JPH04305429A - Twist-wrapping film - Google Patents
Twist-wrapping filmInfo
- Publication number
- JPH04305429A JPH04305429A JP6986191A JP6986191A JPH04305429A JP H04305429 A JPH04305429 A JP H04305429A JP 6986191 A JP6986191 A JP 6986191A JP 6986191 A JP6986191 A JP 6986191A JP H04305429 A JPH04305429 A JP H04305429A
- Authority
- JP
- Japan
- Prior art keywords
- stretching
- twist
- film
- temperature
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 229920006280 packaging film Polymers 0.000 claims description 9
- 239000012785 packaging film Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000704 physical effect Effects 0.000 abstract description 4
- -1 poly(vinyl benzoate) Polymers 0.000 description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- 235000003403 Limnocharis flava Nutrition 0.000 description 3
- 244000278243 Limnocharis flava Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003440 styrenes Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002021 Aerosil® TT 600 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- KCFQLCPMVCXRHF-UHFFFAOYSA-N O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] Chemical compound O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] KCFQLCPMVCXRHF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 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
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- FAARTQSZKSBAOS-UHFFFAOYSA-N barium(2+);diphosphite Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])[O-].[O-]P([O-])[O-] FAARTQSZKSBAOS-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical group O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- DGVMNQYBHPSIJS-UHFFFAOYSA-N dimagnesium;2,2,6,6-tetraoxido-1,3,5,7-tetraoxa-2,4,6-trisilaspiro[3.3]heptane;hydrate Chemical compound O.[Mg+2].[Mg+2].O1[Si]([O-])([O-])O[Si]21O[Si]([O-])([O-])O2 DGVMNQYBHPSIJS-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007786 electrostatic charging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- BMQVDVJKPMGHDO-UHFFFAOYSA-K magnesium;potassium;chloride;sulfate;trihydrate Chemical compound O.O.O.[Mg+2].[Cl-].[K+].[O-]S([O-])(=O)=O BMQVDVJKPMGHDO-UHFFFAOYSA-K 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003197 poly( p-chlorostyrene) Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate 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
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はひねり包装用フィルムに
関し、詳しくは特定の素材からなるフィルムを二軸延伸
したフィルムであって、透明性，光沢性，弾性率に優れ
たひねり保持度の高いひねり包装に好適なフィルムに関
する。[Industrial Application Field] The present invention relates to a twist packaging film, and more specifically, it is a biaxially stretched film made of a specific material, which has excellent transparency, gloss, and elastic modulus, and has a high twist retention. This invention relates to a film suitable for twist packaging.
【０００２】0002
【従来の技術】従来、菓子等を一個ずつ包装するひねり
包装用のフィルムとしては、パラフィン紙やセロハン等
が使用されている。しかし、パラフィン紙は透明性が不
充分であり、包装の内容物が確認し難く、デイスプレイ
効果が低いという欠点がある。また、セロハンは透明性
，光沢性に優れているが、原料チップの不足によりコス
トが高いものとなるばかりでなく、さらに夏期，冬期の
湿度変化や吸湿によって、物性や寸法が大きく変化する
ため、ひねり保持度の著しい低下，破れ等が生じるとい
う問題がある。2. Description of the Related Art Conventionally, paraffin paper, cellophane, and the like have been used as films for twist wrapping for wrapping sweets and the like one by one. However, paraffin paper has drawbacks such as insufficient transparency, difficulty in confirming the contents of the package, and poor display effect. In addition, although cellophane has excellent transparency and gloss, it is not only expensive due to the lack of raw material chips, but also its physical properties and dimensions change greatly due to changes in humidity and moisture absorption during summer and winter. There are problems such as a significant decrease in twist retention and tearing.
【０００３】このように、充分物性の満足できるひねり
包装用のフィルムは未だ開発されておらず、湿度変化に
対して物性が安定でひねり保持度が高く、デイスプレイ
効果の高い透明性，光沢性に優れたフィルムの開発が望
まれている。さらに、多色印刷を行う場合に、ピッチず
れを起こさない弾性率の高いフィルムであることが要求
されている。[0003] As described above, a film for twist packaging with sufficiently satisfactory physical properties has not yet been developed, and it has stable physical properties against changes in humidity, high twist retention, and transparency and gloss for high display effects. The development of superior films is desired. Furthermore, when performing multicolor printing, a film is required to have a high elastic modulus that does not cause pitch deviation.
【０００４】0004
【発明が解決しようとする課題】本発明者らは、上記従
来のフィルムの問題点を解消し、高い透明性，光沢性，
湿度安定性，ひねり保持度，弾性率等を有するひねり包
装に好適なフィルムの開発を目的として鋭意研究を重ね
た。[Problems to be Solved by the Invention] The present inventors have solved the above-mentioned problems of conventional films, and have achieved high transparency, gloss, and
We conducted extensive research with the aim of developing a film suitable for twist packaging that has humidity stability, twist retention, elastic modulus, etc.
【０００５】[0005]
【課題を解決するための手段】その結果、シンジオタク
チック構造を有するスチレン系重合体あるいはその組成
物からなるフィルムであって、二軸延伸したフィルムが
、上記の目的を満足したひねり包装に好適なフィルムで
あることを見出した。本発明は、かかる知見に基いて完
成したものである。[Means for Solving the Problems] As a result, a biaxially stretched film made of a styrenic polymer having a syndiotactic structure or a composition thereof is suitable for twist packaging that satisfies the above objectives. I found it to be a great film. The present invention was completed based on this knowledge.
【０００６】すなわち、本発明はシンジオタクチック構
造を有するスチレン系重合体またはその組成物からなる
延伸用予備成形体を、二軸延伸してなるひねり包装用フ
ィルムを提供するものである。That is, the present invention provides a twist packaging film obtained by biaxially stretching a preform for stretching made of a styrenic polymer having a syndiotactic structure or a composition thereof.
【０００７】本発明において、シンジオタクチック構造
を有するスチレン系重合体あるいはその組成物をひねり
包装用フィルム素材として用いる。このシンジオタクチ
ック構造を有するスチレン系重合体とは、立体化学構造
がシンジオタクチック構造、即ち、炭素−炭素結合から
形成される主鎖に対して側鎖であるフェニル基や置換フ
ェニル基が交互に反対方向に位置する立体構造を有する
ものであり、そのタクティシティーは同位体炭素による
核磁気共鳴法（ １３Ｃ−ＮＭＲ法）により定量される
。１３Ｃ−ＮＭＲ法により測定されるタクティシティー
は、連続する複数個の構成単位の存在割合、例えば２個
の場合はダイアッド，３個の場合はトリアッド，５個の
場合はペンタッドによって示すことができるが、本発明
に言うシンジオタクチック構造を有するスチレン系重合
体とは、通常はラセミダイアッドで７５％以上、好まし
くは８５％以上、若しくはラセミペンタッドで３０％以
上、好ましくは５０％以上のシンジオタクティシティー
を有するポリスチレン，ポリ（ アルキルスチレン），
ポリ（ ハロゲン化スチレン），ポリ（ アルコキシス
チレン），ポリ（ ビニル安息香酸エステル）， こ
れらの水素化重合体およびこれらの混合物、あるいはこ
れらの構造単位を含む共重合体を指称する。In the present invention, a styrenic polymer having a syndiotactic structure or a composition thereof is used as a film material for twist packaging. Styrenic polymers with a syndiotactic structure have a syndiotactic stereochemical structure, that is, phenyl groups or substituted phenyl groups as side chains alternate with the main chain formed from carbon-carbon bonds. It has a three-dimensional structure located in the opposite direction, and its tacticity is determined by nuclear magnetic resonance method (13C-NMR method) using carbon isotope. Tacticity measured by the 13C-NMR method can be expressed by the proportion of consecutive constituent units, for example, dyads in the case of 2 units, triads in the case of 3 units, and pentads in the case of 5 units. The styrenic polymer having a syndiotactic structure according to the present invention usually has a syndiotactic structure of 75% or more, preferably 85% or more in racemic dyads, or 30% or more, preferably 50% or more in racemic pentads. Polystyrene with otakucity, poly(alkylstyrene),
Refers to poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoate), hydrogenated polymers thereof, mixtures thereof, or copolymers containing structural units of these.
