WO2018221495A1 - Film coextrudé de polyéthylène, film stratifié de polyéthylène et matériau d'emballage utilisant ledit film coextrudé - Google Patents

Film coextrudé de polyéthylène, film stratifié de polyéthylène et matériau d'emballage utilisant ledit film coextrudé Download PDF

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WO2018221495A1
WO2018221495A1 PCT/JP2018/020495 JP2018020495W WO2018221495A1 WO 2018221495 A1 WO2018221495 A1 WO 2018221495A1 JP 2018020495 W JP2018020495 W JP 2018020495W WO 2018221495 A1 WO2018221495 A1 WO 2018221495A1
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Prior art keywords
polyethylene
film
polyethylene film
electron beam
heat
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PCT/JP2018/020495
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English (en)
Japanese (ja)
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山田　憲一
高橋　秀明
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大日本印刷株式会社
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Priority claimed from JP2017106603A external-priority patent/JP6969161B2/ja
Priority claimed from JP2017106601A external-priority patent/JP6969160B2/ja
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2018221495A1 publication Critical patent/WO2018221495A1/fr

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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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

Definitions

  • the present invention relates to a polyethylene co-pressed film, and more specifically, a polyethylene co-pressed film comprising a polyethylene film substrate which is an electron beam irradiation layer and a polyethylene film layer having heat sealability, and a packaging material using the same.
  • the present invention also relates to a polyethylene laminated film, and more particularly, to a polyethylene laminated film comprising a polyethylene film substrate that is an electron beam irradiation layer and a heat-sealable polyethylene film, and a packaging material using the same.
  • a film made of polyethylene (hereinafter simply referred to as “polyethylene film”) has moderate flexibility, is excellent in transparency, moisture resistance, chemical resistance, etc., and is inexpensive. in use.
  • polyethylene has a melting point of about 100 to 140 ° C. depending on the type, but is generally used as a sealant film in the packaging material field.
  • polyethylene is inferior in heat resistance and inadequate in strength, so when used as a packaging material, the heat resistance and strength of polyester film, nylon film, etc. It is used as a laminate that laminates an excellent resin film and polyethylene film, and the packaging material can be produced by heat sealing the end of the laminate with the polyethylene film side inside the packaging material.
  • the packaging material can be produced by heat sealing the end of the laminate with the polyethylene film side inside the packaging material.
  • Japanese Patent Application No. 2015-213095 the present inventors have proposed a laminate comprising a polyethylene film irradiated with an electron beam and a polyethylene film having heat sealing properties.
  • a polyethylene film irradiated with an electron beam By irradiating the polyethylene film with an electron beam, its heat resistance and strength can be improved, so that a packaging material can be produced only from polyethylene.
  • the laminate produced as described above is affected by the influence of the electron beam that has passed through the polyethylene film irradiated with the electron beam, even though the polyethylene film having heat sealability is not directly irradiated with the electron beam. Because it is received somewhat, active radicals (for example, hydroper radicals) are likely to be generated by the action of light and heat during storage, and as a result, heat sealability can be reduced. There was room for improvement. Furthermore, the present inventors have now found that the laminate produced by irradiation with an electron beam tends to decrease its breaking strength over time.
  • the inventors of the present invention surprisingly prevent the heat sealability and the breaking strength from decreasing with time by surprisingly adding a hindered amine-based antioxidant to the polyethylene film irradiated with the electron beam. I found that I can do it.
  • an object of the present invention is to provide a polyethylene co-pressed film capable of producing a packaging material using only the polyethylene film, and capable of preventing a heat sealability and a decrease in breaking strength over time. It is. Another object of the present invention is to provide a polyethylene laminated film capable of producing a packaging material only with a polyethylene film, and capable of preventing a decrease in breaking strength over time. Furthermore, another object of the present invention is to provide a packaging material using a polyethylene co-pressed film or a polyethylene laminated film.
  • the polyethylene co-pressed film of the present invention comprises a polyethylene film substrate and a polyethylene film layer
  • the polyethylene film substrate is an electron beam irradiation layer containing polyethylene and a hindered amine antioxidant
  • the polyethylene film layer contains polyethylene, and the outer surface has heat sealability.
  • the content of hindered amine antioxidant in the polyethylene film substrate is preferably 1% by mass or more and 30% by mass or less.
  • the polyethylene film substrate preferably contains low-density polyethylene and / or linear low-density polyethylene as polyethylene.
  • the polyethylene film layer preferably contains medium density polyethylene.
  • the packaging material of the present invention is made of the above polyethylene co-pressed film, and the polyethylene film layer is located inside the packaging material.
  • the polyethylene laminated film of the present invention comprises a polyethylene film substrate and a heat-sealable polyethylene film,
  • the polyethylene film base material is an electron beam irradiation layer containing polyethylene and a hindered amine-based antioxidant.
  • the content of hindered amine antioxidant in the polyethylene film substrate is preferably 1% by mass or more and 30% by mass or less.
