as a main component or containing polyethylene and an adhesive resin, wherein the polyethylene in at least one layer selected from the first surface resin layer, the polyethylene intermediate layer, and the second surface resin layer contains at least one type of polyethylene selected from high density polyethylene and medium density polyethylene, or has a density of more than 0.930 g/ cm3 and not more than 0.960 g/ cm3 .
- the content ratio of the polyethylene is 60% by mass or more and 95% by mass or less, and the content ratio of the adhesive resin is 5% by mass or more and 40% by mass or less.
- a barrier substrate comprising at least a first vapor-deposited film, the stretched substrate according to any one of [1] to [20] above, and a second vapor-deposited film, in this order, wherein the first vapor-deposited film is provided on a surface of the first surface resin layer, and the second vapor-deposited film is provided on a surface of the second surface resin layer.
- a laminate comprising at least the barrier substrate according to [21] or [22] above and a heat seal layer.
- the laminate according to [23] or [24] comprising at least a first heat seal layer, the barrier substrate, and a second heat seal layer, in this order.
- a printed film comprising the biaxially stretched polyethylene film according to any one of [1] to [11] above, and a printed layer provided on at least one surface of the film.
- a barrier substrate comprising the biaxially stretched polyethylene film according to any one of [1] to [11] above, and a vapor-deposited film provided on at least one surface of the film.
- High density polyethylene Metallocene HDPE, ethylene-1-octene copolymer, Density: 0.955 g/cm 3 , Melting point: 130° C. MFR: 1.5g/10min.
- Linear low density polyethylene (LLDPE) Dow Chemical's INNATE TF80 Metallocene LLDPE, ethylene-1-octene copolymer, Density: 0.926 g/cm 3 , MFR: 1.7 g/10 min.
- Acid-modified random polypropylene (MAH-r-PP) OREVAC 18722, manufactured by Arkema; Maleic anhydride graft modified random polypropylene, Density: 0.900 g/cm 3 , Melting point: 143° C. MFR: 7.0g/10min.
- Acid-modified linear low-density polyethylene (MAH-LLDPE) OREVAC 18302N, manufactured by Arkema; Maleic anhydride graft modified linear low density polyethylene, Density: 0.912 g/cm 3 , Melting point: 123° C. MFR: 1.5g/10min.
- Compatibilizer Dow Chemical, RETAIN 3000, Maleic anhydride grafted polyethylene, Density: 0.870g/ cm3 ⁇ Anti-blocking agent (AB agent) Silica particles, average particle size: 3.5 ⁇ m
- a blended polyethylene (A) was prepared by mixing 40 parts of HDPE and 60 parts of LLDPE (INNATE TF80).
- a blended polyethylene (B1) was prepared by mixing 90 parts of LLDPE (INNATE TF80) and 10 parts of acid-modified LLDPE (OREVAC 18302N).
- a blended polyethylene (B2) was prepared by mixing 18 parts of HDPE, 72 parts of LLDPE (INNATE TF80) and 10 parts of acid-modified LLDPE (OREVAC 18302N).
- a polyethylene blend (C) was prepared by mixing 40 parts of HDPE, 60 parts of LLDPE (INNATE TF80), and 0.2 parts (2,000 ppm) of an AB agent.
- a blended polyethylene (D) was prepared by mixing 20 parts of HDPE, 80 parts of LLDPE (INNATE TF80), and 0.2 part (2,000 ppm) of an AB agent.
- a blended polypropylene (A) was prepared by mixing 90 parts of random polypropylene (FS5612) and 10 parts of acid-modified random polypropylene (OREVAC 18722).
- a blend polypropylene (B) was prepared by mixing 80 parts of homopolypropylene (FS3031) and 20 parts of random polypropylene (FS5612).
- a blend polyamide (A) was prepared by mixing 50 parts of an aromatic polyamide (MXD6) and 50 parts of an aliphatic polyamide (Polyamide 6 1020).
- Example 1A Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (QF580); Homopolypropylene (FS3031), Adhesive resin (QF580); Ethylene-vinyl alcohol copolymer (G156B);
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was then sequentially biaxially stretched by stretching 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- the stretched substrate thus obtained is A second surface resin layer (EVOH layer) having a thickness of 1 ⁇ m; a second adhesive resin layer having a thickness of 1.5 ⁇ m; A polypropylene intermediate layer having a thickness of 13 ⁇ m; A first adhesive resin layer having a thickness of 1.5 ⁇ m; A first surface resin layer (EVOH layer) having a thickness of 1 ⁇ m; are provided in this order.
- the surface of the alumina vapor deposition film was coated with the above-mentioned barrier coating agent by spin coating, and then heat-treated in an oven at 100° C. for 8 seconds to form a barrier coating layer with a thickness of 0.3 ⁇ m. In this way, a barrier substrate was obtained.
- a 30 nm thick silica vapor deposition film was formed on each of the first and second surface resin layers of the stretched substrate instead of the alumina vapor deposition film, and the above barrier coat layer was further formed on the silica vapor deposition film to obtain a barrier substrate.
- Example 2A Polyamide (Polyamide 6 1020), Adhesive resin (QF580); Homopolypropylene (FS3031), Adhesive resin (QF580); Polyamide (Polyamide 6 1020),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 3A Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); LLDPE (INNATE TF80), Adhesive resin (NF587); Ethylene-vinyl alcohol copolymer (G156B);
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 11A An aromatic polyamide (MXD6); Adhesive resin (QF580); Homopolypropylene (FS3031), Adhesive resin (QF580); An aromatic polyamide (MXD6);
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 12A A blend polyamide (A), Adhesive resin (QF580); Homopolypropylene (FS3031), Adhesive resin (QF580); A blend polyamide (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 13A An aromatic polyamide (MXD6); Adhesive resin (NF587); LLDPE (INNATE TF80), Adhesive resin (NF587); An aromatic polyamide (MXD6);
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 14A A blend polyamide (A), Adhesive resin (NF587); LLDPE (INNATE TF80), Adhesive resin (NF587); A blend polyamide (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 21A Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); A blended polyethylene (A); Adhesive resin (NF587); Ethylene-vinyl alcohol copolymer (G156B);
- the five-layer film was obtained by co-extrusion of the above-mentioned mixture by T-die casting.
- the film was then subjected to sequential biaxial stretching treatment, stretching 5 times in the machine direction (MD) and then stretching 8.5 times in the width direction (TD), to produce a stretched substrate (biaxially stretched film) having a thickness of 25 ⁇ m.
- MD machine direction
- TD width direction
- Example 21A biaxial stretching was successfully performed.
- three types of barrier substrates were produced in the same manner as in Example 1A.
- Example 22A to 24A A stretched substrate and a barrier substrate were prepared in the same manner as in Example 21A, except that an aliphatic polyamide (polyamide 6 1020), an aromatic polyamide (MXD6) or a blended polyamide (A) was used instead of the ethylene-vinyl alcohol copolymer (G156B). In Examples 22A to 24A, biaxial stretching was successfully performed.
- Example 1B Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 2B Polyamide (Polyamide 6 1020), Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 3B Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), Blended polyethylene (B1),
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 4B Polyamide (Polyamide 6 1020), Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), Blended polyethylene (B1),
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 11B An aromatic polyamide (MXD6); Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (A),
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 12B A blend polyamide (A), Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 13B An aromatic polyamide (MXD6); Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), Blended polyethylene (B1),
- MD6 machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 14B A blend polyamide (A), Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), Blended polyethylene (B1),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 21B Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); A blended polyethylene (A); A blended polyethylene (A); Blended polyethylene (B1), The five-layer film was obtained by co-extrusion of the above-mentioned mixture by T-die casting. The film was then subjected to sequential biaxial stretching treatment, stretching 5 times in the machine direction (MD) and then stretching 8.5 times in the width direction (TD), to produce a stretched substrate (biaxially stretched film) having a thickness of 25 ⁇ m. In Example 21B, biaxial stretching was successfully performed. Using the stretched substrate, three types of barrier substrates were produced in the same manner as in Example 1A.
- Example 22B to 24B A stretched substrate and a barrier substrate were prepared in the same manner as in Example 21B, except that an aliphatic polyamide (polyamide 6 1020), an aromatic polyamide (MXD6) or a blended polyamide (A) was used instead of the ethylene-vinyl alcohol copolymer (G156B). In Examples 22B to 24B, biaxial stretching was successfully performed.
- Example 1C Blended polypropylene (A), Homopolypropylene (FS3031), Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (A),
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 2C Blended polyethylene (B1), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), Blended polyethylene (B1),
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- the five-layer film was obtained by co-extrusion by T-die casting.
- the film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 25 ⁇ m.
- MD machine direction
- TD width direction
- Example 11C biaxial stretching was successfully performed.
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- the five layers were co-extruded by a T-die casting method to obtain a five-layer film.
- the film was then sequentially biaxially stretched by stretching 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m.
- barrier substrates Three types were prepared as follows. An aluminum (AL) film having a thickness of 30 nm was formed by vapor deposition on the surface of the second outer resin layer of the stretched substrate by a PVD method, thus obtaining a barrier substrate. On the surface of the second surface resin layer of the stretched substrate, a 30 nm thick alumina vapor deposition film was formed by PVD. The barrier coating agent prepared in Example 1A was coated on the surface of the alumina vapor deposition film by spin coating, and the coating was heated in an oven at 100° C. for 8 seconds to form a 0.3 ⁇ m thick barrier coating layer. In this way, a barrier substrate was obtained.
- AL aluminum
- a 30 nm thick silica vapor deposition film was formed on the surface of the second surface resin layer of the stretched substrate instead of the alumina vapor deposition film, and the above barrier coat layer was further formed on the silica vapor deposition film to obtain a barrier substrate.
- Example 2D Blended polyethylene (B1), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 3D Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (B); The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 4D Polyamide (Polyamide 6 1020), Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (B); The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 5D Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 6D Polyamide (Polyamide 6 1020), Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 11D An aromatic polyamide (MXD6); Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (B); The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 12D A blend polyamide (A), Adhesive resin (QF580); Homopolypropylene (FS3031), Homopolypropylene (FS3031), Blended polypropylene (B); The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 13D An aromatic polyamide (MXD6); Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 14D A blend polyamide (A), Adhesive resin (NF587); LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), LLDPE (INNATE TF80), The five layers were co-extruded by a T-die casting method to obtain a five-layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 21D Blended polyethylene (B1), A blended polyethylene (A); A blended polyethylene (A); A blended polyethylene (A); A blended polyethylene (D); The five-layer film was obtained by co-extrusion by T-die casting. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 25 ⁇ m. In Example 21D, biaxial stretching was successfully performed. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 22D A stretched substrate and a barrier substrate were prepared in the same manner as in Example 21D, except that the blending composition of polyethylene and the like in each layer was changed as shown in Table 12. In Example 22D, biaxial stretching could be performed well. In Table 12, the blending amount of the AB agent in the first surface resin layer was 2,000 ppm.
- Example 31D Ethylene-vinyl alcohol copolymer (G156B); Adhesive resin (NF587); A blended polyethylene (A); A blended polyethylene (A); A blended polyethylene (C); The five-layer film was obtained by co-extrusion of the above-mentioned mixture by T-die casting. The film was then subjected to sequential biaxial stretching treatment, stretching 5 times in the machine direction (MD) and then stretching 8.5 times in the width direction (TD), to produce a stretched substrate (biaxially stretched film) having a thickness of 25 ⁇ m. In Example 31D, biaxial stretching was successfully performed. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 32D to 34D A stretched substrate and a barrier substrate were prepared in the same manner as in Example 31D, except that an aliphatic polyamide (polyamide 6 1020), an aromatic polyamide (MXD6) or a blended polyamide (A) was used instead of the ethylene-vinyl alcohol copolymer (G156B). In Examples 32D to 34D, biaxial stretching was successfully performed.
- Example 1 A monolayer film was obtained by extruding homopolypropylene (FS3031) using a T-die casting method. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- MD machine direction
- TD width direction
- Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A.
- Example 1D Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Example 2 A monolayer film was obtained by extruding LLDPE (INNATE TF80) by a T-die casting method. The film was stretched 5 times in the machine direction (MD direction) and then 8.5 times in the width direction (TD direction) to produce a stretched substrate (biaxially stretched film) with a thickness of 18 ⁇ m. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1A. Three types of barrier substrates were produced using the stretched substrate in the same manner as in Example 1D.
- Examples 11A to 14A, 21A to 24A, 11B to 14B, 21B to 24B, 11C, 11D to 14D, 21D to 22D, 31D to 34D, and the comparative examples listed in the same table as these examples are as follows.
- D Oxygen permeability is 2.0 or more and less than 10.
- E Oxygen permeability is 10 or more and less than 30.
- F Oxygen permeability is 30 or more and less than 100.
- G Oxygen permeability is 100 or more.
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 1A and 3A, except that the polyolefin intermediate layer contained about 23% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 1A and 3A). Stretched substrates and barrier substrates were prepared in the same manner as in Examples 2A and 4A, except that the polyolefin intermediate layer contained about 11.5% by weight of a compatibilizer (RETAIN 3000).
- Example 21A The results of each evaluation in this example were comparable to those of Example 21A. Stretched substrates and barrier substrates were prepared in the same manner as in Examples 22A to 24A, except that the polyethylene intermediate layer contained about 11.5% by weight of a compatibilizer (RETAIN 3000). The results of each evaluation in these examples were comparable to the results of the examples with the corresponding layer configurations (Examples 22A to 24A).
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 1B and 3B, except that the second polyolefin layer contained about 12% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 1B and 3B). Stretched substrates and barrier substrates were prepared in the same manner as in Examples 2B and 4B, except that the second polyolefin layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 2B and 4B).
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 11B to 14B, except that the second polyolefin layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 11B to 14B).
- a stretched substrate and a barrier substrate were prepared in the same manner as in Example 21B, except that the second polyethylene layer contained about 12% by weight of a compatibilizer (RETAIN 3000). The results of each evaluation in this example were comparable to those of Example 21B.
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 22B to 24B, except that the second polyethylene layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of each evaluation in these examples were comparable to the results of the examples with the corresponding layer configurations (Examples 22B to 24B).
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 3D and 5D, except that the second polyolefin layer contained about 12% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 3D and 5D). Stretched substrates and barrier substrates were prepared in the same manner as in Examples 4D and 6D, except that the second polyolefin layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 4D and 6D).
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 11D to 14D, except that the second polyolefin layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of the gas barrier test and T-peel test in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 11D to 14D).
- a stretched substrate and a barrier substrate were prepared in the same manner as in Example 31D, except that the second polyethylene layer contained about 12% by weight of a compatibilizer (RETAIN 3000). The results of each evaluation in this example were comparable to those of Example 31D.
- Stretched substrates and barrier substrates were prepared in the same manner as in Examples 32D to 34D, except that the second polyethylene layer contained about 4% by weight of a compatibilizer (RETAIN 3000). The results of each evaluation in these examples were comparable to the results of the examples with the corresponding layer configurations (Examples 32D to 34D).
- the stretched substrate and the barrier substrate were prepared in the same manner as in Examples 21B to 24B and Example 11C, except that the blended polyethylene (B2) was used instead of the blended polyethylene (B1).
- the results of the evaluations in these examples were comparable to those of the examples with the corresponding layer configurations (Examples 21B to 24B and Example 11C).
