TWI811346B - Multilayer films and packaging materials - Google Patents
Multilayer films and packaging materials Download PDFInfo
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- TWI811346B TWI811346B TW108114412A TW108114412A TWI811346B TW I811346 B TWI811346 B TW I811346B TW 108114412 A TW108114412 A TW 108114412A TW 108114412 A TW108114412 A TW 108114412A TW I811346 B TWI811346 B TW I811346B
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- Taiwan
- Prior art keywords
- layer
- mass
- resin
- intermediate layer
- film
- Prior art date
Links
- 239000005022 packaging material Substances 0.000 title claims description 12
- 239000010410 layer Substances 0.000 claims abstract description 116
- 229920005989 resin Polymers 0.000 claims abstract description 105
- 239000011347 resin Substances 0.000 claims abstract description 105
- 239000002344 surface layer Substances 0.000 claims abstract description 41
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 36
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 36
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 36
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 32
- -1 polypropylene Polymers 0.000 claims abstract description 29
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 24
- 239000004743 Polypropylene Substances 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 15
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000007789 sealing Methods 0.000 description 37
- 229920001577 copolymer Polymers 0.000 description 19
- 238000004806 packaging method and process Methods 0.000 description 19
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 17
- 239000000654 additive Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 229920005673 polypropylene based resin Polymers 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 229920013716 polyethylene resin Polymers 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001384 propylene homopolymer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000181 anti-adherent effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 2
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- RNWDNEVYZAPIBG-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OC)C2 RNWDNEVYZAPIBG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229920006302 stretch film Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
本發明之目的在於提供一種多層薄膜,有良好的熱封性和耐衝擊性、易撕裂性,並且即使在暴露於高溫高濕環境下之後暴露於低溫環境下的情況,朝單向的撕裂性仍然優異。 本發明是一種多層薄膜,其係由將聚丙烯系樹脂作為主成分之表面層(A)、將直鏈低密度聚乙烯作為主成分之中間層(B)、將環狀聚烯烴系樹脂作為主成分之中間層(C)、及熱封層(D),以(A)/(B)/(C)/(D)的順序疊層而成,該中間層(B)所包含的樹脂成分中的直鏈低密度聚乙烯之含量為65質量%以上,藉由此多層薄膜能夠實現良好的熱封性和耐衝擊性、易撕裂性,並且實現暴露於高溫高濕環境下之後暴露於低溫環境下時合適的撕裂性。The object of the present invention is to provide a multi-layer film that has good heat sealability, impact resistance, and tearability, and can be torn in one direction even after being exposed to a high temperature and high humidity environment and then to a low temperature environment. The crackability is still excellent. The present invention is a multilayer film composed of a surface layer (A) containing polypropylene resin as the main component, an intermediate layer (B) containing linear low-density polyethylene as the main component, and a cyclic polyolefin resin as the main component. The main components of the middle layer (C) and the heat sealing layer (D) are laminated in the order (A)/(B)/(C)/(D). The resin contained in the middle layer (B) The content of linear low-density polyethylene in the composition is more than 65% by mass. This multi-layer film can achieve good heat sealability, impact resistance, and tearability, and can be exposed to high temperature and high humidity environments. Suitable tearability in low temperature environments.
Description
本發明係關於使用於食品或醫療用品等之包裝材料的多層薄膜,更詳細而言,係關於可實現具有良好裂開性之包裝材料的多層薄膜。The present invention relates to a multilayer film used as a packaging material for food, medical supplies, etc., and more specifically, to a multilayer film capable of realizing a packaging material having good tearability.
作為食品或醫療用品等的包裝材料,從保護內容物的觀點而言尋求著具有良好的熱封性和耐衝擊性,加上當使用時輕易取出內容物的易開封性和易撕裂性。作為具有良好的熱封性和耐衝擊性、與易撕裂性之薄膜,例如,揭示了一種多層薄膜,其係以特定的厚度比率疊層了多層的將不具環狀結構之聚烯烴系樹脂作為主成分之層、與將環狀聚烯烴系樹脂作為主成分之層而成(例如,參照專利文獻1)。該多層薄膜是藉由該構成,而兼備合適的熱封性和耐衝擊性、與易撕裂性,並且撕裂時的直線切割性優異,故具有極為良好的撕裂開封性。 [先前技術文獻] [專利文獻]As packaging materials for food, medical supplies, etc., from the viewpoint of protecting the contents, it is required to have good heat sealing properties and impact resistance, as well as easy opening and tearing properties to easily remove the contents when used. As a film having good heat sealability, impact resistance, and tearability, for example, a multilayer film is disclosed in which multiple layers of polyolefin-based resin without a cyclic structure are laminated at a specific thickness ratio. A layer containing a cyclic polyolefin-based resin as a main component and a layer containing a cyclic polyolefin-based resin as a main component are formed (for example, see Patent Document 1). Due to this structure, the multilayer film has both suitable heat sealing properties, impact resistance, and easy tearing properties, and has excellent straight-line cutting properties when tearing, so it has extremely good tear-opening properties. [Prior technical literature] [Patent Document]
[專利文獻1] 日本特開2015-089619號公報[Patent Document 1] Japanese Patent Application Publication No. 2015-089619
[發明所欲解決之問題][Problem to be solved by the invention]
包裝材料,根據其使用用途,會有因熱封後的煮沸殺菌等而暴露於高溫高濕環境下、或在之後的物流階段因冷藏或冷凍而暴露於低溫環境下的情況。對於這樣的包裝材料,尋求即使受到各式各樣的溫度變化之影響後仍具有合適的裂開性。Packaging materials, depending on their use, may be exposed to high temperature and high humidity environments due to boiling and sterilization after heat sealing, or may be exposed to low temperature environments due to refrigeration or freezing in the subsequent logistics stage. For such packaging materials, it is sought to have appropriate rupture properties even after being affected by various temperature changes.
本發明所欲解決之問題,是在於提供一種多層薄膜,有良好的熱封性和耐衝擊性、易撕裂性,並且即使在暴露於高溫高濕環境下之後暴露於低溫環境下的情況朝單向的撕裂性仍然優異。 [解決問題之手段]The problem to be solved by the present invention is to provide a multi-layer film that has good heat sealability, impact resistance, and tearability, and can withstand even after being exposed to a high temperature and high humidity environment and then to a low temperature environment. The one-way tearability is still excellent. [Means to solve problems]
本發明是一種多層薄膜,其係由將聚丙烯系樹脂作為主成分之表面層(A)、將直鏈低密度聚乙烯作為主成分之中間層(B)、將環狀聚烯烴系樹脂作為主成分之中間層(C)、及熱封層(D),以(A)/(B)/(C)/(D)的順序疊層而成,該中間層(B)所包含的樹脂成分中的直鏈低密度聚乙烯之含量為65質量%以上,藉由此多層薄膜來解決上述問題。 [發明之效果]The present invention is a multilayer film composed of a surface layer (A) containing polypropylene resin as the main component, an intermediate layer (B) containing linear low-density polyethylene as the main component, and a cyclic polyolefin resin as the main component. The main components of the middle layer (C) and the heat sealing layer (D) are laminated in the order (A)/(B)/(C)/(D). The resin contained in the middle layer (B) The content of linear low-density polyethylene in the composition is more than 65% by mass. This multi-layer film solves the above problems. [Effects of the invention]
本發明之多層薄膜,由於有良好的熱封性和耐衝擊性、易撕裂性,並且即使受到暴露於高溫高濕環境或低溫環境下的情況等之溫濕度變化時仍具有朝單向的優異撕裂性,故能夠合適地應用在熱封後進行煮沸殺菌的食品、醫療用品之包裝用途上。The multi-layer film of the present invention has good heat sealing properties, impact resistance, and easy tearing properties, and it still has one-way stability even when exposed to temperature and humidity changes such as exposure to high temperature and high humidity environments or low temperature environments. It has excellent tearing properties, so it can be suitably used in the packaging of food and medical supplies that are boiled and sterilized after heat sealing.
本發明之多層薄膜,其係由將聚丙烯系樹脂作為主成分之表面層(A)、將直鏈低密度聚乙烯作為主成分之中間層(B)、將環狀聚烯烴系樹脂作為主成分之中間層(C)、及熱封層(D),以(A)/(B)/(C)/(D)的順序疊層而成,該中間層(B)所包含的樹脂成分中的直鏈低密度聚乙烯之含量為65質量%以上。The multilayer film of the present invention consists of a surface layer (A) containing polypropylene resin as its main component, an intermediate layer (B) containing linear low-density polyethylene as its main component, and a cyclic polyolefin resin as its main component. The intermediate layer (C) and the heat sealing layer (D) of the components are laminated in the order (A)/(B)/(C)/(D). The resin component contained in the intermediate layer (B) The content of linear low-density polyethylene in it is more than 65% by mass.