  • the polyethylene film substrate preferably contains low-density polyethylene and / or linear low-density polyethylene as polyethylene.
  • the heat-sealable polyethylene film preferably contains medium density polyethylene.
  • the packaging material of the present invention is a packaging material comprising the above-mentioned polyethylene laminated film, A heat-sealable polyethylene film is located inside the packaging material.
  • a polyethylene co-pressed film capable of producing a packaging material only from polyethylene and a polyethylene co-pressed film capable of preventing deterioration of heat sealability and rupture strength over time, and thereby The produced packaging material can be provided.
  • a polyethylene laminated film capable of producing a packaging material only from polyethylene and a polyethylene laminated film capable of preventing a decrease in breaking strength over time, and a packaging produced thereby. Material can be provided.
  • 1 is a schematic cross-sectional view of a polyethylene co-pressed film according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view of a polyethylene co-pressed film according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view of a polyethylene co-pressed film according to an embodiment of the present invention. It is a section schematic diagram of the polyethylene lamination film by one embodiment of the present invention. It is a section schematic diagram of the polyethylene lamination film by one embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view of a polyethylene co-pressed film 10 of the present invention in one embodiment.
  • the polyethylene co-pressed film 10 includes a polyethylene film substrate 1 that is an electron beam irradiation layer and a polyethylene film layer 2.
  • the polyethylene co-pressed film 10 includes a form-stable layer 3 between the polyethylene film substrate 1 and the polyethylene film layer 2.
  • the hatching part in a figure represents the part which the electron beam irradiation and the crosslinking density improved.
  • the thickness of the polyethylene co-pressed film is preferably 10 ⁇ m or more and 300 ⁇ m or less, more preferably 30 ⁇ m or more and 200 ⁇ m or less, and further preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the polyethylene film substrate included in the polyethylene co-pressed film according to the present invention is a layer containing polyethylene and a hindered amine antioxidant, and is a layer irradiated with an electron beam (hereinafter simply referred to as “electron beam irradiation layer”). It is.
  • the polyethylene co-pressed film includes such a polyethylene film substrate, the heat resistance and strength of the polyethylene co-pressed film surface can be improved, and physical properties required as an outer layer of a packaging material or the like can be satisfied. .
  • the electron beam irradiation layer is not limited to one having a cross-linked density on one side (surface corresponding to the outer layer of the packaging material) improved by electron beam irradiation (see FIG. 1), but also a polyethylene film base. Includes those with improved crosslink density on both sides of the material (see FIG. 3).
  • crosslink density of polyethylene changes depending on the presence or absence of electron beam irradiation is not clear, but is considered as follows. That is, when a polyethylene film is irradiated with an electron beam, a carbon-hydrogen bond in polyethylene near the film surface is cut, and radicals are generated at the cut bond ends. The generated radicals are considered to come into contact with other polyethylene molecular chains due to the molecular motion of the molecular chains, pull out hydrogen atoms and bond with carbon atoms in the polyethylene molecular chains, resulting in the formation of a crosslinked structure. .
  • Polyethylene films usually tend to shrink when heated, but dimensional stability tends to improve as the crosslink density increases. For this reason, polyethylene films with different crosslink densities on the front and back surfaces curl like a bimetal when heated. Therefore, as a simple method for confirming that the crosslinking density is different between the front and back surfaces of the polyethylene film, it can be confirmed by heating the polyethylene film irradiated with the electron beam only on one side.
  • the polyethylene film substrate is immersed in an organic solvent such as methyl ethyl ketone, the insoluble film remaining without being dissolved is dried, the mass is measured, and before dissolution
  • the gel fraction of the polyethylene film substrate is preferably 10% or more and 80% or less, more preferably 20% or more and 80% or less, and further preferably 30% or more and 80% or less.
  • polyethylene contained in the polyethylene film substrate examples include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
  • the polyethylene film substrate may contain two or more of these polyethylenes.
  • low-density polyethylene and linear low-density polyethylene are preferable because a crosslinking reaction occurs favorably and heat resistance, strength, and the like can be significantly improved.
  • density of 0.87 g / cm 3 or more, 0.91 g / cm 3 or less of polyethylene of low density polyethylene, density of 0.91 g / cm 3 greater, 0.96 g / cm 3 or less of polyethylene are referred to as medium density polyethylene and polyethylene having a density greater than 0.96 g / cm 3 is referred to as high density polyethylene.
  • the polyethylene having different density and branching as described above can be obtained by appropriately selecting the polymerization method.
  • a polymerization catalyst using a multi-site catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high-pressure ion polymerization, It is preferable to carry out by one stage or two or more stages.
  • the above single-site catalyst is a catalyst that can form a uniform active species, and is usually adjusted by bringing a metallocene transition metal compound or a nonmetallocene transition metal compound into contact with an activation cocatalyst. .
