JP4318175B2 - Heat-fusible propylene polymer laminated film and use thereof - Google Patents
Heat-fusible propylene polymer laminated film and use thereof Download PDFInfo
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- JP4318175B2 JP4318175B2 JP2003431763A JP2003431763A JP4318175B2 JP 4318175 B2 JP4318175 B2 JP 4318175B2 JP 2003431763 A JP2003431763 A JP 2003431763A JP 2003431763 A JP2003431763 A JP 2003431763A JP 4318175 B2 JP4318175 B2 JP 4318175B2
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- propylene
- heat
- laminated film
- based polymer
- fusible
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- 229920001155 polypropylene Polymers 0.000 title claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 66
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 66
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000004711 α-olefin Substances 0.000 claims description 34
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000002667 nucleating agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001384 propylene homopolymer Polymers 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 235000008429 bread Nutrition 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000013305 food Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 46
- 239000003054 catalyst Substances 0.000 description 17
- 230000000903 blocking effect Effects 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000012793 heat-sealing layer Substances 0.000 description 9
- 229920005604 random copolymer Polymers 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 235000012970 cakes Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 101150048952 TPM-1 gene Proteins 0.000 description 1
- 101150023247 Tefm gene Proteins 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IYYGCUZHHGZXGJ-UHFFFAOYSA-N but-1-ene;ethene;prop-1-ene Chemical compound C=C.CC=C.CCC=C IYYGCUZHHGZXGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000016019 chocolate confectionery Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000009474 immediate action Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000011980 kaminsky catalyst Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019685 rice crackers Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は高速、低圧下における低温ヒートシール性に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性、易カット性等を有する熱融着性プロピレン系重合体積層フィルム及びその用途に関する。 The present invention is a heat-fusible propylene-based polymer laminated film having excellent low-temperature heat-sealability at high speed and low pressure, and having anti-blocking properties, slip properties suitable for packaging materials, transparency, easy-cut properties, and the like, and uses thereof About.
プロピレン系ランダム共重合体から得られるフィルムは低密度ポリエチレン、線状低密度ポリエチレン等のエチレン系重合体から得られるフィルムに比べて、ヒートシール強度、透明性、腰の強さ、耐ブロッキング性、ホットタック性、耐傷付き性、耐熱性等に優れるので、菓子、おにぎり、鮨、パン、ケ−キ、野菜、麺等の食品、或いはシャツ、ズボン等の衣料品を始めとする日用品等あらゆる分野の製品の包装材料として広く使用されている。そして、かかるプロピレン系ランダム共重合体からなるフィルムは低密度ポリエチレン、線状低密度ポリエチレン等のエチレン系重合体からなるフィルムに比べると低温ヒートシール性に劣ることから、その改良が常に要求されている。低温ヒートシール性を改良する方法としては、例えば結晶性プロピレンランダム共重合体と１−ブテン系ランダム共重合体との組成物（特許文献１）、メタロセン触媒を用いた重合方法により得られるプロピレン・α―オレフィンランダム共重合体（例えば、特許文献２）等、種々提案されている。しかしながら、いずれのフィルムも低温ヒートシール性と剛性、密封性、ラミネート強度、耐ブロッキング性、易カット性等のバランスに優れるものは得られていない。 Films obtained from propylene random copolymers are heat-seal strength, transparency, waist strength, blocking resistance compared to films obtained from ethylene polymers such as low-density polyethylene and linear low-density polyethylene. Because it has excellent hot tack, scratch resistance, heat resistance, etc., it can be used in various fields such as confectionery, rice balls, rice cakes, bread, cakes, vegetables, noodles and other daily necessities such as shirts and pants. Widely used as packaging material for products. And since a film made of such a propylene-based random copolymer is inferior in low-temperature heat-sealability as compared with a film made of an ethylene-based polymer such as low-density polyethylene and linear low-density polyethylene, its improvement is always required. Yes. Examples of the method for improving the low temperature heat sealability include a composition of a crystalline propylene random copolymer and a 1-butene random copolymer (Patent Document 1), and a propylene-polymer obtained by a polymerization method using a metallocene catalyst. Various α-olefin random copolymers (for example, Patent Document 2) have been proposed. However, none of the films has an excellent balance of low-temperature heat-sealing properties and rigidity, sealing properties, laminate strength, blocking resistance, easy cutting properties and the like.
そこで本発明は、高速、低圧下における低温ヒートシール性に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性、易カット性等を有する熱融着性プロピレン系重合体多層フィルムを得ることを目的として種々検討した。 Accordingly, the present invention provides a heat-fusible propylene-based polymer multilayer film that is excellent in low-temperature heat-sealability at high speed and low pressure, and has anti-blocking properties, slip properties suitable for packaging materials, transparency, easy-cut properties, and the like. Various studies were conducted for the purpose of obtaining.
すなわち本発明は、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃及び融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満のプロピレン・α―オレフィン共重合体（Ａ）から得られる熱融着層の片面に、結晶化核剤（Ｂ）を含むプロピレン系重合体（Ｃ）組成物から得られる中間層を介してプロピレン・α―オレフィン共重合体（Ａ）から得られるラミネート層が積層されてなることを特徴とする熱融着性プロピレン系重合体積層フィルム及びその用途に関する。 That is, in the present invention, the peak temperature (Tp) determined from the DSC-based crystal melting curve is 110 to 140 ° C., and the difference (Te−Ts) between the melting start temperature (Ts) and the melting end temperature (Te) is 45 ° C. On one side of a heat-sealing layer obtained from a propylene / α-olefin copolymer (A) of less than, via an intermediate layer obtained from a propylene-based polymer (C) composition containing a crystallization nucleating agent (B) The present invention relates to a heat-fusible propylene-based polymer laminated film characterized by laminating a laminate layer obtained from a propylene / α-olefin copolymer (A) and its use.
