TW201400269A - Manufacturing method of phase difference film made of Polypropylene-series resin - Google Patents
Manufacturing method of phase difference film made of Polypropylene-series resin Download PDFInfo
- Publication number
- TW201400269A TW201400269A TW102109624A TW102109624A TW201400269A TW 201400269 A TW201400269 A TW 201400269A TW 102109624 A TW102109624 A TW 102109624A TW 102109624 A TW102109624 A TW 102109624A TW 201400269 A TW201400269 A TW 201400269A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- polypropylene
- retardation
- resin
- retardation film
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 93
- 239000011347 resin Substances 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 37
- -1 Polypropylene Polymers 0.000 claims abstract description 32
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 229920005673 polypropylene based resin Polymers 0.000 claims description 19
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 63
- 230000003287 optical effect Effects 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 253
- 230000000052 comparative effect Effects 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 24
- 238000007664 blowing Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- FAWUHEYSSPPNSH-UHFFFAOYSA-N 2,3,4-trimethylpent-1-ene Chemical compound CC(C)C(C)C(C)=C FAWUHEYSSPPNSH-UHFFFAOYSA-N 0.000 description 2
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-UHFFFAOYSA-N 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- RXYYKIMRVXDSFR-UHFFFAOYSA-N 3,3-dimethylhex-1-ene Chemical compound CCCC(C)(C)C=C RXYYKIMRVXDSFR-UHFFFAOYSA-N 0.000 description 2
- ZNQRZLWSGCOUEI-UHFFFAOYSA-N 3-ethyl-2-methylhept-1-ene Chemical compound CCCCC(CC)C(C)=C ZNQRZLWSGCOUEI-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 2
- TWCRBBJSQAZZQB-UHFFFAOYSA-N 3-methylidenehexane Chemical compound CCCC(=C)CC TWCRBBJSQAZZQB-UHFFFAOYSA-N 0.000 description 2
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- FYUUBXZYRPRIHC-UHFFFAOYSA-N 4-methylideneheptane Chemical compound CCCC(=C)CCC FYUUBXZYRPRIHC-UHFFFAOYSA-N 0.000 description 2
- ITKIOIGYCHMPKI-UHFFFAOYSA-N 4-methylidenenonane Chemical compound CCCCCC(=C)CCC ITKIOIGYCHMPKI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- NCRNCSZWOOYBQF-UHFFFAOYSA-N 1,1-Dimethoxydecane Chemical compound CCCCCCCCCC(OC)OC NCRNCSZWOOYBQF-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- LIMAEKMEXJTSNI-UHFFFAOYSA-N 2,3-dimethylpent-1-ene Chemical compound CCC(C)C(C)=C LIMAEKMEXJTSNI-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- YXLCVBVDFKWWRW-UHFFFAOYSA-N 3-methyl-4-methylidenehexane Chemical compound CCC(C)C(=C)CC YXLCVBVDFKWWRW-UHFFFAOYSA-N 0.000 description 1
- OWFGSRKLLAIWCL-UHFFFAOYSA-N C(C)(C)(C)C(C(OC)(OC)CC)CCCCCCCC Chemical compound C(C)(C)(C)C(C(OC)(OC)CC)CCCCCCCC OWFGSRKLLAIWCL-UHFFFAOYSA-N 0.000 description 1
- WDOYTBNLUWHCRW-UHFFFAOYSA-N C(C)(C)(C)C(C(OC)(OC)CCC)CCCCCCCC Chemical compound C(C)(C)(C)C(C(OC)(OC)CCC)CCCCCCCC WDOYTBNLUWHCRW-UHFFFAOYSA-N 0.000 description 1
- GMLKASBTJKNVTR-UHFFFAOYSA-N C1(CCCCC1)CCC(CCCCCCCCC)(OC)OC Chemical compound C1(CCCCC1)CCC(CCCCCCCCC)(OC)OC GMLKASBTJKNVTR-UHFFFAOYSA-N 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- LWBWGOJHWAARSS-UHFFFAOYSA-N diethylalumanyloxy(diethyl)alumane Chemical compound CC[Al](CC)O[Al](CC)CC LWBWGOJHWAARSS-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920006302 stretch film Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Abstract
Description
本發明係關於具有二軸性，且具有高光學均勻性的聚丙烯系樹脂製相位差膜之製造方法。 The present invention relates to a method for producing a polypropylene-based resin retardation film which has biaxiality and has high optical uniformity.
液晶顯示裝置(液晶面板)的構成構件之相位差膜或偏光片保護膜等光學膜，為了提高對比或視角，追求高的光學均勻性。此外，於相位差膜，有正的C板或負的C板等，追求二軸性的用途，正的C板作為VA(垂直配向)用相位差膜等來使用。 An optical film such as a retardation film or a polarizer protective film of a constituent member of a liquid crystal display device (liquid crystal panel) pursues high optical uniformity in order to improve contrast or viewing angle. In addition, in the retardation film, there is a positive C plate or a negative C plate, and the like, and a positive C plate is used as a VA (vertical alignment) retardation film or the like.
此處，相位差膜，通常把分子為無配向狀態的相位差膜整卷膜，以使分子在相同方向，且同程度配向的方式進行延伸而製造。總之，藉由控制配向軸與配向度，而使相位差膜呈現二軸性或光學均勻性。 Here, the retardation film is usually produced by stretching a film in which the molecules are in an unaligned state, so that the molecules are aligned in the same direction and aligned to the same extent. In summary, the retardation film exhibits biaxiality or optical uniformity by controlling the alignment axis and the alignment.
於專利文獻1，記載著使聚丙烯系樹脂製的膜橫向單軸延伸3倍以上10倍以下的相位差膜之製造方法。 Patent Document 1 describes a method for producing a retardation film in which a film made of a polypropylene resin is uniaxially stretched three times or more and 10 times or less in the transverse direction.
於專利文獻2，記載著藉由T型模具法所得到的膜作橫向單軸延伸而得到相位差膜的方法。 Patent Document 2 describes a method of obtaining a retardation film by laterally uniaxially stretching a film obtained by a T-die method.
[專利文獻1]日本特開2010-49072號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-49072
[專利文獻2]日本特開2009-166290號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-166290
然而，針對記載於前述專利文獻1、2的藉由橫向單軸延伸所得到的相位差膜的二軸性以及光學均勻性，還要求進一步的改良。 However, further improvement is required for the biaxiality and optical uniformity of the retardation film obtained by the lateral uniaxial stretching described in Patent Documents 1 and 2 described above.
在此，本發明之目的在於提供於具有適度的二軸性，且具有高光學均勻性的聚丙烯系樹脂製相位差膜之製造方法。 Here, an object of the present invention is to provide a method for producing a polypropylene-based resin retardation film which has moderate biaxiality and has high optical uniformity.
亦即，本發明係關於聚丙烯系樹脂製相位差膜之製造方法，係包含：加熱熔融聚丙烯系樹脂得到膜狀熔融樹脂，藉由以1根輥冷卻固化該膜狀熔融樹脂，得到以R0表示的面內相位差值滿足下式(1)的膜F的步驟，以及加熱該膜F，藉由在膜F的寬幅方向，延伸加熱的膜F至1.9倍以上3.0倍以下，而得到NZ係數1.3以上4.0以下的聚丙烯系樹脂製相位差膜的步驟之方法。 In other words, the present invention relates to a method for producing a retardation film made of a polypropylene resin, comprising: heating a molten polypropylene resin to obtain a film-like molten resin, and curing the film-like molten resin by one roll to obtain The in-plane phase difference value represented by R0 satisfies the step of the film F of the following formula (1), and the film F is heated, by extending the heated film F to 1.9 times or more and 3.0 times or less in the wide direction of the film F, and A method of obtaining a step of a polypropylene-based resin retardation film having an NZ coefficient of 1.3 or more and 4.0 or less.
1.5×10-4×d≦R0 式(1) 1.5×10 -4 ×d≦R0 (1)
(式(1)中、d為膜F的厚度(nm))。 (In the formula (1), d is the thickness (nm) of the film F).
根據本發明，可以製造具有二軸性，且具有高光學均勻性的聚丙烯系樹脂製相位差膜。 According to the present invention, a polypropylene-based resin retardation film having biaxiality and high optical uniformity can be produced.
1b‧‧‧膜製造系統 1b‧‧‧Film manufacturing system
1‧‧‧比較例1之膜製造系統 1‧‧‧Film manufacturing system of Comparative Example 1
10‧‧‧壓出機 10‧‧‧Extrusion machine
12‧‧‧T型模 12‧‧‧T-mode
12a‧‧‧吐出口 12a‧‧‧Exporting
14‧‧‧可彈性變形之金屬輥 14‧‧‧Elastically deformable metal roller
14a‧‧‧可彈性變形的金屬輥之金屬外筒 14a‧‧‧Metal outer cylinder of elastically deformable metal roller
14b‧‧‧薄壁金屬外筒 14b‧‧‧thin wall metal outer tube
14c‧‧‧可彈性變形的金屬輥之流體軸筒 14c‧‧‧Liquid shaft of elastically deformable metal roller
16‧‧‧第1冷卻輥 16‧‧‧1st chill roll
16a，18a‧‧‧金屬外筒 16a, 18a‧‧‧metal outer tube
16b，18b‧‧‧流體軸筒 16b, 18b‧‧‧ fluid shaft
18‧‧‧第2冷卻輥 18‧‧‧2nd cooling roller
19‧‧‧接觸輥 19‧‧‧Contact roller
20‧‧‧預熱區 20‧‧‧Preheating zone
21‧‧‧延伸區 21‧‧‧Extension
22‧‧‧熱固定區 22‧‧‧Hot fixed area
23‧‧‧夾盤(chuck) 23‧‧‧ chuck (chuck)
25‧‧‧延伸膜 25‧‧‧Stretch film
30‧‧‧上側噴嘴 30‧‧‧Upper nozzle
32‧‧‧下側噴嘴 32‧‧‧Bottom nozzle
38‧‧‧衝壓噴嘴 38‧‧‧Pressing nozzle
38a‧‧‧面 38a‧‧‧ face
44‧‧‧開口 44‧‧‧ openings
100‧‧‧烤爐 100‧‧‧ oven
100a‧‧‧上面 100a‧‧‧above
100b‧‧‧下面 100b‧‧‧ below
60‧‧‧精密減速機及馬達 60‧‧‧Precision reducer and motor
A‧‧‧膜之搬送方向 A‧‧‧film transport direction
B‧‧‧風之吹出方向(下方向) B‧‧‧Wind blowing direction (downward direction)
C‧‧‧風之吹出方向(上方向) C‧‧‧Wind direction (upward direction)
F‧‧‧膜 F‧‧‧ film
H‧‧‧氣隙 H‧‧‧ air gap
圖1係顯示以1根輥冷卻固化膜狀熔融樹脂時使用的膜製造系統之一個態樣之圖。 Fig. 1 is a view showing an aspect of a film production system used when cooling a film-like molten resin by one roll.
圖2係顯示以2根輥冷卻固化膜狀熔融樹脂時使用的膜製造系統之一個態樣之圖。 Fig. 2 is a view showing an aspect of a film production system used when cooling a film-like molten resin by two rolls.
圖3係顯示於膜F的寬幅方向延伸(橫向延伸)膜F時使用的延伸裝置之一個態樣之圖。 Fig. 3 is a view showing an aspect of the stretching device used when the film F is extended in the width direction (laterally extending) of the film F.
圖4係顯示於膜F的寬幅方向延伸(橫向延伸)膜F時使用的延伸裝置之剖面圖。 Fig. 4 is a cross-sectional view showing an extension device used when the film F is extended in the width direction (laterally extending) of the film F.
圖5係顯示延伸裝置具備的衝壓噴嘴的剖面圖。 Fig. 5 is a cross-sectional view showing a press nozzle provided in the extension device.