- Examples 1AA to 4AA The stretched substrates and barrier substrates of Examples 1AA to 4AA were produced in the same manner as in Examples 1A to 4A, except that the thickness of the first adhesive resin layer was changed to 2 ⁇ m, the thickness of the polyolefin intermediate layer was changed to 19 ⁇ m, the thickness of the second adhesive resin layer was changed to 2 ⁇ m, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 1AA to 4AA were comparable to the results of the examples (Examples 1A to 4A) with the corresponding example numbers.
- Examples 11AA to 14AA The stretched substrates and barrier substrates of Examples 11AA to 14AA were produced in the same manner as in Examples 11A to 14A, except that the thickness of the first adhesive resin layer was changed to 2 ⁇ m, the thickness of the polyolefin intermediate layer was changed to 19 ⁇ m, the thickness of the second adhesive resin layer was changed to 2 ⁇ m, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 11AA to 14AA were comparable to the results of the examples (Examples 11A to 14A) with the corresponding example numbers.
- Examples 21AA to 24AA The stretched substrates and barrier substrates of Examples 21AA to 24AA were produced in the same manner as in Examples 21A to 24A, except that the thickness of the first adhesive resin layer was changed to 1.5 ⁇ m, the thickness of the polyethylene intermediate layer was changed to 13 ⁇ m, the thickness of the second adhesive resin layer was changed to 1.5 ⁇ m, and the thickness of the stretched substrate was changed to 18 ⁇ m. In Examples 21AA to 24AA, biaxial stretching could be performed well. The results of each evaluation in Examples 21AA to 24AA were comparable to the results of the examples (Examples 21A to 24A) with the corresponding example numbers.
- Example 11BB to 14BB The stretched substrates and barrier substrates of Examples 11BB to 14BB were prepared in the same manner as in Examples 11B to 14B, except that the thickness of the first polyolefin layer was changed to 2 ⁇ m, the thickness of the second polyolefin layer was changed to 19 ⁇ m, the thickness of the adhesive resin layer was changed to 2 ⁇ m, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 11BB to 14BB were comparable to the results of the examples (Examples 11B to 14B) with the corresponding example numbers.
- Example 1CC to 2CC The stretched substrates and barrier substrates of Examples 1CC to 2CC were prepared in the same manner as in Examples 1C to 2C, except that the thicknesses of the first polyolefin layer, second polyolefin layer, and third polyolefin layer were changed to 2 ⁇ m, 19 ⁇ m, and 2 ⁇ m, respectively, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 1CC to 2CC were comparable to the results of the examples (Examples 1C to 2C) with the corresponding Example numbers.
- Example 11CC The stretched substrate and barrier substrate of Example 11CC were produced in the same manner as in Example 11C, except that the thickness of the first polyethylene layer was changed to 1.5 ⁇ m, the thickness of the second polyethylene layer was changed to 13 ⁇ m, the thickness of the third polyethylene layer was changed to 1.5 ⁇ m, and the thickness of the stretched substrate was changed to 18 ⁇ m. In Example 11CC, biaxial stretching was successfully performed. The results of each evaluation in Example 11CC were comparable to those in Example 11C.
- Examples 1DD to 2DD The stretched substrates and barrier substrates of Examples 1DD to 2DD were prepared in the same manner as in Examples 1D to 2D, except that the thicknesses of the first polyolefin layer, second polyolefin layer, and third polyolefin layer were changed to 2 ⁇ m, 19 ⁇ m, and 2 ⁇ m, respectively, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 1DD to 2DD were comparable to the results of the examples (Examples 1D to 2D) with the corresponding example numbers.
- Examples 3DD to 6DD The stretched substrates and barrier substrates of Examples 3DD to 6DD were prepared in the same manner as in Examples 3D to 6D, except that the thicknesses of the first polyolefin layer, second polyolefin layer, and adhesive resin layer were changed to 2 ⁇ m, 19 ⁇ m, and 2 ⁇ m, respectively, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 3DD to 6DD were comparable to the results of the examples (Examples 3D to 6D) with the corresponding Example numbers.
- Example 11DD to 14DD The stretched substrates and barrier substrates of Examples 11DD to 14DD were prepared in the same manner as in Examples 11D to 14D, except that the thicknesses of the first polyolefin layer, second polyolefin layer, and adhesive resin layer were changed to 2 ⁇ m, 19 ⁇ m, and 2 ⁇ m, respectively, and the thickness of the stretched substrate was changed to 25 ⁇ m.
- the results of each evaluation in Examples 11DD to 14DD were comparable to the results of the examples (Examples 11D to 14D) with the corresponding example numbers.
- Example 21DD to 22DD The stretched substrates and barrier substrates of Examples 21DD to 22DD were produced in the same manner as in Examples 21D to 22D, except that the thicknesses of the first polyethylene layer, second polyethylene layer, and third polyethylene layer were changed to 1.5 ⁇ m, 13 ⁇ m, and 1.5 ⁇ m, respectively, and the thickness of the stretched substrate was changed to 18 ⁇ m.
- Examples 21DD to 22DD biaxial stretching was successfully performed.
- the results of each evaluation in Examples 21DD to 22DD were comparable to the results of the examples (Examples 21D to 22D) with the corresponding Example numbers.
- Examples 31DD to 34DD The stretched substrates and barrier substrates of Examples 31DD to 34DD were produced in the same manner as in Examples 31D to 34D, except that the thickness of the first polyethylene layer was changed to 1.5 ⁇ m, the thickness of the second polyethylene layer was changed to 13 ⁇ m, the thickness of the adhesive resin layer was changed to 1.5 ⁇ m, and the thickness of the stretched substrate was changed to 18 ⁇ m.
- biaxial stretching could be performed well.
- the results of each evaluation in Examples 31DD to 34DD were comparable to the results of the examples (Examples 31D to 34D) with the corresponding example numbers.
- Comparative Examples 1A to 2A Stretched substrates and barrier substrates of Comparative Examples 1A to 2A were prepared in the same manner as in Comparative Examples 1 and 2, except that the thickness of the stretched substrate was changed to 25 ⁇ m. The results were comparable to those of the comparative examples having the corresponding comparative example numbers (Comparative Examples 1 and 2).
- biaxially oriented polyethylene film [Materials for biaxially oriented polyethylene film] The following materials were used in making the biaxially oriented polyethylene film: ⁇ High density polyethylene (HDPE) Metallocene HDPE, ethylene-1-octene copolymer, density: 0.955 g/cm 3 , melting point: 130°C, MFR: 1.5 g/10 min. Linear low density polyethylene (LLDPE) Dow Chemical's INNATE TF80 Metallocene LLDPE, ethylene-1-octene copolymer, Density: 0.926 g/cm 3 , MFR: 1.7 g/10 min.
- Anti-blocking agent (AB agent) Silica particles, average particle size: 3.5 ⁇ m
- Example 1E A polyethylene blend (Ae) was prepared by mixing 20 parts of HDPE, 80 parts of LLDPE, and 0.2 parts (2,000 ppm) of AB agent.
- a polyethylene blend (Be) was prepared by mixing 20 parts of HDPE and 80 parts of LLDPE.
- the biaxially stretched polyethylene film thus obtained comprises, in this order, a second surface resin layer (blend polyethylene (Ae) layer) having a thickness of 1 ⁇ m, a third polyethylene layer (blend polyethylene (Be) layer) having a thickness of 2 ⁇ m, a second polyethylene layer (blend polyethylene (Be) layer) having a thickness of 19 ⁇ m, a first polyethylene layer (blend polyethylene (Be) layer) having a thickness of 2 ⁇ m, and a first surface resin layer (blend polyethylene (Ae) layer) having a thickness of 1 ⁇ m.
- Example 2E to 4E Biaxially stretched polyethylene films having a thickness of 25 ⁇ m were produced in the same manner as in Example 1E, except that the polyethylene composition of each layer was changed as shown in Table 14. In Examples 2E to 4E, biaxial stretching could be performed well. In Table 14, the amount of AB agent in the surface resin layer was 2,000 ppm in each case.
- Example 5E A mixture of 40 parts HDPE and 60 parts LLDPE was extruded into a single layer by T-die casting to obtain a single layer film. The film was stretched 5 times in the machine direction (MD) and then 8.5 times in the width direction (TD) to produce a biaxially stretched polyethylene film with a thickness of 25 ⁇ m. In Example 5E, biaxial stretching was performed well.
- Heat resistance evaluation 1 Print resistance evaluation
- the surface of the biaxially stretched polyethylene film prepared above was subjected to a corona discharge treatment. An image was formed on the corona discharge treated surface of the film by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics Corporation, product name: Finart). The heat resistance was evaluated according to the following criteria. A: No significant shrinkage of the film occurred when the print dried. B: Significant shrinkage of the film occurred when the print dried.
- Heat resistance evaluation 2 170°C heat seal resistance evaluation
- the surface of the biaxially stretched polyethylene film prepared above was subjected to a corona discharge treatment.
- An image was formed on the corona discharge treated surface of the film by gravure printing using an oil-based gravure ink (manufactured by DIC Graphics Corporation, product name: Finart) to obtain a printed film.
- the printed film was bonded to a 40 ⁇ m-thick LLDPE film obtained by forming Evolue SP2020 (manufactured by Mitsui Chemicals) as a single layer film using a urethane-based dry lamination adhesive.
- the LLDPE film surfaces of the laminate films thus bonded were placed facing each other, and one side was sandwiched between an aluminum sealing bar set to 170°C to perform heat sealing (at a pressure of 1 kgf/ cm2 for 1 second), and the thermal shrinkage state of the laminate film at the heat-sealed portion was confirmed.
- the heat resistance was evaluated according to the following criteria. A: The film did not shrink when heat sealed at 170°C. B: When heat sealed at 170°C, the film hardly shrank at all. C: The film significantly shrunk when heat sealed at 170°C.
- Examples 1EE to 4EE The biaxially stretched polyethylene films of Examples 1EE to 4EE were produced in the same manner as in Examples 1E to 4E, except that the thicknesses of the first polyethylene layer, second polyethylene layer, and third polyethylene layer were changed to 1.5 ⁇ m, 13 ⁇ m, and 1.5 ⁇ m, respectively, and the thickness of the biaxially stretched polyethylene film was changed to 18 ⁇ m. In Examples 1EE to 4EE, biaxial stretching could be performed well. The results of each evaluation in Examples 1EE to 4EE were equivalent to the results of the examples (Examples 1E to 4E) with the corresponding example numbers.
- Example 5EE and Comparative Example 1EE A biaxially oriented polyethylene film of Example 5EE was produced in the same manner as in Example 5E, except that the thickness of the biaxially oriented polyethylene film was changed to 18 ⁇ m. The results of each evaluation in Example 5EE were comparable to those in Example 5E.
- a biaxially oriented polyethylene film of Comparative Example 1EE was produced in the same manner as in Comparative Example 1E, except that the thickness of the biaxially oriented polyethylene film was changed to 18 ⁇ m. The results of each evaluation in Comparative Example 1EE were equivalent to those in Comparative Example 1E.