【０００８】なお、ここでポリ（アルキルスチレン）と
しては、ポリ（ メチルスチレン），ポリ（ エチルス
チレン），ポリ（プロピルスチレン），ポリ（ ブチル
スチレン），ポリ（ フェニルスチレン），ポリ（ ビ
ニルナフタレン），ポリ（ ビニルスチレン），ポリ（
アセナフチレン）などがあり、ポリ（ ハロゲン化ス
チレン）としては、ポリ（ クロロスチレン），ポリ（
ブロモスチレン），ポリ（ フルオロスチレン） な
どがある。また、ポリ（ アルコキシスチレン）として
は、ポリ（ メトキシスチレン），ポリ（ エトキシス
チレン）などがある。これらのうち特に好ましいスチレ
ン系重合体としては、ポリスチレン，ポリ（ ｐ−メチ
ルスチレン）， ポリ（ｍ−メチルスチレン），
ポリ（ ｐ−ターシャリーブチルスチレン） ，ポリ（
ｐ−クロロスチレン）， ポリ（ ｍ−クロロスチ
レン）， ポリ（ ｐ−フルオロスチレン） 、また
スチレンとｐ−メチルスチレンとの共重合体をあげるこ
とができる（特開昭６２−１８７７０８号公報）。[0008] Here, poly(alkylstyrene) includes poly(methylstyrene), poly(ethylstyrene), poly(propylstyrene), poly(butylstyrene), poly(phenylstyrene), poly(vinylnaphthalene). , poly(vinylstyrene), poly(
Examples of poly(halogenated styrene) include poly(chlorostyrene) and poly(chlorostyrene).
These include bromostyrene) and poly(fluorostyrene). Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly(p-methylstyrene), poly(m-methylstyrene),
Poly(p-tert-butylstyrene), Poly(
p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and a copolymer of styrene and p-methylstyrene (Japanese Unexamined Patent Publication No. 187708/1983).
【０００９】更に、スチレン系共重合体におけるコモノ
マーとしては、上述の如きスチレン系重合体のモノマー
のほか、エチレン，プロピレン，ブテン，ヘキセン，オ
クテン等のオレフィンモノマー、ブタジエン，イソプレ
ン等のジエンモノマー、環状ジエンモノマーやメタクリ
ル酸メチル，無水マレイン酸，アクリロニトリル等の極
性ビニルモノマー等をあげることができる。Furthermore, as comonomers in the styrene-based copolymer, in addition to the above-mentioned styrene-based polymer monomers, olefin monomers such as ethylene, propylene, butene, hexene, and octene, diene monomers such as butadiene and isoprene, and cyclic Examples include diene monomers, methyl methacrylate, maleic anhydride, polar vinyl monomers such as acrylonitrile, and the like.
【００１０】またこのスチレン系重合体は、分子量につ
いて特に制限はないが、重量平均分子量が １０，００
０ 〜３，０００，０００ のものが好ましく、とりわ
け５０，０００〜 １，５００，０００のものが最適で
ある。ここで重量平均分子量が １０，０００ 未満で
あると、延伸が充分にできない。さらに、分子量分布に
ついてもその広狭は制約がなく、 様々なものを充当す
ることが可能であるが、重量平均分子量（Ｍｗ）／数平
均分子量（Ｍｎ）が１．５〜８が好ましい。なお、この
シンジオタクチック構造を有するスチレン系重合体は、
従来のアタクチック構造のスチレン系重合体に比べて耐
熱性が格段に優れている。[0010] There is no particular restriction on the molecular weight of this styrene polymer, but the weight average molecular weight is 10,00
A value of 0 to 3,000,000 is preferred, and a value of 50,000 to 1,500,000 is particularly optimal. If the weight average molecular weight is less than 10,000, sufficient stretching cannot be achieved. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used, but it is preferable that the ratio of weight average molecular weight (Mw)/number average molecular weight (Mn) is 1.5 to 8. In addition, this styrenic polymer having a syndiotactic structure is
It has much better heat resistance than conventional styrene polymers with an atactic structure.
【００１１】このようなシンジオタクチック構造を有す
るスチレン系樹脂は、例えば不活性炭化水素溶媒中また
は溶媒の不存在下に、チタン化合物及び水とトリアルキ
ルアルミニウムの縮合生成物を触媒として、スチレン系
単量体（上記スチレン系重合体に対応する単量体）を重
合することにより製造することができる（ 特開昭６２
−１８７７０８号公報） 。また、ポリ（ ハロゲン化
アルキルスチレン）については特開平１−４６９１２号
公報，これらの水素化重合体は特開平１−１７８５０５
号公報に記載された手法により得ることができる。[0011]Styrenic resins having such a syndiotactic structure can be produced by styrene-based resins using a titanium compound and a condensation product of water and trialkylaluminium as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrenic polymers) (Japanese Patent Application Laid-Open No. 1983-1999)
-187708). Poly(halogenated alkylstyrene) is disclosed in JP-A-1-46912, and hydrogenated polymers of these are disclosed in JP-A-1-178505.
It can be obtained by the method described in the publication.
【００１２】本発明に用いる素材は、基本的には上記ス
チレン系重合体からなるが、このスチレン系重合体に、
一般に使用されている他の樹脂，ゴム，無機微粒子，酸
化防止剤，核剤，可塑剤，相溶化剤，着色剤，帯電防止
剤などを添加した組成物からなるものでもよい。[0012] The material used in the present invention basically consists of the above-mentioned styrene polymer, but this styrenic polymer contains
It may also be made of a composition to which other commonly used resins, rubbers, inorganic fine particles, antioxidants, nucleating agents, plasticizers, compatibilizers, colorants, antistatic agents, etc. are added.
【００１３】ここで好適に使用できる無機微粒子として
は、ＩＡ族，ＩＩＡ 族，ＩＶＡ 族，ＶＩＡ 族，Ｖ
ＩＩＡ族，ＶＩＩＩ族，ＩＢ族，ＩＩＢ 族，ＩＩＩＢ
族，ＩＶＢ 族元素の酸化物，水酸化物，硫化物，窒素
化物，ハロゲン化物，炭酸塩，酢酸塩，燐酸塩，亜燐酸
塩，有機カルボン酸塩，珪酸塩，チタン酸塩，硼酸塩及
びそれらの含水化合物、それらを中心とする複合化合物
，天然鉱物粒子などがある。具体的には、弗化リチウム
，硼砂（硼酸ナトリウム含水塩） 等のＩＡ族元素化合
物、炭酸マグネシウム，燐酸マグネシウム，酸化マグネ
シウム（マグネシア），塩化マグネシウム，酢酸マグネ
シウム，弗化マグネシウム，チタン酸マグネシウム，珪
酸マグネシウム，珪酸マグネシウム含水塩（タルク），
炭酸カルシウム，燐酸カルシウム，亜燐酸カルシウム，
硫酸カルシウム（石膏），酢酸カルシウム，テレフタル
酸カルシウム，水酸化カルシウム，珪酸カルシウム，弗
化カルシウム，チタン酸カルシウム，チタン酸ストロン
チウム，炭酸バリウム，燐酸バリウム，硫酸バリウム，
亜燐酸バリウム等のＩＩＡ 族元素化合物、二酸化チタ
ン（チタニア），一酸化チタン，窒化チタン，二酸化ジ
ルコニウム（ジルコニア），一酸化ジルコニウム等のＩ
ＶＡ 族元素化合物、二酸化モリブデン，三酸化モリブ
デン，硫化モリブデン等のＶＩＡ 族元素化合物、塩化
マンガン，酢酸マンガン等のＶＩＩＡ族元素化合物、塩
化コバルト，酢酸コバルト等のＶＩＩＩ族元素化合物、
沃化第一銅等のＩＢ族元素化合物、酸化亜鉛，酢酸亜鉛
等のＩＩＢ 族元素化合物、酸化アルミニウム（アルミ
ナ），水酸化アルミニウム，弗化アルミニウム，アルミ
ノシリケート（珪酸アルミナ，カオリン，カオリナイト
）等のＩＩＩＢ族元素化合物、酸化珪素（シリカ，シリ
カゲル），石墨，カーボン，グラファイト，ガラス等の
ＩＶＢ族元素化合物、カーナル石，カイナイト，雲母（
マイカ，キンウンモ），バイロース鉱等の天然鉱物の粒
子が挙げられる。この無機微粒子の平均粒径は、特に制
限はないが、好ましくは０．０１〜１００μｍ、より好
ましくは０．０１〜３μｍで、組成物中の含量は、０．
００１〜３重量％、好ましくは０．００５〜１重量％で
ある。[0013] Inorganic fine particles that can be suitably used here include IA group, IIA group, IVA group, VIA group, V
Group IIA, Group VIII, Group IB, Group IIB, IIIB
Oxides, hydroxides, sulfides, nitrides, halides, carbonates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and of Group IVB elements These include water-containing compounds, composite compounds centered on them, and natural mineral particles. Specifically, Group IA element compounds such as lithium fluoride, borax (sodium borate hydrate), magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, and silicic acid. Magnesium, magnesium silicate hydrate (talc),
Calcium carbonate, calcium phosphate, calcium phosphite,
Calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, strontium titanate, barium carbonate, barium phosphate, barium sulfate,
Group IIA element compounds such as barium phosphite, IA compounds such as titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), zirconium monoxide, etc.