[表面層(A)] 本發明之多層薄膜的表面層(A),是將聚丙烯系樹脂作為主成分之層。作為該聚丙烯系樹脂,例如可舉出:丙烯同元聚合物、丙烯-α-烯烴無規共聚物,例如丙烯-乙烯共聚物、丙烯-丁-1-烯共聚物、丙烯-乙烯-丁-1-烯共聚物、茂金屬觸媒系聚丙烯等。這些可以各自單獨使用,也可以併用。在使用這些聚丙烯系樹脂作為表面層(A)的情況,薄膜的耐熱性會提升。並且,在以單體使用的情況中,由於此表面層(A)會成為包裝材料的表層,而能夠作為具有光澤的包裝材料。[Surface layer (A)] The surface layer (A) of the multilayer film of the present invention is a layer containing polypropylene resin as its main component. Examples of the polypropylene-based resin include propylene homopolymers and propylene-α-olefin random copolymers, such as propylene-ethylene copolymers, propylene-but-1-ene copolymers, and propylene-ethylene-butylene copolymers. -1-ene copolymer, metallocene catalyst polypropylene, etc. These may be used individually or in combination. When these polypropylene-based resins are used as the surface layer (A), the heat resistance of the film is improved. Furthermore, when used as a single substance, this surface layer (A) becomes the surface layer of the packaging material, so that it can be used as a packaging material with gloss.
又,作為使用於表面層(A)的樹脂,併用丙烯同元聚合物與丙烯-乙烯無規共聚物亦佳。丙烯同元聚合物,可期待提升耐熱性和剛性;丙烯-乙烯無規共聚物,可期待提升光澤性。藉由併用這些聚丙烯系樹脂,會較容易獲得具有耐熱性、光澤性之包裝材料。Furthermore, as the resin used for the surface layer (A), it is also preferable to use a propylene homopolymer and a propylene-ethylene random copolymer in combination. Propylene homopolymer is expected to improve heat resistance and rigidity; propylene-ethylene random copolymer is expected to improve gloss. By using these polypropylene resins in combination, it is easier to obtain packaging materials with heat resistance and gloss.
再者,這些聚丙烯系樹脂,較佳者是MFR(熔體流動速率)(230℃)為0.5~30.0g/10分,熔點為110~165℃,更佳者是MFR(230℃)為2.0~15.0g/10分,熔點為115~162℃。若MFR及熔點在此範圍,則薄膜的成膜性提升。Furthermore, these polypropylene-based resins preferably have an MFR (melt flow rate) (230°C) of 0.5 to 30.0 g/10 minutes and a melting point of 110 to 165°C. More preferably, the MFR (230°C) is 0.5 to 30.0 g/10 minutes. 2.0~15.0g/10 minutes, melting point is 115~162℃. If the MFR and melting point are within this range, the film-forming properties of the film are improved.
作為該其他的α-烯烴,例如可舉出:乙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-庚烯、4-甲基-戊-1-烯、4-甲基-己-1-烯等,也可以是同時將這些的2種以上進行共聚而成。作為共聚形式,無規共聚、嵌段共聚的任一種皆可使用。Examples of the other α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, and 4-methyl-pent-1-ene. , 4-methyl-hex-1-ene, etc., or two or more of these may be copolymerized simultaneously. As the copolymerization form, any of random copolymerization and block copolymerization can be used.
在此等之中,較佳是與乙烯的共聚物。又,作為共聚物之中其他的α-烯烴的含有率,較佳為2~23莫耳%,更佳為2.5~15莫耳%。Among these, a copolymer with ethylene is preferred. In addition, the content of other α-olefins in the copolymer is preferably 2 to 23 mol%, more preferably 2.5 to 15 mol%.
表面層(A),是將上述聚丙烯系樹脂作為主成分者,在無損於本發明之效果的範圍,也可以併用可共擠壓的其他樹脂。另外,所謂的「作為主成分」具體而言是指用於表面層(A)的樹脂成分之中的70質量%以上為聚丙烯系樹脂,較佳是80質量%以上為聚丙烯系樹脂,更佳是90質量%以上為聚丙烯系樹脂。The surface layer (A) contains the above-mentioned polypropylene-based resin as a main component. Other resins that can be co-extruded may be used together in the range that does not impair the effects of the present invention. In addition, "as the main component" specifically means that 70% by mass or more of the resin component used for the surface layer (A) is a polypropylene-based resin, and preferably 80% by mass or more is a polypropylene-based resin. More preferably, 90% by mass or more is polypropylene-based resin.
作為使用於表面層(A)之上述聚丙烯系樹脂以外的樹脂,能夠使用包裝用薄膜所使用的各種樹脂,在其中,能夠較佳地使用乙烯系樹脂等之烯烴系樹脂。作為乙烯系樹脂,能夠使用超低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、線性中密度聚乙烯(LMDPE)、中密度聚乙烯(MDPE)等之聚乙烯樹脂、或乙烯-乙酸乙烯酯共聚物(EVA)等。As resins other than the above-mentioned polypropylene-based resin used for the surface layer (A), various resins used in packaging films can be used, and among them, olefin-based resins such as ethylene-based resins can be preferably used. As the vinyl resin, very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), linear medium density polyethylene (LMDPE), medium density polyethylene (MDPE), etc. can be used Polyethylene resin, or ethylene-vinyl acetate copolymer (EVA), etc.
在使用烯烴系樹脂作為上述丙烯系樹脂以外的樹脂的情況,其含量較佳為表面層(A)所包含的樹脂成分中的30質量%以下,進而較佳為10質量%以下,更佳為5質量%以下。When an olefin-based resin is used as the resin other than the above-mentioned propylene-based resin, the content is preferably 30 mass% or less of the resin component contained in the surface layer (A), more preferably 10 mass% or less, and even more preferably 5% by mass or less.
又,雖然也可以使用環狀聚烯烴系樹脂作為烯烴系樹脂,但表面層(A)所包含的樹脂成分中的環狀聚烯烴系樹脂之含量較佳為設於10質量%以下,更佳為設於5質量%以下,實質上不使用亦佳。In addition, although a cyclic polyolefin-based resin can also be used as the olefin-based resin, the content of the cyclic polyolefin-based resin in the resin component contained in the surface layer (A) is preferably 10 mass % or less, more preferably In order to set it at 5 mass % or less, it is better not to use it substantially.
在本發明使用的表面層(A)中,亦可以併用上述以外的其他樹脂。作為該其他樹脂,例如能夠例示:聚乙烯系彈性體、聚丙烯系彈性體、丁烯系彈性體等之熱塑性彈性體;乙烯-甲基丙烯酸甲酯共聚物(EMMA)、乙烯-丙烯酸乙酯共聚物(EEA)、乙烯-丙烯酸甲酯(EMA)共聚物、乙烯-丙烯酸乙酯-馬來酸酐共聚物(E-EA-MAH)、乙烯-丙烯酸共聚物(EAA)、乙烯-甲基丙烯酸共聚物(EMAA)等之乙烯系共聚物;更進一步是乙烯-丙烯酸共聚物的離子聚合物、乙烯-甲基丙烯酸共聚物的離子聚合物等。In the surface layer (A) used in the present invention, other resins other than those mentioned above may be used together. Examples of the other resin include thermoplastic elastomers such as polyethylene elastomers, polypropylene elastomers, and butylene elastomers; ethylene-methyl methacrylate copolymer (EMMA), and ethylene-ethyl acrylate. Copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid Ethylene copolymers such as copolymer (EMAA); furthermore, ionic polymers of ethylene-acrylic acid copolymers, ionic polymers of ethylene-methacrylic acid copolymers, etc.
在使用上述其他的樹脂的情況,其含量較佳是以表面層(A)所包含的樹脂成分中的30質量%以下來使用更佳是10質量%以下,再更佳是5質量%以下。When the other resins mentioned above are used, their content is preferably 30% by mass or less of the resin component contained in the surface layer (A), more preferably 10% by mass or less, and still more preferably 5% by mass or less.
於表面層(A)中,在上述樹脂成分以外也可以適當併用各種添加劑等。作為添加劑,例如能夠適當使用潤滑劑、抗黏連劑、紫外線吸收劑、光安定劑、抗靜電劑、防霧劑等、著色劑等。在使用這些添加劑的情況,相對於100質量份的使用於表面層(A)之樹脂成分,較佳是以2質量份以下,更佳是以0.01~1質量份左右來使用。In the surface layer (A), in addition to the above-mentioned resin components, various additives and the like may be appropriately used in combination. As additives, for example, lubricants, anti-blocking agents, ultraviolet absorbers, light stabilizers, antistatic agents, anti-fogging agents, colorants, etc. can be appropriately used. When using these additives, it is preferable that they are used in an amount of 2 parts by mass or less, and more preferably about 0.01 to 1 part by mass relative to 100 parts by mass of the resin component used in the surface layer (A).
尤其是為了賦予薄膜成形時的加工適性、填充機的包裝適性,表面層(A)的摩擦係數在0.9以下,其中較佳是在0.8以下,故適當添加潤滑劑或抗黏連劑到表面層(A)中亦佳。In particular, in order to provide processing suitability during film formation and packaging suitability in filling machines, the friction coefficient of the surface layer (A) is 0.9 or less, and preferably 0.8 or less, so a lubricant or anti-adhesive agent is appropriately added to the surface layer. (A) is also good.