  • the single site catalyst is preferable because the active site structure is uniform as compared with the multisite catalyst, and a polymer having a high molecular weight and a high degree of uniformity can be polymerized.
  • the metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and if necessary, an organometallic compound, and each catalyst component of the support. is there.
  • the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like.
  • substituted cyclopentadienyl groups include hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl substituted alkyl groups, silyl substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups. It has at least one kind of substituent selected from a group and the like.
  • the substituted cyclopentadienyl group may have two or more substituents, and the substituents are bonded to each other to form a ring, and an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof, etc. It may be formed. Rings formed by bonding substituents to each other may further have substituents.
  • transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton examples include zirconium, titanium, hafnium and the like, and zirconium and hafnium are particularly preferable.
  • the transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a bridging group.
  • crosslinking group examples include C1-C4 alkylene groups, silylene groups, dialkylsilylene groups, substituted arylene groups such as diarylsilylene groups, and substituted germylene groups such as dialkylgermylene groups and diarylgermylene groups.
  • it is a substituted silylene group.
  • the transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can use one or a mixture of two or more as a catalyst component.
  • the co-catalyst means a catalyst that can effectively make the transition metal compound of Group IV of the above periodic table as a polymerization catalyst, or can neutralize ionic charges in a catalytically activated state.
  • Co-catalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, active hydrogen group-containing or non-containing cations and non-coordinating anions.
  • Ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, phenoxy compounds containing a fluoro group, and the like.
  • the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound carrier.
  • the support is preferably a porous oxide of an inorganic or organic compound.
  • an ion-exchange layered silicate such as montmorillonite, SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and the like, or a mixture thereof.
  • examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organic aluminum is preferably used.
  • polyethylene includes copolymers of ethylene and other monomers in addition to HDPE, MDPE, LDPE, and LLDPE.
  • examples of the ethylene copolymer include a copolymer composed of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 4-methyl-1-pentene, 6-methyl- 1-heptene and the like can be mentioned.
  • a copolymer with vinyl acetate, an acrylic ester, etc. may be sufficient.
  • polyethylene derived from biomass-derived ethylene may be used instead of ethylene obtained from fossil fuel. Since such biomass-derived polyethylene is a carbon-neutral material, it can be made into a packaging material with even less environmental impact.
  • Such polyethylene derived from biomass can be produced, for example, by a method described in JP2013-177531A. Moreover, you may use the biomass-derived polyethylene resin (for example, green PE etc. which are marketed from the Braschem company) marketed.
  • the polyethylene film base material contains a hindered amine-based antioxidant, which can prevent deterioration in heat sealability and breaking strength of the polyethylene co-pressed film irradiated with the electron beam over time.
  • hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl).
  • the content of the hindered amine antioxidant in the polyethylene film substrate is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass. % Or more and 10% by mass or less is more preferable.
  • a phenolic antioxidant an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a hydroxylamine antioxidant, and the like may be included as long as the effects of the invention are not impaired.
  • Polyethylene film substrate is film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength,
  • plastic compounding agents and additives can be included for the purpose of improving and modifying others. Moreover, the addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. Examples of common additives include fillers, cross-linking agents, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.
  • the thickness of the polyethylene film substrate is arbitrary depending on the application, but is usually about 5 ⁇ m to 200 ⁇ m, preferably about 5 ⁇ m to 100 ⁇ m.
  • the thickness can be appropriately adjusted according to the screw rotation speed of the melt extruder, the rotation speed of the cooling roll, and the like.
  • the polyethylene film layer provided in the laminate according to the present invention is made of a polyethylene film, and the outer surface (the surface opposite to the side on which the polyethylene film substrate is provided) has at least heat sealability.
  • the polyethylene co-pressed film has different physical properties (for example, strength, etc.) between the polyethylene film substrate and the layer provided on the polyethylene film substrate while using the same material (polyethylene). It can be set as the laminated body from which heat resistance, heat seal property, etc. differ.
  • the polyethylene film layer only needs to have at least a heat seal property on the outer surface (the surface opposite to the side on which the polyethylene film substrate is provided). As a result, the crosslink density of the polyethylene film layer on the substrate side may be improved (see FIG. 3). By setting it as such a structure, the heat resistance and intensity
  • the polyethylene film layer includes, as polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene copolymer, biomass-derived polyethylene, and the like. Among these, from the viewpoint of heat sealability, low density polyethylene, medium density polyethylene, and linear low density polyethylene are preferable. Further, from the viewpoint of preventing the heat sealability from being lowered due to electron beam irradiation, medium density polyethylene is preferable.
  • the polyethylene film layer may contain two or more kinds of the above-described polyethylene.
  • the polyethylene film layer may contain the above-mentioned antioxidant, and preferably contains a hindered amine-based antioxidant.
  • the thickness of the polyethylene film layer is arbitrary depending on the application, but is usually about 5 ⁇ m or more and 200 ⁇ m, preferably about 10 ⁇ m or more and about 200 ⁇ m or less, more preferably about 15 ⁇ m or more and about 160 ⁇ m or less.