- Second adhesive resin layer Adhesive resin layer, first adhesive resin layer 32 Second adhesive resin layer 40 Vapor deposition film, first vapor deposition film 42 Second vapor deposition film 60 Adhesive layer, first adhesive layer 62 Second adhesive layer 70 Polyolefin stretched substrate 80 Heat seal layer, first heat seal layer 82 Second heat seal layer 120 Tube container 121 Tube container body 122 Head 123 Body 124 Shoulder 125 Extraction port 126 Cap 127 Screw 128 Fused portion 129 Bottom seal portion
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Abstract
Description
高密度ポリエチレンの密度は、好ましくは0.945g/cm3を超える。高密度ポリエチレンの密度の上限は、例えば0.965g/cm3であり、好ましくは0.960g/cm3である。中密度ポリエチレンの密度は、好ましくは0.930g/cm3を超えて0.945g/cm3以下である。低密度ポリエチレンの密度は、好ましくは0.860g/cm3以上0.930g/cm3以下、より好ましくは0.900g/cm3以上0.930g/cm3以下である。直鎖状低密度ポリエチレンの密度は、好ましくは0.860g/cm3以上0.930g/cm3以下、より好ましくは0.900g/cm3以上0.930g/cm3以下である。本明細書において、ポリエチレンの密度は、JIS K7112:1999のD法(密度勾配管法、23℃)に準拠して測定される。
本明細書において、「多層」とは、2層以上を意味する。
本開示の第1の態様の延伸基材は、
ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
を厚さ方向にこの順に少なくとも備える。
以下、「厚さ方向にこの順に備える」を単に「この順に備える」と記載する。
ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、
ポリプロピレンを主成分として含有するポリプロピレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
第1の態様の延伸基材は、一実施形態において、ポリエチレン系延伸基材であり、
ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備え、ポリエチレン中間層の少なくとも1層におけるポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する。
ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
を厚さ方向にこの順に少なくとも備える。
ポリプロピレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリプロピレンを主成分として含有するポリプロピレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
第2の態様の延伸基材は、一実施形態において、ポリエチレン系延伸基材であり、
ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備え、第1の表面樹脂層およびポリエチレン中間層から選択される少なくとも1層におけるポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する。
ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ポリオレフィンと接着性樹脂とを含有する第2の表面樹脂層と、
を厚さ方向にこの順に少なくとも備える。
ポリプロピレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリプロピレンを主成分として含有するポリプロピレン中間層と、
ポリプロピレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
第3の態様の延伸基材は、一実施形態において、ポリエチレン系延伸基材であり、
ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ポリエチレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、
ポリエチレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備え、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層から選択される少なくとも1層におけるポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する。
ポリオレフィンを主成分として含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する、または、ポリオレフィンと接着性樹脂とを含有する第2の表面樹脂層と、
を厚さ方向にこの順に少なくとも備える。
第2の表面樹脂層がガスバリア性樹脂を主成分として含有する第4の態様の延伸基材を「第4Aの態様の延伸基材」とも記載する。第2の表面樹脂層がポリオレフィンと接着性樹脂とを含有する第4の態様の延伸基材を「第4Bの態様の延伸基材」とも記載する。
ポリプロピレンを主成分として含有する第1の表面樹脂層と、
ポリプロピレンを主成分として含有するポリプロピレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
第4Aの態様の延伸基材は、一実施形態において、ポリエチレン系延伸基材であり、
ポリエチレンを主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
ポリプロピレンを主成分として含有する第1の表面樹脂層と、
ポリプロピレンを主成分として含有するポリプロピレン中間層と、
ポリプロピレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
第4Bの態様の延伸基材は、一実施形態において、ポリエチレン系延伸基材であり、
ポリエチレンを主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ポリエチレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備える。
ポリエチレンを主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、
ガスバリア性樹脂を主成分として含有する、または、ポリエチレンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備え、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層から選択される少なくとも1層におけるポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する。
延伸基材は、第1の面と、第1の面に対向する第2の面と、を有する。一実施形態において、第1の表面樹脂層は第1の面を構成し、第2の表面樹脂層は第2の面を構成する。
延伸基材は、一実施形態において、第1の表面樹脂層を構成する材料と、ポリオレフィン中間層を構成する材料と、延伸基材が接着性樹脂層を備える場合は接着性樹脂層を構成する材料と、第2の表面樹脂層を構成する材料とを、共押出製膜して積層フィルムを作製した後、該積層フィルムを延伸処理して得られた樹脂フィルムである。2軸延伸ポリエチレンフィルムは、一実施形態において、第1の表面樹脂層を構成する材料と、ポリエチレン中間層を構成する材料と、第2の表面樹脂層を構成する材料とを、共押出製膜して積層フィルムを作製した後、該積層フィルムを2軸延伸処理して得られた樹脂フィルムである。
なお、押出機におけるこれらの押出温度は一例に過ぎず、適宜変更できる。
ポリオレフィン中間層は、ポリオレフィンを主成分として含有する。ポリオレフィンとしては、例えば、ポリプロピレン、ポリエチレン、ポリブテンおよびポリメチルペンテンが挙げられる。これらの中でも、ポリプロピレンおよびポリエチレンが好ましい。ポリオレフィン中間層としては、例えば、ポリプロピレンを主成分として含有するポリプロピレン層、およびポリエチレンを主成分として含有するポリエチレン層が好ましい。
以下、上記層構成を有する延伸基材について説明する。
以下、上記層構成を有する延伸基材について説明する。
ポリプロピレン中間層は、ポリプロピレンを主成分として含有する。
ポリプロピレンとしては、例えば、ホモポリプロピレン、ランダムポリプロピレンおよびブロックポリプロピレンが挙げられる。これらの中でも、延伸基材の耐熱性という観点から、ホモポリプロピレンが好ましい。
ポリエチレン中間層は、ポリエチレンを主成分として含有する。
ポリエチレンとしては、例えば、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレンおよび直鎖状低密度ポリエチレンが好ましい。延伸基材の強度および耐熱性という観点からは、高密度ポリエチレンおよび中密度ポリエチレンが好ましい。延伸基材の製膜性および加工性という観点からは、直鎖状低密度ポリエチレンおよび中密度ポリエチレンが好ましい。
以下、ガスバリア性樹脂を主成分として含有する表面樹脂層(G)について説明する。
第1の態様の延伸基材における第1および第2の表面樹脂層は、それぞれ独立して、ガスバリア性樹脂を主成分として含有する。第2の態様の延伸基材における第2の表面樹脂層は、ガスバリア性樹脂を主成分として含有する。第4Aの態様の延伸基材における第2の表面樹脂層は、ガスバリア性樹脂を主成分として含有する。このような表面樹脂層(G)は表面平滑性に優れる傾向にあり、表面樹脂層(G)の表面に設けられた蒸着膜は、表面樹脂層(G)との密着性に優れ、ガスバリア性を良好に発揮できる傾向にある。
以下の例示において、ポリアミドを「PA」とも記載する。
表面樹脂層(G)は、上記添加剤を含有してもよい。
以下、ポリオレフィンと接着性樹脂とを含有する表面樹脂層(AH)について説明する。
第2の態様の延伸基材における第1の表面樹脂層は、ポリオレフィンと接着性樹脂とを含有する。第3の態様の延伸基材における第1および第2の表面樹脂層は、それぞれ独立して、ポリオレフィンと接着性樹脂とを含有する。第4Bの態様の延伸基材における第2の表面樹脂層は、ポリオレフィンと接着性樹脂とを含有する。このような表面樹脂層(AH)の表面に設けられた蒸着膜は、表面樹脂層(AH)との密着性に優れ、ガスバリア性を良好に発揮できる傾向にある。
第2の態様の延伸基材の一実施形態において、第1の表面樹脂層におけるポリオレフィンがポリエチレンを含み、接着性樹脂が酸変性ポリエチレンを含み、ポリオレフィン中間層がポリエチレンを主成分として含有する。
表面樹脂層(AH)は、上記添加剤を含有してもよい。
以下、ポリオレフィンを主成分として含有する表面樹脂層(PO)について説明する。
第4の態様の延伸基材における第1の表面樹脂層は、ポリオレフィンを主成分として含有する。ポリオレフィンとしては、例えば、ポリプロピレン、ポリエチレン、ポリブテンおよびポリメチルペンテンが挙げられる。これらの中でも、ポリプロピレンおよびポリエチレンが好ましい。表面樹脂層(PO)としては、例えば、ポリプロピレンを主成分として含有する層、およびポリエチレンを主成分として含有する層が好ましい。
表面樹脂層(PO)は、上記添加剤を含有してもよい。
高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計を、以下「含有割合A」と記載する。ここで、高密度ポリエチレンのみでもよく、中密度ポリエチレンのみでもよく、高密度ポリエチレンおよび中密度ポリエチレンの混合物でもよい。
一実施形態の延伸基材において、第1の表面樹脂層における含有割合Aよりもポリエチレン中間層における含有割合Aの方が大きく、所望により、ポリエチレン中間層における含有割合Aよりも第2の表面樹脂層における含有割合Aの方が小さい。このような延伸基材は、表面平滑性、透明性、印刷性および蒸着密着性と、耐熱性と、のバランスに優れる傾向にある。ポリエチレン中間層と上記表面樹脂層とにおける含有割合Aの差は、例えば10質量%以上でもよく、50質量%以下でもよく、40質量%以下でもよく、30質量%以下でもよい。
一実施形態の延伸基材において、第1の表面樹脂層における含有割合Aよりもポリエチレン中間層における含有割合Aの方が小さく、所望により、ポリエチレン中間層における含有割合Aよりも第2の表面樹脂層における含有割合Aの方が大きい。このような延伸基材は、2軸延伸性と耐熱性とのバランスに優れる傾向にある。上記表面樹脂層とポリエチレン中間層とにおける含有割合Aの差は、例えば10質量%以上でもよく、50質量%以下でもよく、40質量%以下でもよく、30質量%以下でもよい。
一実施形態の延伸基材において、第1の表面樹脂層、ポリエチレン中間層、および所望により第2の表面樹脂層における含有割合Aが、それぞれ略同等である。例えば、第1の表面樹脂層、ポリエチレン中間層、および所望により第2の表面樹脂層のうち、含有割合Aが最も大きい層と含有割合Aが最も小さい層との該含有割合Aの差が、10質量%未満である。
第1の態様の延伸基材は、第1の表面樹脂層とポリオレフィン中間層との間に、第1の接着性樹脂層をさらに備えてもよい。第1の態様の延伸基材は、ポリオレフィン中間層と第2の表面樹脂層との間に、第2の接着性樹脂層をさらに備えてもよい。第2の態様および第4Aの態様の延伸基材は、ポリオレフィン中間層と第2の表面樹脂層との間に、接着性樹脂層をさらに備えてもよい。このような延伸基材は、例えば、ポリオレフィン中間層と表面樹脂層との接着性に優れる。
接着性樹脂としては、例えば、酸変性樹脂、シリコーン樹脂、エポキシ樹脂およびフェノール樹脂が挙げられ、酸変性樹脂が好ましい。酸変性樹脂としては、例えば、酸変性ポリオレフィンおよび酸変性ビニル樹脂が挙げられる。これらの中でも、酸変性ポリオレフィンが好ましく、酸変性ポリプロピレンおよび酸変性ポリエチレンがより好ましい。ポリプロピレン系延伸基材の場合は、リサイクル性や、ポリプロピレン層と表面樹脂層との両者に対する接着性という観点から、酸変性ポリプロピレンがさらに好ましく、耐熱性および接着性という観点から、酸変性ランダムポリプロピレンおよび酸変性ホモポリプロピレンがよりさらに好ましく、酸変性ランダムポリプロピレンが特に好ましい。ポリエチレン系延伸基材の場合は、リサイクル性や、ポリエチレン層と表面樹脂層との両者に対する接着性という観点から、酸変性ポリエチレンがさらに好ましく、酸変性直鎖状低密度ポリエチレンがよりさらに好ましい。酸変性ポリオレフィンの詳細(構成や、MFR、密度およびTmなどの物性)については表面樹脂層(AH)の欄にて説明したとおりであり、本欄での説明は省略する。
第5の態様の延伸基材は、ポリエチレン層(1)を備える。
ポリエチレン層(1)は、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含有し、好ましくは高密度ポリエチレンを含有する。したがって、ポリエチレン層(1)を備える延伸基材は、例えば耐熱性が高く、具体的には、印刷時の乾燥およびヒートシール時の加熱に対する耐性、フィルムに対して蒸着を行う場合における蒸着耐性に優れる。また、ポリエチレン層(1)は、例えば剛性が高く、フィルムに対して蒸着を行う場合においてフィルムの搬送速度を上げることができ、したがって生産性を上げることができる。
ポリエチレン層(1)は、例えば、高密度ポリエチレンと他のポリエチレンとの混合物を主成分として含有してもよく、中密度ポリエチレンと他のポリエチレンとの混合物を主成分として含有してもよく、高密度ポリエチレンと中密度ポリエチレンと他のポリエチレンとの混合物を主成分として含有してもよい。
主成分が上記混合物であるとは、ポリエチレン層(1)中の上記混合物の含有割合が50質量%超であることを意味し、上記含有割合は、好ましくは60質量%以上、より好ましくは70質量%以上、さらに好ましくは80質量%以上である。
上記高密度ポリエチレンは、例えば、エチレンの単独重合体でもよく、エチレン-α-オレフィン共重合体でもよく、これらの混合物でもよい。上記中密度ポリエチレンは、例えば、エチレンの単独重合体でもよく、エチレン-α-オレフィン共重合体でもよく、これらの混合物でもよい。
上記他のポリエチレンとしては、例えば、直鎖状低密度ポリエチレンおよび高圧法低密度ポリエチレンから選択される少なくとも1種が挙げられ、直鎖状低密度ポリエチレンでもよく、高圧法低密度ポリエチレンでもよく、直鎖状低密度ポリエチレンおよび高圧法低密度ポリエチレンの混合物でもよい。
ポリエチレン層(1)における高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計は、100質量%以下であり、2軸延伸性という観点から、好ましくは90質量%以下、より好ましくは85質量%以下、さらに好ましくは80質量%以下であり、70質量%以下でもよく、65質量%以下でもよく、60質量%以下でもよい。
ポリエチレン層(1)における高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計は、例えば10質量%以上100質量%以下であり、好ましくは20質量%以上60質量%以下である。
ポリエチレン層(1)における直鎖状低密度ポリエチレンの含有割合は、耐熱性という観点から、好ましくは90質量%以下、より好ましくは85質量%以下、さらに好ましくは80質量%以下であり、70質量%以下でもよく、65質量%以下でもよく、60質量%以下でもよい。
ポリエチレン層(1)における直鎖状低密度ポリエチレンの含有割合は、例えば10質量%以上90質量%以下であり、好ましくは40質量%以上80質量%以下である。
ポリエチレン層(1)におけるポリエチレンの含有割合は、好ましくは80質量%以上、より好ましくは85質量%以上、さらに好ましくは90質量%以上、特に好ましくは95質量%以上である。
第6の態様の延伸基材は、ポリエチレン層(2)を備える。
ポリエチレン層(2)は、ポリエチレンを主成分として含有し、該ポリエチレンは、0.930g/cm3超0.960g/cm3以下の密度を有する。ポリエチレン層(2)における上記ポリエチレンの密度は、好ましくは0.931g/cm3以上0.955g/cm3以下、より好ましくは0.931g/cm3以上0.950g/cm3以下である。
式中、Σは、iについて1~n(ポリエチレンがn種存在)までWi×Diの和を取ることを意味し、nは2以上の整数であり、Wiはi番目のポリエチレンの質量分率を示し、Diはi番目のポリエチレンの密度(g/cm3)を示す。