本發明之製造NZ係數1.3以上4.0以下的聚丙烯系樹脂製相位差膜(以下，亦簡化記載為「相位差膜」)的方法，特徵為：加熱熔融聚丙烯系樹脂得到膜狀熔融樹脂，藉由以1根輥(以下，亦記載為「第1冷卻 輥」)冷卻固化該膜狀熔融樹脂，得到面內相位差值(R0)滿足下列式(1)的膜(以下，亦記載為「膜F」)之後，加熱該膜F，在膜F的寬幅方向，延伸加熱的膜F至1.9倍以上3.0倍以下。 A method for producing a retardation film made of a polypropylene resin having an NZ coefficient of 1.3 or more and 4.0 or less (hereinafter, also referred to as "phase difference film" as described) is characterized in that a film-like molten resin is obtained by heating a molten polypropylene resin. By using one roller (hereinafter, also referred to as "first cooling" The roll ") is cooled and solidified to obtain a film-like molten resin, and a film having the in-plane retardation value (R0) satisfying the following formula (1) (hereinafter also referred to as "film F") is obtained, and then the film F is heated in the film F. In the wide direction, the heated film F is extended to 1.9 times or more and 3.0 times or less.
1.5×10-4×d≦R0 式(1) 1.5×10 -4 ×d≦R0 (1)
(式(1)中、d為膜F的厚度(nm))。 (In the formula (1), d is the thickness (nm) of the film F).
此處，所謂NZ係數，是表現折射率向異性的指標，以下列之式(A)表現。 Here, the NZ coefficient is an index indicating the refractive index anisotropy and is expressed by the following formula (A).
NZ係数=(nx-xz)/(nx-ny) 式(A) NZ coefficient=(nx-xz)/(nx-ny) Equation (A)
(式A)中，nx為相位差膜的面內之主折射率(遲向軸)，ny為相位差膜的面內之主折射率(進向軸)，nz為相位差膜的厚度方向之主折射率) In the formula (A), nx is the in-plane principal refractive index (latency axis) of the retardation film, ny is the in-plane principal refractive index (forward axis) of the retardation film, and nz is the thickness direction of the retardation film. Main refractive index)
NZ係數越接近於一，意味著單軸性越強，NZ係數為1.3以上4.0以下，意味著所得到的相位差膜具有適度的二軸性。 The closer the NZ coefficient is to one, the stronger the uniaxiality, and the NZ coefficient is 1.3 or more and 4.0 or less, which means that the obtained retardation film has moderate biaxiality.
藉由本發明之製造相位差膜的方法，可以得到NZ係數為1.3以上4.0以下，亦即具有二軸性的聚丙烯系樹脂製相位差膜。NZ係數為1.3以上4.0以下的相位差膜，特別可以適切地用於VA(垂直配向；Vertical Alignment)用相位差膜。以本發明的方法所得到的相位差 膜，也可以作為使用於TN(Twisted Nematic)模式、STN(Super Twisted Nematic)模式、IPS(In-Plane Switching)模式等各種液晶顯示裝置的相位差膜來使用。 According to the method for producing a retardation film of the present invention, a polypropylene-based resin retardation film having an NZ coefficient of 1.3 or more and 4.0 or less, that is, a biaxial property can be obtained. A retardation film having an NZ coefficient of 1.3 or more and 4.0 or less can be suitably used for a retardation film for VA (Vertical Alignment). Phase difference obtained by the method of the present invention The film can also be used as a retardation film used in various liquid crystal display devices such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, and IPS (In-Plane Switching) mode.
作為使用於本發明的聚丙烯系樹脂，例如為丙烯之單獨聚合物、乙烯及碳數4~20之α-烯烴構成的群所選擇之1種以上的單體與丙烯之共聚合物。此外，為這些之混合物亦可。 The polypropylene-based resin to be used in the present invention is, for example, a copolymer of one or more monomers selected from the group consisting of a single polymer of propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms and propylene. In addition, a mixture of these may also be used.
作為前述之α-烯烴，具體而言可以舉出1-丁烯、2-甲基-1-丙烯、1-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、1-己烯、2-乙基-1-丁烯、2,3-二甲基-1-丁烯、2-甲基-1-戊烯、3-甲基-1-戊烯、4-甲基-1-戊烯、3,3-二甲基-1-丁烯、1-庚烯、2-甲基-1-己烯、2,3-二甲基-1-戊烯、2-乙基-1-戊烯、1-辛烯、2-乙基-1-己烯、3,3-二甲基-1-己烯、2-丙基-1-庚烯、2-甲基-3-乙基-1-庚烯、2,3,4-三甲基-1-戊烯、2-丙基-1-戊烯、2,3-二乙基-1-丁烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十三碳烯、1-十四碳烯、1-十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1-十九碳烯等；碳數4~12之α-烯烴為更佳，例如，1-丁烯、2-甲基-1-丙烯、1-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、1-己烯、2-乙基-1-丁烯、2,3-二甲基-1-丁烯、2-甲基-1-戊烯、3-甲基-1-戊烯、4-甲基1-戊烯、3,3-二甲基-1-丁烯、1-庚烯、2-甲基-1-己烯、2,3-二甲基-1-戊烯、2-乙基-1-戊烯、1-辛烯、2-乙基-1-己烯、3,3-二甲基-1-己烯、2-丙基-1-庚烯、2-甲基-3-乙基-1-庚烯、2,3,4-三甲基-1-戊烯、2- 丙基-1-戊烯、2,3-二乙基-1-丁烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二烯等。特別是由共聚合性的觀點來看，較佳者為1-丁烯、1-戊烯、1-己烯、1-辛烯，更佳者為1-丁烯、1-己烯。 Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, and 3-methyl-1-butene. Alkene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene , 2-ethyl-1-pentene, 1-octene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-propyl-1-heptene, 2 -methyl-3-ethyl-1-heptene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene Alkene, 1-decene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-ten Hexaene, 1-heptadecene, 1-octadecene, 1-nonadecene, etc.; α-olefin having 4 to 12 carbon atoms is more preferable, for example, 1-butene, 2-methyl group 1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-di Methyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl 1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 2-methyl-1-hexene 2,3-Dimethyl-1-pentene, 2-ethyl-1-pentene, 1-octene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene , 2-propyl-1-heptene, 2-methyl-3-ethyl-1-heptene, 2,3,4-trimethyl-1-pentene, 2- Propyl-1-pentene, 2,3-diethyl-1-butene, 1-decene, 1-decene, 1-undecene, 1-dodecene, and the like. In particular, from the viewpoint of copolymerizability, 1-butene, 1-pentene, 1-hexene, 1-octene is preferred, and 1-butene and 1-hexene are more preferred.
作為本發明使用的聚丙烯系樹脂之例，例如可舉出丙烯-乙烯共聚物、丙烯-α-烯烴共聚物、丙烯-乙烯-α-烯烴共聚物等。更具體地說，作為丙烯-α-烯烴，例如可以舉出丙烯-1-丁烯共聚物、丙烯-1-戊烯共聚物、丙烯-1-己烯共聚物、丙烯-1-辛烯共聚物等，作為丙烯-乙烯-α-烯烴共聚物，例如可以舉出丙烯-乙烯-1-丁烯共聚物、丙烯-乙烯-1-己烯共聚物、丙烯-乙烯-1-辛烯共聚物等。作為本發明之丙烯系聚合物，較佳者為丙烯-乙烯共聚物，丙烯-1-丁烯共聚物，丙烯-1-戊烯共聚物、丙烯-1-己烯共聚物、丙烯-1-辛烯共聚物、丙烯-乙烯-1-丁烯共聚物、丙烯-乙烯-1-己烯共聚物；較佳者為丙烯-乙烯共聚物、丙烯-1-丁烯共聚物、丙烯-1-己烯共聚物、丙烯-乙烯-1-丁烯共聚物、丙烯-乙烯-1-己烯共聚物。 Examples of the polypropylene-based resin used in the present invention include a propylene-ethylene copolymer, a propylene-α-olefin copolymer, and a propylene-ethylene-α-olefin copolymer. More specifically, examples of the propylene-α-olefin include a propylene-1-butene copolymer, a propylene-1-pentene copolymer, a propylene-1-hexene copolymer, and a propylene-1-octene copolymer. Examples of the propylene-ethylene-α-olefin copolymer include a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, and a propylene-ethylene-1-octene copolymer. Wait. The propylene-based polymer of the present invention is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-pentene copolymer, a propylene-1-hexene copolymer, or a propylene-1- Octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer; preferably propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1- Hexene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer.
使用於本發明的聚丙烯系樹脂為共聚物的場合，來自該共聚物之共單體的構成單位的含量，由透明性與耐熱性的平衡的觀點來看，以超過0重量%而在40重量%以下為較佳。此外，在相同的觀點下，以超過0重量%而在30重量%以下更佳。又，2種以上共單體與丙烯之共聚物的場合，來自該共聚物所含的所有共單體的構成單位的合計含量，以在前述範圍為較佳。 When the polypropylene resin used in the present invention is a copolymer, the content of the constituent unit of the comonomer derived from the copolymer is more than 0% by weight and is 40% from the viewpoint of balance between transparency and heat resistance. The weight % or less is preferred. Further, from the same viewpoint, it is more preferably 0% by weight or more and 30% by weight or less. Further, in the case of copolymers of two or more kinds of comonomers and propylene, the total content of the constituent units derived from all the comonomers contained in the copolymer is preferably in the above range.
作為使用於本發明的聚丙烯系樹脂之製造方法，可以舉出使用公知的聚合用觸媒單獨具合丙烯的方法，或共聚合由乙烯及碳數4~20之α-烯烴構成的群所選擇之1種以上的單體與丙烯之方法。作為公知的聚合觸媒，例如可以舉出(1)以鎂、鈦及鹵素為必須成分之固體觸媒成分等所構成的Ti-Mg系觸媒，(2)於以鎂、鈦及鹵素為必須成分的固體觸媒成分，組合有機鋁化合物，因應需要與電子供給性化合物等之第3成分組合之觸媒系，(3)有機茂金屬(metallocene)系觸媒等。 The method for producing the polypropylene resin to be used in the present invention includes a method in which propylene is separately used by using a known polymerization catalyst, or a group selected from ethylene and a group of α to olefin having 4 to 20 carbon atoms. A method of one or more kinds of monomers and propylene. Examples of the known polymerization catalyst include (1) a Ti-Mg-based catalyst composed of a solid catalyst component containing magnesium, titanium, and a halogen as essential components, and (2) magnesium, titanium, and halogen. A solid catalyst component of a required component, a combination of an organoaluminum compound, a catalyst system which is required to be combined with a third component such as an electron-donating compound, and (3) an organic metallocene catalyst.