本発明の熱融着性プロピレン系重合体積層フィルムは、低温ヒートシ−ル性、耐ブロッキング性、包装材料に好適なスリップ性、透明性、易カット性等を有する。 The heat-fusible propylene-based polymer laminated film of the present invention has low-temperature heat sealability, blocking resistance, slip properties suitable for packaging materials, transparency, easy cut properties, and the like.
プロピレン・α−オレフィンランダム共重合体（Ａ）
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃、好ましくは１１５〜１３０℃、融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満、好ましくは３０〜４０℃の範囲にあり、好ましくは融解開始温度（Ｔｓ）とピーク温度（Ｔｐ）との差（Ｔｐ−Ｔｓ）が３５℃未満、より好ましくは２５〜３４℃の範囲にある。プロピレン・α−オレフィン共重合体（Ａ）のα―オレフィンの含有量は上記熱融解特性を有する限りとくに制限はされないが、通常はα―オレフィンの含有量は１．０〜２０重量％、より好ましくは１．５〜１５重量％の範囲にある。α―オレフィンとしては、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等が例示できる。これらの中では、エチレン及び／又は１−ブテンとのランダム共重合体が好ましい。又、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルムとすることができる限り特に限定はされないが、通常０．５〜２０ｇ／１０分、好ましくは２〜１０ｇ／１０分の範囲にある。本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は通常、分子量分布（重量平均分子量Ｍｗと数平均分子量Ｍｎとの比で表される）が２〜３の範囲にある。
本発明に係わるプロピレン・α―オレフィン共重合体（Ａ）は、熱融着性プロピレン系重合体積層フィルムの、熱融着層の原料及びラミネート層の原料となる。
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）の上記ピーク温度（Ｔｐ）、融解開始温度（Ｔｓ）及び融解終了温度（Ｔｅ）は以下の方法で測定した。プロピレン・α−オレフィン共重合体（Ａ）約５ｍｇを秤量し、セイコ−電子工業株式会社製の示差走査熱量計（タイプＤＳＣ２２０モジュ−ル）を用いて、昇温速度；１０℃／分で２００℃まで昇温し、２００℃で５分間保持した後、降温速度；１００℃／分で０℃まで冷却し、再度、昇温速度；１０℃／分で０℃〜２００℃まで昇温したときの融解曲線を測定し、かかる融解曲線から、ＡＳＴＭ Ｄ３４１８−９９の方法に習い、融解曲線からピ−ク温度（Ｔｐ）、融解開始温度（Ｔｓ）、融解終了温度（Ｔｅ）を求めた。尚、本発明では、ＡＳＴＭ Ｄ３４１８−９９に記載の（Ｔｐｍ１）を（Ｔｐ）、（Ｔｅｉｍ）を（Ｔｓ）及び（Ｔｅｆｍ）を（Ｔｅ）とした。
Propylene / α-olefin random copolymer (A)
The propylene / α-olefin copolymer (A) according to the present invention has a peak temperature (Tp) determined from a crystal melting curve based on DSC of 110 to 140 ° C., preferably 115 to 130 ° C., and a melting start temperature (Ts). ) And the melting end temperature (Te) (Te−Ts) is less than 45 ° C., preferably in the range of 30-40 ° C., preferably the difference between the melting start temperature (Ts) and the peak temperature (Tp) ( Tp−Ts) is less than 35 ° C., more preferably in the range of 25 to 34 ° C. The α-olefin content of the propylene / α-olefin copolymer (A) is not particularly limited as long as it has the above-mentioned heat melting characteristics, but usually the α-olefin content is 1.0 to 20% by weight, more Preferably it exists in the range of 1.5 to 15 weight%. Examples of the α-olefin include ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. In these, the random copolymer with ethylene and / or 1-butene is preferable. The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) is not particularly limited as long as it can be made into a film, but is usually 0.5 to 20 g / 10 minutes, preferably 2 to 10 g / 10. In the range of minutes. The propylene / α-olefin copolymer (A) according to the present invention usually has a molecular weight distribution (expressed by a ratio of the weight average molecular weight Mw and the number average molecular weight Mn) in the range of 2 to 3.
The propylene / α-olefin copolymer (A) according to the present invention is a raw material for the heat-fusible layer and a raw material for the laminate layer of the heat-fusible propylene-based polymer laminated film.
The peak temperature (Tp), melting start temperature (Ts) and melting end temperature (Te) of the propylene / α-olefin copolymer (A) according to the present invention were measured by the following methods. About 5 mg of propylene / α-olefin copolymer (A) is weighed, and using a differential scanning calorimeter (type DSC220 module) manufactured by Seiko Denshi Kogyo Co., Ltd., the heating rate is 200 ° C./min. When the temperature was raised to 0 ° C. and held at 200 ° C. for 5 minutes, the temperature was lowered to 0 ° C. at 100 ° C./min, and again raised to 0 ° C. to 200 ° C. at 10 ° C./min. the melting curve is measured, and from such melting curve, learn the methods of ASTM D 3418-99, melting curve Karapi - peak temperature (Tp), the melting start temperature (Ts), was determined melting end temperature (Te). In the present invention, (Tpm1) described in ASTM D 3418-99 is (Tp), (Tim) is (Ts), and (Tefm) is (Te).