ポリエチレン層(2)は、上記添加剤を含有してもよい。
以下、第5および第6の態様の延伸基材について説明する。
第5の態様の延伸基材(2軸延伸ポリエチレンフィルム)は、一実施形態において、ポリエチレン層(1)からなる単層フィルムである。第5の態様の延伸基材(2軸延伸ポリエチレンフィルム)は、一実施形態において、2層以上のポリエチレン層を備え、該ポリエチレン層の少なくとも1層がポリエチレン層(1)であり、好ましくは、全ての該ポリエチレン層がポリエチレン層(1)である。
上記ポリエチレン層は、ポリエチレン以外の上記樹脂材料を含有してもよい。
上記ポリエチレン層は、上記添加剤を含有してもよい。
ポリエチレンを主成分として含有する第1の表面樹脂層と、
ポリエチレンを主成分として含有するポリエチレン中間層と、
ポリエチレンを主成分として含有する第2の表面樹脂層と、
を厚さ方向にこの順に少なくとも備え、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層から選択される少なくとも1層が、ポリエチレン層(1)またはポリエチレン層(2)である。耐熱性という観点から、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層のいずれも、ポリエチレン層(1)またはポリエチレン層(2)であることが好ましい。
以下、「厚さ方向にこの順に備える」を単に「この順に備える」とも記載する。
2軸延伸ポリエチレンフィルムは、ポリエチレン中間層を2層以上備えてもよい。
高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計を、以下「含有割合A」と記載する。ここで、高密度ポリエチレンのみでもよく、中密度ポリエチレンのみでもよく、高密度ポリエチレンおよび中密度ポリエチレンの混合物でもよい。
一実施形態の2軸延伸ポリエチレンフィルムにおいて、第1の表面樹脂層における含有割合Aよりもポリエチレン中間層における含有割合Aの方が大きく、ポリエチレン中間層における含有割合Aよりも第2の表面樹脂層における含有割合Aの方が小さい。このようなフィルムは、表面平滑性、透明性、印刷性および蒸着密着性と、耐熱性と、のバランスに優れる傾向にある。ポリエチレン中間層と上記表面樹脂層とにおける含有割合Aの差は、例えば10質量%以上でもよく、30質量%以下でもよい。
一実施形態の2軸延伸ポリエチレンフィルムにおいて、第1の表面樹脂層における含有割合Aよりもポリエチレン中間層における含有割合Aの方が小さく、ポリエチレン中間層における含有割合Aよりも第2の表面樹脂層における含有割合Aの方が大きい。このようなフィルムは、2軸延伸性と耐熱性とのバランスに優れる傾向にある。上記表面樹脂層とポリエチレン中間層とにおける含有割合Aの差は、例えば10質量%以上でもよく、30質量%以下でもよい。
一実施形態の2軸延伸ポリエチレンフィルムにおいて、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層における含有割合Aが、それぞれ略同等である。例えば、第1の表面樹脂層、ポリエチレン中間層および第2の表面樹脂層のうち、含有割合Aが最も大きい層と含有割合Aが最も小さい層との該含有割合Aの差が、10質量%未満である。
粒子は、樹脂粒子系のアンチブロッキング剤でもよい。これにより、例えば、一方の表面樹脂層が樹脂粒子系のアンチブロッキング剤を含有し、他方の表面樹脂層上に蒸着膜を備える後述するバリア性基材の場合、該基材をロール状体で保管する際に粒子が蒸着膜を傷つける可能性を低減できる。これは、樹脂粒子系のアンチブロッキング剤は、無機化合物系のアンチブロッキング剤よりも、通常は凹凸が小さく、また柔らかいためである。
以下、本開示の2軸延伸ポリエチレンフィルムの層構成について、図面を参照しながら数例を挙げる。
図9に示す2軸延伸ポリエチレンフィルム1Aは、ポリエチレン層10からなる。
図10に示す2軸延伸ポリエチレンフィルム1Aは、第1の表面樹脂層20と、ポリエチレン層10(ポリエチレン中間層)と、第2の表面樹脂層22と、をこの順に備える。
図11に示す2軸延伸ポリエチレンフィルム1Aは、第1の表面樹脂層20と、第1のポリエチレン層11と、第2のポリエチレン層12と、第3のポリエチレン層13と、第2の表面樹脂層22と、をこの順に備える。
本開示の延伸基材の酸素透過度(単位:cc/(m2・day・atm))は、例えば、30未満でもよく、25未満でもよく、18未満でもよく、10未満でもよく、5.0未満でもよい。酸素透過度は、JIS K7126-2:2006に準拠して、温度23℃、湿度90%RH環境下にて測定される。
本開示の第1~第3の態様のバリア性基材は、
上述した第1~第3の態様のいずれかの延伸基材と、
上記延伸基材における第1の表面樹脂層および第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、
を備える。
上述した第4の態様の延伸基材と、
上記延伸基材における第2の表面樹脂層の表面に設けられている蒸着膜と、
を備える。
上述した第5~第6の態様のいずれかの延伸基材と、
上記延伸基材における少なくとも一方の面上に設けられている蒸着膜(例えば、第1の表面樹脂層および第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜)と、
を備える。
第1の蒸着膜と、
上述した延伸基材と、
第2の蒸着膜と、
を厚さ方向にこの順に少なくとも備える。
本開示のバリア性基材は、蒸着膜を備え、ガスバリア性に優れる。したがって、このようなバリア性基材を用いて作製した包装容器は、ガスバリア性に優れる。本開示のバリア性基材は、一実施形態において、第1の蒸着膜と第2の蒸着膜とを備え、ガスバリア性により優れる。このようなバリア性基材は、延伸基材の両面上に蒸着膜を備えることから、ピンホールによるガスバリア性の低下を抑制できる。
第1の蒸着膜が金属蒸着膜であり、第2の蒸着膜が金属蒸着膜でもよく、ここで両者は同一でもよく異なってもよい。第1の蒸着膜および第2の蒸着膜の一方が金属蒸着膜であり、他方が無機酸化物蒸着膜または透明蒸着膜でもよい。第1の蒸着膜が無機酸化物蒸着膜または透明蒸着膜でもよく、第2の蒸着膜が無機酸化物蒸着膜または透明蒸着膜でもよく、ここで両者は同一でもよく異なってもよい。
本開示のバリア性基材は、蒸着膜上に、バリアコート層をさらに備えてもよい。すなわち、バリア性基材は、蒸着膜における延伸基材側の面とは反対側の面上に、バリアコート層をさらに備えてもよい。このようなバリア性基材は、例えば、酸素バリア性および水蒸気バリア性に優れるとともに、蒸着膜が酸化アルミニウムおよび酸化ケイ素などの無機酸化物から構成される場合は、蒸着膜におけるクラックの発生を効果的に抑制できる。
バリア性基材は、一実施形態において、バリアコート層と、第1の蒸着膜としての無機酸化物蒸着膜と、第1の表面樹脂層と、ポリオレフィン中間層と、第2の表面樹脂層と、第2の蒸着膜としての金属蒸着膜と、をこの順に備える。
バリア性基材は、一実施形態において、第1のバリアコート層と、第1の蒸着膜としての無機酸化物蒸着膜と、第1の表面樹脂層と、ポリオレフィン中間層と、第2の表面樹脂層と、第2の蒸着膜としての無機酸化物蒸着膜と、第2のバリアコート層と、をこの順に備える。
バリア性基材は、一実施形態において、第1の表面樹脂層と、ポリオレフィン中間層と、第2の表面樹脂層と、無機酸化物蒸着膜と、バリアコート層と、をこの順に備える。
バリア性基材は、一実施形態において、バリアコート層と、第1の蒸着膜としての無機酸化物蒸着膜と、2軸延伸ポリエチレンフィルムと、第2の蒸着膜としての金属蒸着膜と、をこの順に備える。
バリア性基材は、一実施形態において、第1のバリアコート層と、第1の蒸着膜としての無機酸化物蒸着膜と、2軸延伸ポリエチレンフィルムと、第2の蒸着膜としての無機酸化物蒸着膜と、第2のバリアコート層と、をこの順に備える。
バリア性基材は、一実施形態において、2軸延伸ポリエチレンフィルムと、無機酸化物蒸着膜と、バリアコート層と、をこの順に備える。
バリア性基材は、延伸基材における第1の面(または第1の表面樹脂層の表面)上に、第3の蒸着膜と、第3のバリアコート層と、第4の蒸着膜と、第4のバリアコート層と、をこの順に備えてもよい。バリア性基材は、延伸基材における第2の面(または第2の表面樹脂層の表面)上に、第3の蒸着膜と、第3のバリアコート層と、第4の蒸着膜と、第4のバリアコート層と、をこの順に備えてもよい。
バリア性基材は、第6のバリアコート層と、第6の蒸着膜と、第5のバリアコート層と、第5の蒸着膜と、延伸基材と、第3の蒸着膜と、第3のバリアコート層と、第4の蒸着膜と、第4のバリアコート層と、をこの順に少なくとも備えてもよく、蒸着膜およびバリアコート層のさらなる積層膜を備えてもよい。
金属アルコキシド、水溶性高分子、ゾルゲル法触媒、水、有機溶剤、および必要に応じてシランカップリング剤等を混合して、ガスバリア性組成物を調製する。組成物中では、次第に重縮合反応が進行する。蒸着膜に、常法により、上記組成物を塗布し乾燥する。この乾燥により、金属アルコキシドおよび水溶性高分子(組成物がシランカップリング剤を含む場合は、シランカップリング剤も)の重縮合がさらに進行し、複合ポリマーの層が形成される。上記操作を繰り返して、複数の複合ポリマー層を積層してもよい。例えば、塗布された上記組成物を、好ましくは20℃以上、より好ましくは50℃以上、さらに好ましくは70℃以上の温度で、好ましくは150℃以下、より好ましくは120℃以下、さらに好ましくは100℃以下の温度で、1秒以上10分以下加熱する。これにより、ガスバリア性塗布膜を形成できる。
以下、本開示のバリア性基材の層構成について、図面を参照しながら数例を挙げる。この図面において、本開示の延伸基材の層構成についても説明する。
本開示のバリア性基材の酸素透過度(単位:cc/(m2・day・atm))は、例えば、30未満でもよく、20未満でもよく、10未満でもよく、5.0未満でもよく、4.0未満でもよく、3.0未満でもよく、2.0未満でもよく、1.5未満でもよく、1.0未満でもよく、0.8未満でもよく、0.5未満でもよく、0.3未満でもよく、0.2未満でもよい。酸素透過度の下限値は、例えば0.01でもよい。酸素透過度は、JIS K7126-2:2006に準拠して、温度23℃、湿度90%RH環境下にて測定される。
本開示の積層体は、上述した延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。
本開示の第1の態様の積層体は、本開示の第1の態様の延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。本開示の第2の態様の積層体は、本開示の第2の態様の延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。本開示の第3の態様の積層体は、本開示の第3の態様の延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。本開示の第4の態様の積層体は、本開示の第4の態様の延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。本開示の第5または第6の態様の積層体は、本開示の第5または第6の態様の延伸基材、印刷基材またはバリア性基材と、ヒートシール層と、を少なくとも備える。
本開示の積層体の総厚さは、一実施形態において、40μm以上でもよく、60μm以上でもよく、80μm以上でもよく、100μm以上でもよく、120μm以上でもよく、140μm以上でもよく、400μm以下でもよく、350μm以下でもよく、300μm以下でもよく、例えば40μm以上400μm以下である。積層体の総厚さは、例えば包装容器の用途または形態に応じて適宜変更できる。
本開示の積層体は、本開示の延伸基材、印刷基材またはバリア性基材を備える。本開示の積層体は、延伸基材を2つ以上備えてもよい。本開示の積層体は、印刷基材を2つ以上備えてもよい。本開示の積層体は、バリア性基材を2つ以上備えてもよい。延伸基材、印刷基材およびバリア性基材の詳細については上述したとおりであり、本欄での詳細な説明は省略する。
本開示の積層体は、上述した延伸基材、バリア性基材およびポリオレフィン延伸基材等の基材の一方の面または両方の面上に、印刷層を備えてもよい。本開示の積層体は、後述する第2のヒートシール層上に、印刷層を備えてもよい。
本開示の積層体は、後述する第2のヒートシール層上に設けられた印刷層上に、印刷層の耐擦傷性および耐候性を良好にするために、表面保護層を備えてもよい。本開示の積層体は、印刷層の全領域を覆う表面保護層を備えることが好ましい。印刷層の視認性という観点から、表面保護層は、可視光領域において透明性を有することが好ましく、無色透明であることがより好ましい。
本開示の積層体は、ヒートシール層を備える。
ヒートシール層は、熱によって溶融し相互に融着し得る熱融着性樹脂を主成分として含有する。熱融着性樹脂としては、例えば、ポリエチレン、ポリプロピレンおよびポリメチルペンテンなどのポリオレフィン、環状ポリオレフィン、環状オレフィンコポリマー、アイオノマー樹脂、酸変性ポリオレフィンおよびエチレン-(メタ)アクリル酸エステル-不飽和カルボン酸の三元共重合体が挙げられる。ポリエチレンとしては、例えば、直鎖状低密度ポリエチレン、高圧法低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体およびエチレン-(メタ)アクリル酸エステル共重合体が挙げられる。酸変性ポリオレフィンとしては、例えば、ポリエチレンおよびポリプロピレン等のポリオレフィンを(メタ)アクリル酸および無水マレイン酸等の不飽和カルボン酸系化合物で変性した樹脂が挙げられる。
バリア性基材を備える第2の態様の積層体において、バリア性基材は、第1の蒸着膜が第1のヒートシール層側を向き、第2の蒸着膜が第2のヒートシール層側を向くように、配置されていることが好ましい。すなわち上記積層体は、第2のヒートシール層と、第2の蒸着膜と、第2の表面樹脂層と、ポリオレフィン中間層と、第1の表面樹脂層と、第1の蒸着膜と、第1のヒートシール層と、をこの順に備えることが好ましい。
バリア性基材を備える第4の態様の積層体において、バリア性基材は、第1の表面樹脂層が第1のヒートシール層側を向き、蒸着膜が第2のヒートシール層側を向くように、配置されていることが好ましい。すなわち上記積層体は、第2のヒートシール層と、蒸着膜と、第2の表面樹脂層と、ポリオレフィン中間層と、第1の表面樹脂層と、第1のヒートシール層と、をこの順に備えることが好ましい。
延伸基材または印刷基材を備える第2の態様および第4の態様の積層体において、延伸基材および印刷基材は、第1の表面樹脂層が第1のヒートシール層側を向き、第2の表面樹脂層が第2のヒートシール層側を向くように、配置されていることが好ましい。すなわち上記積層体は、第2のヒートシール層と、第2の表面樹脂層と、ポリオレフィン中間層と、第1の表面樹脂層と、第1のヒートシール層と、をこの順に備えることが好ましい。
ヒートシール層の厚さは、ヒートシール性および包装容器のリサイクル性という観点から、10μm以上でもよく、20μm以上でもよく、30μm以上でもよく、50μm以上でもよく、60μm以上でもよく、70μm以上でもよく、80μm以上でもよい。ヒートシール層の厚さは、積層体の加工性という観点から、300μm以下でもよく、200μm以下でもよく、150μm以下でもよい。ヒートシール層の厚さは、例えば10μm以上300μm以下である。第1および第2のヒートシール層の厚さも、それぞれ独立して、上記範囲内であることが好ましい。ヒートシール層の厚さは、例えば包装容器の用途または形態に応じて適宜変更できる。小袋の場合は、ヒートシール層の厚さは、例えば20μm以上60μm以下でもよいが、特に限定されない。スタンディングパウチの場合は、ヒートシール層の厚さは、例えば60μm以上150μm以下でもよいが、特に限定されない。チューブ容器の場合は、ヒートシール層の厚さは、例えば、50μm以上でもよく、60μm以上でもよく、70μm以上でもよく、80μm以上でもよいが、特に限定されない。
本開示の積層体は、延伸基材、印刷基材またはバリア性基材と、ヒートシール層との間などの任意の層間に、接着層を備えてもよい。このような積層体は、例えば、延伸基材、印刷基材またはバリア性基材と、ヒートシール層との密着性に優れる。
以下、本開示の積層体の層構成について、数例を挙げる。
図4Aに示す積層体2は、バリア性基材1と、接着層60と、ヒートシール層80とをこの順に備え、具体的には、第2の蒸着膜42と、第2の表面樹脂層22と、ポリオレフィン中間層10と、第1の表面樹脂層20と、第1の蒸着膜40と、接着層60と、ヒートシール層80とをこの順に備える。積層体2は、図示せぬ印刷層をさらに備えてもよく、例えば、バリア性基材1における第1の蒸着膜40上または第2の蒸着膜42上に、印刷層をさらに備えてもよい。
本開示の積層体は、包装材料用途に好適に使用できる。包装材料は、包装容器を作製するために使用される。本開示の積層体を少なくとも用いることにより、ガスバリア性に優れる包装容器を製造できる。
本開示の包装袋は、例えば、
1つ以上の本開示の積層体と、
上記積層体のヒートシール層同士が接合されているシール部と、
内容物を収容する収容部と、
を有する。
シール部は、収容部を画成する内縁を含む。
本開示のチューブ容器本体は、本開示の積層体を備える。
以下、本開示のチューブ容器本体について図面を参照しながら説明する。図7は、チューブ容器120の構成を簡略的に示す図であり、図8は、図7のA-A断面図である。図7に示すように、チューブ容器本体121は、頭部122と胴部123とを備え、該胴部123が本開示の積層体により構成されている。
頭部122は、胴部123の一端に連接している肩部124と、肩部124に連接している抽出口部125とを備える。一実施形態において、注出口部125は、キャップ126を螺合するための螺条127を備える。
本開示のチューブ容器本体121において、胴部123は、頭部122の肩部124に連接されている。胴部123は、例えば、本開示の積層体の一方の端部の第1のヒートシール層側表面と、他方の端部の第2のヒートシール層側表面とが接するように重ね合わせて筒状に丸め、重ね合わされた部分をヒートシールすることにより形成された融着部128を備える。胴部123は、例えば、筒状に丸めた積層体の開口部をヒートシールすることにより形成された底シール部129を備える。
以下、本開示のチューブ容器について図面を参照しながら説明する。図7に示すように、本開示のチューブ容器120は、チューブ容器本体121と、頭部122に装着されるキャップ26とを備える。
チューブ容器本体については上述したため、ここでは記載を省略する。
キャップは、頭部の抽出口部に着脱可能に装着されており、抽出口部を閉鎖する役割を担う。一実施形態において、キャップは、熱可塑性樹脂を含有する樹脂組成物により形成されている。熱可塑性樹脂としては、例えば、ポリエチレンおよびポリプロピレンなどのポリオレフィン、ポリエステル、セルロース樹脂ならびにビニル樹脂が挙げられる。上記樹脂組成物は、上記添加剤を含有してもよい。
[1]ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備える、延伸基材。