作為使用於本發明的聚丙烯系樹脂之製造的觸媒系，在這些之中，最為一般的是在以鎂、鈦及鹵素為必須成分的固體觸媒成分，組合有機鋁化合物與電子供給性化合物之觸媒系。更具體地說，作為有機鋁化合物，較佳者為三乙基鋁、三異丁基鋁、三乙基鋁與二乙基鋁氯化物之混合物以及四乙基二鋁氧烷(tetraethyldialumoxane)；作為電子供給性化合物，較佳者為環己基乙基二甲氧基矽烷、tert-丁基-n-丙基二甲氧基矽烷，tert-丁基乙基二甲氧基矽烷、二環戊基二甲氧基矽烷。作為以鎂、鈦及鹵素為必須成分的固體觸媒成分，例如可以舉出日本特開昭61-218606號公報、特開昭61-287904號公報、特開平7-216017號公報等所記載之觸媒系。作為有機茂金屬(metallocene)觸媒，例如可以舉出日本特許第2587251號、特許第2627669號、特許第2668732號所記載之觸媒系。 Among the catalyst systems used in the production of the polypropylene-based resin of the present invention, among these, the most common ones are solid catalyst components containing magnesium, titanium and halogen as essential components, and the combination of the organoaluminum compound and the electron supply property. The catalyst system of the compound. More specifically, as the organoaluminum compound, preferred are triethyl aluminum, triisobutyl aluminum, a mixture of triethyl aluminum and diethyl aluminum chloride, and tetraethyldialumoxane; As the electron-donating compound, preferred are cyclohexylethyldimethoxydecane, tert-butyl-n-propyldimethoxydecane, tert-butylethyldimethoxydecane, and dicyclopentane. Dimethoxy decane. For example, the solid catalyst component containing magnesium, titanium, and a halogen as an essential component is described in, for example, JP-A-61-218606, JP-A-61-287904, JP-A-7-216017, and the like. Catalyst system. Examples of the organic metallocene catalyst include a catalyst system described in Japanese Patent No. 2,587,251, Japanese Patent No. 2,627,669, and No. 2,668,732.
作為使用於本發明的聚丙烯系樹脂的聚合方法，可以舉出以己烷、庚烷、辛烷、癸烷、環己烷、甲基環己烷、苯、甲苯、二甲苯等碳氫化合物為代表的惰性溶劑之溶劑聚合法、把液狀的單體作為溶劑使用的塊狀聚合法、在氣體之單體中進行聚合之氣相聚合法等，較佳者為後處理容易的塊狀聚合法或氣相具合法。這些聚合法，可以為批次式進行，亦可為連續式進行。 Examples of the polymerization method of the polypropylene resin used in the present invention include hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene. A solvent polymerization method of an inert solvent, a bulk polymerization method using a liquid monomer as a solvent, a gas phase polymerization method in which a monomer in a gas is polymerized, and the like are preferably a bulk polymerization which is easy to post-process. The law or gas phase is legal. These polymerization methods can be carried out in batch mode or in continuous mode.
使用於本發明的聚丙烯系樹脂的立體規則性，亦可為同排聚合物(isotactic)、對排聚合物(syndiotactic)、雜排聚合物(atactic)之任一形式。使用於本發明的丙烯系樹脂，由耐熱性的觀點來看，以對排聚合物(syndiotactic)或同排聚合物(isotactic)之丙烯系樹脂為佳。 The stereoregularity of the polypropylene-based resin used in the present invention may be any form of isotactic, syndiotactic, or atactic. The propylene-based resin to be used in the present invention is preferably a propylene-based resin which is a syndiotactic or isotactic propylene-based resin from the viewpoint of heat resistance.
使用於本發明的聚丙烯系樹脂之熔流速率(melt flow rate)(MFR)依照JIS K 7210標準，在溫度230℃，荷重21.18N下測定之值，較佳者為0.1g/10分~200g/10分，更佳者為0.5g/10分~50g/10分。藉由使用MFR在此範圍之聚丙烯系樹脂，可以不對壓出機施加過大的負荷，而成形均勻的膜。 The melt flow rate (MFR) of the polypropylene-based resin used in the present invention is measured in accordance with JIS K 7210 at a temperature of 230 ° C and a load of 21.18 N, preferably 0.1 g/10 min. 200g/10 minutes, more preferably 0.5g/10 minutes ~ 50g/10 minutes. By using a polypropylene-based resin having an MFR in this range, a uniform film can be formed without applying an excessive load to the extruder.
使用於本發明的聚丙烯系樹脂的分子量分布較佳為1~20。分子量分布係在溶媒使用140℃之鄰二氯苯，標準試料使用聚苯乙烯進行測定及計算求出之Mn與Mw之比(=Mw/Mn)。Mw表示聚丙烯系樹脂的重量平均分子量，Mn表示聚丙烯系樹脂之數量平均分子量。 The polypropylene resin used in the present invention preferably has a molecular weight distribution of from 1 to 20. The molecular weight distribution was measured by using 140 ° C of o-dichlorobenzene in a solvent, and the ratio of Mn to Mw (=Mw/Mn) determined by a standard sample using polystyrene. Mw represents the weight average molecular weight of the polypropylene resin, and Mn represents the number average molecular weight of the polypropylene resin.
於使用在本發明的聚丙烯系樹脂，在不阻礙本發明的效果的範圍內配合公知的添加劑亦可。 In the polypropylene resin of the present invention, a known additive may be blended in a range that does not inhibit the effects of the present invention.
作為添加劑，例如可以舉出防氧化劑、紫外線吸收劑、防帶電劑、滑劑、造核劑、防霧劑、抗結塊劑(antiblocking)等，亦可併用這些之中的複數種。 Examples of the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an antifogging agent, an antiblocking agent, and the like, and a plurality of these may be used in combination.
作為前述防氧化劑，可以舉出酚系防氧化劑、磷系防氧化劑、硫系防氧化劑、受阻胺系防氧化劑(HALS)，或於1分子中具有例如酚系與磷系之防氧化機構的單元之複合型防氧化劑。 Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hindered amine-based antioxidant (HALS), or a unit having, for example, a phenol-based or phosphorus-based oxidation preventing mechanism in one molecule. Composite antioxidant.
作為前述紫外線吸收劑，可以舉出2-羥基二苯甲酮、羥基苯並三唑系等紫外線吸收劑，或安息酸鹽系等之紫外線遮斷劑等。 Examples of the ultraviolet absorber include ultraviolet absorbers such as 2-hydroxybenzophenone and hydroxybenzotriazole, and ultraviolet blocking agents such as benzoate.
作為前述防帶電劑，可舉出高分子型、低聚物型、單體型等。 Examples of the antistatic agent include a polymer type, an oligomer type, and a monomer type.
作為前述滑劑，可以舉出芥酸醯胺(erucamide)、油酸醯胺等高級脂肪酸醯胺，或是硬脂酸等高級脂肪酸、及其金屬鹽等。 Examples of the slip agent include higher fatty acid guanamine such as erucamide and oleic acid amide, and higher fatty acids such as stearic acid, and metal salts thereof.
作為前述造核劑，例如可以舉出山梨糖醇(sorbitol)系造核劑、有機磷酸鹽系造核劑、聚乙烯環烷等高分子系造核劑等。作為抗結塊劑(antiblocking)，可以使用球狀，或者接近球狀的形狀之微粒子，不管是無機系或有機系。 Examples of the nucleating agent include a sorbitol-based nucleating agent, an organic phosphate-based nucleating agent, and a polymer-based nucleating agent such as polyethylene cycloalkane. As the antiblocking agent, a spherical shape, or a particle shape close to a spherical shape, whether inorganic or organic, can be used.
在本發明之相位差膜之製造方法，加熱熔融聚丙烯系樹脂得到膜狀熔融樹脂，以1根輥冷卻固化該膜狀熔融樹脂。藉由以1根輥冷卻固化膜狀熔融樹脂，可以 縮小厚度方向的配向而對膜的流動方向賦予配向。 In the method for producing a retardation film of the present invention, a molten polypropylene resin is heated to obtain a film-like molten resin, and the film-like molten resin is cooled and solidified by one roll. By cooling the film-like molten resin with one roll, it is possible to The alignment in the thickness direction is reduced to impart an alignment to the flow direction of the film.
使用膜狀熔融樹脂製造膜F，進而使用該膜F製造相位差膜的場合，通常膜F的寬幅方向的兩末端會被切掉。在本發明，使膜狀熔融樹脂與第1冷卻輥接觸，所以在與膜F的不切掉的部分對應之膜狀熔融樹脂的部分，不藉由輔助冷卻手段對該膜狀熔融樹脂的厚度方向施加力量。作為藉由輔助冷卻手段對膜狀熔融樹脂的厚度方向施加力量的方法，可以舉出把與第1冷卻輥不同的輥，例如可彈性變形的輥把膜狀熔融樹脂之該部分往第1冷卻輥按壓的方法，靜電方式把膜狀熔融樹脂之該部分按壓於第1冷卻輥的方法(以下，記載為靜電針扎(pinning)法)，把空氣吹噴網膜狀熔融樹脂之該部分使膜狀熔融樹脂的外部分按壓於第1冷卻輥的方法。 When the film F is produced using a film-like molten resin and the retardation film is produced using the film F, the both ends of the film F in the width direction are usually cut off. In the present invention, since the film-like molten resin is brought into contact with the first cooling roll, the thickness of the film-like molten resin is not supported by the auxiliary cooling means in the portion of the film-like molten resin corresponding to the uncut portion of the film F. Apply force to the direction. As a method of applying a force to the thickness direction of the film-shaped molten resin by the auxiliary cooling means, a roller different from the first cooling roll, for example, an elastically deformable roller, is used to cool the portion of the film-shaped molten resin to the first cooling. The method of pressing the roller, the method of pressing the portion of the film-like molten resin to the first cooling roll by electrostatic means (hereinafter, referred to as an electrostatic pinning method), and blowing the portion of the air-sprayed film-like molten resin to the film A method in which the outer portion of the molten resin is pressed against the first cooling roll.
在對應於膜F的切除部分之膜狀熔融樹脂的部分，為了使該部分與第1冷卻輥接觸，對該部分吹噴空氣，或者對該部分適用靜電針扎法為較佳。 In the portion corresponding to the film-like molten resin of the cut portion of the film F, in order to bring the portion into contact with the first cooling roll, it is preferable to apply air to the portion or apply an electrostatic pinning method to the portion.
為了製造透明性高的膜F，第1冷卻輥的表面溫度較佳者為-5℃以上30℃以下，更佳者為5℃以上25℃以下。若為5℃以上25℃以下的話，空氣中的水分不容易結露於第1冷卻輥，可更安定地得到具有高透明性的膜F。 In order to produce the film F having high transparency, the surface temperature of the first cooling roll is preferably -5 ° C or more and 30 ° C or less, and more preferably 5 ° C or more and 25 ° C or less. When the temperature is 5° C. or more and 25° C. or less, the moisture in the air does not easily condense on the first cooling roll, and the film F having high transparency can be obtained more stably.
第1冷卻輥的內部以設有流路較佳。使膜狀熔融樹脂冷卻固化時，以使流路內的液體進入第1冷卻輥時的入口溫度，與流路內的液體流出第1冷卻輥時的出口 溫度之溫度差在2℃以內的方式來調整流動於前述流路內的液體的流量為較佳。如此進行的話，可得厚度偏差很小，跨整個面具有均勻的透明性的相位差膜。 It is preferable that the inside of the first cooling roll is provided with a flow path. When the film-shaped molten resin is cooled and solidified, the inlet temperature when the liquid in the flow path enters the first cooling roll and the outlet when the liquid in the flow path flows out of the first cooling roll It is preferable to adjust the flow rate of the liquid flowing in the flow path so that the temperature difference of the temperature is within 2 °C. In this way, a retardation film having a small thickness deviation and uniform transparency across the entire surface can be obtained.
空氣間隙，以20mm以上250mm以下為佳，20mm以上100mm以下為更佳。所謂空氣間隙，是由膜狀熔融樹脂被壓出的T型模的吐出口起，直到膜狀熔融樹脂接觸到第1冷卻輥的地點為止的長度。空氣間隙為20mm以上250mm以下的話，膜F的寬幅方向上的配向程度不容易產生差異，所以橫向延伸該膜F而得的相位差膜，其寬幅方向的相位差更為均勻。 The air gap is preferably 20 mm or more and 250 mm or less, and more preferably 20 mm or more and 100 mm or less. The air gap is the length from the discharge port of the T-die extruded from the film-shaped molten resin until the film-like molten resin contacts the first cooling roll. When the air gap is 20 mm or more and 250 mm or less, the degree of alignment of the film F in the wide direction is not easily different. Therefore, the retardation film obtained by extending the film F in the lateral direction has a more uniform phase difference in the width direction.