  • the polyethylene co-pressed film of the present invention may include a form-stable layer containing medium density polyethylene and / or high density polyethylene between the polyethylene film substrate and the polyethylene film layer.
  • a form-stable layer containing medium density polyethylene and / or high density polyethylene between the polyethylene film substrate and the polyethylene film layer.
  • the form-stable layer may contain the above-described antioxidant, and preferably contains a hindered amine antioxidant.
  • the thickness of the form-stable layer is arbitrary depending on the application, but is usually about 5 ⁇ m to 100 ⁇ m, preferably about 10 ⁇ m to 80 ⁇ m, more preferably about 10 ⁇ m to 60 ⁇ m.
  • the polyethylene co-pressed film according to the present invention may include a barrier film between arbitrary layers as desired.
  • the barrier film can be formed by vapor-depositing a metal foil such as an aluminum foil, a metal such as aluminum, or an inorganic oxide such as aluminum oxide or silicon oxide on the surface of a polyethylene film layer or the like.
  • a vapor deposition method a conventionally known method can be employed.
  • a physical vapor deposition method Physical Vapor Deposition method, PVD method
  • PVD method Physical Vapor Deposition method
  • a vacuum vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a plasma chemical vapor deposition method.
  • chemical vapor deposition such as thermal chemical vapor deposition and photochemical vapor deposition.
  • CVD chemical vapor deposition
  • a vacuum vapor deposition method is mainly used and a plasma chemical vapor deposition method is also used partially.
  • a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.
  • the degree of vacuum of the deposition chamber is preferably about 10 ⁇ 2 mbar or more and about 10 ⁇ 8 mbar or less, particularly about 10 ⁇ 3 mbar or more and about 10 ⁇ 7 mbar or less before introducing oxygen, and after introducing oxygen, It is preferably about 10 ⁇ 1 mbar or more and about 10 ⁇ 6 mbar or less, more preferably about 10 ⁇ 2 mbar or more and about 10 ⁇ 5 mbar or less.
  • the amount of oxygen introduced varies depending on the size of the vapor deposition machine.
  • an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem.
  • the film conveyance speed is preferably about 10 m / min or more and 800 m / min or less, particularly about 50 m / min or more and 600 m / min or less.
  • the surface of the deposited film formed as described above may be subjected to oxygen plasma treatment.
  • the amount of oxygen introduced for the oxygen plasma treatment varies depending on the size of the vapor deposition apparatus, but is usually about 50 sccm to 2000 sccm, and particularly preferably about 300 sccm to 800 sccm.
  • sccm means the average amount of oxygen introduced (cc) per minute in the standard state (STP: 0 ° C., 1 atm).
  • an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem.
  • the adhesion when the polyethylene film substrate is bonded to the barrier film formed on the polyethylene film layer or the like is improved.
  • the method for producing a polyethylene co-pressed film of the present invention comprises a resin composition for a polyethylene film substrate, a resin composition for a polyethylene film layer, and a desired composition by a melt co-extrusion method such as an inflation extrusion method or a T-die extrusion method.
  • the method includes heating and melting the form-stabilizing layer resin composition and extrusion molding, and irradiating the molded product with an electron beam.
  • the manufacturing method of the polyethylene co-pressing film of this invention may include the process of printing with respect to a polyethylene co-pressing film.
  • a conventionally known electron beam irradiation apparatus can be used for the electron beam irradiation on the molded product.
  • a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.), a line irradiation type low energy electron beam.
  • An irradiation apparatus (EB-ENGINE, manufactured by Hamamatsu Photonics Co., Ltd.), a drum roll type electron beam irradiation apparatus (EZ-CURE, manufactured by I Electron Beam Co., Ltd.), and the like.
  • the dose of the electron beam applied to the polyethylene film substrate is preferably in the range of 10 kGy to 2000 kGy, more preferably in the range of 20 kGy to 1000 kGy.
  • the electron beam acceleration voltage is preferably in the range of 30 kV to 300 kV, more preferably in the range of 50 kV to 300 kV, and still more preferably in the range of 50 kV to 250 kV.
  • the irradiation energy of the electron beam is preferably in the range of 20 keV or more and 750 keV or less, more preferably in the range of 25 keV or more and 500 keV or less, further preferably in the range of 30 keV or more and 400 keV or less, and more preferably 20 keV or more.
  • the range of 200 keV or less is particularly preferable.
  • the oxygen concentration in the electron beam irradiation apparatus is preferably 500 ppm or less, and more preferably 100 ppm or less.
  • generation of ozone can be suppressed, and radicals generated by electron beam irradiation can be suppressed from being deactivated by oxygen in the atmosphere. it can.
  • Such a condition can be achieved, for example, by setting the inside of the apparatus to an inert gas (nitrogen, argon, etc.) atmosphere.