表面層(A)相對於多層薄膜的厚度比率,從易於獲得良好的裂開性,尤其是朝單向的優異裂開性、或合適的剛性和耐熱性、包裝機械適性等而言,作為表面層(A)相對於多層薄膜之總厚度的厚度比率,較佳是在10~40%的範圍,特佳是在10~30%的範圍。The thickness ratio of the surface layer (A) relative to the multilayer film is used as a surface layer from the viewpoint of easy acquisition of good cleavability, especially excellent cleavage in one direction, appropriate rigidity, heat resistance, packaging machine suitability, etc. The thickness ratio of layer (A) to the total thickness of the multilayer film is preferably in the range of 10 to 40%, particularly preferably in the range of 10 to 30%.
[中間層(B)] 本發明之多層薄膜的第一中間層(B),是將直鏈低密度聚乙烯作為主成分之層。透過疊層了將直鏈低密度聚乙烯作為主成分之中間層(B)到將環狀聚烯烴系樹脂作為主成分之中間層(C)上,能夠實現具有合適的耐衝擊性,並且實現即使暴露於高溫高濕環境下或低溫環境下後朝單向的撕裂性仍然優異的多層薄膜。使用於中間層(B)之直鏈低密度聚乙烯的密度,從易於獲得良好的裂開性和耐衝擊性而言,較佳為0.930g/cm3 以下,進而較佳為0.925g/cm3 以下,更佳為0.910~0.920g/cm3 。又,中間層(B)之層中的樹脂成分的平均密度較佳為0.930g/cm3 以下,更佳為0.915~0.930g/cm3 。[Intermediate Layer (B)] The first intermediate layer (B) of the multilayer film of the present invention is a layer containing linear low-density polyethylene as its main component. By laminating an intermediate layer (B) containing linear low-density polyethylene as a main component on an intermediate layer (C) containing a cyclic polyolefin-based resin as a main component, it is possible to achieve appropriate impact resistance and achieve A multi-layer film with excellent one-way tearability even after being exposed to high temperature, high humidity or low temperature environments. The density of the linear low-density polyethylene used in the intermediate layer (B) is preferably 0.930 g/cm 3 or less, and more preferably 0.925 g/cm from the viewpoint of easily obtaining good cracking properties and impact resistance. 3 or less, more preferably 0.910 to 0.920g/cm 3 . Moreover, the average density of the resin component in the intermediate layer (B) is preferably 0.930 g/cm 3 or less, more preferably 0.915 to 0.930 g/cm 3 .
直鏈低密度聚乙烯的MFR是在0.1~20g/10分(190℃,21.18N),較佳是為0.3~10g/10分(190℃,21.18N),更佳是為0.5~5g/10分(190℃,21.18N)。MFR若在此範圍內,由於可獲得良好的成膜性而較佳。The MFR of linear low-density polyethylene is 0.1~20g/10min (190℃, 21.18N), preferably 0.3~10g/10min (190℃, 21.18N), more preferably 0.5~5g/ 10 minutes (190℃, 21.18N). If the MFR is within this range, good film-forming properties can be obtained, which is preferable.
在本發明中,透過將中間層(B)中的直鏈低密度聚乙烯的含量設為中間層(B)所包含的樹脂成分中的65質量%以上,能夠實現合適的耐衝擊性,即使暴露於高溫高濕環境下或低溫環境下後仍優異的朝單向撕裂性。該含量較佳是在中間層(B)所包含的樹脂成分中的68質量%以上,進而較佳是在70質量%以上,更佳是在75質量%以上,特佳是在80質量%以上。又,中間層(B)所包含的樹脂成分中,也可以100質量%是直鏈低密度聚乙烯。In the present invention, by setting the linear low-density polyethylene content in the intermediate layer (B) to 65% by mass or more of the resin component contained in the intermediate layer (B), appropriate impact resistance can be achieved even if Excellent one-way tearability after exposure to high temperature, high humidity or low temperature environments. The content is preferably 68% by mass or more of the resin component contained in the intermediate layer (B), more preferably 70% by mass or more, more preferably 75% by mass or more, and particularly preferably 80% by mass or more. . Moreover, 100% by mass of the resin component contained in the intermediate layer (B) may be linear low-density polyethylene.
於中間層(B)中,在無損於本發明之效果的範圍,也可以併用上述直鏈低密度聚乙烯以外的其他樹脂。作為該其他能夠併用的樹脂種類,例如能夠例示:於上述表面層(A)已例示之直鏈低密度聚乙烯系樹脂以外的聚乙烯系樹脂、或聚丙烯系樹脂等之烯烴系樹脂。其中,由於高密度聚乙烯易於提升剛性和易裂開性故較佳。在使用烯烴系樹脂作為上述直鏈低密度聚乙烯以外的樹脂的情況,其含量較佳是在中間層(B)所包含的樹脂成分中的35質量%以下,進而較佳是在30質量%以下,更佳是在20質量%以下,特佳是在10質量%以下。In the intermediate layer (B), resins other than the above-mentioned linear low-density polyethylene may be used together in a range that does not impair the effects of the present invention. Examples of other types of resins that can be used together include polyethylene resins other than the linear low-density polyethylene resins exemplified for the surface layer (A), or olefin resins such as polypropylene resins. Among them, high-density polyethylene is preferred because it is easy to increase rigidity and crackability. When an olefin-based resin is used as the resin other than the linear low-density polyethylene, the content is preferably 35 mass% or less of the resin component contained in the intermediate layer (B), and more preferably 30 mass% below, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
又,雖然也可以使用環狀聚烯烴系樹脂作為烯烴系樹脂,但中間層(B)所包含的樹脂成分中的環狀聚烯烴系樹脂之含量較佳為設於10質量%以下,更佳為設於5質量%以下,實質上不使用亦佳。In addition, although a cyclic polyolefin-based resin can also be used as the olefin-based resin, the content of the cyclic polyolefin-based resin in the resin component contained in the intermediate layer (B) is preferably 10 mass % or less, more preferably In order to set it at 5 mass % or less, it is better not to use it substantially.
再者,於中間層(B)中,亦可以併用上述以外的其他樹脂,作為該其他樹脂,能夠例示:於表面層(A)已例示之熱塑性彈性體或乙烯系共聚物、離子聚合物等。在使用該其他樹脂的情況,其含量較佳是以中間層(B)所包含的樹脂成分中的35質量%以下來使用,進而較佳是在30質量%以下,更佳是在20質量%以下,特佳是在10質量%以下。In addition, in the intermediate layer (B), other resins other than the above may be used together. Examples of the other resins include the thermoplastic elastomers, ethylene copolymers, ionomers, etc. exemplified in the surface layer (A). . When using this other resin, its content is preferably 35% by mass or less of the resin component contained in the intermediate layer (B), more preferably 30% by mass or less, and more preferably 20% by mass. Below, it is particularly preferable that the content is 10% by mass or less.
於中間層(B)中,在上述樹脂成分以外也可以適當併用各種添加劑等。作為添加劑,例如能夠適當使用潤滑劑、抗黏連劑、紫外線吸收劑、光安定劑、抗靜電劑、防霧劑等、著色劑等。在使用這些添加劑的情況,相對於100質量份的使用於中間層(B)之樹脂成分,較佳是以2質量份以下,更佳是以0.01~1質量份左右來使用。In the intermediate layer (B), in addition to the above-mentioned resin components, various additives and the like may be appropriately used in combination. As additives, for example, lubricants, anti-blocking agents, ultraviolet absorbers, light stabilizers, antistatic agents, anti-fogging agents, colorants, etc. can be appropriately used. When using these additives, it is preferable that they are used in an amount of 2 parts by mass or less, and more preferably about 0.01 to 1 part by mass relative to 100 parts by mass of the resin component used in the intermediate layer (B).
作為將該聚乙烯系樹脂(B)作為主成分之中間層(B)相對於多層薄膜(I)的厚度比率,從有方向性的易開封性、與其他的性能平衡,尤其是耐低溫衝擊性的觀點而言,必須在30%以上,特佳是在40~65%的範圍。The thickness ratio of the intermediate layer (B) containing the polyethylene resin (B) as a main component to the multilayer film (I) is determined by balancing directional ease of opening and other properties, especially low temperature impact resistance. From a sexual perspective, it must be above 30%, and the best range is between 40 and 65%.