VA group element compounds, VIA group element compounds such as molybdenum dioxide, molybdenum trioxide, and molybdenum sulfide; VIIA group element compounds such as manganese chloride and manganese acetate; VIII group element compounds such as cobalt chloride and cobalt acetate;
IB group element compounds such as cuprous iodide, IIB group element compounds such as zinc oxide and zinc acetate, aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite), etc. Group IIIB element compounds, silicon oxide (silica, silica gel), graphite, carbon, graphite, glass, etc., Group IVB element compounds, carnalite, kainite, mica (
Examples include particles of natural minerals such as mica, phlegm), villose ore, etc. The average particle size of the inorganic fine particles is not particularly limited, but is preferably 0.01 to 100 μm, more preferably 0.01 to 3 μm, and the content in the composition is 0.01 to 100 μm, more preferably 0.01 to 3 μm.
0.001 to 3% by weight, preferably 0.005 to 1% by weight.
【００１４】また、前述の無機微粒子はフィルム面の滑
り性を改善する上で、効果的な成分であるが、本発明の
目的を阻害しない限り、他の種類あるいは他の粒径の微
粒子，無機充填材等を含むものであってもよい。上記無
機微粒子は、最終的な成形品（フィルム）に含有される
が、含有させる方法に限定はない。例えば、スチレン系
単量体の重合中の任意の過程で添加あるいは析出させる
方法、溶融押出する任意の過程で添加する方法が挙げら
れる。[0014]Although the above-mentioned inorganic fine particles are an effective component for improving the slipperiness of the film surface, fine particles of other types or particle sizes, or inorganic It may also contain a filler or the like. The above-mentioned inorganic fine particles are contained in the final molded product (film), but there is no limitation on the method of containing them. Examples include a method of adding or precipitating the styrenic monomer at any step during polymerization, and a method of adding at any step of melt extrusion.
【００１５】一方、上述したシンジオタクチック構造を
有するスチレン系重合体と共に用いることのできる他の
樹脂としては、各種のものがあるが、例えば、アタクチ
ック構造のスチレン系重合体，アイソタクチック構造の
スチレン系重合体，スチレン−無水マレイン酸共重合体
，ポリフェニレンエーテル等は、前述のシンジオタクチ
ック構造のスチレン系重合体と相溶しやすく、延伸用予
備成形体（原反シート，フィルム等）を作成するときの
結晶化の制御に有効で、その後の延伸性が向上し、延伸
条件の制御が容易で、且つ力学物性に優れたフィルムを
得ることができる。このうち、アタクチック構造および
／またはアイソタクチック構造のスチレン系重合体を含
有させる場合、シンジオタクチック構造のスチレン系重
合体と同様のモノマーからなるものが好ましい。また、
これら相溶性樹脂成分の含有割合は７０〜１重量％、特
に好ましくは５０〜２重量％とすればよい。ここで相溶
性樹脂成分の含有割合が７０重量％を超えると、シンジ
オタクチック構造のスチレン系重合体の長所である耐熱
性等が損なわれるため好ましくない。On the other hand, there are various other resins that can be used together with the above-mentioned styrenic polymer having a syndiotactic structure, such as styrenic polymers having an atactic structure and isotactic structure. Styrenic polymers, styrene-maleic anhydride copolymers, polyphenylene ethers, etc. are easily compatible with the above-mentioned syndiotactic structure styrenic polymers, and can be used as preforms for stretching (raw sheets, films, etc.). It is effective in controlling crystallization during production, improves subsequent stretchability, allows easy control of stretching conditions, and provides a film with excellent mechanical properties. Among these, when a styrene polymer having an atactic structure and/or an isotactic structure is contained, it is preferable to use a monomer similar to the styrene polymer having a syndiotactic structure. Also,
The content ratio of these compatible resin components may be 70 to 1% by weight, particularly preferably 50 to 2% by weight. If the content of the compatible resin component exceeds 70% by weight, it is not preferable because the advantages of the syndiotactic styrene polymer, such as heat resistance, will be impaired.
【００１６】また、非相溶性樹脂としては、例えば、ポ
リエチレン，ポリプロピレン，ポリブテン，ポリペンテ
ン等のポリオレフィン、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
ト等のポリエステル、ナイロン−６やナイロン−６，６
等のポリアミド、ポリフェニレンスルフィド等のポリチ
オエーテル、ポリカーボネート、ポリアリレート、ポリ
スルホン、ポリエーテルエーテルケトン、ポリエーテル
スルホン、ポリイミド、テフロン等のハロゲン化ビニル
系重合体、ポリメタクリル酸メチル等のアクリル系重合
体、ポリビニルアルコール等、上記相溶性の樹脂以外は
すべて相当し、さらに、上記相溶性の樹脂を含む架橋樹
脂が挙げられる。これらの樹脂は、本発明のシンジオタ
クチック構造のスチレン系重合体と非相溶であるため、
少量含有する場合、シンジオタクチック構造のスチレン
系重合体中に島のように分散させることができ、延伸後
に程良い光沢を与えたり、表面のすべり性を改良するの
に有効である。これら非相溶性樹脂成分の含有割合は、
光沢を目的とする場合は５０〜２重量％、表面性の制御
を目的とする場合、０．００１〜５重量％が好ましい。
また、製品として使用する温度が高い場合は、耐熱性の
ある樹脂を用いることが好ましい。Examples of the incompatible resin include polyolefins such as polyethylene, polypropylene, polybutene, and polypentene, polyethylene terephthalate,
Polyesters such as polybutylene terephthalate and polyethylene naphthalate, nylon-6 and nylon-6,6
Polyamides such as polyphenylene sulfide, polythioethers such as polycarbonates, polyarylates, polysulfones, polyetheretherketones, polyethersulfones, polyimides, halogenated vinyl polymers such as Teflon, acrylic polymers such as polymethyl methacrylate, All resins other than the above-mentioned compatible resins such as polyvinyl alcohol are applicable, and crosslinked resins including the above-mentioned compatible resins are also included. These resins are incompatible with the syndiotactic structure styrenic polymer of the present invention,
When contained in a small amount, it can be dispersed like islands in a styrenic polymer having a syndiotactic structure, and is effective in imparting a suitable gloss after stretching and improving surface slipperiness. The content ratio of these incompatible resin components is
When the purpose is to improve gloss, the amount is preferably 50 to 2% by weight, and when the purpose is to control surface properties, the amount is preferably from 0.001 to 5% by weight. Furthermore, if the temperature at which the product is used is high, it is preferable to use a heat-resistant resin.