[2]前記第1の表面樹脂層および前記第2の表面樹脂層における前記ガスバリア性樹脂が、それぞれ独立して、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、前記[1]に記載の延伸基材。
[3]前記ポリオレフィン中間層が、ポリプロピレンを主成分として含有するポリプロピレン層、またはポリエチレンを主成分として含有するポリエチレン層である、前記[1]または[2]に記載の延伸基材。
[4]前記ポリプロピレン層における前記ポリプロピレンが、ホモポリプロピレンを含み、前記ポリエチレン層における前記ポリエチレンが、直鎖状低密度ポリエチレンを含む、前記[3]に記載の延伸基材。
[5]前記ポリオレフィン中間層が相溶化剤をさらに含有する、前記[1]~[4]のいずれか一項に記載の延伸基材。
[6]前記延伸基材が、前記第1の表面樹脂層と前記ポリオレフィン中間層との間に、第1の接着性樹脂層をさらに備え、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、第2の接着性樹脂層をさらに備える、前記[1]~[5]のいずれか一項に記載の延伸基材。
[7]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、4μm以上60μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[1]~[6]のいずれか一項に記載の延伸基材。
[8]前記延伸基材におけるポリオレフィンの含有割合が、60質量%以上である、前記[1]~[7]のいずれか一項に記載の延伸基材。
[9]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[8]のいずれか一項に記載の延伸基材。
[10]前記延伸基材が、2軸延伸基材である、前記[1]~[9]のいずれか一項に記載の延伸基材。
[11]前記[1]~[10]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[12]第1の蒸着膜と、前記[1]~[10]のいずれか一項に記載の延伸基材と、第2の蒸着膜と、をこの順に少なくとも備え、前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、バリア性基材。
[13]前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、金属蒸着膜であるか、前記第1の蒸着膜が無機酸化物蒸着膜であり、前記第2の蒸着膜が金属蒸着膜であるか、前記第1の蒸着膜が金属蒸着膜であり、前記第2の蒸着膜が無機酸化物蒸着膜であるか、または、前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、無機酸化物蒸着膜である、前記[12]に記載のバリア性基材。
[14]前記無機酸化物蒸着膜がアルミナ蒸着膜、シリカ蒸着膜または酸化炭化珪素蒸着膜であり、前記金属蒸着膜がアルミニウム蒸着膜である、前記[13]に記載のバリア性基材。
[1]ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備える、延伸基材。
[2]前記第1の表面樹脂層における前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[1]に記載の延伸基材。
[3]前記第1の表面樹脂層における前記ポリオレフィンがポリプロピレンを含み、前記第1の表面樹脂層における前記接着性樹脂が酸変性ポリプロピレンを含み、前記ポリオレフィン中間層がポリプロピレンを主成分として含有するか、または、前記第1の表面樹脂層における前記ポリオレフィンがポリエチレンを含み、前記第1の表面樹脂層における前記接着性樹脂が酸変性ポリエチレンを含み、前記ポリオレフィン中間層がポリエチレンを主成分として含有する、前記[1]または[2]に記載の延伸基材。
[4]前記第1の表面樹脂層における前記ポリプロピレンがランダムポリプロピレンを含み、前記第1の表面樹脂層における前記接着性樹脂が酸変性ランダムポリプロピレンを含み、前記ポリオレフィン中間層における前記ポリプロピレンがホモポリプロピレンを含む、前記[3]に記載の延伸基材。
[5]前記第2の表面樹脂層における前記ガスバリア性樹脂が、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、前記[1]~[4]のいずれか一項に記載の延伸基材。
[6]前記延伸基材が前記ポリオレフィン中間層を2層以上備える、前記[1]~[5]のいずれか一項に記載の延伸基材。
[7]前記ポリオレフィン中間層の少なくとも1層が、相溶化剤をさらに含有する、前記[6]に記載の延伸基材。
[8]前記延伸基材が、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[1]~[7]のいずれか一項に記載の延伸基材。
[9]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、5μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[1]~[8]のいずれか一項に記載の延伸基材。
[10]前記延伸基材におけるポリオレフィンの含有割合が、70質量%以上である、前記[1]~[9]のいずれか一項に記載の延伸基材。
[11]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[10]のいずれか一項に記載の延伸基材。
[12]前記延伸基材が、2軸延伸基材である、前記[1]~[11]のいずれか一項に記載の延伸基材。
[13]前記[1]~[12]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[14]第1の蒸着膜と、前記[1]~[12]のいずれか一項に記載の延伸基材と、第2の蒸着膜と、をこの順に少なくとも備えるバリア性基材であって、前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、バリア性基材。
[15]前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、金属蒸着膜であるか、前記第1の蒸着膜が無機酸化物蒸着膜であり、前記第2の蒸着膜が金属蒸着膜であるか、前記第1の蒸着膜が金属蒸着膜であり、前記第2の蒸着膜が無機酸化物蒸着膜であるか、または、前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、無機酸化物蒸着膜である、前記[14]に記載のバリア性基材。
[16]前記無機酸化物蒸着膜がアルミナ蒸着膜、シリカ蒸着膜または酸化炭化珪素蒸着膜であり、前記金属蒸着膜がアルミニウム蒸着膜である、前記[15]に記載のバリア性基材。
[1]ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ポリオレフィンと接着性樹脂とを含有する第2の表面樹脂層と、をこの順に少なくとも備える、延伸基材。
[2]前記第1の表面樹脂層および前記第2の表面樹脂層において、それぞれ独立して、前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[1]に記載の延伸基材。
[3]前記第1の表面樹脂層における前記ポリオレフィンがポリプロピレンを含み、前記第1の表面樹脂層における前記接着性樹脂が酸変性ポリプロピレンを含み、前記ポリオレフィン中間層がポリプロピレンを主成分として含み、前記第2の表面樹脂層における前記ポリオレフィンがポリプロピレンを含み、前記第2の表面樹脂層における前記接着性樹脂が酸変性ポリプロピレンを含むか、または、前記第1の表面樹脂層における前記ポリオレフィンがポリエチレンを含み、前記第1の表面樹脂層における前記接着性樹脂が酸変性ポリエチレンを含み、前記ポリオレフィン中間層がポリエチレンを主成分として含み、前記第2の表面樹脂層における前記ポリオレフィンがポリエチレンを含み、前記第2の表面樹脂層における前記接着性樹脂が酸変性ポリエチレンを含む、前記[1]または[2]に記載の延伸基材。
[4]前記第1の表面樹脂層および前記第2の表面樹脂層における前記ポリプロピレンが、それぞれ独立して、ランダムポリプロピレンを含み、前記第1の表面樹脂層および前記第2の表面樹脂層における前記接着性樹脂が、それぞれ独立して、酸変性ランダムポリプロピレンを含み、前記ポリオレフィン中間層における前記ポリプロピレンが、ホモポリプロピレンを含む、前記[3]に記載の延伸基材。
[5]前記延伸基材が前記ポリオレフィン中間層を2層以上備える、前記[1]~[4]のいずれか一項に記載の延伸基材。
[6]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、6μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[1]~[5]のいずれか一項に記載の延伸基材。
[7]前記延伸基材におけるポリオレフィンの含有割合が、80質量%以上である、前記[1]~[6]のいずれか一項に記載の延伸基材。
[8]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[7]のいずれか一項に記載の延伸基材。
[9]前記延伸基材が、2軸延伸基材である、前記[1]~[8]のいずれか一項に記載の延伸基材。
[10]前記[1]~[9]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[11]第1の蒸着膜と、前記[1]~[9]のいずれか一項に記載の延伸基材と、第2の蒸着膜と、をこの順に少なくとも備えるバリア性基材であって、前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、バリア性基材。
[12]前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、金属蒸着膜であるか、前記第1の蒸着膜が無機酸化物蒸着膜であり、前記第2の蒸着膜が金属蒸着膜であるか、前記第1の蒸着膜が金属蒸着膜であり、前記第2の蒸着膜が無機酸化物蒸着膜であるか、または、前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、無機酸化物蒸着膜である、前記[11]に記載のバリア性基材。
[13]前記無機酸化物蒸着膜がアルミナ蒸着膜、シリカ蒸着膜または酸化炭化珪素蒸着膜であり、前記金属蒸着膜がアルミニウム蒸着膜である、前記[12]に記載のバリア性基材。
[1]ポリオレフィンを主成分として含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ポリオレフィンと接着性樹脂とを含有する第2の表面樹脂層と、をこの順に少なくとも備える、延伸基材。
[2]前記第2の表面樹脂層において、前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[1]に記載の延伸基材。
[3]前記第2の表面樹脂層における前記ポリオレフィンがポリプロピレンを含み、前記第2の表面樹脂層における前記接着性樹脂が酸変性ポリプロピレンを含み、前記ポリオレフィン中間層がポリプロピレンを主成分として含み、前記第1の表面樹脂層がポリプロピレンを主成分として含むか、または、前記第2の表面樹脂層における前記ポリオレフィンがポリエチレンを含み、前記第2の表面樹脂層における前記接着性樹脂が酸変性ポリエチレンを含み、前記ポリオレフィン中間層がポリエチレンを主成分として含み、前記第1の表面樹脂層がポリエチレンを主成分として含む、前記[1]または[2]に記載の延伸基材。
[4]前記第2の表面樹脂層における前記ポリプロピレンが、ランダムポリプロピレンを含み、前記第2の表面樹脂層における前記接着性樹脂が、酸変性ランダムポリプロピレンを含み、前記ポリオレフィン中間層および前記第1の表面樹脂層における前記ポリプロピレンが、それぞれ独立して、ホモポリプロピレンを含む、前記[3]に記載の延伸基材。
[5]ポリオレフィンを主成分として含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備える、延伸基材。
[6]前記第2の表面樹脂層における前記ガスバリア性樹脂が、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、前記[5]に記載の延伸基材。
[7]前記ポリオレフィン中間層および前記第1の表面樹脂層が、それぞれ独立して、ポリプロピレンまたはポリエチレンを主成分として含む、前記[5]または[6]に記載の延伸基材。
[8]前記ポリオレフィン中間層および前記第1の表面樹脂層における前記ポリプロピレンが、それぞれ独立して、ホモポリプロピレンを含む、前記[7]に記載の延伸基材。
[9]前記延伸基材が、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[5]~[8]のいずれか一項に記載の延伸基材。
[10]前記ポリオレフィン中間層が、相溶化剤をさらに含有する、前記[5]~[9]のいずれか一項に記載の延伸基材。
[11]前記延伸基材が、前記ポリオレフィン中間層を2層以上備える、前記[1]~[10]のいずれか一項に記載の延伸基材。
[12]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、5μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[1]~[11]のいずれか一項に記載の延伸基材。
[13]前記延伸基材におけるポリオレフィンの含有割合が、80質量%以上である、前記[1]~[12]のいずれか一項に記載の延伸基材。
[14]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[13]のいずれか一項に記載の延伸基材。
[15]前記延伸基材が、2軸延伸基材である、前記[1]~[14]のいずれか一項に記載の延伸基材。
[16]前記[1]~[15]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第2の表面樹脂層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[17]前記蒸着膜が、金属蒸着膜または無機酸化物蒸着膜である、前記[16]に記載のバリア性基材。
[18]前記蒸着膜が、アルミニウム蒸着膜、アルミナ蒸着膜、シリカ蒸着膜または酸化炭化珪素蒸着膜である、前記[16]または[17]に記載のバリア性基材。
[1]ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記第1の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含み、前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、延伸基材。
[2]前記延伸基材が、前記第1の表面樹脂層と前記ポリオレフィン中間層との間に、第1の接着性樹脂層をさらに備え、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、第2の接着性樹脂層をさらに備える、前記[1]に記載の延伸基材。
[3]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、4μm以上60μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[1]または[2]に記載の延伸基材。
[4]ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、延伸基材。
[5]前記第1の表面樹脂層における前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[4]に記載の延伸基材。
[6]前記延伸基材が、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[4]または[5]に記載の延伸基材。
[7]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、5μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[4]~[6]のいずれか一項に記載の延伸基材。
[8]ポリオレフィンを主成分として含有する第1の表面樹脂層と、ポリオレフィンを主成分として含有するポリオレフィン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、延伸基材。
[9]前記延伸基材が、前記ポリオレフィン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[8]に記載の延伸基材。
[10]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリオレフィン中間層の厚さが、5μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[8]または[9]に記載の延伸基材。
[11]前記ポリオレフィン中間層が相溶化剤をさらに含有する、前記[1]~[10]のいずれか一項に記載の延伸基材。
[12]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[11]のいずれか一項に記載の延伸基材。
[13]前記延伸基材が、2軸延伸基材である、前記[1]~[12]のいずれか一項に記載の延伸基材。
[14]前記[1]~[7]、[11]~[13]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を備えるか、または、前記[8]~[13]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第2の表面樹脂層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[15]第1の蒸着膜と、前記[1]~[13]のいずれか一項に記載の延伸基材と、第2の蒸着膜と、をこの順に少なくとも備え、前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、バリア性基材。
[16]前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、金属蒸着膜であるか、前記第1の蒸着膜が無機酸化物蒸着膜であり、前記第2の蒸着膜が金属蒸着膜であるか、前記第1の蒸着膜が金属蒸着膜であり、前記第2の蒸着膜が無機酸化物蒸着膜であるか、または、前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、無機酸化物蒸着膜である、前記[15]に記載のバリア性基材。
[17]前記無機酸化物蒸着膜がアルミナ蒸着膜、シリカ蒸着膜または酸化炭化珪素蒸着膜であり、前記金属蒸着膜がアルミニウム蒸着膜である、前記[16]に記載のバリア性基材。