[中間層(C)] 藉由在本發明之多層薄膜的第二中間層(C)中含有環狀聚烯烴系樹脂,能夠實現優異的易撕裂性和直線切割性。作為該環狀聚烯烴系樹脂,例如可舉出:降莰烯系聚合物、乙烯脂環式烴聚合物、環狀共軛二烯聚合物等。在這些之中,較佳為降莰烯系聚合物。又,作為降莰烯系聚合物,可舉出:降莰烯系單體的開環聚合物(以下,稱為「COP」。)、將降莰烯系單體與乙烯等之烯烴共聚合而成的降莰烯系共聚物(以下,稱為「COC」。)等。又,COP及COC的氫化物亦特佳。再者,環狀聚烯烴系樹脂的重量平均分子量較佳為5,000~500,000,更佳為7,000~300,000。[Middle layer (C)] By containing the cyclic polyolefin-based resin in the second intermediate layer (C) of the multilayer film of the present invention, excellent tearability and linear cutting properties can be achieved. Examples of the cyclic polyolefin-based resin include norbornene-based polymers, ethylene alicyclic hydrocarbon polymers, cyclic conjugated diene polymers, and the like. Among these, norbornene-based polymers are preferred. Examples of the norbornene-based polymer include ring-opened polymers of norbornene-based monomers (hereinafter referred to as "COP"), and copolymerization of norbornene-based monomers and olefins such as ethylene. Norbornene-based copolymers (hereinafter referred to as "COC"), etc. In addition, hydrides of COP and COC are also particularly suitable. Furthermore, the weight average molecular weight of the cyclic polyolefin-based resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
該降莰烯系聚合物與當作原料的降莰烯系單體,是具有降莰烯環的脂環族系單體。作為這樣的降莰烯系單體,例如可舉出:降莰烯、四環十二烯、亞乙基降莰烯、乙烯基降莰烯、亞乙基四環十二烯、雙環戊二烯、二甲橋四氫茀、苯基降莰烯、甲氧羰基降莰烯、甲氧羰基四環十二烯等。這些降莰烯系單體可以單獨使用,也可以併用2種以上。The norbornene-based polymer and the norbornene-based monomer used as raw materials are alicyclic monomers having a norbornene ring. Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylene norbornene, vinylnorbornene, ethylenetetracyclododecene, and dicyclopentadiene. Alkene, dimethyl-bridged tetrahydrofuran, phenylnorbornene, methoxycarbonylnorbornene, methoxycarbonyltetracyclododecene, etc. These norbornene-based monomers may be used alone, or two or more types may be used in combination.
該降莰烯系共聚物,是將該降莰烯系單體與可共聚合的烯烴共聚合而成,作為這樣的烯烴,例如可舉出:乙烯、丙烯、1-丁烯等之具有2~20個碳原子數的烯烴;環丁烯、環戊烯、環己烯等之環烯烴;1,4-己二烯等之非共軛二烯等。The norbornene-based copolymer is obtained by copolymerizing the norbornene-based monomer and a copolymerizable olefin. Examples of such olefin include: ethylene, propylene, 1-butene, etc. having 2 Alkenes with ~20 carbon atoms; cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, etc.; non-conjugated dienes such as 1,4-hexadiene, etc.
中間層(C)中所包含的環狀聚烯烴系樹脂的含量,較佳是在中間層(C)所包含的樹脂成分中的70質量%以上,進而較佳是在80質量%以上,更佳是在90質量%以上。藉由將環狀聚烯烴系樹脂的含量設在該範圍,無損於耐衝擊性,且變得易於實現合適的易撕裂性和直線切割性。The content of the cyclic polyolefin-based resin contained in the intermediate layer (C) is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 70% by mass or more of the resin components contained in the intermediate layer (C). Preferably, it is above 90% by mass. By setting the content of the cyclic polyolefin-based resin within this range, impact resistance is not impaired, and appropriate tearability and straight-line cutting properties become easy to achieve.
又,使用於中間層(C)中的環狀聚烯烴系樹脂,其玻璃轉移溫度較佳為140℃以下,進而較佳為50~140℃,更佳為70~120℃。藉由使用該玻璃轉移溫度者來作為環狀聚烯烴系樹脂,易於獲得良好的耐熱性和剛性,而且還易於提升對於墜落等的耐破袋性。再者,易於獲得良好的互溶性,並易於抑制外觀不均。玻璃轉移溫度(Tg),是藉由DSC(示差掃描測熱法)所測量獲得的値。Furthermore, the glass transition temperature of the cyclic polyolefin-based resin used in the intermediate layer (C) is preferably 140°C or lower, more preferably 50 to 140°C, and even more preferably 70 to 120°C. By using this glass transition temperature as the cyclic polyolefin-based resin, it is easy to obtain good heat resistance and rigidity, and it is also easy to improve the bag breakage resistance against falling and the like. Furthermore, it is easy to obtain good mutual solubility and suppress uneven appearance. Glass transition temperature (Tg) is a value measured by DSC (differential scanning calorimetry).
又,雖然也可以併用不同玻璃轉移溫度的環狀聚烯烴系樹脂,但從擠壓適性、成本、易裂開性等的觀點而言,較佳是其60質量%以上為玻璃轉移點在120℃以下的環狀聚烯烴系樹脂。Furthermore, cyclic polyolefin-based resins with different glass transition temperatures may be used together, but from the viewpoint of extrusion suitability, cost, ease of cracking, etc., it is preferable that 60% by mass or more of the resin has a glass transition point of 120 Cyclic polyolefin-based resin below ℃.
環狀聚烯烴系樹脂的MFR為0.2~17g/10分(230℃,21.18N),較佳為3~15g/10分(230℃,21.18N),更佳為5~13g/10分(230℃,21.18N)。MFR若在此範圍,則考量在與直鏈狀低密度聚乙烯的互溶性優異、而且在各種的多層成膜法中可獲得良好的成膜性之觀點較佳。The MFR of the cyclic polyolefin-based resin is 0.2 to 17 g/10 minutes (230°C, 21.18N), preferably 3 to 15 g/10 minutes (230°C, 21.18N), and more preferably 5 to 13 g/10 minutes ( 230℃, 21.18N). If the MFR is within this range, it is preferable from the viewpoint of excellent compatibility with linear low-density polyethylene and good film-forming properties in various multilayer film-forming methods.
就能夠使用來作為本發明所使用之環狀聚烯烴系樹脂的市售品而言,作為降莰烯系單體的開環聚合物(COP),例如可舉出:日本瑞翁股份有限公司製的「ZEONOR(ZEONOR)」等;作為降莰烯系共聚物(COC),例如可舉出:三井化學股份有限公司製的「APEL」、Polyplastics公司製的「TOPAS(TOPAS)」等。As for commercially available products that can be used as the cyclic polyolefin-based resin used in the present invention, examples of ring-opened polymers (COP) of norbornene-based monomers include: Nippon Zeon Co., Ltd. "ZEONOR (ZEONOR)" manufactured by Mitsui Chemicals Co., Ltd.; examples of the norbornene-based copolymer (COC) include "APEL" manufactured by Mitsui Chemicals Co., Ltd., "TOPAS (TOPAS)" manufactured by Polyplastics Co., Ltd., and the like.
作為中間層(C)中的樹脂成分,雖然僅含有上述環狀聚烯烴系樹脂亦佳,但在無損於本發明之效果的範圍,也可以併用這些樹脂成分以外的其他樹脂。作為其他能夠併用的樹脂種類,例如能夠例示:於上述表面層(A)已例示之聚乙烯系樹脂或聚丙烯系樹脂等之環狀聚烯烴系樹脂以外的不具環狀結構之烯烴系樹脂。在使用這些不具環狀結構之烯烴系樹脂的情況,較佳是設於中間層(C)所包含的樹脂成分中的30質量%以下,進而較佳是設於20質量%以下,更佳是設於10質量%以下。且下限雖然沒有特別限制,只要依照期望的特性,在1質量%以上的含量適當使用即可。As the resin component in the intermediate layer (C), it is preferable to contain only the above-mentioned cyclic polyolefin-based resin. However, other resins other than these resin components may be used together in a range that does not impair the effects of the present invention. Examples of other types of resins that can be used together include olefin resins without a cyclic structure other than cyclic polyolefin resins such as polyethylene resins and polypropylene resins illustrated for the surface layer (A). When using these olefin-based resins without a cyclic structure, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 30% by mass or less of the resin component contained in the intermediate layer (C). Set below 10% by mass. There is no particular lower limit as long as the content is 1% by mass or more according to the desired characteristics.
於中間層(C)中,在上述樹脂成分以外也可以適當併用各種添加劑等。作為添加劑,例如能夠適當使用潤滑劑、抗黏連劑、紫外線吸收劑、光安定劑、抗靜電劑、防霧劑等、著色劑等。在使用這些添加劑的情況,相對於100質量份的使用於中間層(C)之樹脂成分,較佳是以2質量份以下,更佳是以0.01~1質量份左右來使用。In the intermediate layer (C), in addition to the above-mentioned resin components, various additives and the like may be appropriately used in combination. As additives, for example, lubricants, anti-blocking agents, ultraviolet absorbers, light stabilizers, antistatic agents, anti-fogging agents, colorants, etc. can be appropriately used. When using these additives, it is preferable that they are used in an amount of 2 parts by mass or less, and more preferably about 0.01 to 1 part by mass relative to 100 parts by mass of the resin component used in the intermediate layer (C).
又,作為中間層(C)相對於多層薄膜的厚度比率,就成本面與成膜性或薄膜的捲曲性的觀點而言,較佳為30%以下;就後述的藉由共擠壓疊層法實行的成膜為良好而言,較佳為5%以上。In addition, the thickness ratio of the intermediate layer (C) to the multilayer film is preferably 30% or less from the viewpoint of cost, film-forming properties, or film curlability; in terms of lamination by co-extrusion described below, In order to achieve good film formation by the method, it is preferably more than 5%.