膜F，其面內相位差值(R0)滿足下列之式(1)。面內相位差值(R0)不滿足式(1)的場合，為了要得到具有適度的二軸性的相位差膜，只能夠在次一步驟使膜F橫向延伸未滿1.9倍而已，無法得到光學均勻性優異的相位差膜。 The film F whose in-plane phase difference value (R0) satisfies the following formula (1). When the in-plane retardation value (R0) does not satisfy the formula (1), in order to obtain a retardation film having a moderate biaxiality, the film F can be stretched laterally less than 1.9 times in the next step, and the film cannot be obtained. A retardation film excellent in optical uniformity.
1.5×10-4×d≦R0 式(1) 1.5×10 -4 ×d≦R0 (1)
(式(1)中、d為膜F的厚度(nm))。 (In the formula (1), d is the thickness (nm) of the film F).
膜F的面內相位差值(R0)，較佳者為滿足下列之式(4)，更佳者為滿足下列之式(5)者。亦即，膜F的厚度為100μm的場合，面內相位差值(R0)滿足15nm以上，較佳為20nm以上，更佳為40nm以上。面內相位差 值(R0)的上限，沒有特別限制，但使用通常的抽拉設備的場合，較佳者為滿足下列之式(6)。膜F的厚度為100μm的場合，面內相位差值(R0)，較佳為1000nm以下。 The in-plane retardation value (R0) of the film F is preferably such that the following formula (4) is satisfied, and more preferably, the following formula (5) is satisfied. That is, when the thickness of the film F is 100 μm, the in-plane retardation value (R0) satisfies 15 nm or more, preferably 20 nm or more, and more preferably 40 nm or more. In-plane phase difference The upper limit of the value (R0) is not particularly limited, but in the case of using a usual drawing device, it is preferable to satisfy the following formula (6). When the thickness of the film F is 100 μm, the in-plane retardation value (R0) is preferably 1000 nm or less.
2.0×10-4×d≦R0 式(4) 2.0×10 -4 ×d≦R0 (4)
4.0×10-4×d≦R0 式(5) 4.0×10 -4 ×d≦R0 (5)
1.0×10-2×d≧R0 式(6) 1.0×10 -2 ×d≧R0 (6)
(式(4)、(5)、(6)中、d為膜F的厚度(nm))。 (In the formulas (4), (5), and (6), d is the thickness (nm) of the film F).
進而，膜F以滿足以下之式(7)為佳。 Further, the film F is preferably in the following formula (7).
Rth<0.68R0+40×10-6/d 式(7) Rth<0.68R0+40×10 -6 /d (7)
(式(7)中，Rth為膜F的厚度方向的相位差值，R0為膜F的面內相位差值，d為膜F的厚度(nm)) (In the formula (7), Rth is the phase difference value in the thickness direction of the film F, R0 is the in-plane phase difference value of the film F, and d is the thickness (nm) of the film F)
使用滿足式(7)的膜F得到的相位差膜，膜厚度方向的相位差值的散佈(dispersion)很小。使用滿足式(8)之膜F，進而更佳。 With the retardation film obtained by satisfying the film F of the formula (7), the dispersion of the phase difference value in the film thickness direction is small. It is more preferable to use the film F which satisfies the formula (8).
Rth<0.68R0+40×10-6/d 式(8) Rth<0.68R0+40×10 -6 /d (8)
測定膜F的厚度的方法，沒有特別限制，可以使用X線方式，β線方式，分光干涉式，接觸式，靜電電容式等各種方法來測定厚度。 The method of measuring the thickness of the film F is not particularly limited, and the thickness can be measured by various methods such as an X-ray method, a β-line method, a spectroscopic interference type, a contact type, and a capacitance type.
將膜F延伸於膜F的寬幅方向時的延伸倍率，為1.9倍以上3.0倍以下，較佳為2.1倍以上3.0倍以下，更佳為2.3倍以上3.0倍以下。未滿1.9的話，延伸後的膜其相位差值的均勻性很差，超過3.0的話單軸性變強，所以無法得到具有1.3以上4.0以下的NZ係數之相位差膜。 The stretching ratio when the film F is extended in the width direction of the film F is 1.9 times or more and 3.0 times or less, preferably 2.1 times or more and 3.0 times or less, more preferably 2.3 times or more and 3.0 times or less. When it is less than 1.9, the film after stretching has a poor uniformity of the phase difference value, and when it exceeds 3.0, the uniaxiality becomes strong, so that a retardation film having an NZ coefficient of 1.3 or more and 4.0 or less cannot be obtained.
參照圖式說明本發明之適切的實施型態。又，於說明，具有同一要素或同一機能的要素使用同一符號，省略重複說明。 Suitable embodiments of the invention are described with reference to the drawings. In addition, the same elements or elements having the same function are denoted by the same reference numerals, and the description thereof will not be repeated.
首先，參照圖1，說明使用於膜F的製造方法的膜製造系統1b的構成。膜製造系統1b，具備壓出機10、T型模12、第1冷卻輥16、第2冷卻輥18。 First, the configuration of the film production system 1b used in the method of manufacturing the film F will be described with reference to Fig. 1 . The film production system 1b includes an extruder 10, a T-die 12, a first cooling roll 16, and a second cooling roll 18.
壓出機10，熔融混練投入的聚丙烯系樹脂而壓出，使熔融混練的聚丙烯系樹脂(熔融樹脂)往T型模12搬送者。 The extruder 10 melts and kneads the charged polypropylene resin and presses it, and conveys the melt-kneaded polypropylene resin (molten resin) to the T-die 12 .
T型模12，與壓出機10連接，於其內部具有使由壓出機10搬送來的熔融樹脂擴展於橫方向之用的歧管(未圖示)。此外，於T型模12，於其下部設有與歧管連通同時吐出藉由歧管被擴展於橫方向的熔融樹脂的吐出口12a。因此，T型模12的吐出口12a所吐出的熔融樹脂，為膜狀。 The T-die 12 is connected to the extruder 10, and has a manifold (not shown) for expanding the molten resin conveyed by the extruder 10 in the lateral direction. Further, in the T-die 12, a discharge port 12a that communicates with the manifold and discharges the molten resin expanded in the lateral direction by the manifold is provided at the lower portion thereof. Therefore, the molten resin discharged from the discharge port 12a of the T-die 12 is in the form of a film.
作為T型模12，以在熔融樹脂的流路之壁面 上沒有微小的階差或傷痕者為較佳。T型模12的吐出口12a部分(唇部分)，係與熔融樹脂之摩擦係數小的材料，而且以硬材料鍍層，被進行了塗布(coating)等(例如，碳化鎢系、氟素系之特殊電鍍)的話，可以縮小吐出口12a的先端部分的曲率半徑(使吐出口12a的先端部分成為所謂的銳邊(sharp edge)的形狀)，所以較佳。特別是可以使吐出口12的先端部分的曲率減少這一點，因此以碳化鎢為主成分的材料被熔射於吐出口12a的先端部分是較佳的。 As the T-die 12, on the wall surface of the flow path of the molten resin Those with no slight steps or scars are preferred. The portion (lip portion) of the discharge port 12a of the T-die 12 is a material having a small coefficient of friction with the molten resin, and is coated with a hard material and coated (for example, tungsten carbide or fluorine). In the case of the special plating, it is preferable to reduce the radius of curvature of the tip end portion of the discharge port 12a (the tip end portion of the discharge port 12a is in the shape of a so-called sharp edge). In particular, since the curvature of the tip end portion of the discharge port 12 can be reduced, it is preferable that a material containing tungsten carbide as a main component is melted at the tip end portion of the discharge port 12a.
T型模12的吐出口12a的先端部分，以熔融樹脂的流路的壁面的吐出口12a之曲率半徑為0.3mm以下，亦即所謂的銳邊(sharp edge)的形狀為較佳。曲率半徑，進而更佳者為0.001mm以上，0.05mm以下。曲率半徑未滿0.001mm的話，唇部有容易缺損的傾向，缺損的話會招致膜缺陷。0.3mm以下的話，可以抑制吐出口12a之出口渣的發生，同時也可見到抑制模頭線(die line)的效果，可以製造外觀的均勻性更為優異的模F以及聚丙烯系樹脂製相位差膜。 In the tip end portion of the discharge port 12a of the T-die 12, the radius of curvature of the discharge port 12a of the wall surface of the flow path of the molten resin is preferably 0.3 mm or less, that is, a so-called sharp edge shape. The radius of curvature, and more preferably 0.001 mm or more, 0.05 mm or less. When the radius of curvature is less than 0.001 mm, the lip tends to be easily damaged, and if it is defective, the film defect is caused. When the thickness is 0.3 mm or less, the occurrence of the exit slag of the discharge port 12a can be suppressed, and the effect of suppressing the die line can be seen, and the mold F and the polypropylene resin phase can be manufactured with more excellent uniformity in appearance. Poor film.
第1冷卻輥16及第2冷卻輥18的表面，藉由被施以H-Cr電鍍、鎳系電鍍等電鍍材料，或碳化鎢系、氧化鋁-二氧化鈦系、氧化鉻系等熔射材料來形成為較佳。電鍍或熔射材料上，被施以各種塗布亦可。電鍍或熔射材料內含有添加物亦可。作為塗布材料或前述添加物，可以舉例半金屬氧化物、金屬氧化物、鐵氟龍系、氟系等。 The surfaces of the first cooling roll 16 and the second cooling roll 18 are applied with a plating material such as H-Cr plating or nickel plating, or a molten material such as tungsten carbide, alumina-titania or chrome oxide. It is preferably formed. Various coatings may be applied to the plating or the molten material. The plating or the molten material may contain additives. As the coating material or the above additives, a semimetal oxide, a metal oxide, a Teflon system, a fluorine system or the like can be exemplified.
第1冷卻輥16及第2冷卻輥18，其直徑為200nm~800mm，表面粗糙度為0.3S以下之鏡面為較佳。 It is preferable that the first cooling roll 16 and the second cooling roll 18 have a mirror surface having a diameter of 200 nm to 800 mm and a surface roughness of 0.3 S or less.
於第1冷卻輥16及第2冷卻輥18的內部，以設有流路較佳。藉由於該流路內使液體流動，可以調整各輥的表面溫度。為了得到使厚度偏差減少，跨整個面具有均勻的透明性的膜F，進入各輥16、18的流路時的液體溫度，與流出各輥16、18的流路時的液體溫度之溫度差以在2℃以內為佳。藉由調整液體的流量，可以控制溫度差。一般而言，液體的流量越多，溫度差變得越小。此外，為了得到膜的流動方向之厚度偏差很小的膜F，針對第1冷卻輥16及第2冷卻輥18，以使用遊星輥減速機或遊星齒輪減速機為較佳。 It is preferable to provide a flow path inside the first cooling roll 16 and the second cooling roll 18. The surface temperature of each roller can be adjusted by causing the liquid to flow in the flow path. In order to obtain a film F having uniform transparency across the entire surface, the temperature difference between the liquid temperature at the time of entering the flow paths of the rolls 16 and 18 and the temperature of the liquid flowing out of the flow paths of the rolls 16 and 18 is obtained. It is preferably within 2 ° C. The temperature difference can be controlled by adjusting the flow rate of the liquid. In general, the more the flow rate of the liquid, the smaller the temperature difference becomes. Further, in order to obtain the film F having a small thickness variation in the flow direction of the film, it is preferable to use the planetary roller reducer or the planetary gear reducer for the first cooling roll 16 and the second cooling roll 18.