[1]ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記ポリエチレン中間層の少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、0.930g/cm3超0.960g/cm3以下の密度を有する、延伸基材。
[2]前記第1の表面樹脂層および前記第2の表面樹脂層における前記ガスバリア性樹脂が、それぞれ独立して、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、前記[1]に記載の延伸基材。
[3]前記第1の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含み、前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、前記[1]または[2]に記載の延伸基材。
[4]前記延伸基材が、前記第1の表面樹脂層と前記ポリエチレン中間層との間に、第1の接着性樹脂層をさらに備え、前記ポリエチレン中間層と前記第2の表面樹脂層との間に、第2の接着性樹脂層をさらに備える、前記[1]~[3]のいずれか一項に記載の延伸基材。
[5]ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記第1の表面樹脂層および前記ポリエチレン中間層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、0.930g/cm3超0.960g/cm3以下の密度を有する、延伸基材。
[6]前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、前記[5]に記載の延伸基材。
[7]前記第1の表面樹脂層における前記ポリエチレンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[5]または[6]に記載の延伸基材。
[8]前記延伸基材が、前記ポリエチレン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[5]~[7]のいずれか一項に記載の延伸基材。
[9]ポリエチレンと接着性樹脂とを含有する第1の表面樹脂層と、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、ポリエチレンと接着性樹脂とを含有する第2の表面樹脂層と、をこの順に少なくとも備え、前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、0.930g/cm3超0.960g/cm3以下の密度を有する、延伸基材。
[10]前記第1の表面樹脂層および前記第2の表面樹脂層において、それぞれ独立して、前記ポリエチレンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[9]に記載の延伸基材。
[11]ポリエチレンを主成分として含有する第1の表面樹脂層と、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層と、ガスバリア性樹脂を主成分として含有する、または、ポリエチレンと接着性樹脂とを含有する、第2の表面樹脂層と、をこの順に少なくとも備え、前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、0.930g/cm3超0.960g/cm3以下の密度を有する、延伸基材。
[12]前記第2の表面樹脂層における前記ガスバリア性樹脂が、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、前記[11]に記載の延伸基材。
[13]前記第2の表面樹脂層における前記ガスバリア性樹脂が、芳香族ポリアミドを含む、前記[11]または[12]に記載の延伸基材。
[14]前記第2の表面樹脂層において、前記ポリエチレンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、前記[11]~[13]のいずれか一項に記載の延伸基材。
[15]前記第2の表面樹脂層が、前記ガスバリア性樹脂を主成分として含有し、記延伸基材が、前記ポリエチレン中間層と前記第2の表面樹脂層との間に、接着性樹脂層をさらに備える、前記[11]~[14]のいずれか一項に記載の延伸基材。
[16]前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、前記[1]~[15]のいずれか一項に記載の延伸基材。
[17]前記延伸基材が、2軸延伸基材である、前記[1]~[16]のいずれか一項に記載の延伸基材。
[18]前記ポリエチレン中間層の少なくとも1層が、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンと、直鎖状低密度ポリエチレンとを含有する、前記[1]~[17]のいずれか一項に記載の延伸基材。
[19]前記ポリエチレン中間層の少なくとも1層における高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計が、20質量%以上60質量%以下であり、直鎖状低密度ポリエチレンの含有割合が、40質量%以上80質量%以下である、前記[18]に記載の延伸基材。
[20]前記高密度ポリエチレンが、0.945g/cm3超0.960g/cm3以下の密度を有するエチレン-α-オレフィン共重合体であり、前記直鎖状低密度ポリエチレンが、0.930g/cm3以下の密度を有するエチレン-α-オレフィン共重合体である、前記[18]または[19]に記載の延伸基材。
[21]前記[1]~[10]、[16]~[20]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を備えるか、または、前記[11]~[20]のいずれか一項に記載の延伸基材と、前記延伸基材における前記第2の表面樹脂層の表面に設けられている蒸着膜と、を備える、バリア性基材。
[22]第1の蒸着膜と、前記[1]~[20]のいずれか一項に記載の延伸基材と、第2の蒸着膜と、をこの順に少なくとも備え、前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、バリア性基材。
[23]前記[21]または[22]に記載のバリア性基材と、ヒートシール層と、を少なくとも備える、積層体。
[24]前記ヒートシール層が、ポリエチレンを主成分として含有し、前記積層体全体におけるポリエチレンの含有割合が、80質量%以上である、前記[23]に記載の積層体。
[25]第1のヒートシール層と、前記バリア性基材と、第2のヒートシール層と、をこの順に少なくとも備える、前記[23]または[24]に記載の積層体。
[1]高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含有するポリエチレン層を備える、2軸延伸ポリエチレンフィルム。
[2]ポリエチレンを主成分として含有するポリエチレン層を備え、前記ポリエチレン層に含まれる前記ポリエチレンは、0.930g/cm3超0.960g/cm3以下の密度を有する、2軸延伸ポリエチレンフィルム。
[3]前記ポリエチレン層が、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンと、直鎖状低密度ポリエチレンとを含有する、前記[1]または[2]に記載の2軸延伸ポリエチレンフィルム。
[4]前記ポリエチレン層における高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計が、20質量%以上60質量%以下であり、直鎖状低密度ポリエチレンの含有割合が、40質量%以上80質量%以下である、前記[3]に記載の2軸延伸ポリエチレンフィルム。
[5]前記高密度ポリエチレンが、0.945g/cm3超0.960g/cm3以下の密度を有するエチレン-α-オレフィン共重合体であり、前記直鎖状低密度ポリエチレンが、0.930g/cm3以下の密度を有するエチレン-α-オレフィン共重合体である、前記[3]または[4]に記載の2軸延伸ポリエチレンフィルム。
[6]前記2軸延伸ポリエチレンフィルムが、第1の表面樹脂層と、ポリエチレン中間層と、第2の表面樹脂層と、を備え、前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層が、それぞれ独立して、前記ポリエチレン層である、前記[1]~[5]のいずれか一項に記載の2軸延伸ポリエチレンフィルム。
[7]前記2軸延伸ポリエチレンフィルムが、前記ポリエチレン中間層を2層以上備える、前記[6]に記載の2軸延伸ポリエチレンフィルム。
[8]前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層が、それぞれ独立して、0.945g/cm3超0.960g/cm3以下の密度を有するエチレン-α-オレフィン共重合体である高密度ポリエチレンと、0.930g/cm3以下の密度を有するエチレン-α-オレフィン共重合体である直鎖状低密度ポリエチレンと、を含有する、前記[6]または[7]に記載の2軸延伸ポリエチレンフィルム。
[9]前記第1の表面樹脂層の厚さが、0.3μm以上15μm以下であり、前記ポリエチレン中間層の厚さが、6μm以上100μm以下であり、前記第2の表面樹脂層の厚さが、0.3μm以上15μm以下である、前記[6]~[8]のいずれか一項に記載の2軸延伸ポリエチレンフィルム。
[10]前記2軸延伸ポリエチレンフィルムが、前記ポリエチレン層からなる単層フィルムであるか、または、少なくとも前記ポリエチレン層を備える多層フィルムである、前記[1]~[9]のいずれか一項に記載の2軸延伸ポリエチレンフィルム。
[11]前記2軸延伸ポリエチレンフィルムが、共押出樹脂フィルムの2軸延伸フィルムである、前記[10]に記載の2軸延伸ポリエチレンフィルム。
[12]前記[1]~[11]のいずれか一項に記載の2軸延伸ポリエチレンフィルムと、前記フィルムにおける少なくとも一方の面上に設けられている印刷層と、を備える、印刷フィルム。
[13]前記[1]~[11]のいずれか一項に記載の2軸延伸ポリエチレンフィルムと、前記フィルムにおける少なくとも一方の面上に設けられている蒸着膜と、を備える、バリア性基材。
[14]前記[1]~[11]のいずれか一項に記載の2軸延伸ポリエチレンフィルム、前記[12]に記載の印刷フィルム、または前記[13]に記載のバリア性基材と、ヒートシール層と、を少なくとも備える、積層体。
[15]前記ヒートシール層が、ポリエチレンを主成分として含有し、前記積層体全体におけるポリエチレンの含有割合が、80質量%以上である、前記[14]に記載の積層体。
以下、実施例により本開示の第1~第4の態様の延伸基材およびバリア性基材をより具体的に説明するが、本開示の延伸基材およびバリア性基材は以下の実施例に限定されない。以下の記載において「質量部」は単に「部」と記載する。
延伸基材の作製において、以下の材料を用いた。
・エチレン-ビニルアルコール共重合体(EVOH)
クラレ製、エバールG156B、融点:157℃、
MFR:6.4g/10分、エチレン含有割合:48モル%
・脂肪族ポリアミド(脂肪族PA)
UBE製、ポリアミド6(PA6) 1020、
融点:220℃、相対粘度:3.04
・芳香族ポリアミド(芳香族PA)
三菱ガス化学製、MXナイロン(MXD6) S6007、
ポリメタキシリレンアジパミド、融点:240℃、相対粘度:2.7
・接着性樹脂(酸変性r-PP)
三井化学製、アドマーQF580、
無水マレイン酸グラフト変性ランダムポリプロピレン、
密度:0.900g/cm3、融点:140℃、
MFR:7.7g/10分
・接着性樹脂(酸変性LLDPE)
三井化学製、アドマーNF587、
無水マレイン酸グラフト変性直鎖状低密度ポリエチレン、
密度:0.910g/cm3、融点:120℃、
MFR:2.3g/10分
・ホモポリプロピレン(h-PP)
The Polyolefin Company(Singapore)製、
COSMOPLENE FS3031、密度:0.900g/cm3、
融点:168℃、MFR:3.4g/10分、
アイソタクチックインデックス:98%
・ランダムポリプロピレン(r-PP)
The Polyolefin Company(Singapore)製、
COSMOPLENE FS5612、密度:0.900g/cm3、
融点:134℃、MFR:5.5g/10分
・高密度ポリエチレン(HDPE)
メタロセンHDPE、エチレン-1-オクテン共重合体、
密度:0.955g/cm3、融点:130℃、
MFR:1.5g/10分
・直鎖状低密度ポリエチレン(LLDPE)
ダウケミカル製、INNATE TF80、
メタロセンLLDPE、エチレン-1-オクテン共重合体、
密度:0.926g/cm3、MFR:1.7g/10分
・酸変性ランダムポリプロピレン(MAH-r-PP)
アルケマ社製、OREVAC 18722、
無水マレイン酸グラフト変性ランダムポリプロピレン、
密度:0.900g/cm3、融点:143℃、
MFR:7.0g/10分
・酸変性直鎖状低密度ポリエチレン(MAH-LLDPE)
アルケマ社製、OREVAC 18302N、
無水マレイン酸グラフト変性直鎖状低密度ポリエチレン、
密度:0.912g/cm3、融点:123℃、
MFR:1.5g/10分
・相溶化剤
ダウケミカル製、RETAIN 3000、
無水マレイン酸グラフト変性ポリエチレン、
密度:0.870g/cm3
・アンチブロッキング剤(AB剤)
シリカ粒子、平均粒子径:3.5μm
40部のHDPEと60部のLLDPE(INNATE TF80)とを混合して、ブレンドポリエチレン(A)を調製した。
90部のLLDPE(INNATE TF80)と10部の酸変性LLDPE(OREVAC 18302N)とを混合して、ブレンドポリエチレン(B1)を調製した。
18部のHDPEと72部のLLDPE(INNATE TF80)と10部の酸変性LLDPE(OREVAC 18302N)とを混合して、ブレンドポリエチレン(B2)を調製した。
40部のHDPEと60部のLLDPE(INNATE TF80)と0.2部(2,000ppm)のAB剤とを混合して、ブレンドポリエチレン(C)を調製した。
20部のHDPEと80部のLLDPE(INNATE TF80)と0.2部(2,000ppm)のAB剤とを混合して、ブレンドポリエチレン(D)を調製した。
90部のランダムポリプロピレン(FS5612)と10部の酸変性ランダムポリプロピレン(OREVAC 18722)とを混合して、ブレンドポリプロピレン(A)を調製した。
80部のホモポリプロピレン(FS3031)と20部のランダムポリプロピレン(FS5612)とを混合して、ブレンドポリプロピレン(B)を調製した。
50部の芳香族ポリアミド(MXD6)と50部の脂肪族ポリアミド(ポリアミド6 1020)とを混合して、ブレンドポリアミド(A)を調製した。
[実施例1A]
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
接着性樹脂(QF580)と、
エチレン-ビニルアルコール共重合体(G156B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。
厚さ1μmの第2の表面樹脂層(EVOH層)と、
厚さ1.5μmの第2の接着性樹脂層と、
厚さ13μmのポリプロピレン中間層と、
厚さ1.5μmの第1の接着性樹脂層と、
厚さ1μmの第1の表面樹脂層(EVOH層)と、
をこの順に備える。
延伸基材の第1の表面樹脂層および第2の表面樹脂層のそれぞれの面上に、PVD法により、厚さ30nmのアルミニウム(AL)蒸着膜を形成した。このようにして、バリア性基材を得た。
延伸基材の第1の表面樹脂層および第2の表面樹脂層のそれぞれの面上に、PVD法により、厚さ30nmのアルミナ蒸着膜を形成した。水47.69gと、イソプロピルアルコール22.8gと、0.5N塩酸1.13gとを混合して、溶液を得た。この溶液に、金属アルコキシドとしてテトラエトキシシラン27.04gと、シランカップリング剤として3-グリシドキシプロピルトリエトキシシラン1.35gとを、10℃となるように冷却しながら混合して、溶液Aを得た。水溶性高分子としてケン化度99%以上、重合度2,400のポリビニルアルコール4.14gと、水91.07gと、イソプロピルアルコール4.79gとを混合して、溶液Bを得た。溶液Aと溶液Bとを、質量基準で溶液A/溶液Bが65.5/34.5となるように混合して、バリアコート剤を得た。アルミナ蒸着膜の表面に、上記バリアコート剤をスピンコート法によりコーティングし、オーブンにて100℃で8秒間の加熱処理を施して、厚さ0.3μmのバリアコート層を形成した。このようにして、バリア性基材を得た。
延伸基材の第1の表面樹脂層および第2の表面樹脂層のそれぞれの面上に、アルミナ蒸着膜にかえて、厚さ30nmのシリカ蒸着膜を形成し、さらに該シリカ蒸着膜上に上記バリアコート層を形成した。このようにして、バリア性基材を得た。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
接着性樹脂(QF580)と、
ポリアミド(ポリアミド6 1020)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
接着性樹脂(NF587)と、
エチレン-ビニルアルコール共重合体(G156B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
接着性樹脂(NF587)と、
ポリアミド(ポリアミド6 1020)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。上記延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
接着性樹脂(QF580)と、
芳香族ポリアミド(MXD6)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
接着性樹脂(QF580)と、
ブレンドポリアミド(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
接着性樹脂(NF587)と、
芳香族ポリアミド(MXD6)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
接着性樹脂(NF587)と、
ブレンドポリアミド(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
ブレンドポリエチレン(A)と、
接着性樹脂(NF587)と、
エチレン-ビニルアルコール共重合体(G156B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの延伸基材(2軸延伸フィルム)を作製した。実施例21Aでは、2軸延伸を良好に行うことができた。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)にかえて、脂肪族ポリアミド(ポリアミド6 1020)、芳香族ポリアミド(MXD6)またはブレンドポリアミド(A)を用いたこと以外は実施例21Aと同様にして、延伸基材およびバリア性基材を作製した。実施例22A~24Aでは、2軸延伸を良好に行うことができた。
[実施例1B]