【００１７】本発明のフィルムは、上記シンジオタクチ
ック構造のスチレン系重合体あるいはこれに他の成分を
配合した組成物を素材とした延伸用予備成形体（原反シ
ート，フィルム等）を二軸延伸したものである。この延
伸用予備成形体を製造するには、様々な手法によればよ
いが、例えば上記シンジオタクチック構造のスチレン系
重合体あるいはその組成物を、通常は押出成形（あるい
は共押出成形）して、延伸用予備成形体（フィルム，シ
ートまたはチューブ）とする。この成形にあっては、上
記成形素材の加熱溶融したものを押出成形機にて所定形
状に成形するのが一般的であるが、成形素材を加熱溶融
させずに、軟化した状態で成形してもよい。ここで用い
る押出成形機は、一軸押出成形機，二軸押出成形機のい
ずれでもよく、またベント付き，ベント無しのいずれで
もよいが、一軸の直列タンデム型が好ましい。なお、押
出機には適当なメッシュを使用すれば、夾雑物や異物を
除去することができる。特に平滑面を有する延伸フィル
ムを作成する場合にはメッシュは、１００メッシュ以上
が好ましく、とりわけ４００メッシュ以上が最適である
。ここでこれらのメッシュを用いる際には、メッシュそ
のものの耐圧，強度を考慮して、上記以下の番手を前後
に入れても良い。またメッシュの形状は、平板状，円筒
状等適当に選定して使用することができる。The film of the present invention is produced by biaxially stretching a preformed object (original sheet, film, etc.) made of the above-mentioned styrene-based polymer having a syndiotactic structure or a composition containing the same and other components. It has been stretched. Various methods can be used to produce this preform for stretching, but for example, the above-mentioned syndiotactic styrenic polymer or its composition is usually extruded (or coextruded). , a preform for stretching (film, sheet or tube). In this molding, it is common to heat and melt the above-mentioned molding material and mold it into a predetermined shape using an extrusion molding machine, but the molding material is molded in a softened state without being heated and melted. Good too. The extruder used here may be either a single-screw extruder or a twin-screw extruder, and may be either with or without a vent, but a single-screw tandem type is preferred. Note that impurities and foreign matter can be removed by using a suitable mesh in the extruder. In particular, when producing a stretched film with a smooth surface, the mesh is preferably 100 mesh or more, most preferably 400 mesh or more. When using these meshes, the mesh size below the above may be used in consideration of the pressure resistance and strength of the mesh itself. Moreover, the shape of the mesh can be appropriately selected and used, such as a flat plate shape or a cylindrical shape.
【００１８】またここで押出条件は、特に制限はなく、
様々な状況に応じて適宜選定すればよいが、好ましくは
温度を成形素材の融点〜分解温度より５０℃高い温度の
範囲で選定する。融点より低い温度では溶融不可能であ
り、分解温度より５０℃高い温度を超えると、分解が著
しく、押出機内での発泡等の不良現象を招く。用いるダ
イはＴ−ダイ，円環ダイ等をあげることができる。[0018] Also, there are no particular restrictions on the extrusion conditions;
The temperature may be selected as appropriate depending on various situations, but preferably the temperature is selected within the range of 50° C. higher than the melting point of the molding material to the decomposition temperature. It cannot be melted at a temperature lower than the melting point, and if the temperature exceeds the decomposition temperature by 50° C., the decomposition is significant, leading to defects such as foaming in the extruder. The die used may be a T-die, an annular die, or the like.
【００１９】なお、本明細書において、分解温度とは、
熱重量測定により測定された１％の重量減少を起こす温
度である。例えば、シンジオタクチック構造のスチレン
系重合体の場合、ガラス転移温度（Ｔｇ）は９０〜１０
０℃，融点（Ｔｍ）２６０〜２７５℃，分解温度（Ｔｄ
）３２０℃である。したがって、溶融温度は２７０〜３
５０℃が好ましい。[0019] In this specification, decomposition temperature means
This is the temperature at which a weight loss of 1% occurs as determined by thermogravimetry. For example, in the case of a styrenic polymer with a syndiotactic structure, the glass transition temperature (Tg) is 90 to 10
0℃, melting point (Tm) 260-275℃, decomposition temperature (Td
) 320°C. Therefore, the melting temperature is 270-3
50°C is preferred.
【００２０】上記押出成形後、得られた延伸用予備成形
体を冷却固化する。この際の冷媒は、気体，液体，金属
ロール等各種のものを使用することができる。金属ロー
ル等を用いる場合、エアナイフ，エアチャンバー，タッ
チロール，静電印荷等の方法によると厚みムラや波うち
防止に効果的である。冷却固化の温度は、通常は０℃〜
延伸用予備成形体のガラス転移温度より３０℃高い温度
の範囲、好ましくは２０℃〜ガラス転移温度の範囲であ
る。０℃未満では、冷却速度が必要以上に速くなり、シ
ートの剛性が瞬間的に増加することから、固化途中の溶
融体が波打ち、安定した成形ができない。また、ガラス
転移温度より３０℃高い温度を超えると、固化された成
形体の結晶化度が増加し、延伸適性が悪化する。具体的
には、０〜１３０℃、好ましくは２０〜９０℃で冷却固
化を行う。冷却固化の条件としては、比較的配向の少な
い状態に成形するのが好ましい。After the above extrusion molding, the obtained preform for stretching is cooled and solidified. As the refrigerant at this time, various types such as gas, liquid, and metal rolls can be used. When using a metal roll or the like, methods such as an air knife, air chamber, touch roll, and electrostatic charging are effective in preventing thickness unevenness and waviness. The temperature of cooling and solidification is usually 0℃~
The temperature range is 30° C. higher than the glass transition temperature of the preform for stretching, preferably 20° C. to the glass transition temperature. If the temperature is less than 0°C, the cooling rate becomes faster than necessary, and the rigidity of the sheet increases instantaneously, causing the molten material to wave during solidification, making stable molding impossible. Moreover, when the temperature exceeds 30° C. higher than the glass transition temperature, the degree of crystallinity of the solidified molded article increases and the suitability for stretching deteriorates. Specifically, cooling and solidification are performed at 0 to 130°C, preferably 20 to 90°C. As conditions for cooling and solidifying, it is preferable to form the material into a state with relatively little orientation.
【００２１】本発明のフィルムはこのようにして得られ
た延伸用予備成形体を、二軸延伸したフィルムである。
ここで、二軸延伸の方法については特に制限はなく、従
来から一般に行われている方法でよく、縦方向及び横方
向に同時に延伸してもよく、また任意の順序で逐次延伸
してもよい。また、二軸延伸の処理を多段階で行ったフ
ィルムでもよい。このような二軸延伸における条件等は
特に制限なく、素材の種類，フィルム厚さ等により適宜
選択して行うことができる。The film of the present invention is a film obtained by biaxially stretching the preform for stretching thus obtained. Here, there is no particular restriction on the method of biaxial stretching, and any conventionally commonly used method may be used, and stretching may be carried out simultaneously in the longitudinal and transverse directions, or sequentially in any order. . Moreover, a film subjected to biaxial stretching treatment in multiple stages may also be used. The conditions for such biaxial stretching are not particularly limited, and can be appropriately selected depending on the type of material, film thickness, etc.
【００２２】本発明において、フィルム面内のいずれの
方向にも優れた機械的強度を有するフィルムを効率良く
製造するために、上述で得られた延伸用予備成形体に、
二段階の二軸延伸、特にガラス転移温度〜冷結晶化温度
の範囲で縦・横の二方向に同時にあるいはガラス転移温
度〜融点の範囲で逐次に二軸延伸し、次いでガラス転移
温度〜融点の範囲で同時二軸延伸を行うことが好ましい
。この二段階延伸を行って得られたフィルムは特に好適
なひねり特性を有するものである。In the present invention, in order to efficiently produce a film having excellent mechanical strength in any direction within the film plane, the preform for stretching obtained above is subjected to the following steps:
Two-stage biaxial stretching, particularly biaxial stretching in the vertical and horizontal directions simultaneously in the range of glass transition temperature to cold crystallization temperature or sequentially in the range of glass transition temperature to melting point, and then biaxial stretching in the range of glass transition temperature to melting point. It is preferable to carry out simultaneous biaxial stretching within a range. The film obtained by performing this two-step stretching has particularly suitable twisting characteristics.