  • polyethylene film is susceptible to thermal shrinkage, it is preferable to perform electron beam irradiation simultaneously with cooling using a cooling drum or the like.
  • FIG. 4 is a schematic cross-sectional view of the polyethylene laminated film 20 of the present invention in one embodiment.
  • the polyethylene laminated film 20 includes a polyethylene film substrate 4 that is an electron beam irradiation layer, and a heat-sealable polyethylene fill 52.
  • the polyethylene laminated film 20 includes a form-stable layer 6 between the polyethylene film substrate 4 and the polyethylene film layer 5.
  • the hatching part in a figure represents the part which the electron beam irradiation and the crosslinking density improved.
  • the thickness of the polyethylene laminated film is preferably 10 ⁇ m or more and 300 ⁇ m or less, more preferably 30 ⁇ m or more and 200 ⁇ m or less, and further preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the polyethylene film substrate provided in the polyethylene laminated film according to the present invention is a layer containing polyethylene and a hindered amine-based antioxidant and irradiated with an electron beam (hereinafter simply referred to as “electron beam irradiation layer”).
  • electron beam irradiation layer an electron beam
  • the polyethylene film substrate is an electron beam irradiation layer, and as described above, the cross-linking density of the entire polyethylene film substrate is improved not only in the cross-linked density improved only on the surface irradiated with the electron beam. Including things.
  • the gel fraction of the polyethylene film substrate is preferably 10% or more and 80% or less, more preferably 20% or more and 80% or less, and further preferably 30% or more and 80% or less.
  • polyethylene contained in the polyethylene film substrate examples include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
  • the polyethylene film substrate may contain two or more of these polyethylenes.
  • low-density polyethylene and linear low-density polyethylene are preferable because a crosslinking reaction occurs favorably and heat resistance, strength, and the like can be significantly improved.
  • polyethylene includes copolymers of ethylene and other monomers in addition to HDPE, MDPE, LDPE, and LLDPE.
  • the ethylene copolymer is as described above.
  • it may replace with ethylene obtained from a fossil fuel and may use the polyethylene which used ethylene derived from biomass as the raw material.
  • the polyethylene film substrate contains a hindered amine-based antioxidant, which can prevent a decrease in the breaking strength of the polyethylene laminated film irradiated with the electron beam over time.
  • a hindered amine-based antioxidant which can prevent a decrease in the breaking strength of the polyethylene laminated film irradiated with the electron beam over time.
  • Specific examples of the hindered amine antioxidant are as described above.
  • the polyethylene film substrate may contain two or more of the above hindered amine antioxidants.
  • the content of the hindered amine antioxidant in the polyethylene film substrate is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass. % Or more and 10% by mass or less is more preferable.
  • a phenolic antioxidant an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a hydroxylamine antioxidant, and the like may be included as long as the effects of the invention are not impaired.
  • Polyethylene film substrate is film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength,
  • plastic compounding agents and additives can be included for the purpose of improving and modifying others. Moreover, the addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. Examples of common additives include fillers, cross-linking agents, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.
  • the thickness of the polyethylene film substrate is arbitrary depending on the application, but is usually about 5 ⁇ m to 200 ⁇ m, preferably about 5 ⁇ m to 100 ⁇ m.
  • the thickness can be appropriately adjusted according to the screw rotation speed of the melt extruder, the rotation speed of the cooling roll, and the like.
  • the polyethylene laminated film has a heat-sealable polyethylene film, while the physical properties that are different between the polyethylene film substrate and the layer provided on the polyethylene film substrate (for example, strength, It can be set as the laminated body which has heat resistance, heat seal property, etc.). Moreover, by setting it as such a structure, it can print on the surface which is not exposed, for example, an adhesive surface with the polyethylene film of a polyethylene film base material, and can prevent deterioration with time of printing.
  • the polyethylene film provided in the polyethylene laminated film of the present invention may be provided with an outer surface (a surface opposite to the side on which the polyethylene film substrate is provided) having at least a heat-sealing property. As a result of irradiating the surface with the electron beam, the crosslink density of the polyethylene film layer on the substrate side may be improved.
  • the polyethylene film comprises high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene copolymer, biomass-derived polyethylene, and the like as polyethylene.
  • low density polyethylene, medium density polyethylene, and linear low density polyethylene are preferable.
  • a medium density polyethylene is preferable.
  • the polyethylene film may contain two or more kinds of the above-described polyethylene.
  • the polyethylene film may contain the above-mentioned antioxidant, and preferably contains a hindered amine-based antioxidant.
  • the thickness of the polyethylene film is arbitrary depending on the use, but is usually about 5 ⁇ m or more and about 200 ⁇ m, preferably about 10 ⁇ m or more and about 200 ⁇ m or less, more preferably about 15 ⁇ m or more and about 160 ⁇ m or less.
  • the polyethylene laminated film of the present invention may include a form-stable layer containing medium density polyethylene and / or high density polyethylene between the polyethylene film substrate and the polyethylene film.