結晶化核剤（Ｂ）
本発明に係わる結晶化核剤（Ｂ）は、プロピレン系重合体の結晶化速度を高めるものであれば特に限定はされず、種々公知の結晶化核剤（単に核剤ともいう）であり、具体的には、高密度ポリエチレン、ジベンジリデンソルビト−ル、ビスソルビト−ル、トリベンジリデンソルビト−ル、クロル置換ジベンジリデンソルビト−ル、メチル置換ジベンジリデンソルビト−ル、ヒドロキシ−ジ−アルミニウム、ビスソルビシ−ル、リン酸ビスナトリウムメチレンビスアシッドホスフェ−トナトリウム塩、アジピン酸、安息香酸等を例示できる。
結晶化核剤（Ｂ）のプロピレン系重合体（Ｃ）への添加量は、通常０．０１〜２重量％、好ましくは０．１〜１重量％の範囲であり、かかる結晶化核剤を含むプロピレン系重合体（Ｃ）組成物を熱融着性プロピレン系重合体積層フィルムの中間層とすることにより、易カット性が優れた熱融着性プロピレン系重合体積層フィルムが得られる。
Crystallization nucleating agent (B)
The crystallization nucleating agent (B) according to the present invention is not particularly limited as long as it increases the crystallization rate of the propylene-based polymer, and is a variety of known crystallization nucleating agents (also simply referred to as nucleating agents). Specifically, high-density polyethylene, dibenzylidene sorbitol, bissorbitol, tribenzylidene sorbitol, chloro-substituted dibenzylidene sorbitol, methyl-substituted dibenzylidene sorbitol, hydroxy-di-aluminum Bissorbicyl, bissodium phosphate, methylene bisacid phosphate sodium salt, adipic acid, benzoic acid and the like.
The amount of the crystallization nucleating agent (B) added to the propylene polymer (C) is usually in the range of 0.01 to 2% by weight, preferably 0.1 to 1% by weight. By using the propylene-based polymer (C) composition as an intermediate layer of the heat-fusible propylene-based polymer laminated film, a heat-fusible propylene-based polymer laminated film having excellent easy cutting properties can be obtained.
プロピレン系重合体（Ｃ）
本発明に係わるプロピレン系重合体（Ｃ）は、プロピレンの単独重合体またはプロピレンと１０重量％以下、好ましくは５重量％以下のα−オレフィンとの共重合体、あるいは単独重合体と共重合体との組成物である。α−オレフィンは、プロピレン以外の通常炭素数２〜１０のα−オレフィンであって、例えば、エチレン、１−ブテン、３−メチル−１−ブテン、１―ペンテン、３―メチル―１―ペンテン、４−メチル−１−ペンテン、１―へキセン、１―オクテン等を挙げることができる。これらα−オレフィンの中でも、フィルムにした場合の剛性や易カット性の面からプロピレン単独重合体が好ましい。
かかるプロピレン系重合体（Ｃ）は、フィルムとして成形できる限り、特に限定はされないが、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）が、通常０．１〜１００ｇ／１０分、好ましくは１〜５０ｇ／１０分の範囲にある。
Propylene polymer (C)
The propylene-based polymer (C) according to the present invention is a propylene homopolymer or a copolymer of propylene and 10 wt% or less, preferably 5 wt% or less of an α-olefin, or a homopolymer and a copolymer. And the composition. The α-olefin is usually an α-olefin having 2 to 10 carbon atoms other than propylene, such as ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned. Among these α-olefins, a propylene homopolymer is preferable from the viewpoint of rigidity and easy cutability when formed into a film.
The propylene-based polymer (C) is not particularly limited as long as it can be formed as a film, but MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) is usually 0.1 to 100 g / 10 min. , Preferably in the range of 1-50 g / 10 min.
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）、プロピレン系重合体（Ｃ）には本発明の目的を損なわない範囲で、通常用いられる酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、ブロッキング防止剤、滑剤、核剤、顔料等の添加剤或いは他の重合体を必要に応じて配合することができる。
中でも、熱融着性プロピレン系重合体積層フィルムの熱融着層及びラミネ−ト層を構成するプロピレン・α−オレフィン共重合体（Ａ）にはシリカ、タルク、雲母、ゼオライトや更には金属アルコキシドを焼成して得た金属酸化物等の無機化合物粒子、ポリメタクリル酸メチル、メラミンホルマリン樹脂、メラミン尿素樹脂、ポリエステル樹脂等の有機化合物粒子等、種々公知のブロッキング防止剤を０．０１〜１重量％添加しておくと、更に耐ブロッキング性が改良されたフィルムが得られるので好ましい。これらの中でも、シリカ、ポリメタクリル酸メチルが耐ブロッキング性、透明性の面から特に好ましい。
又、熱融着性プロピレン系重合体積層フィルムの熱融着層及びラミネ−ト層を構成するプロピレン・α−オレフィン共重合体（Ａ）には、炭化水素系、脂肪酸系、高級アルコ−ル系、脂肪族アミド系、金属石鹸系、エステル系等、種々公知の滑剤を０．０１〜１重量％添加しておくと、更にスリップ性が改良されたフィルムが得られるので好ましい。これらの中でも即効性のあるエルカ酸アミドと遅効性のビスオレイン酸アミドあるいはベヘニン酸アミド等の併用系にするとフィルム成形直後とその後の裁断加工時、更には印刷、ラミネ−ト、製袋加工時等の作業性をバランス良く改善することができる。
The propylene / α-olefin copolymer (A) and the propylene-based polymer (C) according to the present invention are not limited to the purpose of the present invention, and usually used antioxidants, weathering stabilizers, antistatic agents, Additives such as antifogging agents, antiblocking agents, lubricants, nucleating agents, pigments or other polymers can be blended as necessary.