【００２３】この二軸延伸についてさらに詳しく説明す
れば次の如くである。一段目の延伸を逐次二軸延伸法で
行う場合、縦延伸は延伸用予備成形体を加熱し、延伸す
ることによって実施される。この延伸温度としては、ガ
ラス転移温度〜融点、好ましくはガラス転移温度以上、
冷結晶化温度（Ｔｃｃ） 以下の範囲（更に好ましくは
、ガラス転移温度以上、冷結晶化温度より１０℃低い温
度以下）の範囲で選定する。ガラス転移温度未満では、
軟化が不充分であるため延伸が困難となり、融点、特に
冷結晶化温度を超えると、結晶化の進行により均一な延
伸が困難となる。The biaxial stretching will be explained in more detail as follows. When the first stage of stretching is performed by a sequential biaxial stretching method, the longitudinal stretching is carried out by heating and stretching the preformed body for stretching. The stretching temperature ranges from the glass transition temperature to the melting point, preferably above the glass transition temperature,
Cold Crystallization Temperature (Tcc) Select within the following range (more preferably above the glass transition temperature and below a temperature 10° C. lower than the cold crystallization temperature). Below the glass transition temperature,
Insufficient softening makes stretching difficult, and when the melting point, particularly the cold crystallization temperature, is exceeded, crystallization progresses, making uniform stretching difficult.
【００２４】またこの縦延伸は、常法によればよい。な
かでもロール間一軸延伸は、縦延伸方法の中で一般的か
つ最も生産性の高い方法であり、これによれば、最低、
二対のニップロール間及びガイドロールで固定され走行
するフィルムを、ニップロールの前工程あるいはロール
自体及び／又はロール間で間接的に加熱し、二対のニッ
プロールの周速差により、縦方向に延伸することができ
る。延伸倍率は、特に制限はなく、通常１．２〜５倍で
、好ましくは２〜４．５倍の範囲で選択すればよい。[0024] This longitudinal stretching may be carried out by a conventional method. Among these, inter-roll uniaxial stretching is the most common and most productive method among longitudinal stretching methods, and according to this, the minimum
A running film fixed between two pairs of nip rolls and a guide roll is heated indirectly in the process before the nip rolls or the roll itself and/or between the rolls, and stretched in the longitudinal direction by the difference in circumferential speed between the two pairs of nip rolls. be able to. The stretching ratio is not particularly limited and may be selected in the range of usually 1.2 to 5 times, preferably 2 to 4.5 times.
【００２５】この二軸延伸では、上記縦延伸を行うこと
により、得られる縦延伸フィルムの複屈折の絶対値｜Δ
ｎ｜が３×１０−３〜７０×１０−３の範囲になるよう
にすることが好ましい。ここで｜Δｎ｜が３×１０−３
未満では、縦方向の延伸効果が充分でなく、また７０×
１０−３を超えると、縦方向に延伸過剰となり、次段階
の横延伸が困難且つ不均一になり易い。なお、複屈折の
絶対値｜Δｎ｜は、縦方向の屈折率ｎＭＤと横方向の屈
折率ｎＴＤとの差であり、偏光顕微鏡にセットされたベ
レクのコンペンセータや、偏光子を組み合わせたレーザ
ーによる強度測定あるいは直接、アッベの屈折計により
ｎＭＤおよびｎＴＤを測定することにより得られる。[0025] In this biaxial stretching, the absolute value of birefringence of the longitudinally stretched film obtained by performing the above longitudinal stretching is
It is preferable that n| is in the range of 3×10 −3 to 70×10 −3 . Here |Δn| is 3×10−3
If it is less than 70×, the stretching effect in the longitudinal direction will not be sufficient.
If it exceeds 10-3, the stretching will be excessive in the machine direction, and the next step of horizontal stretching will be difficult and likely to be non-uniform. The absolute value of birefringence |Δn| is the difference between the refractive index nMD in the longitudinal direction and the refractive index nTD in the lateral direction, and is the difference between the refractive index nMD in the longitudinal direction and the refractive index nTD in the lateral direction, and the intensity determined by a Berek compensator set on a polarizing microscope or a laser combined with a polarizer. It can be obtained by measurement or directly by measuring nMD and nTD with an Abbe refractometer.
【００２６】逐次二軸延伸法では、次に、このようにし
て得た縦延伸フィルムを、横方向に延伸する。延伸は常
法をはじめ様々な手法によればよく、特に制限はない。
中でもテンター横延伸は、一般的に走行中のフィルムの
両端を連続的に走行するクリップ等で固持し、その固持
したままの状態で適当な温度雰囲気中にフィルムを搬入
し、両端のクリップ間の距離をクリップが走行するレー
ルの軌道を変えることにより変化させ、横方向に延伸す
るものである。この際の延伸温度は、適宜選定すればよ
いが、通常はガラス転移温度以上、融点以下、好ましく
はガラス転移温度より５℃高い温度以上、融点より３０
℃低い温度以下、より好ましくはガラス転移温度より１
０℃高い温度以上、融点より４０℃低い温度以下にする
。ここで、延伸温度がガラス転移温度未満では、軟化が
不充分のため延伸が困難な場合があり、また融点を超え
ると、延伸の効果がない。In the sequential biaxial stretching method, the longitudinally stretched film thus obtained is then stretched in the transverse direction. Stretching may be carried out by various methods including conventional methods, and is not particularly limited. Among these, in tenter horizontal stretching, the ends of the running film are generally held in place by continuously running clips, etc., and the film is carried into an atmosphere at an appropriate temperature while being held in place, and the film is stretched between the clips at both ends. The distance is changed by changing the track of the rail on which the clip runs, and the clip extends in the lateral direction. The stretching temperature at this time may be selected as appropriate, but is usually above the glass transition temperature and below the melting point, preferably above 5°C higher than the glass transition temperature, and 30°C above the melting point.
℃ lower temperature or lower, more preferably 1°C lower than the glass transition temperature
The temperature should be at least 0°C higher and 40°C lower than the melting point. Here, if the stretching temperature is lower than the glass transition temperature, stretching may be difficult due to insufficient softening, and if it exceeds the melting point, the stretching has no effect.
【００２７】横延伸は、延伸倍率については特に制限は
なく、状況に応じて適宜定めればよいが、一般的には１
．５〜５倍、好ましくは２．０〜４．５倍の範囲とする
。ここで延伸倍率が、１．５倍未満では充分な延伸が行
えず、得られる延伸フィルムの横方向の機械的強度が充
分でない。一方、５倍を超えると、延伸過剰となり、延
伸破壊を招きやすくなる。[0027] In the transverse stretching, there is no particular restriction on the stretching ratio, and it may be determined as appropriate depending on the situation, but in general, the stretching ratio is 1.
．． The range is 5 to 5 times, preferably 2.0 to 4.5 times. If the stretching ratio is less than 1.5 times, sufficient stretching cannot be carried out, and the resulting stretched film will not have sufficient mechanical strength in the transverse direction. On the other hand, if it exceeds 5 times, the stretching becomes excessive, which tends to cause stretching failure.
【００２８】上記の二軸延伸の態様において、延伸を同
時二軸延伸で行う場合には、この同時二軸延伸方法とし
て、テンターによる方法，気体圧力を利用してバブリン
グによる方法，圧延による方法など様々であり、縦・横
同時に延伸できるものであれば良く、特に制限はない。
これらの方法を適当に選定あるいは組み合わせて適用す
ればよい。延伸倍率は縦・横ともに、１．２〜５．０倍
、好ましくは１．５〜５．０倍とするが、縦，横の延伸
倍率が異なってもよい。また、全面積倍率（縦横の延伸
倍率の積）が２〜２５倍となるように延伸を行う。全面
積倍率が２倍未満のときは、延伸効果は充分に発現せず
、２５倍を超えると、次段の延伸成形が困難となる場合
がある。特に全面積倍率が３〜２５倍となるように延伸
を行うのが好ましい。[0028] In the above-mentioned biaxial stretching mode, when the stretching is carried out by simultaneous biaxial stretching, the simultaneous biaxial stretching method may include a method using a tenter, a method using bubbling using gas pressure, a method using rolling, etc. There are various types, and there is no particular restriction as long as it can be stretched both vertically and horizontally. These methods may be appropriately selected or combined. The stretching ratio is 1.2 to 5.0 times, preferably 1.5 to 5.0 times in both length and width, but the stretching ratio in length and width may be different. Further, stretching is performed so that the total area magnification (product of longitudinal and lateral stretching magnifications) is 2 to 25 times. When the total area magnification is less than 2 times, the stretching effect is not sufficiently exhibited, and when it exceeds 25 times, the next step of stretch forming may become difficult. In particular, it is preferable to carry out the stretching so that the total area magnification is 3 to 25 times.