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの延伸基材(2軸延伸フィルム)を作製した。実施例21Bでは、2軸延伸を良好に行うことができた。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)にかえて、脂肪族ポリアミド(ポリアミド6 1020)、芳香族ポリアミド(MXD6)またはブレンドポリアミド(A)を用いたこと以外は実施例21Bと同様にして、延伸基材およびバリア性基材を作製した。実施例22B~24Bでは、2軸延伸を良好に行うことができた。
[実施例1C]
ブレンドポリプロピレン(A)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(A)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリエチレン(B1)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
ブレンドポリエチレン(B1)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(B1)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの延伸基材(2軸延伸フィルム)を作製した。実施例11Cでは、2軸延伸を良好に行うことができた。延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。
[実施例1D]
ブレンドポリプロピレン(A)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。
延伸基材の第2の表面樹脂層の面上に、PVD法により、厚さ30nmのアルミニウム(AL)蒸着膜を形成した。このようにして、バリア性基材を得た。
延伸基材の第2の表面樹脂層の面上に、PVD法により、厚さ30nmのアルミナ蒸着膜を形成した。アルミナ蒸着膜の表面に、実施例1Aで調製した上記バリアコート剤をスピンコート法によりコーティングし、オーブンにて100℃で8秒間の加熱処理を施して、厚さ0.3μmのバリアコート層を形成した。このようにして、バリア性基材を得た。
延伸基材の第2の表面樹脂層の面上に、アルミナ蒸着膜にかえて、厚さ30nmのシリカ蒸着膜を形成し、さらに該シリカ蒸着膜上に上記バリアコート層を形成した。このようにして、バリア性基材を得た。
ブレンドポリエチレン(B1)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
ポリアミド(ポリアミド6 1020)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(QF580)と、
ホモポリプロピレン(FS3031)と、
ホモポリプロピレン(FS3031)と、
ブレンドポリプロピレン(B)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
芳香族ポリアミド(MXD6)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
ブレンドポリアミド(A)と、
接着性樹脂(NF587)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
LLDPE(INNATE TF80)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
ブレンドポリエチレン(B1)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(D)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの延伸基材(2軸延伸フィルム)を作製した。実施例21Dでは、2軸延伸を良好に行うことができた。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
各層のポリエチレン等の配合組成を表12に記載したとおりに変更したこと以外は実施例21Dと同様にして、延伸基材およびバリア性基材を作製した。実施例22Dでは、2軸延伸を良好に行うことができた。表12において、第1の表面樹脂層におけるAB剤の配合量は、2,000ppmである。
エチレン-ビニルアルコール共重合体(G156B)と、
接着性樹脂(NF587)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(A)と、
ブレンドポリエチレン(C)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの延伸基材(2軸延伸フィルム)を作製した。実施例31Dでは、2軸延伸を良好に行うことができた。延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
エチレン-ビニルアルコール共重合体(G156B)にかえて、脂肪族ポリアミド(ポリアミド6 1020)、芳香族ポリアミド(MXD6)またはブレンドポリアミド(A)を用いたこと以外は実施例31Dと同様にして、延伸基材およびバリア性基材を作製した。実施例32D~34Dでは、2軸延伸を良好に行うことができた。
ホモポリプロピレン(FS3031)をTダイキャスト法により単層押出製膜して、単層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。上記延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。上記延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
LLDPE(INNATE TF80)をTダイキャスト法により単層押出製膜して、単層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ18μmの延伸基材(2軸延伸フィルム)を作製した。上記延伸基材を用いて、実施例1Aと同様にして、3種のバリア性基材を作製した。上記延伸基材を用いて、実施例1Dと同様にして、3種のバリア性基材を作製した。
実施例および比較例で得られた各延伸基材および各バリア性基材(以下「試験片」ともいう)について、酸素透過度(cc/(m2・day・atm))および水蒸気透過度(g/(m2・day))を以下の方法により測定した。評価結果を各表に記載する。
酸素透過度測定装置(MOCON社製、OX-TRAN2/20)を用いて、JIS K7126-2:2006に準拠して、温度23℃、湿度90%RH環境下における試験片の酸素透過度を測定した。
A:酸素透過度が0.2未満である。
B:酸素透過度が0.2以上0.8未満である。
C:酸素透過度が0.8以上2.0未満である。
D:酸素透過度が2.0以上10未満である。
E:酸素透過度が10以上100未満である。
F:酸素透過度が100以上である。
A:酸素透過度が0.2未満である。
B:酸素透過度が0.2以上0.8未満である。
C:酸素透過度が0.8以上2.0未満である。
D:酸素透過度が2.0以上10未満である。
E:酸素透過度が10以上30未満である。
F:酸素透過度が30以上100未満である。
G:酸素透過度が100以上である。
A:酸素透過度が1.0未満である。
B:酸素透過度が1.0以上5.0未満である。
C:酸素透過度が5.0以上10未満である。
D:酸素透過度が10以上100未満である。
E:酸素透過度が100以上である。
A:酸素透過度が0.5未満である。
B:酸素透過度が0.5以上1.5未満である。
C:酸素透過度が1.5以上5.0未満である。
D:酸素透過度が5.0以上10未満である。
E:酸素透過度が10以上100未満である。
F:酸素透過度が100以上である。
水蒸気透過度測定装置(MOCON社製、PERMATRAN-w 3/33)を用いて、JIS K7129-2:2019に準拠して、温度40℃、湿度90%RH環境下における試験片の水蒸気透過度を測定した。
A:水蒸気透過度が0.2未満である。
B:水蒸気透過度が0.2以上1.5未満である。
C:水蒸気透過度が1.5以上10未満である。
D:水蒸気透過度が10以上100未満である。
E:水蒸気透過度が100以上である。
A:水蒸気透過度が0.2未満である。
B:水蒸気透過度が0.2以上0.8未満である。
C:水蒸気透過度が0.8以上1.5未満である。
D:水蒸気透過度が1.5以上3.0未満である。
E:水蒸気透過度が3.0以上5.0未満である。
F:水蒸気透過度が5.0以上10未満である。
G:水蒸気透過度が10以上100未満である。
A:水蒸気透過度が1.0未満である。
B:水蒸気透過度が1.0以上5.0未満である。
C:水蒸気透過度が5.0以上10未満である。
D:水蒸気透過度が10以上100未満である。
E:水蒸気透過度が100以上である。
A:水蒸気透過度が0.5未満である。
B:水蒸気透過度が0.5以上1.5未満である。
C:水蒸気透過度が1.5以上5.0未満である。
D:水蒸気透過度が5.0以上10未満である。
E:水蒸気透過度が10以上100未満である。
F:水蒸気透過度が100以上である。
実施例および比較例で得られた各バリア性基材の蒸着膜面またはバリアコート層面に対して、片面がコロナ処理された厚さ20μmの一般OPPフィルムを、塗布量3g/m2のウレタン系接着剤(ロックペイント社製、RU77T/H7)により貼り合わせ、幅15mmの試験片を作製した。JIS K6854-3:1999(接着剤-はく離接着強さ試験方法-第3部:T形はく離)に準拠して、引張試験機((株)オリエンテック製、テンシロン万能材料試験機)を用いて、試験速度:50mm/min、温度:23℃の条件でT形剥離試験を行い、各層に対する蒸着膜の剥離強度(N/15mm)を測定した。結果を各表に記載する。
上記で作製した延伸基材の表面にコロナ放電処理を行った。延伸基材のコロナ放電処理面に、油性グラビアインキ(DICグラフィックス(株)製、商品名:フィナート)を用いて、グラビア印刷法により、画像を形成した。耐熱性を以下の基準で評価した。
A:印刷の乾燥時に延伸基材の大きな収縮は発生しなかった。
B:印刷の乾燥時に延伸基材の大きな収縮が発生した。
上記で作製した延伸基材の表面にコロナ放電処理を行った。延伸基材のコロナ放電処理面に、油性グラビアインキ(DICグラフィックス(株)製、商品名:フィナート)を用いて、グラビア印刷法により、画像を形成して、印刷フィルムを得た。印刷フィルムを、エボリューSP2020(三井化学製)を単層膜として製膜して得られた厚さ40μmのLLDPEフィルムと、ウレタン系ドライラミネート接着剤で貼り合わせた。
上記貼り合せたラミネートフィルムのLLDPEフィルム面同士を向かい合わせて、片側を170℃に設定したアルミ製シールバーから挟み込むようにヒートシール(1kgf/cm2の圧力で1秒間)を行い、そのヒートシール部のラミネートフィルムの熱収縮状態を確認した。
耐熱性を以下の基準で評価した。
A:170℃ヒートシール時にフィルムの収縮は発生しなかった。
B:170℃ヒートシール時にフィルムの収縮はほとんど発生しなかった。
C:170℃ヒートシール時にフィルムの大きな収縮が発生した。
ポリオレフィン中間層において相溶化剤(RETAIN 3000)を約23質量%配合したこと以外は実施例1Aおよび3Aと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験よびT形剥離試験の結果は、対応する層構成の実施例(実施例1A,3A)と同程度であった。
ポリオレフィン中間層において相溶化剤(RETAIN 3000)を約11.5質量%配合したこと以外は実施例2Aおよび4Aと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験よびT形剥離試験の結果は、対応する層構成の実施例(実施例2A,4A)と同程度であった。
ポリオレフィン中間層において相溶化剤(RETAIN 3000)を約11.5質量%配合したこと以外は実施例11A~14Aと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験およびT形剥離試験の結果は、対応する層構成の実施例(実施例11A~14A)の結果と同程度であった。
ポリエチレン中間層において相溶化剤(RETAIN 3000)を約23質量%配合したこと以外は実施例21Aと同様にして、延伸基材およびバリア性基材を作製した。この実施例における各評価の結果は、実施例21Aの結果と同程度であった。
ポリエチレン中間層において相溶化剤(RETAIN 3000)を約11.5質量%配合したこと以外は実施例22A~24Aと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例における各評価の結果は、対応する層構成の実施例(実施例22A~24A)の結果と同程度であった。
第2のポリオレフィン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例2Bおよび4Bと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験よびT形剥離試験の結果は、対応する層構成の実施例(実施例2B,4B)と同程度であった。
第2のポリオレフィン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例11B~14Bと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験およびT形剥離試験の結果は、対応する層構成の実施例(実施例11B~14B)の結果と同程度であった。
第2のポリエチレン層において相溶化剤(RETAIN 3000)を約12質量%配合したこと以外は実施例21Bと同様にして、延伸基材およびバリア性基材を作製した。この実施例における各評価の結果は、実施例21Bの結果と同程度であった。
第2のポリエチレン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例22B~24Bと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例における各評価の結果は、対応する層構成の実施例(実施例22B~24B)の結果と同程度であった。
第2のポリオレフィン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例4Dおよび6Dと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験よびT形剥離試験の結果は、対応する層構成の実施例(実施例4D,6D)と同程度であった。
第2のポリオレフィン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例11D~14Dと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例におけるガスバリア性試験およびT形剥離試験の結果は、対応する層構成の実施例(実施例11D~14D)の結果と同程度であった。
第2のポリエチレン層において相溶化剤(RETAIN 3000)を約12質量%配合したこと以外は実施例31Dと同様にして、延伸基材およびバリア性基材を作製した。この実施例における各評価の結果は、実施例31Dの結果と同程度であった。
第2のポリエチレン層において相溶化剤(RETAIN 3000)を約4質量%配合したこと以外は実施例32D~34Dと同様にして、延伸基材およびバリア性基材を作製した。これらの実施例における各評価の結果は、対応する層構成の実施例(実施例32D~34D)の結果と同程度であった。
第1の接着性樹脂層の厚さを2μmに、ポリオレフィン中間層の厚さを19μmに、第2の接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例1A~4Aと同様にして、実施例1AA~4AAの延伸基材およびバリア性基材を作製した。実施例1AA~4AAにおける各評価の結果は、対応する実施例番号の実施例(実施例1A~4A)の結果と同程度であった。
第1の接着性樹脂層の厚さを2μmに、ポリオレフィン中間層の厚さを19μmに、第2の接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例11A~14Aと同様にして、実施例11AA~14AAの延伸基材およびバリア性基材を作製した。実施例11AA~14AAにおける各評価の結果は、対応する実施例番号の実施例(実施例11A~14A)の結果と同程度であった。
第1の接着性樹脂層の厚さを1.5μmに、ポリエチレン中間層の厚さを13μmに、第2の接着性樹脂層の厚さを1.5μmにそれぞれ変更し、延伸基材の厚さを18μmに変更したこと以外は実施例21A~24Aと同様にして、実施例21AA~24AAの延伸基材およびバリア性基材を作製した。実施例21AA~24AAでは、2軸延伸を良好に行うことができた。実施例21AA~24AAにおける各評価の結果は、対応する実施例番号の実施例(実施例21A~24A)の結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例1B~4Bと同様にして、実施例1BB~4BBの延伸基材およびバリア性基材を作製した。実施例1BB~4BBにおける各評価の結果は、対応する実施例番号の実施例(実施例1B~4B)の結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例11B~14Bと同様にして、実施例11BB~14BBの延伸基材およびバリア性基材を作製した。実施例11BB~14BBにおける各評価の結果は、対応する実施例番号の実施例(実施例11B~14B)の結果と同程度であった。
第1のポリエチレン層の厚さを1.5μmに、第2のポリエチレン層の厚さを13μmに、接着性樹脂層の厚さを1.5μmにそれぞれ変更し、延伸基材の厚さを18μmに変更したこと以外は実施例21B~24Bと同様にして、実施例21BB~24BBの延伸基材およびバリア性基材を作製した。実施例21BB~24BBでは、2軸延伸を良好に行うことができた。実施例21BB~24BBにおける各評価の結果は、対応する実施例番号の実施例(実施例21B~24B)の結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、第3のポリオレフィン層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例1C~2Cと同様にして、実施例1CC~2CCの延伸基材およびバリア性基材を作製した。実施例1CC~2CCにおける各評価の結果は、対応する実施例番号の実施例(実施例1C~2C)の結果と同程度であった。