Among them, the propylene / α-olefin copolymer (A) constituting the heat-sealing layer and the laminating layer of the heat-fusible propylene polymer laminated film includes silica, talc, mica, zeolite, and further metal alkoxide. 0.01 to 1 weight of various known anti-blocking agents, such as inorganic compound particles such as metal oxides obtained by firing the above, organic compound particles such as polymethyl methacrylate, melamine formalin resin, melamine urea resin, and polyester resin % Addition is preferable because a film with improved blocking resistance can be obtained. Among these, silica and polymethyl methacrylate are particularly preferable in terms of blocking resistance and transparency.
Further, the propylene / α-olefin copolymer (A) constituting the heat-sealing layer and the laminate layer of the heat-fusible propylene-based polymer laminated film includes hydrocarbon-based, fatty acid-based and higher alcohols. It is preferable to add 0.01 to 1% by weight of various known lubricants such as a system, an aliphatic amide system, a metal soap system, and an ester system because a film with improved slip properties can be obtained. Of these, the combination of immediate action erucic acid amide and slow-acting bisoleic acid amide or behenic acid amide can be used immediately after film formation and at the time of subsequent cutting, as well as printing, lamination and bag making. Etc. can be improved in a balanced manner.
プロピレン・α−オレフィン共重合体（Ａ）の製造方法
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は種々公知の方法、例えば、典型的には固体状チタン触媒成分と有機金属化合物触媒成分から形成される触媒、あるいはこれら両成分および電子供与体から形成される触媒を用いて製造することができる。
Production method of propylene / α-olefin copolymer (A) The propylene / α-olefin copolymer (A) according to the present invention is prepared by various known methods, for example, typically a solid titanium catalyst component and an organometallic compound. It can be produced using a catalyst formed from a catalyst component, or a catalyst formed from both of these components and an electron donor.
固体状チタン触媒成分としては、各種方法で製造された三塩化チタンまたは三塩化チタン組成物、あるいはマグネシウム、ハロゲン、電子供与体、好ましくは芳香族カルボン酸エステルまたはアルキル基含有エーテルおよびチタンを必須成分とする、比表面積が好適には１００ｍ２／ｇ以上の担体付チタン触媒成分が挙げられる。特に後者の担体付触媒成分を用いて製造された重合体が好適である。
有機金属化合物触媒成分としては、有機アルミニウム化合物が好適であり、具体的には、トリアルキルアルミニウム、ジアルキルアルミニウムハライド、アルキルアルミニウムセスキハライド、アルキルアルミニウムジハライドなどが挙げられる。これらの化合物のうち、好適な有機金属化合物触媒成分は、使用する上記チタン触媒成分の種類によって異なる。
電子供与体は、窒素、リン、イオウ、酸素、ケイ素、ホウ素などを含む有機化合物であり、好適な具体例としては、これらの元素を有する有機エステル、有機エーテルなどを挙げることができる。
担体付触媒成分を用いた重合体の製造方法に関しては、たとえば特開昭５０−１０８３８５号、特開昭５０−１２６５９０号、特開昭５１−２０２９７号、特開昭５１−２８１８９号、特開昭５２−１５１６９１号などの各公報に開示されている。
As a solid titanium catalyst component, titanium trichloride or a titanium trichloride composition produced by various methods, or magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are essential components. And a supported titanium catalyst component having a specific surface area of preferably 100 m 2 / g or more. In particular, a polymer produced using the latter supported catalyst component is preferred.
The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, and the like. Among these compounds, a suitable organometallic compound catalyst component varies depending on the type of the titanium catalyst component used.
The electron donor is an organic compound containing nitrogen, phosphorus, sulfur, oxygen, silicon, boron, and the like. Suitable specific examples include organic esters and organic ethers having these elements.
With respect to the method for producing a polymer using a catalyst component with a carrier, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP It is disclosed in each publication such as Sho 52-151691.