【００２９】延伸温度は、一般には予備成形体のガラス
転移温度と冷結晶化温度（Ｔｃｃ） の間で設定すれば
よい。ガラス転移温度未満であると、軟化が不充分で、
延伸が不可能となり、一方冷結晶化温度を超えると、結
晶化の進行により延伸が不均一になりやすいという不都
合がある。The stretching temperature may generally be set between the glass transition temperature and the cold crystallization temperature (Tcc) of the preform. If it is below the glass transition temperature, softening is insufficient,
On the other hand, if the temperature exceeds the cold crystallization temperature, there is a disadvantage that the drawing tends to become non-uniform due to the progress of crystallization.
【００３０】このようにして一段目の二軸延伸を行った
予備成形体を、二段目の同時二軸延伸に付す。この二段
目の同時二軸延伸を行うために用いる延伸装置は、フィ
ルムを縦・横両方向に同時に延伸するものであれば良く
、特に制限はない。例えば、クリップで両端を挟み、そ
の両端のクリップの間隔とクリップ相互の間隔を同時に
広げることによって縦・横両方向に同時に延伸するもの
であっても良い。このとき、同時二軸延伸後のフィルム
の複屈折の絶対値｜Δｎ｜が４０×１０−３以下になる
ように同時二軸延伸を行うことが好ましい。同時二軸延
伸後のフィルムの複屈折の絶対値｜Δｎ｜が４０×１０
−３を超えると、縦・横の強度バランスが悪化する。そ
のため、延伸温度をガラス転移温度（二次転移点）から
融点の範囲、好ましくは一段目の延伸温度より１０℃低
い温度〜融点より４０℃低い温度とし、延伸倍率を縦・
横両方向とも１．２〜５倍、好ましくは１．２〜３．５
倍として延伸を行う。縦・横の延伸倍率は、同じであっ
も異なっていても良い。しかし、延伸倍率が１．２倍未
満であると、強度の高いフィルムが得られず、５倍を超
えると、延伸中の破断が頻発することがあり、安定した
成形が得られにくい。The preform thus subjected to the first stage of biaxial stretching is subjected to the second stage of simultaneous biaxial stretching. The stretching device used to perform the second stage simultaneous biaxial stretching is not particularly limited as long as it can stretch the film simultaneously in both longitudinal and transverse directions. For example, it may be possible to hold both ends with clips and simultaneously widen the gap between the clips at both ends and the gap between the clips to simultaneously stretch in both the vertical and horizontal directions. At this time, it is preferable to perform simultaneous biaxial stretching so that the absolute value |Δn| of birefringence of the film after simultaneous biaxial stretching is 40×10 −3 or less. The absolute value of birefringence of the film after simultaneous biaxial stretching |Δn| is 40×10
If it exceeds -3, the strength balance between vertical and horizontal directions will deteriorate. Therefore, the stretching temperature is set in the range from the glass transition temperature (secondary transition point) to the melting point, preferably from 10°C lower than the first-stage stretching temperature to 40°C lower than the melting point, and the stretching ratio is set in the longitudinal direction.
1.2 to 5 times in both horizontal directions, preferably 1.2 to 3.5
Stretching is performed as a double. The longitudinal and lateral stretching ratios may be the same or different. However, if the stretching ratio is less than 1.2 times, a film with high strength cannot be obtained, and if it exceeds 5 times, breakage may occur frequently during stretching, making it difficult to obtain stable molding.
【００３１】また、この二段目の同時二軸延伸後のフィ
ルムの全面積倍率は１０倍以上、好ましくは１１倍以上
にすることが好ましい。全面積倍率が１０倍未満である
と、充分に両方向に延伸された状態とならず、充分な強
度が得られないことがある。以上のような二軸延伸を行
って得られたフィルムは、機械的特性，ひねり保持度，
光沢性，透明性等に特に優れたものである。The total area magnification of the film after the second simultaneous biaxial stretching is preferably 10 times or more, preferably 11 times or more. If the total area magnification is less than 10 times, it may not be sufficiently stretched in both directions, and sufficient strength may not be obtained. The film obtained by biaxial stretching as described above has mechanical properties, twist retention,
It has particularly excellent gloss and transparency.
【００３２】さらに、本発明のフィルムにおいて、二軸
延伸をした後、必要に応じて熱処理を施したものである
ことが好ましい。この熱処理は、フィルムを緊張状態に
保持して行われ、フィルムが緊張状態にないと、フィル
ムに収縮が生じて、フィルムが不均一になり易い。また
、この際の熱処理温度は、延伸終了したフィルムの融点
以下、好ましくは融点−１００℃以上、融点−５℃以下
の範囲で選定する。その他、最適な温度条件は、オーブ
ン内を通過するフィルムのスピード、つまり処理時間に
より設定すべきである。また処理時間は、各種条件によ
り定めればよいが、通常は設備上、また省力化の為、３
分以下に設定するのが好ましい。熱処理時間が長すぎる
と、成形中にフィルムの破断を招き易い。なお、この際
必要に応じて、巻取後における熱処理（例えばエージン
グ）を、連続ラインとは離れたところで施してもよい。
また、熱処理を行わない場合、機械的強度はほぼ満足さ
れるものの、耐熱性に劣り、熱により容易に変形してし
まうことがある。さらに、熱処理後に、コーティングを
したり、ラミネートや蒸着処理を施すこともできる。さ
らに表面処理のために、プラズマ処理やコロナ処理，火
炎処理等を行ったものでもよい。Furthermore, it is preferable that the film of the present invention is subjected to heat treatment if necessary after biaxial stretching. This heat treatment is performed while keeping the film under tension. If the film is not under tension, the film tends to shrink and become non-uniform. Further, the heat treatment temperature at this time is selected to be below the melting point of the stretched film, preferably within the range of -100°C or more and -5°C or less. In addition, the optimum temperature conditions should be determined by the speed of the film passing through the oven, that is, the processing time. The processing time may be determined depending on various conditions, but it is usually
It is preferable to set it to less than 1 minute. If the heat treatment time is too long, the film is likely to break during molding. At this time, if necessary, heat treatment (for example, aging) after winding may be performed at a location away from the continuous line. Furthermore, when heat treatment is not performed, although the mechanical strength is almost satisfied, the heat resistance is poor and the material may be easily deformed by heat. Furthermore, after the heat treatment, coating, lamination, or vapor deposition treatment can also be performed. Further, for surface treatment, it may be subjected to plasma treatment, corona treatment, flame treatment, etc.
【００３３】本発明のひねり包装用フィルムは、このよ
うな各操作を連続的に行うことによって、製造すること
ができる。本発明のフィルムの厚さは、特に制限はない
が、一般に包装用フィルムとして利用するにあたっては
、５〜５０μｍが操作性等において好ましい。[0033] The twist packaging film of the present invention can be manufactured by continuously performing each of the above operations. The thickness of the film of the present invention is not particularly limited, but in general, when used as a packaging film, it is preferably 5 to 50 μm in terms of operability and the like.
【００３４】[0034]
【実施例】次に、本発明を実施例及び比較例に基づいて
、さらに詳しく説明する。[Examples] Next, the present invention will be explained in more detail based on Examples and Comparative Examples.