[熱封層(D)] 本發明之多層薄膜所使用的熱封層(D),能夠適當使用在各種包裝用薄膜中使用的熱封層。在其中,就易於與該樹脂層(A)、中間層(B)、中間層(C)等疊層之觀點而言,較佳為將聚烯烴系樹脂作為主成分,尤其是將不具環狀結構之聚烯烴系樹脂作為主成分之層。作為該聚烯烴系樹脂,能夠較佳地使用在上述表面層(A)等已例示的聚乙烯系樹脂或聚丙烯系樹脂。[Heat sealing layer (D)] As the heat sealing layer (D) used in the multilayer film of the present invention, heat sealing layers used in various packaging films can be appropriately used. Among them, from the viewpoint of easy lamination with the resin layer (A), the intermediate layer (B), the intermediate layer (C), etc., it is preferable to use a polyolefin-based resin as the main component, and in particular, it is preferable to use a polyolefin-based resin that does not have a cyclic shape. The structure is composed of layers of polyolefin resin as the main component. As the polyolefin-based resin, the polyethylene-based resin or polypropylene-based resin exemplified for the above-mentioned surface layer (A) and the like can be suitably used.
在其中,從強度和密封性、包裝機械適性的觀點而言,較佳為使用密度是0.916~0.935g/cm3 的聚乙烯系樹脂,或者使用係使用茂金屬觸媒所聚合成的丙烯-α-烯烴無規共聚物之聚丙烯樹脂。尤其,就無損於合適的直線切割性等且易於獲得合適的密封性而言,較佳為使用直鏈低密度聚乙烯。再者,就煮沸殺菌步驟中抑制薄膜的相互附著而言,亦是上述密度的範圍較佳。Among them, from the viewpoint of strength, sealing properties, and packaging machine suitability, it is preferable to use a polyethylene resin with a density of 0.916 to 0.935 g/cm 3 or a propylene resin polymerized using a metallocene catalyst. Polypropylene resin of α-olefin random copolymer. In particular, linear low-density polyethylene is preferably used since appropriate straight-cutting properties are not impaired and appropriate sealing properties are easily obtained. Furthermore, in terms of suppressing mutual adhesion of films during the boiling sterilization step, the above-mentioned density range is also preferable.
熱封層(D)所包含的樹脂成分中的上述聚烯烴系樹脂之含量較佳為設於70質量%以上,進而較佳為80質量%以上,更佳為90質量%以上。又,熱封層(D)所包含的樹脂成分中,也可以100質量%是直鏈低密度聚乙烯。The content of the polyolefin-based resin in the resin component contained in the heat seal layer (D) is preferably 70 mass % or more, more preferably 80 mass % or more, and more preferably 90 mass % or more. Moreover, 100 mass % of the resin component contained in the heat-sealing layer (D) may be linear low-density polyethylene.
於中間層(B)中,在無損於本發明之效果的範圍,也可以併用上述聚烯烴系樹脂以外的其他樹脂,作為該其他樹脂,能夠例示:於表面層(A)已例示之熱塑性彈性體或乙烯系共聚物、離子聚合物等。在使用該其他樹脂的情況,其含量較佳是以熱封層(D)所包含的樹脂成分中的30質量%以下來使用,更佳是在10質量%以下,再更佳是在5質量%以下。In the intermediate layer (B), resins other than the above-mentioned polyolefin-based resins may be used together in the range that does not impair the effects of the present invention. Examples of the other resins include the thermoplastic elastic resins exemplified in the surface layer (A). body or vinyl copolymer, ionic polymer, etc. When using this other resin, its content is preferably 30% by mass or less of the resin component contained in the heat sealing layer (D), more preferably 10% by mass or less, and even more preferably 5% by mass or less. %the following.
於熱封層(D)中,在上述樹脂成分以外也可以適當併用各種添加劑等。作為添加劑,例如能夠適當使用潤滑劑、抗黏連劑、紫外線吸收劑、光安定劑、抗靜電劑、防霧劑等、著色劑等。在使用這些添加劑的情況,相對於100質量份的使用於熱封層(D)之樹脂成分,較佳是以2質量份以下,更佳是以0.01~1質量份左右來使用。尤其是為了賦予薄膜成形時的加工適性、充填機的包裝適性,熱封層(D)的摩擦係數在0.9以下,其中較佳是在0.8以下,故適當添加潤滑劑或抗黏連劑到熱封層(D)中亦佳。In the heat sealing layer (D), in addition to the above-mentioned resin components, various additives and the like may be appropriately used in combination. As additives, for example, lubricants, anti-blocking agents, ultraviolet absorbers, light stabilizers, antistatic agents, anti-fogging agents, colorants, etc. can be appropriately used. When using these additives, it is preferable that they are used in an amount of 2 parts by mass or less, and more preferably about 0.01 to 1 part by mass relative to 100 parts by mass of the resin component used in the heat sealing layer (D). In particular, in order to provide processing suitability during film formation and packaging suitability for filling machines, the friction coefficient of the heat seal layer (D) is 0.9 or less, and preferably 0.8 or less, so a lubricant or anti-adhesive agent is appropriately added to the heat seal layer (D). Seal layer (D) is also good.
又,尤其是在以單體使用包裝機械來包裝的情況,就能夠提高密封棒的溫度,能夠提升密封強度的觀點而言,在多層薄膜的表面層(A)與熱封層(D),使用熔點有差異的樹脂較佳,具體而言,較佳為表面層(A)的熔點高於熱封層(D)的熔點10℃以上。Furthermore, especially when a single body is packaged using a packaging machine, from the viewpoint that the temperature of the sealing rod can be increased and the sealing strength can be improved, the surface layer (A) and heat sealing layer (D) of the multilayer film, It is preferable to use resins with different melting points. Specifically, it is preferable that the melting point of the surface layer (A) is 10° C. or more higher than the melting point of the heat seal layer (D).
熱封層(D)相對於多層薄膜之總厚度的厚度比率,從易於獲得合適的裂開性與密封強度而言,較佳是在30%以下,更佳是在10~25%的範圍。The thickness ratio of the heat sealing layer (D) to the total thickness of the multilayer film is preferably 30% or less, more preferably 10 to 25%, in order to easily obtain appropriate crackability and sealing strength.
[多層薄膜] 本發明之多層薄膜(I),係上述表面層(A)、中間層(B)、中間層(C)、及熱封層(D),以(A)/(B)/(C)/(D)的順序疊層而成多層薄膜。本發明之多層薄膜是藉由該構成而成夠實現良好的熱封性和耐衝擊性、易撕裂性,並且實現即使暴露於高溫高濕環境下或低溫環境下後仍優異的朝單向撕裂性。[Multilayer film] The multilayer film (I) of the present invention is the above-mentioned surface layer (A), intermediate layer (B), intermediate layer (C), and heat sealing layer (D), with (A)/(B)/(C)/ (D) is laminated in sequence to form a multilayer film. The multilayer film of the present invention is made of this structure and can achieve good heat sealing properties, impact resistance, and easy tearing properties, and can achieve excellent one-way orientation even after being exposed to high temperature and high humidity environments or low temperature environments. Tearability.
本發明之多層薄膜(I),薄膜的厚度較佳為20~60μm,更佳為30~50μm。若薄膜的厚度在此範圍,易於獲得穩定的密封強度、包裝機械適性、優異的耐針孔性能、易撕裂性能等。In the multilayer film (I) of the present invention, the thickness of the film is preferably 20 to 60 μm, more preferably 30 to 50 μm. If the thickness of the film is within this range, it is easy to obtain stable sealing strength, packaging mechanical suitability, excellent pinhole resistance, easy tearing performance, etc.
又,各層的厚度雖然沒有特別限制,但例如作為表面層(A)的厚度,較佳為3~15μm,更佳為5~12μm。中間層(B)的厚度較佳為8~35μm,更佳為10~30μm。中間層(C)的厚度較佳為1~15μm,更佳為2~10μm。熱封層(D)的厚度較佳為2~20μm,更佳為4~15μm。In addition, the thickness of each layer is not particularly limited, but for example, the thickness of the surface layer (A) is preferably 3 to 15 μm, more preferably 5 to 12 μm. The thickness of the intermediate layer (B) is preferably 8 to 35 μm, more preferably 10 to 30 μm. The thickness of the intermediate layer (C) is preferably 1 to 15 μm, more preferably 2 to 10 μm. The thickness of the heat sealing layer (D) is preferably 2 to 20 μm, more preferably 4 to 15 μm.
本發明之多層薄膜,從保護內容物的觀點而言,其密封強度較佳是在5N/15mm以上,更佳是在10N/15mm以上。From the perspective of protecting the contents, the sealing strength of the multilayer film of the present invention is preferably 5N/15mm or more, and more preferably 10N/15mm or more.
本發明之多層薄膜的霧度,從易於辨識所包裝的內容物而言,較佳是在10%以下,更佳是在8%以下。本發明之多層薄膜,在具有這麼高的透明性的情況,容易實現合適的包裝適性和合適的印刷密合性。The haze of the multi-layer film of the present invention is preferably 10% or less, and more preferably 8% or less from the perspective of easy identification of packaged contents. When the multilayer film of the present invention has such high transparency, it is easy to achieve appropriate packaging suitability and appropriate printing adhesion.