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は、特にはシングルサイト触媒を用いて製造することができる。シングルサイト触媒は、活性点が均一（シングルサイト）である触媒であり、例えばメタロセン触媒（いわゆるカミンスキー触媒）やブルックハート触媒などがあげられる。例えばメタロセン触媒は、メタロセン系遷移金属化合物と、有機アルミニウム化合物および上記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物からなる群から選ばれる少なくとも一種の化合物とからなる触媒であり、無機物に担持されていてもよい。
前記メタロセン系遷移金属化合物としては、例えば特開平５−２０９０１４号、特開平６−１００５７９号、特開平１−３０１７０４号、特開平３−１９３７９６号、特開平５−１４８２８４号、特開２０００−２０４３１号等に記載された化合物などがあげられる。
The propylene / α-olefin copolymer (A) according to the present invention can be produced particularly using a single site catalyst. The single site catalyst is a catalyst having a uniform active site (single site), and examples thereof include a metallocene catalyst (so-called Kaminsky catalyst) and a Brookhart catalyst. For example, a metallocene catalyst is a catalyst composed of a metallocene transition metal compound, an organoaluminum compound, and at least one compound selected from the group consisting of compounds that react with the metallocene transition metal compound to form an ion pair. It may be carried on.
Examples of the metallocene transition metal compound include JP-A-5-209014, JP-A-6-1005209, JP-A-1-301704, JP-A-3-193966, JP-A-5-148284, and JP-A-2000-20431. And the compounds described in No. and the like.
有機アルミニウム化合物としては、アルキルアルミニウム、または鎖状あるいは環状アルミノキサン等があげられる。上記鎖状あるいは環状アルミノキサンは、アルキルアルミニウムと水とを接触させることにより生成される。例えば重合時にアルキルアルミニウムを加えておいて、後で水を添加するか、あるいは錯塩の結晶水または有機、無機化合物の吸着水とアルキルアルミニウムとを反応させることにより得られる。
前記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物は、例えば特表平１−５０１９５０号、特開平３−２０７７０４号、特開２００２−２０４３１号等に記載された化合物などがあげられる。シングルサイト触媒を担持させる前記無機物としては、シリカゲル、ゼオライト、珪藻土等があげられる。
重合方法としては、塊状重合、溶液重合、懸濁重合、気相重合等があげられる。これらの重合はバッチ法であっても連続法であっても良い。重合条件は通常、重合温度；−１００〜＋２５０℃、重合時間；５分〜１０時間、反応圧力；常圧〜３００Ｋｇ／ｃｍ２（ゲージ圧）である。
Examples of the organoaluminum compound include alkylaluminum, chain or cyclic aluminoxane, and the like. The chain or cyclic aluminoxane is produced by bringing alkylaluminum into contact with water. For example, it can be obtained by adding alkylaluminum at the time of polymerization and adding water later, or by reacting crystallization water of a complex salt or adsorbed water of an organic or inorganic compound with alkylaluminum.
Examples of the compound that reacts with the metallocene transition metal compound to form an ion pair include compounds described in JP-A-1-501950, JP-A-3-207704, JP-A-2002-20431, and the like. . Examples of the inorganic substance that supports the single-site catalyst include silica gel, zeolite, diatomaceous earth, and the like.
Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, gas phase polymerization and the like. These polymerizations may be batch processes or continuous processes. The polymerization conditions are usually a polymerization temperature: −100 to + 250 ° C., a polymerization time: 5 minutes to 10 hours, a reaction pressure; a normal pressure to 300 Kg / cm 2 (gauge pressure).
熱融着性プロピレン系重合体積層フィルム
本発明の熱融着性プロピレン系重合体積層フィルムは、前記プロピレン・α―オレフィン共重合体（Ａ）から得られる熱融着層の片面に、結晶化核剤（Ｂ）を含むプロピレン系重合体（Ｃ）組成物から得られる中間層を介して前記プロピレン・α―オレフィン共重合体（Ａ）から得られるラミネート層が積層されてなる。
熱融着性プロピレン系重合体積層フィルムの厚さは用途により種々決定されるが、通常熱融着層の厚さが１〜８０μｍ、好ましくは２〜５０μｍ、中間層の厚さが８〜４９８μｍ、好ましくは１６〜９６μｍ、ラミネート層の厚さが１〜８０μｍ、好ましくは２〜５０μｍの範囲にあり、積層フィルム全体の厚さが、１０〜５００μｍ、好ましくは２０〜１００μｍの範囲にある。
本発明の熱融着性プロピレン系重合体積層フィルムは、プロピレン・α―オレフィン共重合体（Ａ）を熱融着層及びラミネート層とし、中間層として結晶化核剤（Ｂ）を含むプロピレン系重合体（Ｃ）組成物とすることにより、高速、低圧下における低温ヒートシール性に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性、易カット性等を付与できる。
なお、ラミネート層に用いるプロピレン・α―オレフィン共重合体（Ａ）は、熱融着層に用いるプロピレン・α―オレフィン共重合体（Ａ）と同じ範疇の樹脂であるが、熱融着層に用いるプロピレン・α―オレフィン共重合体（Ａ）と同一であっても、異なってもよい。
本発明の熱融着性プロピレン系重合体積層フィルムは、印刷性あるいは他のフィルムとの接着性、滑り性等を改良するために、ラミネート層の表面を、たとえば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理等で表面活性化処理を行っておいてもよい。
又、用途によっては熱融着性プロピレン系重合体積層フィルムのラミネート層に後述の基材層を貼り合せて種々の用途に用いることもできる。
Heat-fusible propylene-based polymer laminated film The heat-fusible propylene-based polymer laminated film of the present invention is crystallized on one side of the heat-fusible layer obtained from the propylene / α-olefin copolymer (A). A laminate layer obtained from the propylene / α-olefin copolymer (A) is laminated via an intermediate layer obtained from a propylene-based polymer (C) composition containing a nucleating agent (B).