於本發明，藉由第1冷卻輥，使膜狀熔融樹脂被冷卻固化，成為膜F，於第2冷卻輥，搬送以第1冷卻輥冷卻固化的膜F。此膜F，其後被施以橫向延伸處理，成為聚丙烯系樹脂製相位差膜。 In the present invention, the film-shaped molten resin is cooled and solidified by the first cooling roll to form the film F, and the film F cooled and solidified by the first cooling roll is transferred to the second cooling roll. This film F was subjected to a lateral stretching treatment to form a retardation film made of a polypropylene resin.
又，製造膜F的速度，係第1冷卻輥16的直徑越大就越快。具體而言，第1冷卻輥16的直徑為600mm的場合，膜F的製造速度，最大為200m/分鐘程度，通常為30m/分鐘程度。 Further, the speed at which the film F is produced is faster as the diameter of the first cooling roll 16 is larger. Specifically, when the diameter of the first cooling roll 16 is 600 mm, the production speed of the film F is at most about 200 m/min, and is usually about 30 m/min.
第1冷卻輥16及第2冷卻輥18，於T型膜12的下方，一般係以排成一列的方式被配列。隨著各輥16、18的旋轉速度、以及由T型膜12的吐出口12a吐出的膜狀熔融樹脂的吐出量等而規定膜F的厚度。 The first cooling roll 16 and the second cooling roll 18 are generally arranged in a line below the T-shaped film 12. The thickness of the film F is defined by the rotation speed of each of the rolls 16 and 18, the discharge amount of the film-like molten resin discharged from the discharge port 12a of the T-shaped film 12, and the like.
圖3係模式顯示相關於本發明的相位差膜的製造方法之適切的橫向延伸的實施型態之工程圖。此相位差膜之製造方法，最好是具有以熱風預熱膜F的預熱步驟、以熱風加熱預熱的膜F同時延伸而得到延伸膜25的延伸步驟、以及以熱風加熱延伸膜25使其安定化的熱固定步驟。 Fig. 3 is a schematic view showing an embodiment of a suitable laterally extending embodiment of the manufacturing method of the retardation film of the present invention. The method for producing the retardation film preferably has a preheating step of preheating the film F by hot air, an extending step of stretching the film F heated by hot air to obtain the stretching film 25, and heating the stretching film 25 by hot air. Its stable heat setting step.
作為相關於本實施型態的相位差膜之製造方法，可以舉出根據拉幅機法之方法。使用於該方法的烤爐100，最好具備進行預熱步驟的預熱區20，進行延伸步驟的延伸區21及進行熱固定步驟的熱固定區22。作為烤爐100，以可以獨立調節分別各區的溫度為較佳。 As a method of manufacturing the retardation film according to this embodiment, a method according to the tenter method can be mentioned. The oven 100 used in the method preferably includes a preheating zone 20 for performing a preheating step, an extension zone 21 for performing the stretching step, and a heat fixing zone 22 for performing the heat fixing step. As the oven 100, it is preferable to independently adjust the temperatures of the respective zones.
圖4係模式顯示相關於本發明的相位差膜的製造方法之適切的實施型態之工程剖面圖。烤爐100內的上面100a，設有複數之上側噴嘴30。烤爐100內的下面100b，設有複數之下側噴嘴32。上側噴嘴30與下側噴嘴32，係以上下對向的方式設置。 Fig. 4 is a cross-sectional view showing the construction of a suitable embodiment of the method for producing a retardation film of the present invention. The upper surface 100a in the oven 100 is provided with a plurality of upper side nozzles 30. The lower surface 100b in the oven 100 is provided with a plurality of lower side nozzles 32. The upper nozzle 30 and the lower nozzle 32 are disposed to face each other.
詳言之，於預熱區20，在烤爐100內的上面及下面設有4對噴嘴(共計8根)，於延伸區21設有10對噴嘴(共計20根)，於熱固定區22設有4對噴嘴(共計8根)。 In detail, in the preheating zone 20, four pairs of nozzles (eight in total) are provided on the upper and lower sides of the oven 100, and ten pairs of nozzles (20 in total) are provided in the extension zone 21 in the heat fixing zone 22 There are 4 pairs of nozzles (8 in total).
設於預熱區20、延伸區21及熱固定區22的上面100a的上側噴嘴30，於下部具有吹出口，可以往下方向(箭頭B方向)吹出熱風。另一方面，分別設於預熱區20、延伸區21及熱固定區22的下側的下側噴嘴32，於 上部具有吹出口，可以往上方向(箭頭C方向)吹出熱風。又，於圖4雖未顯示，但上側噴嘴30及下側噴嘴32，以可使膜F及延伸膜於寬幅方向均勻地加熱的方式，垂直於圖4的紙面的方向上具有特定尺寸的深度。 The upper nozzle 30 provided in the preheating zone 20, the extension zone 21, and the upper surface 100a of the heat fixing zone 22 has an air outlet at the lower portion, and can blow hot air in the downward direction (arrow B direction). On the other hand, the lower nozzles 32 respectively disposed on the lower side of the preheating zone 20, the extension zone 21, and the heat fixing zone 22 are The upper portion has a blower port, and hot air can be blown upward (in the direction of arrow C). Further, although not shown in FIG. 4, the upper nozzle 30 and the lower nozzle 32 have a specific size perpendicular to the direction of the paper surface of FIG. 4 so that the film F and the stretched film can be uniformly heated in the wide direction. depth.
在本實施型態的聚丙烯系樹脂製相位差膜之製造方法，來自預熱區20、延伸區21及熱固定區22的上側噴嘴30及下側噴嘴32的吹出口之熱風的吹出速度，以設定在2~12m/秒為較佳，來自每一根噴嘴30(32)的吹出口的的吹出風量設定為0.1~1m3/秒為較佳。該吹出風速，由得到光學均勻性更進一層優異的相位差膜的觀點來看，以2~10m/秒為佳，以3~8m/秒為更佳。該吹出風量，由得到光學均勻性更進一層優異的相位差膜的觀點來看，以0.1~0.5m3/秒為更佳。 In the method for producing a polypropylene-based resin retardation film of the present embodiment, the blowing speed of the hot air from the outlets of the upper nozzle 30 and the lower nozzle 32 of the preheating zone 20, the extension zone 21, and the heat fixing zone 22 is Preferably, it is set to 2 to 12 m/sec, and the amount of blown air from the air outlet of each nozzle 30 (32) is preferably 0.1 to 1 m 3 /sec. The blowing wind speed is preferably 2 to 10 m/sec and more preferably 3 to 8 m/sec from the viewpoint of obtaining an optical retardation and further improving an excellent retardation film. The amount of the blown air is preferably from 0.1 to 0.5 m 3 /sec from the viewpoint of obtaining an optical retardation further into an excellent retardation film.
預熱區20、延伸區21及熱固定區22之中，預熱區20之該吹出風速為2~12m/秒，每一根噴嘴的吹出口之吹出風量以0.1~1m3/秒為佳。於預熱區20，膜F由室溫被加熱至可延伸的溫度，但膜寬幅不變而以夾盤23保持，所以熱膨脹的膜F會變得更容易下垂。預熱區20之所有的噴嘴30、32之吹出口之熱風的吹出風速為2~12m/秒，每一根噴嘴30、32的吹出風量為0.1~1m3/秒的話，可以充分預熱膜F，而且可以抑制膜F的下垂或上下擺動。又，預熱區20之所有的噴嘴30、32的吹出口之熱風的吹出風速為2~10m/秒為更佳。 Among the preheating zone 20, the extension zone 21 and the heat fixing zone 22, the blowing air velocity of the preheating zone 20 is 2 to 12 m/sec, and the blowing air volume of each nozzle is preferably 0.1 to 1 m 3 /sec. . In the preheating zone 20, the film F is heated from room temperature to an extendable temperature, but the film width is constant and held by the chuck 23, so that the thermally expanded film F becomes easier to sag. The blowing wind speed of the hot air of the nozzles 30 and 32 of all the nozzles 30 and 32 of the preheating zone 20 is 2 to 12 m/sec, and the blowing air volume of each of the nozzles 30 and 32 is 0.1 to 1 m 3 /sec, so that the film can be sufficiently preheated. F, and it is possible to suppress the sagging or up and down swing of the film F. Further, it is more preferable that the blowing wind speed of the hot air of the air outlets of all the nozzles 30 and 32 of the preheating zone 20 is 2 to 10 m/sec.
熱風的吹出風速，可以在噴嘴30、32的熱風 吹出口，使用市售的熱式風速計來進行測定。此外，由吹出口吹出的風量，可以藉由吹出風速與吹出口的面積的積來求出。又，熱風的吹出風速，由測定精度的觀點來看，在各噴嘴的吹出口測量10點程度，而採用其平均值為較佳。 Hot air blowing wind speed, hot air at nozzles 30, 32 The outlet was measured using a commercially available thermal anemometer. Further, the amount of air blown out from the air outlet can be obtained by the product of the air blowing speed and the area of the air outlet. Further, the blowing speed of the hot air is preferably measured at 10 points in the outlet of each nozzle from the viewpoint of measurement accuracy, and the average value thereof is preferably used.
此外，於預熱區20、延伸區21及熱固定區22之所有的區，所有的噴嘴30、32的熱風吹出口之熱風的吹出風速為2~12m/秒為更佳，2~10m/秒進而又更佳。藉此，可以得到相位差極為均勻，而且具有極高的軸精度之聚丙烯系樹脂製相位差膜。 Further, in all the zones of the preheating zone 20, the extension zone 21 and the heat fixing zone 22, the blowing wind speed of the hot air blowing outlets of all the nozzles 30, 32 is preferably 2 to 12 m/sec, preferably 2 to 10 m/ Seconds are even better. Thereby, a polypropylene-based resin retardation film having extremely uniform phase difference and extremely high axial precision can be obtained.
在預熱區20、延伸區21及熱固定區22之所有的區，分別的噴嘴30、32的吹出口之熱風的吹出風速的寬幅方向(垂直於圖4的紙面的方向)之最大值與最小值的差在4m/秒以下為較佳。如此般藉由使用在寬幅方向風速的散布很少的熱風，可以得到寬幅方向的光學均勻性更高的相位差膜。 In all of the preheating zone 20, the extension zone 21, and the heat-fixing zone 22, the maximum width of the blowing wind speed of the nozzles 30, 32 of the nozzles 30, 32 (the direction perpendicular to the plane of the paper of Fig. 4) The difference from the minimum value is preferably 4 m/sec or less. Thus, by using a small amount of hot air spread in a wide direction wind speed, a retardation film having a higher optical uniformity in a wide direction can be obtained.
於烤爐100，由預熱區20、延伸區21及熱固定區22構成的群所選擇之至少1個以上的區，相互對向的上側噴嘴30與下側噴嘴32之間隔L(最短距離)以150mm以上為佳，150~600mm為更佳，150~400mm進而更佳。藉由以這樣的間隔L配置上側噴嘴與下側噴嘴，可以更為確實地抑制各步驟之膜的上下擺動。 In the oven 100, at least one or more zones selected by the group consisting of the preheating zone 20, the extension zone 21, and the heat fixing zone 22, and the interval L between the upper nozzles 30 and the lower nozzles 32 facing each other (the shortest distance) It is preferably 150 mm or more, 150 to 600 mm is better, and 150 to 400 mm is further preferred. By arranging the upper nozzle and the lower nozzle at such an interval L, it is possible to more reliably suppress the vertical swing of the film in each step.