  • a form-stable layer containing medium density polyethylene and / or high density polyethylene between the polyethylene film substrate and the polyethylene film.
  • the form-stable layer may contain the above-described antioxidant, and preferably contains a hindered amine antioxidant.
  • the thickness of the form-stable layer is arbitrary depending on the application, but is usually about 5 ⁇ m to 100 ⁇ m, preferably about 10 ⁇ m to 80 ⁇ m, more preferably about 10 ⁇ m to 60 ⁇ m.
  • the polyethylene laminated film according to the present invention may have a barrier film between arbitrary layers as desired.
  • the barrier film can be formed by vapor-depositing a metal foil such as an aluminum foil, a metal such as aluminum, or an inorganic oxide such as aluminum oxide or silicon oxide on the surface of a polyethylene film layer or the like.
  • a vacuum vapor deposition method is mainly used and a plasma chemical vapor deposition method is also used partially.
  • a composite film composed of two or more layers of vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.
  • the surface of the deposited film formed as described above may be subjected to oxygen plasma treatment.
  • the amount of oxygen introduced for the oxygen plasma treatment varies depending on the size of the vapor deposition apparatus, but is usually about 50 sccm to 2000 sccm, and particularly preferably about 300 sccm to 800 sccm.
  • an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem.
  • the polyethylene laminated film of the present invention can be produced by preparing a polyethylene film substrate and a heat-sealable polyethylene film and laminating them through an adhesive or the like.
  • the polyethylene film substrate and the heat-sealable polyethylene film may be produced by a melt extrusion molding method such as inflation molding or T-die molding, or commercially available ones may be used.
  • the adhesive that can be used conventionally known adhesives can be used, and examples thereof include a two-component curable urethane adhesive, a polyester adhesive, and a polyolefin adhesive.
  • the polyethylene laminated film of the present invention can be produced by forming a heat-sealable polyethylene film on a polyethylene film substrate by melt extrusion molding.
  • the electron beam irradiation to the polyethylene film substrate may be performed before or after lamination with the heat-sealable polyethylene film. From the viewpoint of maintaining the heat sealability of the polyethylene film, it is preferable to irradiate the polyethylene film substrate with an electron beam before lamination with the heat sealable polyethylene film.
  • the printing method is not particularly limited, and can be performed by a printing method such as an inkjet method, a gravure printing method, an offset printing method, a flexographic printing method, a thermal transfer method, a hot stamp (foil stamping), or the like.
  • the above-mentioned apparatus can be used about the apparatus which can be used for the electron beam irradiation to a polyethylene film base material.
  • the dose of the electron beam applied to the polyethylene film substrate is preferably in the range of 10 kGy to 2000 kGy, more preferably in the range of 20 kGy to 1000 kGy.
  • the acceleration voltage of the electron beam is preferably in the range of 30 kV to 300 kV, more preferably in the range of 50 kV to 300 kV, and still more preferably in the range of 50 kV to 250 kV.
  • the irradiation energy of the electron beam is preferably in the range of 20 keV or more and 750 keV or less, more preferably in the range of 25 keV or more and 500 keV or less, and further preferably in the range of 30 keV or more and 400 keV or less. A range of 20 keV or more and 200 keV or less is particularly preferable.
  • the oxygen concentration in the electron beam irradiation apparatus is preferably 500 ppm or less, and more preferably 100 ppm or less.
  • generation of ozone can be suppressed, and radicals generated by electron beam irradiation can be suppressed from being deactivated by oxygen in the atmosphere. it can.
  • Such a condition can be achieved, for example, by setting the inside of the apparatus to an inert gas (nitrogen, argon, etc.) atmosphere.
  • polyethylene film is susceptible to thermal shrinkage, it is preferable to perform electron beam irradiation simultaneously with cooling using a cooling drum or the like.
  • the packaging material according to the present invention is formed by folding the above-mentioned polyethylene co-pressed film in two so that the polyethylene film substrate is located on the outside and the polyethylene film layer is located on the inside (the contents side). It can be manufactured by heat sealing.
  • two polyethylene co-pressed films can be manufactured by superimposing them so that the polyethylene film layers face each other, and heat-sealing the ends thereof.
  • the packaging material according to the present invention is formed by folding the above-mentioned polyethylene laminated film in two so that the polyethylene film base is located on the outside and the polyethylene film is located on the inside (the contents side). It can be manufactured by heat sealing.
  • two polyethylene laminated films can be manufactured by superimposing such that the polyethylene film layers face each other and heat-sealing the end portions and the like.
  • side seal type For example, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type
  • a self-supporting packaging bag standing pouch
  • a heat sealing method for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.
  • the printing method for the polyethylene co-pressed film is not particularly limited, and can be performed by a printing method such as an inkjet method, a gravure printing method, an offset printing method, a flexographic printing method, a thermal transfer method, or a hot stamp (foil stamping).