【００３５】参考例１
（１）トリメチルアルミニウムと水との接触生成物の調
製
アルゴン置換した内容積５００ｍｌをガラス製容器に、
硫酸銅５水塩（ＣｕＳＯ４ ・５Ｈ２ Ｏ） １７．８
ｇ（７１ミリモル）， トルエン２００ｍｌ及びトリ
メチルアルミニウム２４ｍｌ（２５０ミリモル）を入れ
、４０℃で８時間反応させた。その後、固体部分を除去
して得られた溶液から、更に、トルエンを室温下で減圧
留去して接触生成物６．７ｇを得た。このものの凝固点
降下法によって測定した分子量は６１０であった。Reference Example 1 (1) Preparation of contact product of trimethylaluminum and water A glass container with an internal volume of 500 ml, which had been replaced with argon,
Copper sulfate pentahydrate (CuSO4 ・5H2 O) 17.8
g (71 mmol), 200 ml of toluene, and 24 ml (250 mmol) of trimethylaluminum were added, and the mixture was reacted at 40° C. for 8 hours. Thereafter, from the solution obtained by removing the solid portion, toluene was further distilled off under reduced pressure at room temperature to obtain 6.7 g of a contact product. The molecular weight of this product was 610 as measured by freezing point depression method.
【００３６】（２）スチレン系重合体の製造内容積２リ
ットルの反応容器に、上記（１）で得られた接触生成物
をアルミニウム原子として５ミリモル，トリイソブチル
アルミニウムを５ミリモル，ペンタメチルシクロペンタ
ジエニルチタントリメトキシド０．０２５ミリモル及び
精製スチレン１リットルを加え、９０℃で５時間重合反
応を行った。その後、生成物を水酸化ナトリウムのメタ
ノール溶液で触媒成分を分解後、メタノールで繰返し洗
浄し、乾燥して重合体（ポリスチレン） ３０８ｇを得
た。(2) Production of styrenic polymer In a reaction vessel with an internal volume of 2 liters, 5 mmol of the contact product obtained in (1) above as aluminum atoms, 5 mmol of triisobutylaluminum, and pentamethylcyclopenta 0.025 mmol of dienyl titanium trimethoxide and 1 liter of purified styrene were added, and a polymerization reaction was carried out at 90° C. for 5 hours. Thereafter, the product was decomposed with a methanol solution of sodium hydroxide to decompose the catalyst component, washed repeatedly with methanol, and dried to obtain 308 g of a polymer (polystyrene).
【００３７】次いで、この重合体を、１，２，４−トリ
クロロベンゼンを溶媒として、１３５℃でゲルパーミエ
ーションクロマトグラフィーにて測定した。その結果、
この重合体の重量平均分子量は ３８９，０００，重量
平均分子量／数平均分子量は２．６４であった。また融
点及び１３Ｃ−ＮＭＲ測定により、得られた重合体は、
シンジオタクチック構造のポリスチレンであることを確
認した。この重合体のペレットの３００℃，剪断速度２
００／秒での溶融粘度は２×１０４ ポイズであった。Next, this polymer was measured by gel permeation chromatography at 135°C using 1,2,4-trichlorobenzene as a solvent. the result,
The weight average molecular weight of this polymer was 389,000, and the weight average molecular weight/number average molecular weight was 2.64. Furthermore, the obtained polymer was determined by melting point and 13C-NMR measurements.
It was confirmed that it was polystyrene with a syndiotactic structure. Pellet of this polymer at 300℃, shear rate 2
The melt viscosity at 00/sec was 2 x 104 poise.
【００３８】参考例２
精製スチレンモノマー１００重量部に、乾式法シリカ（
デグツサ（株）製アエロジル ＴＴ−６００（ １次
粒子の直径４０μｍのもの ）を０．４部添加し、Ｔ．
ＫホモミキサーＬ型（特殊機化工業製）を用いて、円筒
容器の中で混合攪拌してスチレン混合物を得た。なおこ
の際、ステアリン酸カルシウムを０．０５重量部加えた
。この無機微粒子を分散させたスチレンを用いたことの
他は参考例１と同様に操作した。Reference Example 2 100 parts by weight of purified styrene monomer was added with dry process silica (
0.4 part of Aerosil TT-600 (primary particles with a diameter of 40 μm) manufactured by Degutsusa Co., Ltd. was added, and T.
A styrene mixture was obtained by mixing and stirring in a cylindrical container using a K homomixer L type (manufactured by Tokushu Kika Kogyo). At this time, 0.05 parts by weight of calcium stearate was added. The same procedure as in Reference Example 1 was carried out except that styrene in which the inorganic fine particles were dispersed was used.
【００３９】得られた重合体の重量平均分子量は ３８
８，０００でであり、重量平均分子量／数平均分子量は
２．７０であった。また融点及び１３Ｃ−ＮＭＲ測定に
より得られた重合体はシンジオタクチック構造のポリス
チレンであることを確認した。なおこの重合体中のシリ
カの含量は０．４重量％で、３００℃， 剪断速度２０
０／秒での溶融粘度は２×１０４ ポイズであった。The weight average molecular weight of the obtained polymer was 38
8,000, and the weight average molecular weight/number average molecular weight was 2.70. Furthermore, it was confirmed by melting point and 13C-NMR measurements that the obtained polymer was polystyrene with a syndiotactic structure. The content of silica in this polymer was 0.4% by weight, and the temperature was 300°C and the shear rate was 20.
The melt viscosity at 0/sec was 2 x 104 poise.
【００４０】実施例１
参考例１で得られたスチレン系重合体を充分に減圧乾燥
した後、３００℃に溶融し、キャピラリー付き押出機で
押出し、ストランドをカットしてペレットとした。この
ペレットを１２０℃の熱風乾燥器中で結晶化させた。次
に、結晶化させたペレットを単軸押出機の先端にＴダイ
を取りつけた装置で３２０℃で溶融押出し、７０℃の冷
却ロールで冷却し、原反シートを得た。この原反シート
の結晶化度を示差走査熱量計にて測定したところ１５％
であった。また、この原反シートの冷結晶化温度は１５
０℃であり、ガラス転移点は９８℃であり、融点は２７
０℃であり、分解温度は３２２℃であった。Example 1 The styrenic polymer obtained in Reference Example 1 was thoroughly dried under reduced pressure, then melted at 300°C, extruded using an extruder equipped with a capillary, and pellets were obtained by cutting strands. This pellet was crystallized in a hot air dryer at 120°C. Next, the crystallized pellets were melt-extruded at 320°C using a single-screw extruder equipped with a T-die at the tip, and cooled with a cooling roll at 70°C to obtain a raw sheet. The crystallinity of this original sheet was measured using a differential scanning calorimeter and was 15%.
Met. In addition, the cold crystallization temperature of this raw sheet is 15
0°C, the glass transition point is 98°C, and the melting point is 27°C.
The decomposition temperature was 322°C.
【００４１】この原反シートの両端をチャックで固定し
、チャック間の距離を幅方向に変化させると共に、隣接
したチャック間の距離をも変化させて縦方向にも延伸が
可能な装置を用い、縦・横両方向にそれぞれ３．０倍の
同時二軸延伸を１１０℃の雰囲気下で行った。この時、
原反シートから見た同時二軸延伸後のフィルム面積倍率
は９倍である。[0041] Both ends of this raw sheet are fixed with chucks, and the distance between the chucks is changed in the width direction, and the distance between adjacent chucks is also changed, using a device that can stretch the sheet in the lengthwise direction. Simultaneous biaxial stretching of 3.0 times in both the longitudinal and transverse directions was carried out in an atmosphere at 110°C. At this time,
The area magnification of the film after simultaneous biaxial stretching as seen from the original sheet is 9 times.
【００４２】次に、この同時二軸延伸したフィルムを再
度、上記と同様の装置を用い１２０℃の加熱状態におい
て縦・横それぞれの方向に１．５倍の同時二軸延伸した
。
ここで、再同時二軸延伸終了後のフィルムの原反シート
成形物から見た全面積倍率は２０．２５倍となる。また
、複屈折の絶対値｜Δｎ｜をベレクのコンペンセータに
より測定したところ、２×１０−３を示したこの得られ
たフィルムを２６０℃の雰囲気下において、２分間、緊
張下の熱処理を行った。このフィルムのひねり保持度，
破れ発生率，光沢度，霞度，対湿度寸法安定性及び機械
特性（Ｆ５値）を評価した。結果を表１に示す。なお、
評価方法は以下に示す方法により行った。Next, this simultaneously biaxially stretched film was again simultaneously biaxially stretched by a factor of 1.5 in both the longitudinal and transverse directions under heating at 120° C. using the same apparatus as above. Here, the total area magnification of the film after the re-simultaneous biaxial stretching as viewed from the original sheet molded product is 20.25 times. In addition, the absolute value of birefringence |Δn| was measured using a Berek compensator and showed 2×10−3.The resulting film was heat-treated under tension for 2 minutes in an atmosphere of 260°C. . The twist retention of this film,
The tear occurrence rate, gloss, haze, dimensional stability against humidity, and mechanical properties (F5 value) were evaluated. The results are shown in Table 1. In addition,
The evaluation method was as shown below.