此外，預熱區20、延伸區21及熱固定區22構成的群所選擇之至少1個以上的區所具備的各個的噴嘴 30、32之吹出口之熱風在寬幅方向(垂直於圖4的紙面的方向)之最高溫度與最低溫度的差(△T)全部在2℃以下為較佳，全部在1℃以下又更佳。藉由使用這樣在寬幅方向之溫度差充分小的熱風加熱膜，可以更為抑制寬幅方向的配向性之散佈(dispersion)。又，熱風的溫度為延伸膜F的溫度之溫度範圍。 Further, each of the nozzles included in at least one of the zones selected by the group consisting of the preheating zone 20, the extension zone 21, and the heat fixing zone 22 The difference between the highest temperature and the lowest temperature (ΔT) of the hot air of the blowing outlets of 30 and 32 in the wide direction (the direction perpendicular to the paper surface of Fig. 4) is preferably below 2 ° C, and all are below 1 ° C and more. good. By using the hot air heating film in which the temperature difference in the wide direction is sufficiently small, the dispersion of the alignment in the wide direction can be further suppressed. Further, the temperature of the hot air is a temperature range in which the temperature of the film F is stretched.
接著，參照圖1說明藉由前述之膜製造系統1b製造相位差膜的方法。 Next, a method of manufacturing a retardation film by the above-described film production system 1b will be described with reference to Fig. 1 .
首先，由漏斗(未圖示)對壓出機10投入聚丙烯系樹脂(熔融步驟)。此時，為了抑制樹脂的劣化，對壓出機10供給聚丙烯系樹脂之前，在氮氣中以40℃以上(Tm-20)℃以下的溫度預備乾燥聚丙烯系樹脂1小時~10小時程度為較佳(其中，Tm[℃]係以JIS K 7121所規定的微差掃描熱量測定法之熔解峰溫度，具體而言，使用微差掃描熱量計(DSC)等，把試樣一度加熱至融點以上，然後以特定的速度冷卻至-30℃程度，其後，由以特定的速度升溫同時進行測定所得到的DSC曲線的屈曲點求得的)。此外，壓出機10內，也以20℃~120℃的氮氣，氬氣等惰性氣體來進行氣體置換為佳。又，為了使壓出量儘量一定，齒輪泵的使用是有效的。此外，不純物、異物等會成為問題的場合，亦可因應必要使用葉片盤濾機等過濾元件。 First, a polypropylene resin is introduced into the extruder 10 by a funnel (not shown) (melting step). In this case, in order to suppress deterioration of the resin, before the polypropylene resin is supplied to the extruder 10, the polypropylene resin is preliminarily dried at a temperature of 40 ° C or higher (Tm -20 ° ° C or lower) in nitrogen gas for 1 hour to 10 hours. Preferably, (wherein Tm[°C] is a melting peak temperature of a differential scanning calorimetry method specified by JIS K 7121, specifically, a sample is once heated to a melt using a differential scanning calorimeter (DSC) or the like. Above the point, it is cooled to a temperature of about -30 ° C at a specific speed, and then obtained by the buckling point of the DSC curve obtained by measuring the temperature while heating at a specific speed. Further, in the extruder 10, it is preferable to carry out gas replacement with an inert gas such as nitrogen gas or argon gas at 20 ° C to 120 ° C. Moreover, in order to make the amount of extrusion as constant as possible, the use of a gear pump is effective. In addition, when impurities or foreign matter may become a problem, it is also necessary to use a filter element such as a vane disk filter.
接著，於被加熱至Tm℃以上300℃以下的壓 出機10的壓缸內藉由螺旋槳使聚丙烯系樹脂熔融混練，由T型模12的吐出口12a被成形為膜狀的熔融樹脂在Tm℃以上300℃以下的溫度被吐出(成形步驟)。此膜狀熔融樹脂的溫度，係於T型模12的吐出口12a部分使用樹脂溫度計來測定。 Then, it is heated to a pressure of Tm ° C or more and 300 ° C or less. In the cylinder of the outlet 10, the polypropylene resin is melted and kneaded by a propeller, and the molten resin molded into the film shape by the discharge port 12a of the T-die 12 is discharged at a temperature of Tm ° C or more and 300 ° C or less (forming step). . The temperature of the film-like molten resin was measured in a portion of the discharge port 12a of the T-die 12 using a resin thermometer.
膜狀熔融樹脂的溫度(以下，亦記載為「T1」)未達到融點(Tm)℃的話，樹脂的延展性不夠充分，會由於空氣間隙內之伸展的不均勻而有發生厚度不均的傾向。T1超過300℃的話，會因樹脂劣化，產生氣體等理由而發生唇部分汙損，發生模頭線(die line)等，會有產生膜的外觀不良的傾向。由此觀點，T1以Tm℃以上(Tm+100)℃以下為較佳。設為Tm℃以上(Tm+100)℃以下的話，在壓出步驟可以賦予適度的配向，所以可提高橫向延伸倍率，可以得到均勻的相位差膜。此外，T1超過Tm+100℃的話，不容易加諸配向，橫向單軸延伸時無法提高延伸倍率，會有難以得到光學均一的膜的傾向。 When the temperature of the film-like molten resin (hereinafter also referred to as "T1") does not reach the melting point (Tm) °C, the ductility of the resin is insufficient, and unevenness in thickness occurs in the air gap. tendency. When T1 exceeds 300 °C, the lip portion is stained due to deterioration of the resin, gas generation, and the like, and a die line or the like is generated, which tends to cause a poor appearance of the film. From this point of view, T1 is preferably Tm ° C or more (Tm + 100) ° C or less. When it is set to Tm ° C or more (Tm + 100) ° C or less, an appropriate alignment can be imparted in the extrusion step, so that the lateral stretching ratio can be increased, and a uniform retardation film can be obtained. Further, when T1 exceeds Tm + 100 ° C, it is not easy to add alignment, and when the lateral uniaxial stretching is performed, the stretching ratio cannot be increased, and it is difficult to obtain an optically uniform film.
為了得到膜的流向上之厚度偏差很小的膜F，於T形膜12的入口的上游部分設置樹脂壓力計P，以使流經T形膜12的入口附近的的熔融樹脂的壓力變動在±0.1MPa以下(亦即，熔融樹脂的壓力的最大值與最小值之差為0.2MPa以下)的方式來進行控制為較佳。 In order to obtain the film F having a small thickness deviation in the flow direction of the film, a resin pressure gauge P is provided in the upstream portion of the inlet of the T-shaped film 12 so that the pressure of the molten resin flowing near the inlet of the T-shaped film 12 is varied. It is preferable to control by ±0.1 MPa or less (that is, the difference between the maximum value and the minimum value of the pressure of the molten resin is 0.2 MPa or less).
接著，藉由第1冷卻輥16冷卻此膜狀熔融樹脂使其固化(冷卻步驟)，搬送至第2冷卻輥18。通常，冷卻主要是在第1冷卻輥16進行的。在第1冷卻輥16的下 游側配設接觸輥19亦可。在此場合，在第1冷卻輥16的上游側，膜狀熔融樹脂被冷卻固化，被冷卻固化的膜在第1冷卻輥16的下游側以第1冷卻輥16與接觸輥19夾壓。接觸輥的材質沒有特別限制，例如以橡膠等具有彈性的材質為佳。藉由配設接觸輥，可以抑制在第1冷卻輥16上有來自樹脂之附著物的蓄積，即使長時間加工，前述附著物也不會往膜上轉印，可以高產率得到膜F。此處，第1冷卻輥16的表面溫度T2[℃]，以滿足以下式(9)所示的條件的方式來設定是較佳的。 Then, the film-like molten resin is cooled by the first cooling roll 16 to be solidified (cooling step), and then transferred to the second cooling roll 18. Usually, the cooling is mainly performed by the first cooling roller 16. Under the first cooling roller 16 The contact roller 19 may be disposed on the side of the swim. In this case, the film-like molten resin is cooled and solidified on the upstream side of the first cooling roll 16, and the film which is cooled and solidified is sandwiched by the first cooling roll 16 and the contact roll 19 on the downstream side of the first cooling roll 16. The material of the contact roller is not particularly limited, and for example, a material having elasticity such as rubber is preferable. By arranging the contact roller, accumulation of the deposit from the resin on the first cooling roll 16 can be suppressed, and even if the processing is performed for a long period of time, the deposit is not transferred onto the film, and the film F can be obtained in a high yield. Here, it is preferable that the surface temperature T2 [° C.] of the first cooling roll 16 is set so as to satisfy the condition shown by the following formula (9).
-5≦T2≦30 (9) -5≦T2≦30 (9)
T2在此範圍的話，第1冷卻輥16上不容易有空氣中的水分結露，所以可安定而容易地得到透明性高的膜。 When T2 is in this range, condensation of moisture in the air is less likely to occur on the first cooling roll 16, so that a film having high transparency can be easily obtained by stability.
其後，膜F因應必要把耳部撕除(切斷)，以捲繞機捲取。又，撕除(切斷)膜F的耳部之前，或者撕除(切斷)之後，於膜F的單面或雙面層積保護膜亦可。 Thereafter, the film F is peeled off (cut) as necessary, and taken up by a winder. Further, before the ear portion of the film F is peeled off (cut), or after being peeled off (cut), a protective film may be laminated on one side or both sides of the film F.
作為膜F的厚度，由最佳呈現本發明的效果的觀點，以50μm~500μm為佳，但不特別限定於此範圍。總之，作為膜F的厚度，可以種種的延伸條件來延伸，因應於種種用途的相位差膜而選擇必要的厚度。作為延伸方法，進行橫向單軸延伸。 The thickness of the film F is preferably from 50 μm to 500 μm from the viewpoint of optimally exhibiting the effects of the present invention, but is not particularly limited to this range. In short, the thickness of the film F can be extended by various extension conditions, and the necessary thickness can be selected in accordance with the retardation film for various uses. As an extension method, lateral uniaxial stretching is performed.
本發明之膜F，適度地被賦予配向，其面內相位差值(R0)滿足式(1)。配向的程度，可以藉求出相位差值 而進行評估，相位差值可以使用市售的相位差計進行測定。面內相位差值(R0)，在膜F的厚度為100μm時之值為15nm以上1000nm以下為佳。膜F的相位差值的上限沒有限制。膜F的面內相位差值(R0)不滿足式(1)的話，將該膜F橫向單軸延伸，欲得到所要的NZ係數的聚丙烯系樹脂製相位差膜，而調整延伸條件時，在延伸倍率1.9倍以上，有無法得到所要的NZ係數之膜的傾向。延伸倍率未滿1.9倍的話，膜均勻性有劣化的傾向，組入液晶顯示裝置時，有導致顯示不均的傾向。 The film F of the present invention is moderately imparted with an in-plane retardation value (R0) satisfying the formula (1). The degree of alignment can be used to determine the phase difference For evaluation, the phase difference value can be measured using a commercially available phase difference meter. The in-plane retardation value (R0) is preferably 15 nm or more and 1000 nm or less when the thickness of the film F is 100 μm. The upper limit of the phase difference value of the film F is not limited. When the in-plane retardation value (R0) of the film F does not satisfy the formula (1), the film F is laterally uniaxially stretched, and a polypropylene-based resin retardation film having a desired NZ coefficient is obtained, and when the elongation condition is adjusted, When the stretching ratio is 1.9 or more, there is a tendency that a film having a desired NZ coefficient cannot be obtained. When the stretching ratio is less than 1.9 times, the film uniformity tends to be deteriorated, and when incorporated into a liquid crystal display device, display unevenness tends to occur.
在本實施型態，進行根據拉幅機法之橫向單軸延伸。使用於根據拉幅機法的橫向延伸之烤爐，在膜F送出的上游側，設有複數個可以獨立控制風的溫度及風速的區。烤爐，例如可以把上游側作為預熱區，把下游側作為延伸區。在預熱區及延伸區，設有如圖5所示的衝壓噴嘴38。此處，雖設置衝壓噴嘴38，但噴嘴形狀沒有特別限制，亦可為噴射噴嘴等。 In the present embodiment, lateral uniaxial stretching according to the tenter method is performed. For the oven extending in the lateral direction according to the tenter method, on the upstream side of the film F, a plurality of zones for independently controlling the temperature and wind speed of the wind are provided. For the oven, for example, the upstream side can be used as a preheating zone and the downstream side can be used as an extension zone. In the preheating zone and the extension zone, a stamping nozzle 38 as shown in Fig. 5 is provided. Here, although the press nozzle 38 is provided, the shape of the nozzle is not particularly limited, and may be an injection nozzle or the like.