  • a printing method such as an inkjet method, a gravure printing method, an offset printing method, a flexographic printing method, a thermal transfer method, or a hot stamp (foil stamping).
  • Example 1-1 Linear low density polyethylene (density: 0.904 g / cm 2 , manufactured by Dow Chemical Japan Co., Ltd., trade name: AFFINITY1881G), hindered amine antioxidant (BASF Co., Ltd., trade name: Chimassorb) 2020 FDL) was mixed to obtain a resin composition for a polyethylene film substrate.
  • the content of the hindered amine antioxidant was 5% by mass with respect to 100% by mass of the total mass of the resin composition.
  • the resin composition for a polyethylene film base material obtained as described above is used as a resin composition for a form-stable layer made of medium density polyethylene (density: 0.926 g / cm 2 , manufactured by Dow Chemical Japan Co., Ltd. Name: Dowlex 2098P) and a resin composition for a polyethylene film layer (density: 0.924 g / cm 2 , manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen F208-3) made of medium density polyethylene.
  • the film was coextruded 1: 3: 1 to obtain a molded product.
  • the thickness of the obtained molded product was 50 ⁇ m.
  • Example 1-2 The content of the hindered amine antioxidant in the polyethylene film substrate resin composition is changed to 2.5% by mass, and the hydroxylamine antioxidant is changed to 100% by mass of the polyethylene film substrate resin composition.
  • a polyethylene co-pressed film was obtained in the same manner as in Example 1-1 except that the content was 2.5% by mass.
  • Example 1-1 A polyethylene co-pressed film was obtained in the same manner as in Example 1-1 except that the hindered amine antioxidant was not added to the polyethylene film substrate resin composition.
  • Example 1-2 A polyethylene co-pressed film was obtained in the same manner as in Example 1-1 except that the electron beam was not irradiated.
  • the sample piece after heat sealing was cut into a strip shape with a width of 15 mm, and both ends that were not heat sealed were held by a tensile tester, and the peel strength (N / 15 mm) was obtained under the conditions of a speed of 300 mm / min and a load range of 50 N. It was measured. The measurement results were as shown in Table 1 below.
  • the polyethylene co-pressed film obtained in Comparative Example 1-2 was dissolved during heat sealing, and the sealing strength could not be measured.
  • the sample piece after heat sealing was cut into a strip shape with a width of 15 mm, and both ends that were not heat sealed were held by a tensile tester, and the peel strength (N / 15 mm) was obtained under the conditions of a speed of 300 mm / min and a load range of 50 N. It was measured. The measurement results were as shown in Table 1 below.
  • the polyethylene co-pressed film obtained in Comparative Example 1-2 was dissolved during heat sealing, and the sealing strength could not be measured.
  • Example 2-1 Linear low density polyethylene (density: 0.904 g / cm 2 , manufactured by Dow Chemical Japan Co., Ltd., trade name: AFFINITY1881G), hindered amine antioxidant (BASF Co., Ltd., trade name: Chimassorb) 2020 FDL) was mixed to obtain a resin composition for a polyethylene film substrate.
  • the content of the hindered amine antioxidant was 5% by mass with respect to 100% by mass of the total mass of the resin composition.
  • the polyethylene film substrate resin composition obtained as described above was extruded by inflation extrusion film formation to obtain a polyethylene film substrate having a thickness of 50 ⁇ m.
  • a two-component curable urethane adhesive (Rock Paint Co., Ltd., a product) is applied to a polyethylene film substrate irradiated with an electron beam and a 50 ⁇ m thick linear low density polyethylene film (Toyobo Co., Ltd., product name: L-6100). Name: RU-77T / H-7) to obtain a polyethylene laminated film.
  • Example 2-2 The content of the hindered amine antioxidant in the resin composition for a polyethylene film substrate is changed to 2.5% by mass, and the hydroxylamine antioxidant is added to 100% by mass of the resin composition for a polyethylene film substrate.
  • a polyethylene laminated film was obtained in the same manner as in Example 2-1, except that the content was 2.5% by mass.
  • Example 2-1 A polyethylene laminated film was obtained in the same manner as in Example 2-1, except that the hindered amine-based antioxidant was not added to the polyethylene film substrate resin composition.
  • Example 2-2 A polyethylene laminated film was obtained in the same manner as in Example 2-1, except that the electron beam irradiation was not performed.
  • the sample piece after heat sealing was cut into a strip shape with a width of 15 mm, and both ends that were not heat sealed were held by a tensile tester, and the peel strength (N / 15 mm) was obtained under the conditions of a speed of 300 mm / min and a load range of 50 N. It was measured. The measurement results were as shown in Table 1 below.
  • the polyethylene laminated film obtained in Comparative Example 2-2 was dissolved during heat sealing, and the sealing strength could not be measured.