The thickness of the heat-fusible propylene polymer laminated film is variously determined depending on the use, but the thickness of the heat-sealing layer is usually 1 to 80 μm, preferably 2 to 50 μm, and the thickness of the intermediate layer is 8 to 498 μm. The thickness of the laminate layer is in the range of 1 to 80 μm, preferably 2 to 50 μm, and the total thickness of the laminated film is in the range of 10 to 500 μm, preferably 20 to 100 μm.
The heat-fusible propylene-based polymer laminated film of the present invention comprises a propylene / α-olefin copolymer (A) as a heat-fusible layer and a laminate layer, and a propylene-based polymer containing a crystallization nucleating agent (B) as an intermediate layer. By setting it as a polymer (C) composition, it is excellent in the low-temperature heat-sealing property in high speed and low pressure, and can provide blocking resistance, slip property suitable for a packaging material, transparency, easy cut property, etc.
The propylene / α-olefin copolymer (A) used for the laminate layer is a resin in the same category as the propylene / α-olefin copolymer (A) used for the heat seal layer. It may be the same as or different from the propylene / α-olefin copolymer (A) used.
The heat-fusible propylene-based polymer laminated film of the present invention can be applied to the surface of the laminate layer, for example, corona treatment, flame treatment, plasma, in order to improve printability, adhesion to other films, slipperiness, etc. Surface activation treatment may be performed by treatment, undercoat treatment or the like.
In addition, depending on the application, a base material layer described later can be bonded to the laminate layer of the heat-fusible propylene polymer laminated film, and used for various applications.
本発明の熱融着性プロピレン系重合体積層フィルムは公知の種々公知のフィルム成形方法を採用し得る。その際、フィルム成形するには、熱融着層及びラミネ−ト層を構成する上記組成のプロピレン・α―オレフィン共重合体（Ａ）及び中間層の結晶化核剤（Ｂ）を含むプロピレン系重合体（Ｃ）組成物を所定量計量して直接フィルム成形機に投入する。かかる積層フィルムは夫々別個にフィルムを成形後貼り合せてもよいが、三層構造の多層ダイを用いて共押出し成形による方法が最も好ましい。 The heat-fusible propylene-based polymer laminated film of the present invention can employ various known film forming methods. At that time, for forming a film, a propylene-based material containing the propylene / α-olefin copolymer (A) having the above composition constituting the heat-sealing layer and the laminating layer and the crystallization nucleating agent (B) of the intermediate layer A predetermined amount of the polymer (C) composition is weighed and directly charged into a film forming machine. Such laminated films may be individually laminated after being molded, but a method by coextrusion molding using a multilayer die having a three-layer structure is most preferable.
基材層
本発明に係わる基材層は、熱可塑性樹脂からなるシート状またはフィルム状のもの、紙、アルミニウム箔等からなる。熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４−メチル・１−ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン−６、ナイロン−６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。又、かかる熱可塑性樹脂フィルムからなる基材は、無延伸フィルムであっても、延伸フィルムであっても良いし、１種或いは２種以上の共押し出し品、押出しラミ品、ドライラミ品等の積層体であっても良い。
又、基材層の片面あるいは両面を、本発明の熱融着性プロピレン系重合体積層フィルムのラミネート層との接着性を改良するために、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。基材層の厚さは、通常５〜１０００μｍ、好ましくは９〜１００μｍの範囲にある。
Base Material Layer The base material layer according to the present invention is made of a sheet or film made of thermoplastic resin, paper, aluminum foil or the like. As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable. Further, the substrate made of such a thermoplastic resin film may be an unstretched film or a stretched film, and a laminate of one or more coextruded products, extruded laminate products, dry laminate products, etc. It may be the body.
Further, in order to improve the adhesion of one or both sides of the base material layer to the laminate layer of the heat-fusible propylene polymer laminated film of the present invention, for example, corona treatment, flame treatment, plasma treatment, undercoat Surface activation treatment such as treatment, primer coating treatment, and frame treatment may be performed. The thickness of the base material layer is usually 5 to 1000 μm, preferably 9 to 100 μm.
次に本発明を、実施例を通して説明するが、本発明はそれら実施例によって限定されるものではない。 EXAMPLES Next, although this invention is demonstrated through an Example, this invention is not limited by these Examples.