如圖5所示，設於烤爐的上面100a及下面100b的衝壓噴嘴38，其橫剖面，朝向對向於膜F的面38a具有末端擴展狀的梯形形狀。衝壓噴嘴38，在對向於膜F的面之下側的面38a具有複數之例如圓形的開口44。衝壓噴嘴38的熱風吹出口，藉由設於面38a的複數開口44構成。複數之開口44為熱風的吹出口，熱風由開 口44以特定的風速吹出。開口44，被配置複數個於膜F的長邊方向，同時於寬幅方向也配置複數個。開口44例如可以配置為鋸齒狀。 As shown in Fig. 5, the press nozzles 38 provided on the upper surface 100a and the lower surface 100b of the oven have a trapezoidal shape in which the end faces are extended toward the surface 38a facing the film F in a cross section. The punching nozzle 38 has a plurality of openings 44, for example, circular, on the face 38a on the lower side of the face opposite to the film F. The hot air blowing port of the press nozzle 38 is constituted by a plurality of openings 44 provided on the surface 38a. The plurality of openings 44 are hot air outlets, and the hot air is opened. Port 44 is blown at a specific wind speed. The opening 44 is disposed in plural in the longitudinal direction of the film F, and a plurality of openings are also arranged in the width direction. The opening 44 can be configured, for example, in a zigzag shape.
在預熱區加熱的膜F，在延伸區延伸。延伸加熱了的膜F的溫度為To時，To以滿足下列式(3)的條件為佳。 The film F heated in the preheating zone extends in the extension zone. When the temperature of the film F which is extended and heated is To, it is preferable that To meets the condition of the following formula (3).
Tm-10℃≦To≦Tm℃ (3) Tm-10°C≦To≦Tm°C (3)
聚丙烯系樹脂在得到膜F的過程容易加諸適度的配向。藉由使膜F在1.9倍以上3.0倍以下的倍率橫向單軸延伸，可以得到光學均勻性優異的相位差膜。為了得到光學均勻的相位差膜，橫向延伸倍率較佳為2.0倍以上3.0倍以下，更佳者為2.3倍以上3.0倍以下。橫向單軸延伸倍率若不是1.9倍以上3.0倍以下的話，無法得到NZ係數為1.3以上4.0以下的相位差膜。 The polypropylene resin is easily added to an appropriate alignment in the process of obtaining the film F. By uniaxially stretching the film F at a magnification of 1.9 times or more and 3.0 times or less, a retardation film excellent in optical uniformity can be obtained. In order to obtain an optically uniform retardation film, the lateral stretching ratio is preferably 2.0 times or more and 3.0 times or less, and more preferably 2.3 times or more and 3.0 times or less. When the transverse uniaxial stretching ratio is not 1.9 times or more and 3.0 times or less, a retardation film having an NZ coefficient of 1.3 or more and 4.0 or less cannot be obtained.
以本發明的方法得到的相位差膜，可以廣泛適用於電視、電腦用螢幕，汽車導航裝置，數位相機，行動電話等之大型液晶面板至中小型液晶面板。以本發明的方法得到的相位差膜，特別適於VA用相位差膜。 The retardation film obtained by the method of the present invention can be widely applied to large liquid crystal panels to small and medium-sized liquid crystal panels such as televisions, computer screens, car navigation devices, digital cameras, and mobile phones. The retardation film obtained by the method of the present invention is particularly suitable for a retardation film for VA.
以下，根據實施例及比較例以及圖1更具體地說明本發明，但本發明並不以以下之實施例為限。 Hereinafter, the present invention will be specifically described based on examples and comparative examples and FIG. 1, but the present invention is not limited to the following examples.
(1)面內相位差值(R0)，厚度方向相位差值(Rth)以及NZ係數的評估 (1) In-plane phase difference value (R0), thickness direction phase difference (Rth) and evaluation of NZ coefficient
把膜F以及相位差膜在膜寬幅方向的中央部分將1000mm的寬幅以100mm間隔切出40mm×40mm之大小，分別得到11點之測定用膜。這些，藉由王子計測機器服務(股)製造的KOBRA-WPR，求出面內相位差值(R0)，厚度方向相位差值(Rth)以及NZ係數。將11點的平均作為分別的評估結果。 The film F and the retardation film were cut into a size of 40 mm × 40 mm at a distance of 100 mm at a central portion of the film width direction at a width of 1000 mm to obtain an 11-point film for measurement. These are obtained by KOBRA-WPR manufactured by the prince measuring machine service (share), and the in-plane phase difference value (R0), the thickness direction phase difference value (Rth), and the NZ coefficient are obtained. The average of 11 points was taken as the result of the separate evaluation.
(2)膜的厚度測定 (2) Determination of film thickness
膜F，係對該膜F的寬幅方向平行地以50mm寬幅(膜的流動方向上的距離)切出膜的全寬幅，使用(股)山文製造的厚度計亦即靜電電容式TOF-C(商品名)，以1mm的間隔由膜的寬幅方向之一方端部到另一方的端部為止進行厚度的測定，以測定的膜的中央部之對T形模吐出口的寬幅方向之65%寬的平均值來進行評估。 The film F is formed by cutting the full width of the film in a width direction of 50 mm (distance in the flow direction of the film) in parallel with the width direction of the film F, and using a thickness gauge manufactured by Yamagata, that is, an electrostatic capacitance type. TOF-C (trade name) measures the thickness from one end of the film in the width direction to the other end at intervals of 1 mm, and measures the width of the center portion of the film to the T-die discharge port. The average of the 65% width in the width direction was evaluated.
(3)光軸不均的評估 (3) Evaluation of optical axis unevenness
使用偏光顯微鏡，在製作的相位差膜的寬幅方向中央部分寬幅1000mm的範圍以20mm間隔測定光軸的角度。作為光學均勻性的評估之一，測定了光軸的散布。具體而言，由光軸的最大值減掉最小值，來評估光軸不均。 Using an polarizing microscope, the angle of the optical axis was measured at intervals of 20 mm in the range of 1000 mm in width in the central portion in the wide direction of the produced retardation film. As one of the evaluations of optical uniformity, the dispersion of the optical axis was measured. Specifically, the optical axis unevenness is evaluated by subtracting the minimum value from the maximum value of the optical axis.
作為聚丙烯系樹脂，使用了乙烯-丙烯共聚物(乙烯含量=5重量百分比)，Tm(融點)=138℃，MFR(熔流速 率)=8g/10分鐘，住友化學(股)製造之Noblen W151)。裝置使用圖1所示的裝置。第1冷卻輥16及第2冷卻輥18，係直徑為分別為400nm、350mm，其表面粗糙度為0.1S，表面為鏡面者。第1冷卻輥16及第2冷卻輥18的旋轉速度分別設定為10.0m/分鐘、10.1m/分鐘，空氣間隙H設定為70mm，第1冷卻輥16的表面溫度(T2)設定為15℃。 As the polypropylene-based resin, an ethylene-propylene copolymer (ethylene content = 5 wt%), Tm (melting point) = 138 ° C, MFR (melting flow rate) was used. Rate) = 8g/10 minutes, Noblen W151 manufactured by Sumitomo Chemical Co., Ltd.). The device uses the device shown in Figure 1. The first cooling roll 16 and the second cooling roll 18 have a diameter of 400 nm and 350 mm, respectively, and have a surface roughness of 0.1 S and a mirror surface. The rotational speeds of the first cooling roller 16 and the second cooling roller 18 were set to 10.0 m/min and 10.1 m/min, respectively, and the air gap H was set to 70 mm, and the surface temperature (T2) of the first cooling roller 16 was set to 15 °C.
以加熱至210℃的75mm壓出機10(螺旋槳：L/D=32)，熔融混練了聚丙烯系樹脂。由壓出機10，往接著壓出機10而設置的適配器及T形模12(均被設定於210℃)依序饋送熔融混練的聚丙烯系樹脂，由T形模12的吐出口(唇口)12a吐出膜狀熔融樹脂。T型模12的吐出口12a部分之膜狀熔融樹脂的溫度(T1)為210℃。使該膜狀熔融樹脂，以第1冷卻輥16冷卻而固化，藉由以第2冷卻輥18抽拉，得到厚度90μm的膜F。將膜狀熔融樹脂以第1冷卻輥16冷卻時，不以靜電或空氣等將膜狀熔融樹脂按壓於冷卻輥16。 75mm heated to 210 ° C The extruder 10 (propeller: L/D = 32) melt-kneaded the polypropylene resin. The melt-kneading polypropylene resin is sequentially fed from the extruder 10 to the adapter and the T-die 12 (both set at 210 ° C) provided in the extrusion machine 10, and the discharge port (lip) of the T-die 12 is supplied. The mouth) 12a discharges a film-like molten resin. The temperature (T1) of the film-like molten resin in the portion of the discharge port 12a of the T-die 12 was 210 °C. The film-shaped molten resin was cooled by the first cooling roll 16 and solidified, and was drawn by the second cooling roll 18 to obtain a film F having a thickness of 90 μm. When the film-like molten resin is cooled by the first cooling roll 16, the film-shaped molten resin is not pressed against the cooling roll 16 by static electricity, air, or the like.
所得到的膜F以延伸倍率2.3倍橫向單軸延伸，得到相位差膜。此處，膜F的預熱溫度設定為140℃，延伸溫度設定為130℃。延伸機的預熱區為6m，延伸區為6m。延伸速度設定為2m/分鐘。 The obtained film F was laterally uniaxially stretched at a stretching ratio of 2.3 times to obtain a retardation film. Here, the preheating temperature of the film F was set to 140 ° C, and the extension temperature was set to 130 °C. The preheating zone of the extension machine is 6m and the extension zone is 6m. The extension speed was set to 2 m/min.
除了把壓出機10的溫度設定為230℃，接著壓出機 10設置的適配器及T形模12的溫度設定為230℃以及使橫向單軸延伸倍率為1.9倍以外，與實施例1同樣進行得到相位差膜。熔融樹脂的溫度(T1)為230℃。 In addition to setting the temperature of the extruder 10 to 230 ° C, then the extruder A retardation film was obtained in the same manner as in Example 1 except that the temperature of the adapter and the T-die 12 set in 10 was set to 230 ° C and the lateral uniaxial stretching ratio was 1.9. The temperature (T1) of the molten resin was 230 °C.
除了把壓出機10的溫度設定為180℃，接著壓出機10設置的適配器及T形模12的溫度設定為180℃以及使橫向單軸延伸倍率為2.5倍以外，與實施例1同樣進行得到相位差膜。熔融樹脂的溫度(T1)為180℃。 The same procedure as in the first embodiment was carried out except that the temperature of the extruder 10 was set to 180 ° C, and the temperature of the adapter and the T-die 12 provided in the extruder 10 was set to 180 ° C and the lateral uniaxial stretching ratio was 2.5 times. A retardation film was obtained. The temperature (T1) of the molten resin was 180 °C.
除了使橫向單軸延伸倍率為2.0倍以外，與實施例3同樣得到相位差膜。 A retardation film was obtained in the same manner as in Example 3 except that the lateral uniaxial stretching ratio was 2.0 times.
除了使橫向單軸延伸倍率為2.5倍以外，與實施例1同樣得到相位差膜。 A retardation film was obtained in the same manner as in Example 1 except that the lateral uniaxial stretching ratio was 2.5 times.