  • the sample piece after heat sealing was cut into a strip shape with a width of 15 mm, and both ends that were not heat sealed were held by a tensile tester, and the peel strength (N / 15 mm) was obtained under the conditions of a speed of 300 mm / min and a load range of 50 N. It was measured. The measurement results were as shown in Table 2 below.
  • the polyethylene laminated film obtained in Comparative Example 2-2 was dissolved during heat sealing, and the sealing strength could not be measured.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un film coextrudé de polyéthylène avec lequel des matériaux d'emballage peuvent être produits à l'aide uniquement du film de polyéthylène, et qui est apte à empêcher une réduction dans le temps des propriétés de thermoscellage et de la résistance à la rupture. La solution selon l'invention porte sur un film coextrudé de polyéthylène qui est caractérisé en ce qu'il comprend un matériau de base de film de polyéthylène et une couche de film de polyéthylène, le matériau de base de film de polyéthylène étant une couche d'irradiation par faisceau d'électrons contenant un polyéthylène et un agent anti-oxydant à base d'amine encombrée, et la couche de film de polyéthylène contenant un polyéthylène et présentant une surface extérieure ayant des propriétés de thermoscellage.
PCT/JP2018/020495 2017-05-30 2018-05-29 Film coextrudé de polyéthylène, film stratifié de polyéthylène et matériau d'emballage utilisant ledit film coextrudé WO2018221495A1 (fr)

Applications Claiming Priority (4)

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JP2017-106601 2017-05-30
JP2017-106603 2017-05-30
JP2017106603A JP6969161B2 (ja) 2017-05-30 2017-05-30 ポリエチレン積層フィルムおよびこれを用いた包装材料
JP2017106601A JP6969160B2 (ja) 2017-05-30 2017-05-30 ポリエチレン共押フィルムおよびこれを用いた包装材料

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Publication number Priority date Publication date Assignee Title
JP2020157730A (ja) * 2019-03-28 2020-10-01 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ
JP2020157517A (ja) * 2019-03-25 2020-10-01 大日本印刷株式会社 スパウト付き包装袋用積層体および包装袋
WO2021200811A1 (fr) * 2020-03-30 2021-10-07 住友ベークライト株式会社 Film stratifié
WO2022065313A1 (fr) * 2020-09-25 2022-03-31 凸版印刷株式会社 Stratifié et sachet à fond plat
WO2022131264A1 (fr) * 2020-12-17 2022-06-23 凸版印刷株式会社 Stratifié, sac d'emballage et sachet à fond plat

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JP2002002794A (ja) * 2000-06-26 2002-01-09 Okura Ind Co Ltd 放射線減菌処理用バッグインボックス内袋
WO2013118749A1 (fr) * 2012-02-07 2013-08-15 日本ポリエチレン株式会社 Composition de résine à base de polyéthylène pour couvercle de récipient, et couvercle de récipient
WO2017018479A1 (fr) * 2015-07-28 2017-02-02 大日本印刷株式会社 Film de polyéthylène, stratifié et emballage utilisant ceux-ci
WO2017073751A1 (fr) * 2015-10-29 2017-05-04 大日本印刷株式会社 Film de polyéthylène, stratifié, et emballage utilisant un tel film

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Publication number Priority date Publication date Assignee Title
JP2002002794A (ja) * 2000-06-26 2002-01-09 Okura Ind Co Ltd 放射線減菌処理用バッグインボックス内袋
WO2013118749A1 (fr) * 2012-02-07 2013-08-15 日本ポリエチレン株式会社 Composition de résine à base de polyéthylène pour couvercle de récipient, et couvercle de récipient
WO2017018479A1 (fr) * 2015-07-28 2017-02-02 大日本印刷株式会社 Film de polyéthylène, stratifié et emballage utilisant ceux-ci
WO2017073751A1 (fr) * 2015-10-29 2017-05-04 大日本印刷株式会社 Film de polyéthylène, stratifié, et emballage utilisant un tel film

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Publication number Priority date Publication date Assignee Title
JP2020157517A (ja) * 2019-03-25 2020-10-01 大日本印刷株式会社 スパウト付き包装袋用積層体および包装袋
JP2020157730A (ja) * 2019-03-28 2020-10-01 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ
JP7576232B2 (ja) 2019-03-28 2024-10-31 大日本印刷株式会社 積層体、包装材料、包装袋およびスタンドパウチ
WO2021200811A1 (fr) * 2020-03-30 2021-10-07 住友ベークライト株式会社 Film stratifié
JPWO2021200811A1 (fr) * 2020-03-30 2021-10-07
WO2022065313A1 (fr) * 2020-09-25 2022-03-31 凸版印刷株式会社 Stratifié et sachet à fond plat
WO2022131264A1 (fr) * 2020-12-17 2022-06-23 凸版印刷株式会社 Stratifié, sac d'emballage et sachet à fond plat
EP4245534A4 (fr) * 2020-12-17 2024-04-17 Toppan Inc. Stratifié, sac d'emballage et sachet à fond plat

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