作為本發明之多層薄膜(I)的製造方法,雖然沒有特別限定,但例如可舉出共擠壓法,將樹脂層(A)、中間層(B)、中間層(C)、密封層(D)所使用的各樹脂或樹脂混合物分別以各自的擠壓機進行加熱熔融,藉由共擠壓多層模具法或進料模組法等之方法在熔融狀態以(A)/(B)/(C)/(D)的順序疊層之後,再藉由吹脹或T型模頭-冷卻輥法等成形成薄膜狀。此共擠壓法,因為能比較自由地調整各層的厚度之比率,故可獲得衛生性優異、在成本效率上也優異的多層薄膜而較佳。並且,由於在本發明之中間層(B)所用的聚乙烯系樹脂,與在其他層所使用的高密度聚乙烯、或環狀聚烯烴系樹脂的軟化點(熔點)之差異較大,會有發生相分離或膠體的情況。為了抑制這樣的相分離或膠體的發生,較佳是能夠以較高溫來進行熔融擠壓的T型模具-冷卻輥法。Although the method for producing the multilayer film (I) of the present invention is not particularly limited, for example, a coextrusion method can be used, in which the resin layer (A), the intermediate layer (B), the intermediate layer (C), and the sealing layer ( D) Each resin or resin mixture used is heated and melted in its own extruder, and the molten state is (A)/(B)/ (C)/(D) are sequentially laminated, and then formed into a film shape by inflation or the T-die-cooling roll method. This co-extrusion method is preferable because it can relatively freely adjust the thickness ratio of each layer, so that a multi-layer film with excellent hygiene properties and excellent cost efficiency can be obtained. In addition, since the softening point (melting point) of the polyethylene resin used in the intermediate layer (B) of the present invention is greatly different from that of the high-density polyethylene or cyclic polyolefin resin used in other layers, it may There are cases where phase separation or colloidization occurs. In order to suppress the occurrence of such phase separation or colloid, a T-die-cooling roll method that can perform melt extrusion at a relatively high temperature is preferred.
由於藉由上述的製造方法,本發明之多層薄膜(I)可作為實質上無延伸的多層薄膜而得,故亦能成為藉由真空成形實行的深引伸成形等之二次成形。Since the multilayer film (I) of the present invention can be obtained as a substantially non-stretched multilayer film by the above-mentioned manufacturing method, it can also be used for secondary forming such as deep drawing forming by vacuum forming.
並且,為了提升與印刷印墨的黏接性、或在作為壓合用密封膠膜使用時的壓合適性,較佳為對該樹脂層(A)施以表面處理。作為這樣的表面處理,例如能夠舉出:電暈處理、電漿處理、鉻酸處理、火焰處理、熱風處理、臭氧-紫外線處理等之表面氧化處理,或者噴砂等之表面凹凸處理,但較佳為電暈處理。Furthermore, in order to improve the adhesion with printing ink or the lamination suitability when used as a sealant film for lamination, it is preferable to perform surface treatment on the resin layer (A). Examples of such surface treatment include surface oxidation treatment such as corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, or surface roughening treatment such as sandblasting, but are preferably For corona treatment.
作為由本發明之多層薄膜所構成的包裝材料,可舉出使用於食品、藥品、工業零件、雜貨、雜誌等之用途的包裝袋、包裝容器等。Examples of packaging materials composed of the multilayer film of the present invention include packaging bags and packaging containers used for food, pharmaceuticals, industrial parts, groceries, magazines, and the like.
該包裝袋,較佳是藉由將本發明之多層薄膜(I)的密封層(D)作為熱封層,將密封層(D)彼此重疊並熱封,或者疊合樹脂層(A)與密封層(D)並熱封而形成。例如,能夠將2片該多層薄膜裁切成期望的包裝袋的大小,重疊起來將3邊熱封成為袋狀後,從尚未熱封的1邊填充內容物並熱封而密封起來作為包裝袋使用。並且也可以藉由透過自動包裝機將輥狀的薄膜形成圓筒形並密封端部後,將上下密封來形成包裝袋。This packaging bag is preferably made by using the sealing layer (D) of the multilayer film (I) of the present invention as a heat sealing layer, overlapping the sealing layers (D) with each other and heat sealing, or by laminating the resin layer (A) and The sealing layer (D) is formed by heat sealing. For example, two pieces of the multilayer film can be cut into a desired packaging bag size, overlapped and heat-sealed on three sides to form a bag shape, and then filled with the content from one side that has not yet been heat-sealed and heat-sealed to form a packaging bag. use. In addition, a packaging bag can also be formed by using an automatic packaging machine to form a roll-shaped film into a cylindrical shape, sealing the ends, and then sealing the top and bottom.
又,亦可藉由重疊密封層(D)與可熱封的其他薄膜並熱封來形成包裝袋、容器。此時,作為所使用的其他薄膜,能夠使用機械強度比較弱的LDPE、EVA等之薄膜。再者,亦能夠使用貼合了LDPE、EVA等之薄膜、與撕裂性比較好的延伸薄膜,例如雙軸延伸聚對苯二甲酸乙二酯薄膜(OPET)、雙軸延伸聚丙烯薄膜(OPP)等而成的壓合薄膜。In addition, a packaging bag or container can also be formed by overlapping the sealing layer (D) and other heat-sealable films and heat-sealing them. In this case, as other films used, films such as LDPE and EVA, which have relatively weak mechanical strength, can be used. In addition, you can also use films laminated with LDPE, EVA, etc., and stretch films with relatively good tearability, such as biaxially stretched polyethylene terephthalate film (OPET), biaxially stretched polypropylene film ( Laminated film made of OPP), etc.
本發明之多層薄膜(I),亦能夠與其他基材貼合來使用。作為此時能夠使用的其他基材,雖然沒有特別限定,但從容易展現本發明的效果之觀點而言,較佳為使用具有高剛性、高光澤之塑膠基材,尤其是使用經雙軸延伸的樹脂薄膜。而且在不需要透明性之用途的情況,亦能夠將鋁箔單獨或者組合來使用。The multilayer film (I) of the present invention can also be used in conjunction with other substrates. Although there are no particular limitations on other base materials that can be used at this time, from the viewpoint of easily exhibiting the effects of the present invention, it is preferable to use a plastic base material with high rigidity and high gloss, especially a biaxially stretched plastic base material. resin film. In addition, when transparency is not required, aluminum foils can be used alone or in combination.
作為經延伸的樹脂薄膜,從易撕裂性等之觀點而言,例如可舉出:雙軸延伸聚酯(PET)、易裂開性雙軸延伸聚酯(PET)、雙軸延伸聚丙烯(OPP)、雙軸延伸聚醯胺(PA)、將乙烯-乙烯醇共聚物(EVOH)作為中心層而成的共擠壓雙軸延伸聚丙烯、雙軸延伸乙烯-乙烯醇共聚物(EVOH)、塗佈聚偏二氯乙烯(PVDC)而成的共擠壓雙軸延伸聚丙烯等。這些可以單獨或複合化來使用。Examples of the stretched resin film include biaxially stretched polyester (PET), easily tearable biaxially stretched polyester (PET), and biaxially stretched polypropylene from the viewpoint of easy tearability. (OPP), biaxially stretched polyamide (PA), co-extruded biaxially stretched polypropylene with ethylene-vinyl alcohol copolymer (EVOH) as the central layer, biaxially stretched ethylene-vinyl alcohol copolymer (EVOH) ), co-extruded biaxially stretched polypropylene coated with polyvinylidene chloride (PVDC), etc. These can be used individually or in combination.
作為將該基材疊層於藉由上述的製造方法所獲得的多層薄膜來當作壓合薄膜時的疊層方法,例如可舉出:乾式壓合、濕式壓合、無溶劑壓合、擠壓壓合等之方法。Examples of the lamination method when the base material is laminated on the multilayer film obtained by the above-mentioned production method as a laminate film include dry lamination, wet lamination, solvent-free lamination, Methods such as extrusion and pressing.
作為在該乾式壓合所使用的黏接劑,例如可舉出:聚醚-聚胺酯系黏接劑、聚酯-聚胺酯系黏接劑等。而且雖然亦能夠使用各種黏著劑,但較佳為使用感壓性黏著劑。作為感壓性黏著劑,例如能夠舉出:將聚異丁烯橡膠、丁基橡膠、這些的混合物溶解於苯、甲苯、二甲苯、己烷這類的有機溶劑而成的橡膠系黏著劑;或者,在這些橡膠系黏著劑中摻合松香酸松香酯、萜烯-酚共聚物、萜烯-茚共聚物等之賦黏劑而成者;或者,利用有機溶劑溶解丙烯酸2-乙基己酯-丙烯酸正丁酯共聚物、丙烯酸2-乙基己酯-丙烯酸乙酯-甲基丙烯酸甲酯共聚物等之玻璃轉移點在-20℃以下的丙烯酸系共聚物而成的丙烯酸系黏著劑等。Examples of the adhesive used for dry lamination include polyether-polyurethane adhesives, polyester-polyurethane adhesives, and the like. Moreover, although various adhesives can be used, it is preferable to use a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include rubber-based adhesives in which polyisobutylene rubber, butyl rubber, and mixtures thereof are dissolved in organic solvents such as benzene, toluene, xylene, and hexane; or, These rubber adhesives are blended with adhesive agents such as abietic acid rosin ester, terpene-phenol copolymer, terpene-indene copolymer, etc.; or, an organic solvent is used to dissolve 2-ethylhexyl acrylate- Acrylic adhesives made from acrylic copolymers with a glass transition point below -20°C, such as n-butyl acrylate copolymer and 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer.