【００４３】ひねり保持度 ：テンチ産業株式会
社製、テンチひねり包装機（タテ型）を用いて、毎分５
００個により１．５回ひねり包装を行い、２００時間放
置後のひねり保持度を評価した。
○・・・１回ひねり以上保持
×・・・１回ひねり未満
破れ発生率 ：同上包装時に引き裂けを生じ
た比率を評価した。
光 沢 度 ：ＡＳＴＭ−Ｄ−５２３に
準拠。
霞 度 ：ＡＳＴＭ−Ｄ−１００
３に準拠。
対湿度寸法安定性：２３℃−５０％ＲＨ及び４０℃−９
０％ＲＨの一定雰囲気下に７２時間フィルムを放置した
場合の寸法変化率を測定し評価した。
○・・・変化率２％未満
×・・・変化率２％以上
機械特性（Ｆ５ 値）：ＪＩＳ−Ｃ−２３１８に準拠。[0043] Twist retention rate: Tenchi twist wrapping machine (vertical type) manufactured by Tenchi Sangyo Co., Ltd.
00 pieces were twisted and packaged 1.5 times, and the degree of twist retention after being left for 200 hours was evaluated. ○: Retention for 1 or more twists ×: Less than 1 twist occurrence rate: The ratio of tearing occurring during packaging was evaluated. Gloss level: Compliant with ASTM-D-523. Haze degree: ASTM-D-100
Compliant with 3. Dimensional stability against humidity: 23℃-50%RH and 40℃-9
The dimensional change rate when the film was left in a constant atmosphere of 0% RH for 72 hours was measured and evaluated. ○... Rate of change less than 2% ×... Rate of change 2% or more Mechanical properties (F5 value): Based on JIS-C-2318.
【００４４】実施例２
実施例１において、二段目の同時二軸延伸倍率を、縦，
横それぞれ２倍にしたこと以外は、実施例１と同様にし
てフィルムを得た。得られたフィルムについて、実施例
１と同様にして評価を行った。結果を表１に示す。Example 2 In Example 1, the second stage simultaneous biaxial stretching ratio was changed to longitudinal,
A film was obtained in the same manner as in Example 1 except that the width was doubled. The obtained film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４５】実施例３
上記参考例１で得られたスチレン系重合体を充分に減圧
乾燥した後、３００℃で溶融し、キャピラリー付き押出
機で押出し、ストランドをカットしてペレットとした。
このペレットを１２０℃の熱風乾燥器中で結晶化させた
。結晶化させたペレットを単軸押出機の先端にＴダイを
取りつけた装置で３２０℃で溶融押出し、７０℃冷却ロ
ールで冷却し、原反シートを得た。この原反シートを１
１０℃に加熱し、ロールの周速差を利用した延伸機で縦
方向に３倍の延伸を行った。このとき、延伸されたフィ
ルムの複屈折をベレクのコンペンセータにより測定した
ところ、その絶対値｜Δｎ｜は３５×１０−３を示した
。Example 3 The styrenic polymer obtained in Reference Example 1 was sufficiently dried under reduced pressure, then melted at 300° C., extruded using an extruder equipped with a capillary, and pellets were obtained by cutting strands. This pellet was crystallized in a hot air dryer at 120°C. The crystallized pellets were melt-extruded at 320°C using a single-screw extruder equipped with a T-die at the tip, and cooled with a 70°C cooling roll to obtain a raw sheet. 1 of this raw sheet
The film was heated to 10° C. and stretched 3 times in the longitudinal direction using a stretching machine that utilized the difference in circumferential speed of the rolls. At this time, when the birefringence of the stretched film was measured using a Berek compensator, its absolute value |Δn| was 35×10 −3 .
【００４６】次に、この縦延伸したフィルムの両端をチ
ャックで固定し、チャック間の幅を変化させて横方向に
延伸するいわゆるテンター装置によって１２０℃におい
て３倍の延伸を横方向に行った。この得られたフィルム
を２６０℃の雰囲気下において、２分間、緊張下の熱処
理を行った。得られたフィルムについて、実施例１と同
様にして評価を行った。結果を表１に示す。Next, both ends of this longitudinally stretched film were fixed with chucks, and the film was stretched three times in the transverse direction at 120° C. using a so-called tenter device that stretches the film in the transverse direction while changing the width between the chucks. The obtained film was subjected to heat treatment under tension for 2 minutes in an atmosphere of 260°C. The obtained film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４７】比較例１及び２
市販のセロハン（＃３００）及びパラフィン紙（厚さ２
３μｍ）について、実施例１と同様に評価を行った。結
果を表１に示す。Comparative Examples 1 and 2 Commercially available cellophane (#300) and paraffin paper (thickness 2
3 μm) was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００４８】[0048]
【表１】[Table 1]
【００４９】[0049]
【発明の効果】以上の説明の如く、本発明のひねり包装
用フィルムは、透明性，光沢性等に優れディスプレイ効
果が高く、またひねり保持度，機械特性，湿度等に対す
る寸法安定性等が極めて良好であり、破れ等の発生も殆
どない。さらに、高弾性率のため印刷時にピッチずれし
にくく、多色印刷にも好適である。このように、本発明
のひねり包装用フィルムは、菓子等のひねり包装用のフ
ィルムとして、好適に利用される。[Effects of the Invention] As explained above, the twist packaging film of the present invention has excellent transparency and gloss, has a high display effect, and has excellent twist retention, mechanical properties, and dimensional stability against humidity, etc. It is in good condition and there is almost no tearing or the like. Furthermore, due to its high elastic modulus, it is difficult to shift the pitch during printing, making it suitable for multicolor printing. Thus, the twist packaging film of the present invention is suitably used as a twist packaging film for confectionery and the like.
Claims (3)
レン系重合体またはその組成物からなる延伸用予備成形
体を、二軸延伸してなるひねり包装用フィルム。1. A twist packaging film obtained by biaxially stretching a stretching preform made of a styrenic polymer having a syndiotactic structure or a composition thereof.
るいは同時に二軸延伸してなる請求項１記載のひねり包
装用フィルム。2. The twisted packaging film according to claim 1, which is obtained by biaxially stretching a preform in the longitudinal and transverse directions sequentially or simultaneously.
晶化温度の範囲で縦・横の二方向に同時にあるいはガラ
ス転移温度〜融点の範囲で逐次に二軸延伸し、次いでガ
ラス転移温度〜融点の範囲で同時二軸延伸してなる請求
項１記載のフィルム。3. The preform is biaxially stretched simultaneously in the vertical and horizontal directions within the range of the glass transition temperature to the cold crystallization temperature, or sequentially in the range of the glass transition temperature to the melting point, and then 2. The film according to claim 1, which is simultaneously biaxially stretched within a melting point range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6986191A JP2846490B2 (en) | 1991-04-02 | 1991-04-02 | Twist packaging film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6986191A JP2846490B2 (en) | 1991-04-02 | 1991-04-02 | Twist packaging film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04305429A true JPH04305429A (en) | 1992-10-28 |
| JP2846490B2 JP2846490B2 (en) | 1999-01-13 |
Family
ID=13415010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6986191A Expired - Fee Related JP2846490B2 (en) | 1991-04-02 | 1991-04-02 | Twist packaging film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2846490B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| JPH08323877A (en) * | 1995-05-29 | 1996-12-10 | Toyobo Co Ltd | Biaxially oriented film of syndiotactic polystyrene |
-
1991
- 1991-04-02 JP JP6986191A patent/JP2846490B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| JPH08323877A (en) * | 1995-05-29 | 1996-12-10 | Toyobo Co Ltd | Biaxially oriented film of syndiotactic polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2846490B2 (en) | 1999-01-13 |
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