本発明における各種試験法および評価法は次の通りである。
（１）ヒートシール強度（Ｎ／１５ｍｍ）
ヒートシール強度を測定する前に、予め積層フィルムを３８℃オ−ブン中で１５時間エ−ジングした後放冷した。フィルムの熱融着層面を重ね合せ、所定の温度で、幅５ｍｍのシールバーにより、０．２ＭＰａの圧力で１秒間、フィルムの流れ方向に対して直角方向にヒートシールした後放冷した。これから１５ｍｍ幅の試験片を切り取りクロスヘッド速度５００ｍｍ／分でヒートシール部を剥離し、その強度をヒートシール強度とした。
（２）ブロッキング性
ブロッキング性を測定する前に、積層フィルムを３８℃のオ−ブン中で１５時間エ−ジングした後放冷した。フィルムから２０ｍｍ×１００ｍｍ幅の短冊状の試験片を切り取り、熱融着性面を重ね合せたものを５個ずつ作製し、試験片の中央付近で十字方向に直角に市販のプレパラ−トではさむ。試験片とプレパラ−トが重なった５．２ｃｍ２の面積部分に４ｋｇの荷重を掛け、所定の温度条件で２日間エ−ジングした後、放冷する。その後熱融着層面を重ね合せたものをクロスヘッド速度３００ｍｍ／分で剪断剥離を行い、最大強度をブロッキング力とした。ブロッキング力をｎ＝５で評価し、平均値をブロッキング力（Ｎ／５．２ｃｍ２）とした。
（３）易カット性
易引裂性強度を測定する前に、予め積層フィルムを３８℃オ−ブン中で１５時間エ−ジングした後放冷した。フィルムから幅方向（ＭＤ）６５ｍｍ×流れ方向（ＴＤ）５０ｍｍ幅の短冊状の試験片を５枚切り取る。株式会社東洋精機製作所製の軽荷重引裂試験機を用い、フルスケ−ル１．９６Ｎ条件で引裂強度をｎ＝５で評価、平均値を引裂強度力（Ｎ）とし、易カット性を評価した。
Various test methods and evaluation methods in the present invention are as follows.
(1) Heat seal strength (N / 15mm)
Prior to measuring the heat seal strength, the laminated film was aged in a 38 ° C. oven for 15 hours and then allowed to cool. The heat-sealing layer surfaces of the film were superposed, and heat-sealed at a predetermined temperature with a seal bar having a width of 5 mm at a pressure of 0.2 MPa for 1 second in a direction perpendicular to the film flow direction, and then allowed to cool. From this, a test piece having a width of 15 mm was cut and the heat seal part was peeled off at a crosshead speed of 500 mm / min, and the strength was defined as the heat seal strength.
(2) Blocking property Before measuring blocking property, the laminated film was aged in a 38 ° C. oven for 15 hours and then allowed to cool. Cut out strips of 20mm x 100mm width from the film, make 5 pieces of heat-sealable surfaces, and sandwich them with a commercially available slide near the center of the test piece at right angles to the cross direction. . A load of 4 kg is applied to the 5.2 cm 2 area where the test piece and the preparation overlap, and after aging at a predetermined temperature condition for 2 days, it is allowed to cool. Thereafter, the heat-sealing layer surfaces were overlapped and subjected to shear peeling at a crosshead speed of 300 mm / min, and the maximum strength was defined as a blocking force. The blocking force was evaluated at n = 5, and the average value was defined as the blocking force (N / 5.2 cm 2 ).
(3) Easy cutting property Before measuring easy tearing strength, the laminated film was aged in a 38 ° C oven for 15 hours and then allowed to cool. Five strip-shaped test pieces having a width direction (MD) 65 mm × flow direction (TD) 50 mm width are cut out from the film. Using a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd., the tear strength was evaluated at n = 5 under the full scale 1.96N condition, and the average value was taken as the tear strength (N), and the easy-cut property was evaluated.
実施例及び比較例で使用した重合体は次の通りである。
（１） プロピレン・エチレンランダム共重合体（１）（ＰＥＲ）
エチレン含有量：３．１重量％、Ｔｓ：９４．０℃、Ｔｐ：１２６．６℃、Ｔｅ：１３１．４℃、Ｔｅ−Ｔｓ：３７．４℃、Ｔｐ−Ｔｓ：３２．６℃、Ｍｗ／Ｍｎ：２．７及びＭＦＲ：７ｇ／１０分。
（２） プロピレン・エチレン・１−ブテンランダム共重合体（ＰＥＢＲ）
エチレン含有量：２．２重量％、１−ブテン含有量：２．０重量％、Ｔｓ：９５．４℃、Ｔｐ：１３９．３℃、Ｔｅ：１５０．３℃、Ｔｅ−Ｔｓ：５４．９℃、Ｔｐ−Ｔｓ：４３．９℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分。
（３）プロピレン単独重合体（ＰＰ）
Ｔｍ：１６０℃、ＭＦＲ：７ｇ／１０分。
The polymers used in Examples and Comparative Examples are as follows.
(1) Propylene / ethylene random copolymer (1) (PER)
Ethylene content: 3.1 wt%, Ts: 94.0 ° C, Tp: 126.6 ° C, Te: 131.4 ° C, Te-Ts: 37.4 ° C, Tp-Ts: 32.6 ° C, Mw / Mn: 2.7 and MFR: 7 g / 10 min.
(2) Propylene / ethylene / 1-butene random copolymer (PEBR)
Ethylene content: 2.2 wt%, 1-butene content: 2.0 wt%, Ts: 95.4 ° C, Tp: 139.3 ° C, Te: 150.3 ° C, Te-Ts: 54.9 C, Tp-Ts: 43.9 ° C, Mw / Mn: 3.9 and MFR: 7 g / 10 min.
(3) Propylene homopolymer (PP)
Tm: 160 ° C., MFR: 7 g / 10 min.