第1のポリエチレン層の厚さを1.5μmに、第2のポリエチレン層の厚さを13μmに、第3のポリエチレン層の厚さを1.5μmにそれぞれ変更し、延伸基材の厚さを18μmに変更したこと以外は実施例11Cと同様にして、実施例11CCの延伸基材およびバリア性基材を作製した。実施例11CCでは、2軸延伸を良好に行うことができた。実施例11CCにおける各評価の結果は、実施例11Cの結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、第3のポリオレフィン層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例1D~2Dと同様にして、実施例1DD~2DDの延伸基材およびバリア性基材を作製した。実施例1DD~2DDにおける各評価の結果は、対応する実施例番号の実施例(実施例1D~2D)の結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例3D~6Dと同様にして、実施例3DD~6DDの延伸基材およびバリア性基材を作製した。実施例3DD~6DDにおける各評価の結果は、対応する実施例番号の実施例(実施例3D~6D)の結果と同程度であった。
第1のポリオレフィン層の厚さを2μmに、第2のポリオレフィン層の厚さを19μmに、接着性樹脂層の厚さを2μmにそれぞれ変更し、延伸基材の厚さを25μmに変更したこと以外は実施例11D~14Dと同様にして、実施例11DD~14DDの延伸基材およびバリア性基材を作製した。実施例11DD~14DDにおける各評価の結果は、対応する実施例番号の実施例(実施例11D~14D)の結果と同程度であった。
第1のポリエチレン層の厚さを1.5μmに、第2のポリエチレン層の厚さを13μmに、第3のポリエチレン層の厚さを1.5μmにそれぞれ変更し、延伸基材の厚さを18μmに変更したこと以外は実施例21D~22Dと同様にして、実施例21DD~22DDの延伸基材およびバリア性基材を作製した。実施例21DD~22DDでは、2軸延伸を良好に行うことができた。実施例21DD~22DDにおける各評価の結果は、対応する実施例番号の実施例(実施例21D~22D)の結果と同程度であった。
第1のポリエチレン層の厚さを1.5μmに、第2のポリエチレン層の厚さを13μmに、接着性樹脂層の厚さを1.5μmにそれぞれ変更し、延伸基材の厚さを18μmに変更したこと以外は実施例31D~34Dと同様にして、実施例31DD~34DDの延伸基材およびバリア性基材を作製した。実施例31DD~34DDでは、2軸延伸を良好に行うことができた。実施例31DD~34DDにおける各評価の結果は、対応する実施例番号の実施例(実施例31D~34D)の結果と同程度であった。
延伸基材の厚さを25μmに変更したこと以外は比較例1~2と同様にして、比較例1A~2Aの延伸基材およびバリア性基材を作製した。比較例1A~2Aにおける各評価の結果は、対応する比較例番号の比較例(比較例1~2)の結果と同程度であった。
以下、実施例により本開示の第5および第6の態様の延伸基材(2軸延伸ポリエチレンフィルム)をより具体的に説明するが、本開示の2軸延伸ポリエチレンフィルムは以下の実施例に限定されない。以下の記載において「質量部」は単に「部」と記載する。
2軸延伸ポリエチレンフィルムの作製において、以下の材料を用いた。
・高密度ポリエチレン(HDPE)
メタロセンHDPE、エチレン-1-オクテン共重合体、密度:0.955g/cm3、融点:130℃、MFR:1.5g/10分
・直鎖状低密度ポリエチレン(LLDPE)
ダウケミカル製、INNATE TF80、
メタロセンLLDPE、エチレン-1-オクテン共重合体、
密度:0.926g/cm3、MFR:1.7g/10分
・アンチブロッキング剤(AB剤)
シリカ粒子、平均粒子径:3.5μm
20部のHDPEと80部のLLDPEと0.2部(2,000ppm)のAB剤とを混合して、ブレンドポリエチレン(Ae)を調製した。20部のHDPEと80部のLLDPEとを混合して、ブレンドポリエチレン(Be)を調製した。
ブレンドポリエチレン(Be)と、
ブレンドポリエチレン(Be)と、
ブレンドポリエチレン(Be)と、
ブレンドポリエチレン(Ae)と、
をTダイキャスト法により5層共押出製膜して、5層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの2軸延伸ポリエチレンフィルムを作製した。実施例1Eでは、2軸延伸を良好に行うことができた。
各層のポリエチレンの配合組成を表14に記載したとおりに変更したこと以外は実施例1Eと同様にして、厚さ25μmの2軸延伸ポリエチレンフィルムを作製した。実施例2E~4Eでは、2軸延伸を良好に行うことができた。表14において、表面樹脂層におけるAB剤の配合量は、いずれも2,000ppmである。
40部のHDPEと60部のLLDPEとの混合物をTダイキャスト法により単層押出製膜して、単層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの2軸延伸ポリエチレンフィルムを作製した。実施例5Eでは、2軸延伸を良好に行うことができた。
LLDPEをTダイキャスト法により単層押出製膜して、単層フィルムを得た。該フィルムに対して、機械方向(MD方向)に5倍延伸、続いて幅方向(TD方向)に8.5倍延伸の逐次2軸延伸処理を行い、厚さ25μmの2軸延伸ポリエチレンフィルムを作製した。
上記で作製した2軸延伸ポリエチレンフィルムの表面にコロナ放電処理を行った。フィルムのコロナ放電処理面に、油性グラビアインキ(DICグラフィックス(株)製、商品名:フィナート)を用いて、グラビア印刷法により、画像を形成した。耐熱性を以下の基準で評価した。
A:印刷の乾燥時にフィルムの大きな収縮は発生しなかった。
B:印刷の乾燥時にフィルムの大きな収縮が発生した。
[耐熱性評価2:170℃ヒートシール耐性評価]
上記で作製した2軸延伸ポリエチレンフィルムの表面にコロナ放電処理を行った。フィルムのコロナ放電処理面に、油性グラビアインキ(DICグラフィックス(株)製、商品名:フィナート)を用いて、グラビア印刷法により、画像を形成して、印刷フィルムを得た。印刷フィルムを、エボリューSP2020(三井化学製)を単層膜として製膜して得られた厚さ40μmのLLDPEフィルムと、ウレタン系ドライラミネート接着剤で貼り合わせた。
上記貼り合せたラミネートフィルムのLLDPEフィルム面同士を向かい合わせて、片側を170℃に設定したアルミ製シールバーから挟み込むようにヒートシール(1kgf/cm2の圧力で1秒間)を行い、そのヒートシール部のラミネートフィルムの熱収縮状態を確認した。
耐熱性を以下の基準で評価した。
A:170℃ヒートシール時にフィルムの収縮は発生しなかった。
B:170℃ヒートシール時にフィルムの収縮はほとんど発生しなかった。
C:170℃ヒートシール時にフィルムの大きな収縮が発生した。
第1のポリエチレン層の厚さを1.5μmに、第2のポリエチレン層の厚さを13μmに、第3のポリエチレン層の厚さを1.5μmにそれぞれ変更し、2軸延伸ポリエチレンフィルムの厚さを18μmに変更したこと以外は実施例1E~4Eと同様にして、実施例1EE~4EEの2軸延伸ポリエチレンフィルムを作製した。実施例1EE~4EEでは、2軸延伸を良好に行うことができた。実施例1EE~4EEにおける各評価の結果は、対応する実施例番号の実施例(実施例1E~4E)の結果と同等であった。
2軸延伸ポリエチレンフィルムの厚さを18μmに変更したこと以外は実施例5Eと同様にして、実施例5EEの2軸延伸ポリエチレンフィルムを作製した。実施例5EEにおける各評価の結果は、実施例5Eの結果と同程度であった。
2軸延伸ポリエチレンフィルムの厚さを18μmに変更したこと以外は比較例1Eと同様にして、比較例1EEの2軸延伸ポリエチレンフィルムを作製した。比較例1EEにおける各評価の結果は、比較例1Eの結果と同等であった。
1A 2軸延伸ポリエチレンフィルム
2 積層体
10 ポリオレフィン中間層
11 第1のポリオレフィン層
12 第2のポリオレフィン層
13 第3のポリオレフィン層
20 第1の表面樹脂層
22 第2の表面樹脂層
30 接着性樹脂層、第1の接着性樹脂層
32 第2の接着性樹脂層
40 蒸着膜、第1の蒸着膜
42 第2の蒸着膜
60 接着層、第1の接着層
62 第2の接着層
70 ポリオレフィン延伸基材
80 ヒートシール層、第1のヒートシール層
82 第2のヒートシール層
120 チューブ容器
121 チューブ容器本体
122 頭部
123 胴部
124 肩部
125 抽出口部
126 キャップ
127 螺条
128 融着部
129 底シール部
Claims (32)
- ガスバリア性樹脂を主成分として含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える、延伸基材。 - 前記延伸基材が、前記ポリオレフィン中間層として、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層を備え、
前記ポリエチレン中間層の少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する、
請求項1に記載の延伸基材。 - ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する第2の表面樹脂層と、
をこの順に少なくとも備える、延伸基材。 - 前記第1の表面樹脂層における前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、請求項3に記載の延伸基材。
- 前記第1の表面樹脂層が、ポリエチレンと接着性樹脂とを含有し、
前記延伸基材が、前記ポリオレフィン中間層として、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層を備え、
前記第1の表面樹脂層および前記ポリエチレン中間層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する、
請求項3または4に記載の延伸基材。 - ポリオレフィンと接着性樹脂とを含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ポリオレフィンと接着性樹脂とを含有する第2の表面樹脂層と、
をこの順に少なくとも備える、延伸基材。 - 前記第1の表面樹脂層および前記第2の表面樹脂層において、それぞれ独立して、前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、請求項6に記載の延伸基材。
- 前記第1の表面樹脂層が、ポリエチレンと接着性樹脂とを含有し、
前記第2の表面樹脂層が、ポリエチレンと接着性樹脂とを含有し、
前記延伸基材が、前記ポリオレフィン中間層として、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層を備え、
前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する、
請求項6または7に記載の延伸基材。 - ポリオレフィンを主成分として含有する第1の表面樹脂層と、
ポリオレフィンを主成分として含有するポリオレフィン中間層と、
ガスバリア性樹脂を主成分として含有する、または、ポリオレフィンと接着性樹脂とを含有する、第2の表面樹脂層と、
をこの順に少なくとも備える、延伸基材。 - 前記第2の表面樹脂層において、前記ポリオレフィンの含有割合が60質量%以上95質量%以下であり、前記接着性樹脂の含有割合が5質量%以上40質量%以下である、請求項9に記載の延伸基材。
- 前記第2の表面樹脂層が、ポリエチレンと接着性樹脂とを含有し、
前記延伸基材が、前記ポリオレフィン中間層として、ポリエチレンを主成分として含有する、1層または2層以上のポリエチレン中間層を備え、
前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層から選択される少なくとも1層における前記ポリエチレンが、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含むか、または、0.930g/cm3超0.960g/cm3以下の密度を有する、
請求項9または10に記載の延伸基材。 - 前記ガスバリア性樹脂が、それぞれ独立して、エチレン-ビニルアルコール共重合体およびポリアミドから選択される少なくとも1種を含む、請求項1~5および9のいずれか一項に記載の延伸基材。
- 前記ガスバリア性樹脂が、芳香族ポリアミドを含む、請求項12に記載の延伸基材。
- 前記ポリオレフィンがポリプロピレンを含み、前記接着性樹脂が酸変性ポリプロピレンを含むか、または、
前記ポリオレフィンがポリエチレンを含み、前記接着性樹脂が酸変性ポリエチレンを含む、
請求項3~11のいずれか一項に記載の延伸基材。 - 前記延伸基材におけるポリオレフィンの含有割合が、60質量%以上である、請求項1~14のいずれか一項に記載の延伸基材。
- 高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンを含有するポリエチレン層を備える2軸延伸ポリエチレンフィルムであるか、または、
ポリエチレンを主成分として含有するポリエチレン層を備え、前記ポリエチレン層に含まれる前記ポリエチレンは、0.930g/cm3超0.960g/cm3以下の密度を有する2軸延伸ポリエチレンフィルムである、
延伸基材。 - 前記ポリエチレン層が、高密度ポリエチレンおよび中密度ポリエチレンから選択される少なくとも1種のポリエチレンと、直鎖状低密度ポリエチレンとを含有する、請求項16に記載の延伸基材。
- 前記ポリエチレン層における高密度ポリエチレンおよび中密度ポリエチレンの含有割合の合計が、20質量%以上60質量%以下であり、直鎖状低密度ポリエチレンの含有割合が、40質量%以上80質量%以下である、請求項17に記載の延伸基材。
- 前記2軸延伸ポリエチレンフィルムが、
第1の表面樹脂層と、
ポリエチレン中間層と、
第2の表面樹脂層と、
を備え、
前記第1の表面樹脂層、前記ポリエチレン中間層および前記第2の表面樹脂層が、それぞれ独立して、前記ポリエチレン層である、
請求項16~18のいずれか一項に記載の延伸基材。 - 前記延伸基材が、共押出樹脂フィルムの延伸フィルムである、請求項1~19のいずれか一項に記載の延伸基材。
- 前記延伸基材が、2軸延伸基材である、請求項1~20のいずれか一項に記載の延伸基材。
- 請求項1~21のいずれか一項に記載の延伸基材と、
前記延伸基材における少なくとも一方の面上に設けられている印刷層と、
を少なくとも備える、印刷基材。 - 請求項1~8のいずれか一項に記載の延伸基材と、前記延伸基材における前記第1の表面樹脂層および前記第2の表面樹脂層から選択される少なくとも1層の表面に設けられている蒸着膜と、を少なくとも備えるか、
請求項9~11のいずれか一項に記載の延伸基材と、前記延伸基材における前記第2の表面樹脂層の表面に設けられている蒸着膜と、を少なくとも備えるか、または、
請求項16~19のいずれか一項に記載の延伸基材と、前記延伸基材における少なくとも一方の面上に設けられている蒸着膜と、を少なくとも備える、
バリア性基材。 - 第1の蒸着膜と、
請求項1~15および19のいずれか一項に記載の延伸基材と、
第2の蒸着膜と、
をこの順に少なくとも備え、
前記第1の蒸着膜は、前記第1の表面樹脂層の表面に設けられており、前記第2の蒸着膜は、前記第2の表面樹脂層の表面に設けられている、
バリア性基材。 - 前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、金属蒸着膜であるか、前記第1の蒸着膜が無機酸化物蒸着膜であり、前記第2の蒸着膜が金属蒸着膜であるか、前記第1の蒸着膜が金属蒸着膜であり、前記第2の蒸着膜が無機酸化物蒸着膜であるか、または、前記第1の蒸着膜および前記第2の蒸着膜が、それぞれ独立して、無機酸化物蒸着膜である、請求項24に記載のバリア性基材。
- 請求項1~21のいずれか一項に記載の延伸基材、請求項22に記載の印刷基材、または請求項23~25のいずれか一項に記載のバリア性基材と、
ヒートシール層と、
を少なくとも備える、積層体。 - 前記ヒートシール層が、ポリオレフィンを主成分として含有し、前記積層体全体におけるポリオレフィンの含有割合が、80質量%以上である、請求項26に記載の積層体。
- 第1のヒートシール層と、
前記延伸基材、前記印刷基材または前記バリア性基材と、
第2のヒートシール層と、
をこの順に少なくとも備える、
請求項26または27に記載の積層体。 - 請求項26~28のいずれか一項に記載の積層体を備える包装容器。
- 包装袋である、請求項29に記載の包装容器。
- 頭部と胴部とを備えるチューブ容器本体であって、
前記頭部は、前記胴部の一端に連接している肩部と、前記肩部に連接している抽出口部とを備え、前記胴部は、請求項28に記載の積層体により構成されている、
チューブ容器本体。 - 請求項31に記載のチューブ容器本体と、
キャップと、
を備えるチューブ容器。
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|---|---|---|---|
| JP2023-094339 | 2023-06-07 | ||
| JP2023-094316 | 2023-06-07 | ||
| JP2023-094321 | 2023-06-07 | ||
| JP2023094339 | 2023-06-07 | ||
| JP2023094316 | 2023-06-07 | ||
| JP2023094328 | 2023-06-07 | ||
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| JP2023094321 | 2023-06-07 | ||
| JP2023125853A JP2025021847A (ja) | 2023-08-01 | 2023-08-01 | 2軸延伸ポリエチレンフィルム |
| JP2023-125853 | 2023-08-01 | ||
| JP2023125858A JP2025021850A (ja) | 2023-08-01 | 2023-08-01 | 延伸基材、バリア性基材、積層体および包装容器 |
| JP2023125863A JP2025021853A (ja) | 2023-08-01 | 2023-08-01 | 延伸基材、バリア性基材、積層体および包装容器 |
| JP2023-125863 | 2023-08-01 | ||
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| JP2023141812A JP2024177011A (ja) | 2023-06-07 | 2023-08-31 | 延伸基材、バリア性基材、積層体および包装容器 |
| JP2023-141803 | 2023-08-31 | ||
| JP2023-141778 | 2023-08-31 | ||
| JP2023-141788 | 2023-08-31 | ||
| JP2023141803A JP2024177010A (ja) | 2023-06-07 | 2023-08-31 | 延伸基材、バリア性基材、積層体および包装容器 |
| JP2023141788A JP2024177009A (ja) | 2023-06-07 | 2023-08-31 | 延伸基材、バリア性基材、積層体および包装容器 |
| JP2023141778A JP2024177008A (ja) | 2023-06-07 | 2023-08-31 | 延伸基材、バリア性基材、積層体および包装容器 |
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