使用了本發明之多層薄膜的包裝材料中,為了削弱初始的撕裂強度以提升開封性,較佳是於密封部形成V型切口、I型切口、穿孔、微孔等任意的撕裂起始部。In packaging materials using the multi-layer film of the present invention, in order to weaken the initial tear strength and improve the unsealability, it is preferable to form any tear initiation such as V-shaped cuts, I-shaped cuts, perforations, micropores, etc. in the sealing part. department.
本發明之多層薄膜,因為有著具方向性的易撕裂性,故作為包裝形態,較合適為:將包裝體的上部用帶子或金屬零件或樹脂製的扣合物等捆紮而成的錢包用包裝,或在與薄膜的機械方向所垂直的方向(TD)上附著了具有再密封機能之夾頭、拉鍊等之線狀扣件而成的再密封性包裝。Since the multilayer film of the present invention has directional tearability, it is suitable as a packaging form for wallets in which the upper part of the package is tied with a tape, metal parts, or resin fasteners. Packaging, or resealable packaging with linear fasteners such as chucks and zippers attached with resealability in the direction (TD) perpendicular to the machine direction of the film.
(實施例1) 作為形成表面層(A)、中間層(B)、中間層(C)及熱封層(D)之各層的樹脂成分,分別使用下述之樹脂,來製備形成各層的樹脂混合物。將形成各層的樹脂混合物分別供給到4台的擠壓機,以在表面層(A)/中間層(B)/中間層(C)/熱封層(D)所形成的疊層薄膜之各層的平均厚度成為7μm/15μm/3μm/5μm的方式,在擠壓溫度為250℃由T型模頭進行共擠壓,並以40℃的水冷金屬冷卻輥來冷卻,成形了全厚為30μm的疊層薄膜。其次,以溼潤張力達到40mN/m的方式對獲得的疊層薄膜的表面層(A)施以電暈放電處理,獲得疊層薄膜。 表面層(A):50質量份的丙烯同元聚合物(密度0.900g/cm3 ,MFR8.0g/10min) (以下,稱為PP(1)。)與50質量份的丙烯-乙烯無規共聚物(密度0.900g/cm3 ,MFR8.0g/10min)(以下,稱為PP(2)。)的混合物。 中間層(B):100質量份的直鏈狀低密度聚乙烯(密度0.918g/cm3 ,MFR4.0g/10min)(以下,稱為LLDPE(1)。)。 中間層(C):100質量份的降莰烯系共聚物(密度1.010g/cm3 ,MFR7.0g/10min) (以下,稱為COC(1)。)。 熱封層(D):100質量份的直鏈狀低密度聚乙烯(密度0.935g/cm3 ,MFR5.0g/10min(以下,稱為LLDPE(2)。)。(Example 1) As the resin component forming each layer of the surface layer (A), the intermediate layer (B), the intermediate layer (C) and the heat sealing layer (D), the following resins were used to prepare the resins forming each layer. mixture. The resin mixture forming each layer is supplied to four extruders respectively, so that each layer of the laminated film is formed in the surface layer (A)/intermediate layer (B)/intermediate layer (C)/heat sealing layer (D) The average thickness was 7μm/15μm/3μm/5μm. The T-die was co-extruded at an extrusion temperature of 250°C and cooled by a water-cooled metal cooling roll at 40°C. A total thickness of 30μm was formed. Laminated films. Next, the surface layer (A) of the obtained laminated film was subjected to corona discharge treatment so that the wetting tension became 40 mN/m, thereby obtaining a laminated film. Surface layer (A): 50 parts by mass of propylene homopolymer (density 0.900 g/cm 3 , MFR 8.0 g/10 min) (hereinafter referred to as PP (1).) and 50 parts by mass of propylene-ethylene random A mixture of copolymers (density 0.900 g/cm 3 , MFR 8.0 g/10 min) (hereinafter referred to as PP (2)). Intermediate layer (B): 100 parts by mass of linear low-density polyethylene (density 0.918 g/cm 3 , MFR 4.0 g/10 min) (hereinafter, referred to as LLDPE (1).). Intermediate layer (C): 100 parts by mass of norbornene-based copolymer (density 1.010 g/cm 3 , MFR 7.0 g/10 min) (hereinafter referred to as COC (1).). Heat sealing layer (D): 100 parts by mass of linear low-density polyethylene (density 0.935 g/cm 3 , MFR 5.0 g/10 min (hereinafter referred to as LLDPE (2)).).
(實施例2) 除了將中間層(B)及熱封層(D)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例1同樣地進行而獲得疊層薄膜。 中間層(B):80質量份的LLDPE(1)與20質量份的高密度聚乙烯(密度0.960g/cm3 ,MFR8.0g/10min)(HDPE(1))的混合物。 熱封層(D):100質量份的LLDPE(1)。(Example 2) A laminated film was obtained in the same manner as in Example 1, except that the resin components of the resin mixture used for the intermediate layer (B) and the heat sealing layer (D) were changed to the following components. Intermediate layer (B): a mixture of 80 parts by mass of LLDPE (1) and 20 parts by mass of high-density polyethylene (density 0.960 g/cm 3 , MFR 8.0 g/10 min) (HDPE (1)). Heat sealing layer (D): 100 parts by mass of LLDPE (1).
(實施例3) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例2同樣地進行而獲得疊層薄膜。 中間層(B):90質量份的LLDPE(1)與10質量份的HDPE(1)的混合物。(Example 3) A laminated film was obtained in the same manner as in Example 2 except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): a mixture of 90 parts by mass of LLDPE (1) and 10 parts by mass of HDPE (1).
(實施例4) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例2同樣地進行而獲得疊層薄膜。 中間層(B):100質量份的LLDPE(1)。(Example 4) A laminated film was obtained in the same manner as in Example 2 except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): 100 parts by mass of LLDPE (1).
(實施例5) 除了將中間層(C)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例4同樣地進行而獲得疊層薄膜。 中間層(C):100質量份的降莰烯系共聚物(密度1.020g/cm3 ,MFR8.0g/10min) (以下,稱為COC(2)。)。(Example 5) A laminated film was obtained in the same manner as in Example 4, except that the resin component of the resin mixture used for the intermediate layer (C) was changed to the following components. Intermediate layer (C): 100 parts by mass of norbornene-based copolymer (density 1.020 g/cm 3 , MFR 8.0 g/10 min) (hereinafter referred to as COC (2).).
(實施例6) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例2同樣地進行而獲得疊層薄膜。 中間層(B):100質量份的直鏈狀低密度聚乙烯(密度0.915g/cm3 ,MFR3.0g/10min)(以下,稱為LLDPE(3)。)。(Example 6) A laminated film was obtained in the same manner as in Example 2, except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): 100 parts by mass of linear low-density polyethylene (density 0.915 g/cm 3 , MFR 3.0 g/10 min) (hereinafter, referred to as LLDPE (3).).
(實施例7) 除了將表面層(A)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例5同樣地進行而獲得疊層薄膜。 表面層(A):70質量份的PP(1)與30質量份的PP(2)的混合物。(Example 7) A laminated film was obtained in the same manner as in Example 5, except that the resin component of the resin mixture used for the surface layer (A) was changed to the following components. Surface layer (A): a mixture of 70 parts by mass of PP (1) and 30 parts by mass of PP (2).
(實施例8) 除了將表面層(A)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例4同樣地進行而獲得疊層薄膜。 表面層(A):50質量份的PP(1)與50質量份的丙烯-α-烯烴無規共聚物(密度0.900g/cm3 ,MFR7.0g/10min)(以下,稱為PP(3)。)的混合物。(Example 8) A laminated film was obtained in the same manner as in Example 4, except that the resin component of the resin mixture used for the surface layer (A) was changed to the following components. Surface layer (A): 50 parts by mass of PP (1) and 50 parts by mass of propylene-α-olefin random copolymer (density 0.900 g/cm 3 , MFR 7.0 g/10 min) (hereinafter referred to as PP (3) ).)mixture.
(比較例1) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例2同樣地進行而獲得疊層薄膜。 中間層(B):65質量份的LLDPE(1)與35質量份的HDPE(1)的混合物。(Comparative example 1) A laminated film was obtained in the same manner as in Example 2 except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): a mixture of 65 parts by mass of LLDPE (1) and 35 parts by mass of HDPE (1).
(比較例2) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例5同樣地進行而獲得疊層薄膜。 中間層(B):65質量份的LLDPE(1)與35質量份的HDPE(1)的混合物。(Comparative example 2) A laminated film was obtained in the same manner as in Example 5, except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): a mixture of 65 parts by mass of LLDPE (1) and 35 parts by mass of HDPE (1).