実施例１
熱融着層としてＰＥＲ、中間層としてＰＰ、及びラミネート層としてＰＥＲを夫々用意して別個の押出機に供給し、Ｔダイ法によって熱融着層／中間層／ラミネ−ト層からなる三層共押出積層フィルムを得た。フィルムの総厚は３０μｍで、各層の厚みは熱融着層：中間層：ラミネート層＝３．０μｍ：２４．０μｍ：３．０μｍであった。尚、中間層を構成するＰＰには、結晶化核剤としてビスソルビト−ル（新日本理化社製 商品名：ゲルオ−ルＭＤ）を５０００ｐｐｍ添加した。
得られた三層共押出積層フィルムの物性等を前記記載の方法で評価した。結果を表１に示す。
Example 1
Three layers consisting of a thermal fusion layer / intermediate layer / laminate layer are prepared by T-die method by preparing PER as a thermal fusion layer, PP as an intermediate layer, and PER as a laminate layer and supplying them to separate extruders. A coextruded laminated film was obtained. The total thickness of the film was 30 μm, and the thickness of each layer was heat fusion layer: intermediate layer: laminate layer = 3.0 μm: 24.0 μm: 3.0 μm. In addition, 5000 ppm of bissorbitol (trade name: Gelol MD, manufactured by Shin Nippon Chemical Co., Ltd.) was added to the PP constituting the intermediate layer as a crystallization nucleating agent.
The physical properties and the like of the obtained three-layer coextrusion laminated film were evaluated by the methods described above. The results are shown in Table 1.
比較例１
実施例１の熱融着層及びとラミネ−ト層に用いたＰＥＲに代えて、ＰＥＢＲを用いる以外は実施例１と同様に行い、三層共押出積層フィルムを得た。
得られた三層共押出積層フィルムの物性等の評価結果を表１に示す。
Comparative Example 1
A three-layer coextrusion laminated film was obtained in the same manner as in Example 1 except that PEBR was used instead of the PER used in the heat-sealing layer and the laminate layer in Example 1.
Table 1 shows evaluation results such as physical properties of the obtained three-layer coextrusion laminated film.
表１から明らかなように、熱融着層とラミネ−ト層に特定のプロピレン・α―オレフィン共重合体を、中間層に結晶化核剤（Ｂ）を含むプロピレン系重合体（Ｃ）組成物を有する熱融着性プロピレン系重合体積層フィルム（実施例１）は、従来のプロピレン・α―オレフィン共重合体を用いた積層フィルム（比較例１）に比べて低温ヒ−トシ−ル性に優れているにもかかわらず耐ブロッキング性が優れていることが分る。又、易カット性も優れていることが分る。 As is apparent from Table 1, the composition of the propylene polymer (C) containing a specific propylene / α-olefin copolymer in the heat-sealing layer and the laminating layer and the crystallization nucleating agent (B) in the intermediate layer The heat-fusible propylene-based polymer laminated film (Example 1) having a product has a low-temperature heat seal property as compared with a conventional laminated film using a propylene / α-olefin copolymer (Comparative Example 1). It can be seen that the anti-blocking property is excellent despite the fact that it is excellent. Moreover, it turns out that easy-cut property is also excellent.
本発明の熱融着性プロピレン系重合体積層フィルムは、低温ヒートシ−ル性、耐ブロッキング性、包装材料に好適なスリップ性、透明性、易カット性等を有する熱融着性プロピレン系重合体積層フィルムとしてそのままでも包装用フィルム、中でも菓子パン、パンケ−キ等のパン類やおにぎり、鮨等の米飯類などの低温ヒートシ−ル性と易カット性を必要とする包装用フィルムとして好適に使用し得る。
又、本発明の熱融着性プロピレン系重合体積層フィルムは更に、低温ヒ−トシ−ル性に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性等の特徴を活かして、上記以外の用途として、飴、せんべい、チョコレ−ト菓子、チョコレ−ト等のお菓子類、珍味等の嗜好品、ハム、ソーセージ、畜肉等の蓄肉加工品、靴下、下着等の衣類、文具及び通販用雑誌類日用雑貨品等の包装材料（規格袋、自働包装用）にも好適である。
The heat-fusible propylene-based polymer laminated film of the present invention is a heat-fusible propylene-based polymer having low-temperature heat seal properties, blocking resistance, slip properties suitable for packaging materials, transparency, easy-cut properties, etc. It is suitable for use as a laminated film as it is as a packaging film, especially as a packaging film that requires low-temperature heat sealability and easy-cutting properties such as breads such as confectionery breads, bread cakes, rice balls, and rice. obtain.
In addition, the heat-fusible propylene-based polymer laminated film of the present invention is further excellent in low-temperature heat seal properties, taking advantage of features such as blocking resistance, slip properties suitable for packaging materials, and transparency, Applications other than the above include sweets such as rice cake, rice crackers, chocolate confectionery, chocolate, etc., delicacy and other favorite products, meat storage products such as ham, sausage, and livestock meat, clothing such as socks and underwear, stationery, and It is also suitable for packaging materials (standard bags, for automatic packaging) such as mail order magazines and daily goods.
Claims (5)
A three-layer coextruded laminated film consisting of a heat-fusion layer / intermediate layer / laminate layer obtained by the T-die method, and a peak temperature (Tp) determined from a crystal melting curve based on DSC of 110 to 140 ° C. and melting Crystallization nuclei are formed on one side of the heat-sealed layer obtained from the propylene / α-olefin copolymer (A) having a difference (Te-Ts) between the starting temperature (Ts) and the melting end temperature (Te) of less than 45 ° C. A laminate layer obtained from the propylene / α-olefin copolymer (A) is laminated through an intermediate layer obtained from a propylene-based polymer (C) composition containing an agent (B). Heat-fusible propylene polymer laminated film.
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