(比較例3) 除了將中間層(B)所使用之樹脂混合物的樹脂成分改成下述成分以外,其餘與實施例1同樣地進行而獲得疊層薄膜。 中間層(B):65質量份的LLDPE(1)與35質量份的HDPE(1)的混合物。(Comparative example 3) A laminated film was obtained in the same manner as in Example 1 except that the resin component of the resin mixture used for the intermediate layer (B) was changed to the following components. Intermediate layer (B): a mixture of 65 parts by mass of LLDPE (1) and 35 parts by mass of HDPE (1).
[耐煮沸性] 用縱向枕型製袋機,將實施例及比較例所獲得的薄膜,以密封層作為內側並在中央密封溫度為160℃、末端密封溫度為150℃的條件來製袋,獲得縱180mm×橫150mm且各密封部的密封寬度為10mm的製袋樣品。使用煮沸殺菌裝置對獲得的製袋樣品施以98℃、30分鐘的加熱處理,並以目視來評估加熱處理後的製袋樣品有無破袋。又,將加熱處理後的製袋樣品冷卻至常溫後,以目視來評估密封面有無相互附著。 ○:無破袋或密封面的相互附著 ×:有破袋或密封面的相互附著[Boiling resistance] Using a longitudinal pillow-type bag making machine, the films obtained in the Examples and Comparative Examples were used to form bags with the sealing layer as the inner side and at a central sealing temperature of 160°C and an end sealing temperature of 150°C to obtain a length of 180 mm × width. 150mm and the sealing width of each sealing part is 10mm. The obtained bag-making samples were heated at 98°C for 30 minutes using a boiling sterilization device, and the bag-making samples after the heat treatment were visually evaluated for bag breakage. In addition, after the heat-treated bag-making sample was cooled to normal temperature, whether the sealing surfaces adhered to each other was visually evaluated. ○: No bag breakage or mutual adhesion of sealing surfaces ×: The bag is broken or the sealing surface is adhered to each other.
[橫裂性] 用縱向枕型製袋機,將實施例及比較例所獲得的薄膜,以密封層作為內側來製袋,獲得縱180mm×橫150mm的製袋樣品。在獲得的製袋樣品的縱向密封部的中央位置,切出5mm的切痕,將該切痕的兩側,以擴展切痕的方式朝縱向側拉伸,並開封至製袋樣品的縱密封面的兩橫端裂開為止。測量開封時的兩橫端部的裂開位置與兩橫端部之縱向的中央位置的距離之差,評估朝橫向的選擇性裂開性。另外,裂開性的評估,進行評估了煮沸殺菌前的製袋樣品、及以與上述[耐煮沸性]評估相同的條件進行煮沸殺菌後在冷藏環境下靜置4小時的製袋樣品。煮沸殺菌前的製袋樣品及煮沸殺菌後冷藏的製袋樣品,係每種分別作成3個,並將此等的平均値作為評估結果。 ○:中央位置與裂開位置的差係兩橫端都未達30mm △:中央位置與裂開位置的差係兩橫端都在30mm以上~40mm以下 ×:未裂開至兩橫端部的製袋樣品為1個以上 [耐衝擊性] 將實施例及比較例所獲得的薄膜,在調整至0℃下的恆溫室內靜置4小時。之後,使用TESTER SANGYO製的BU-302型之Film Impact Tester,在擺錘的前端安裝1.5吋的錘頭,測量藉由薄膜衝擊法得到的衝擊強度。 ○:衝擊強度為0.90(J)以上 △:衝擊強度為0.60以上(J)~未達0.90(J) ×:衝擊強度為未達0.60(J)[Transverse fissure] Using a longitudinal pillow-type bag making machine, the films obtained in Examples and Comparative Examples were used to form bags with the sealing layer as the inner side, and a bag sample having a length of 180 mm and a width of 150 mm was obtained. Cut a 5 mm incision in the center of the longitudinal sealing portion of the obtained bag-making sample, stretch both sides of the incision toward the longitudinal side in a manner that expands the incision, and unseal until the bag-making sample is longitudinally sealed. until the two transverse ends of the surface are split. The difference in distance between the splitting positions of both transverse ends and the longitudinal center positions of both transverse ends at the time of opening was measured to evaluate the selective splitting properties in the transverse direction. In addition, the rupture properties were evaluated by evaluating bag-making samples before boiling sterilization and bag-making samples that were boiled and sterilized under the same conditions as the above [boiling resistance] evaluation and then left to stand in a refrigerated environment for 4 hours. Three bag-making samples before boiling sterilization and refrigerated bag-making samples after boiling sterilization were prepared respectively, and the average value was used as the evaluation result. ○: The difference between the center position and the split position is less than 30mm at both lateral ends. △: The difference between the center position and the split position is between 30mm and 40mm at both transverse ends. ×: There are more than 1 bag-making samples that are not split to both lateral ends. [Impact resistance] The films obtained in Examples and Comparative Examples were left to stand for 4 hours in a constant temperature chamber adjusted to 0°C. After that, a BU-302 Film Impact Tester manufactured by TESTER SANGYO was used to install a 1.5-inch hammer head on the front end of the pendulum to measure the impact strength obtained by the film impact method. ○: Impact strength is 0.90 (J) or more △: Impact strength is 0.60 or more (J) to less than 0.90 (J) ×: Impact strength is less than 0.60(J)
[剛性之測量] 依據ASTM D-882,並且使用TENSILON拉伸試驗機[A&D股份有限公司製]來測量實施例及比較例所獲得的薄膜於23℃的1%切線模數(單位:MPa)。測量是以薄膜製造時的擠壓方向(以下,稱為「MD」)及薄膜橫向(以下,稱為「CD」)來實施。[Measurement of rigidity] The 1% tangent modulus (unit: MPa) of the films obtained in Examples and Comparative Examples at 23° C. was measured in accordance with ASTM D-882 using a TENSILON tensile testing machine [manufactured by A&D Co., Ltd.]. The measurement is carried out in the extrusion direction (hereinafter referred to as "MD") and the transverse direction of the film (hereinafter referred to as "CD") during film production.
[密封強度] 使用實施例及比較例所獲得的薄膜,在150℃、0.2MPa、1秒的條件,作成以密封寬度10mm所熱封而成的試驗片,並裁切成15mm寬,在拉伸試驗機測量密封強度。實施3次相同的評估,將此等的平均値作為評估結果。 ○:熱封強度為5N/15mm以上 ×:熱封強度未達5N/15mm[Seal strength] Using the films obtained in the Examples and Comparative Examples, test pieces were heat-sealed with a sealing width of 10 mm under conditions of 150°C, 0.2 MPa, and 1 second, cut into 15 mm wide, and measured on a tensile testing machine. Seal strength. The same evaluation is performed three times, and the average value is used as the evaluation result. ○: Heat sealing strength is 5N/15mm or more ×: Heat sealing strength does not reach 5N/15mm
[透明性] 依據JIS K7105並使用霧度計(日本電飾工業股份有限公司製)來測量實施例及比較例所獲得的薄膜的霧度(單位:%)。透明性是以下述基準來評估。 ○:霧度未達8% ×:霧度為8%以上[Transparency] The haze (unit: %) of the films obtained in Examples and Comparative Examples was measured using a haze meter (manufactured by Nippon Denshin Industry Co., Ltd.) in accordance with JIS K7105. Transparency is assessed against the following benchmarks. ○: Haze less than 8% ×: Haze is 8% or more
[表面摩擦係數] 依據ASTM-D1894,使用實施例及比較例所獲得的薄膜在23℃、50%RH下,以滑差試驗機法測量表面層(A)彼此的靜摩擦係數及熱封層(D)彼此的靜摩擦係數。 ○:靜摩擦係數未達0.8 ×:靜摩擦係數為0.8以上[Skin friction coefficient] According to ASTM-D1894, the static friction coefficient of the surface layers (A) and the static friction of the heat sealing layers (D) were measured using the slip tester method at 23°C and 50% RH using the films obtained in the Examples and Comparative Examples. coefficient. ○: Static friction coefficient does not reach 0.8 ×: Static friction coefficient is 0.8 or more
將上述所獲得的結果顯示於表1~2。The results obtained above are shown in Tables 1 and 2.
[表1]
[表2]
如同由上述表可明顯得知,實施例1~8的本發明之疊層薄膜,可煮沸殺菌,即使暴露於高溫高濕環境下或低溫環境下後仍顯示出橫裂性,具有合適的耐衝擊強度。另一方面,比較例1~3的疊層薄膜,並未獲得經加熱處理後在低溫環境下的橫裂性、及合適的耐衝擊強度。As can be clearly seen from the above table, the laminated films of the present invention in Examples 1 to 8 can be boiled and sterilized, and still show transverse cracking properties even after being exposed to high temperature and high humidity environments or low temperature environments, and have appropriate resistance. Impact strength. On the other hand, the laminated films of Comparative Examples 1 to 3 did not obtain transverse crack resistance in a low-temperature environment after heat treatment and appropriate impact resistance.
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