除了把延伸溫度設定為134℃以外，與實施例5同樣得到相位差膜。 A retardation film was obtained in the same manner as in Example 5 except that the stretching temperature was changed to 134 °C.
除了把橫向單軸延伸倍率設定為3.0倍以外，與實施 例6同樣得到相位差膜。 In addition to setting the lateral uniaxial stretching ratio to 3.0 times, and implementing In Example 6, a retardation film was also obtained.
作為聚丙烯系樹脂，使用了乙烯-丙烯共聚物(乙烯含量=5重量百分比)，Tm(融點)=138℃，MFR(熔流速率)=8g/10分鐘，住友化學(股)製造之Noblen W151)。裝置使用圖2所示的裝置，亦即具有可彈性變形的金屬輥14與第1冷卻輥16之2根輥的裝置。可彈性變形的金屬輥的表面以不銹鋼構成的薄壁金屬外筒14b構成，其表面粗糙度為0.3S。把可彈性變形的金屬輥14的薄壁金屬外筒14b的表面溫度設定於120℃，第1冷卻輥16的表面溫度(T2)設定為15℃。 As the polypropylene-based resin, an ethylene-propylene copolymer (ethylene content = 5 wt%), Tm (melting point) = 138 ° C, MFR (melt flow rate) = 8 g/10 min, manufactured by Sumitomo Chemical Co., Ltd. was used. Noblen W151). The apparatus uses the apparatus shown in Fig. 2, that is, a device having two rolls of the elastically deformable metal roll 14 and the first cooling roll 16. The surface of the elastically deformable metal roll is composed of a thin-walled metal outer cylinder 14b made of stainless steel, and has a surface roughness of 0.3S. The surface temperature of the thin-walled metal outer cylinder 14b of the elastically deformable metal roll 14 was set to 120 ° C, and the surface temperature (T2) of the first cooling roll 16 was set to 15 °C.
壓出機10的溫度設定為250℃，接著壓出機10而設置的適配器及T型模12的溫度設定為250℃。藉由該壓出機，熔融混練聚丙烯系樹脂，由T型模12的吐出口(唇口)12a吐出膜狀熔融樹脂，以2根輥夾壓該膜狀熔融樹脂使其冷卻固化而得到厚度100μm的膜。使用與在實施例1使用的相同的延伸機，使得到的膜以延伸倍率2.5倍橫向單軸延伸，得到相位差膜。此處，膜的預熱溫度設定為140℃，延伸溫度設定為130℃。延伸機的預熱區為6m，延伸區為6m。延伸速度設定為2m/分鐘。 The temperature of the extruder 10 was set to 250 ° C, and the temperature of the adapter and the T-die 12 provided with the extruder 10 was set to 250 ° C. The polypropylene resin is melt-kneaded by the extruder, and the film-like molten resin is discharged from the discharge port (lip) 12a of the T-die 12, and the film-shaped molten resin is sandwiched between the two rolls to be cooled and solidified. A film having a thickness of 100 μm. Using the same stretching machine as used in Example 1, the obtained film was uniaxially stretched at a stretching ratio of 2.5 times to obtain a retardation film. Here, the preheating temperature of the film was set to 140 ° C, and the extension temperature was set to 130 ° C. The preheating zone of the extension machine is 6m and the extension zone is 6m. The extension speed was set to 2 m/min.
除了使橫向延伸倍率為1.7倍以外，與比較例1同樣 得到相位差膜。 The same as Comparative Example 1 except that the lateral stretching ratio was 1.7 times. A retardation film was obtained.
除了使橫向延伸倍率為1.7倍以外，與實施例2同樣得到相位差膜。 A retardation film was obtained in the same manner as in Example 2 except that the lateral stretching ratio was 1.7.
除了把壓出機10的溫度設為250℃，接著壓出機10設置的適配器及T型模12的溫度設定為250℃，把第1冷卻輥16及第2冷卻輥18的旋轉速度設定為5m/分鐘以外，與實施例3同樣進行得到相位差膜。在壓出步驟得到的膜F的面內相位差值為2nm，厚度方向相位差值為28nm。膜狀熔融樹脂的溫度(T1)為250℃。 The temperature of the extruder 10 and the temperature of the T-die 12 were set to 250 ° C, and the rotational speeds of the first cooling roller 16 and the second cooling roller 18 were set to 250 ° C, and the temperature of the adapter and the T-die 12 provided in the extruder 10 was set to 250 ° C. A retardation film was obtained in the same manner as in Example 3 except for 5 m/min. The in-plane retardation value of the film F obtained in the extrusion step was 2 nm, and the thickness direction retardation value was 28 nm. The temperature (T1) of the film-like molten resin was 250 °C.
除了把橫向單軸延伸倍率設定為4.0倍以外，與比較例1同樣得到相位差膜。 A retardation film was obtained in the same manner as in Comparative Example 1, except that the lateral uniaxial stretching ratio was set to 4.0.
除了把橫向單軸延伸倍率設定為4.0倍以外，與實施例6同樣得到相位差膜。 A retardation film was obtained in the same manner as in Example 6 except that the lateral uniaxial stretching ratio was set to 4.0.
針對實施例及比較例，將結果顯示於表1及表2。 The results are shown in Tables 1 and 2 for the examples and comparative examples.
於實施例1所得到的膜F的面內相位差值為28nm，厚度方向相位差值為53nm，該膜F具有適度的相 位差值。於實施例1得到的相位差膜的面內相位差值及厚度方向相位差值分別為81nm、116nm。以KOBRA-WPR求出相位差膜的NZ係數為1.9，該膜可作為相位差膜使用。 The film F obtained in Example 1 had an in-plane retardation value of 28 nm and a thickness direction retardation value of 53 nm, and the film F had a moderate phase. The difference value. The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 1 were 81 nm and 116 nm, respectively. The NZ coefficient of the retardation film was determined by KOBRA-WPR to be 1.9, and the film was used as a retardation film.
於實施例2得到的相位差膜的面內相位差值及厚度方向相位差值分別為52nm、115nm。此外，NZ係數為2.7。 The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 2 were 52 nm and 115 nm, respectively. In addition, the NZ coefficient is 2.7.
於實施例3得到的相位差膜的面內相位差值及厚度方向相位差值分別為57nm、113nm。此外，NZ係數為2.5。 The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 3 were 57 nm and 113 nm, respectively. In addition, the NZ coefficient is 2.5.
實施例1~3得到的相位差膜，具有適度的正的二軸性，特別是作為VA用相位差膜具有優異的特性平衡。 The retardation film obtained in each of Examples 1 to 3 has moderate positive biaxiality, and particularly has excellent characteristic balance as a retardation film for VA.
於實施例5得到的相位差膜的面內相位差值及厚度方向相位差值分別為106nm、101nm。此外，NZ係數為1.5，具有適度的二軸性，可以作為相位差膜使用。 The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 5 were 106 nm and 101 nm, respectively. In addition, the NZ coefficient is 1.5, which has moderate biaxiality and can be used as a retardation film.
於實施例6得到的相位差膜的面內相位差值及厚度方向相位差值分別為86nm、106nm。此外，NZ係數為1.7，具有適度的二軸性，可以作為相位差膜使用。 The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 6 were 86 nm and 106 nm, respectively. In addition, the NZ coefficient is 1.7, which has moderate biaxiality and can be used as a retardation film.
於實施例7得到的相位差膜的面內相位差值及厚度方向相位差值分別為112nm、94nm。此外，NZ係數為1.3，具有適度的二軸性，可以作為相位差膜使用。 The in-plane retardation value and the thickness direction retardation value of the retardation film obtained in Example 7 were 112 nm and 94 nm, respectively. In addition, the NZ coefficient is 1.3, which has moderate biaxiality and can be used as a retardation film.
在比較例1，以與實施例1幾乎相同的橫向延伸倍率來延伸膜而得到相位差膜。然而所得到的相位差膜的NZ係數為1.1，該膜具有單軸性。這意味著該膜作為 VA用相位差膜是「不適當」的。此外，將比較例1與橫向延伸條件相同的實施例3比較的話，比較例1所得到的相位差膜其NZ係數為1.1，該膜具有單軸性。另一方面，在實施例3所得到的相位差膜的NZ係數為2.5，該膜具有二軸性。 In Comparative Example 1, the film was stretched at almost the same lateral stretching ratio as in Example 1 to obtain a retardation film. However, the obtained retardation film had an NZ coefficient of 1.1, and the film had uniaxiality. This means that the film acts as The retardation film for VA is "inappropriate". Further, when Comparative Example 1 was compared with Example 3 in which the lateral stretching conditions were the same, the retardation film obtained in Comparative Example 1 had an NZ coefficient of 1.1, and the film had uniaxiality. On the other hand, the retardation film obtained in Example 3 had an NZ coefficient of 2.5, and the film had biaxiality.
比較例2所得到的相位差膜，NZ係數為5.9。NZ係數太大，所以該膜作為VA用相位差膜是「不適當」的。 The retardation film obtained in Comparative Example 2 had an NZ coefficient of 5.9. Since the NZ coefficient is too large, the film is "inappropriate" as a retardation film for VA.
比較例3所得到的相位差膜，NZ係數為7.0。NZ係數太大，所以該膜作為VA用相位差膜是「不適當」的。 The retardation film obtained in Comparative Example 3 had an NZ coefficient of 7.0. Since the NZ coefficient is too large, the film is "inappropriate" as a retardation film for VA.
比較例4，與實施例3的橫向延伸條件相同。但是，比較例4所得到的相位差膜，NZ係數為1.1。該膜具有單軸性，作為VA用相位差膜是「不適當」的。 Comparative Example 4 was the same as the lateral stretching condition of Example 3. However, the retardation film obtained in Comparative Example 4 had an NZ coefficient of 1.1. This film has uniaxiality and is "inappropriate" as a retardation film for VA.
比較例5，與實施例1僅有延伸倍率不同。但是，在比較例5得到的相位差膜，NZ係數為1.0，具有單軸性，作為VA用相位差膜是「不適當」的。 In Comparative Example 5, the stretching ratio was different from that in Example 1. However, the retardation film obtained in Comparative Example 5 had an NZ coefficient of 1.0 and uniaxiality, and was "inappropriate" as a retardation film for VA.
比較例6，與實施例5僅有延伸倍率不同。但是，在比較例6得到的相位差膜，NZ係數為1.1，具有單軸性，作為VA用相位差膜是「不適當」的。 In Comparative Example 6, it differed from Example 5 only in the stretching ratio. However, the retardation film obtained in Comparative Example 6 had an NZ coefficient of 1.1 and uniaxiality, and was "inappropriate" as a retardation film for VA.
比較實施例3及比較例1所得到的相位差膜的光軸不均。實施例3所得到的相位差膜的光軸不均為1°，比較例1所得到的相位差膜的光軸不均為8°。實施例3所得到的相位差膜具有優異的光學均勻性，作為相位差 膜呈現優異的特性。 The optical axis unevenness of the retardation film obtained in Example 3 and Comparative Example 1 was compared. The optical axis of the retardation film obtained in Example 3 was not 1°, and the optical axis of the retardation film obtained in Comparative Example 1 was not 8°. The retardation film obtained in Example 3 has excellent optical uniformity as a phase difference The film exhibits excellent properties.
1b‧‧‧膜製造系統 1b‧‧‧Film manufacturing system
10‧‧‧壓出機 10‧‧‧Extrusion machine
12‧‧‧T型模 12‧‧‧T-mode
16‧‧‧第1冷卻輥 16‧‧‧1st chill roll
18‧‧‧第2冷卻輥 18‧‧‧2nd cooling roller
19‧‧‧接觸輥 19‧‧‧Contact roller
60‧‧‧精密減速機及馬達 60‧‧‧Precision reducer and motor
100‧‧‧烤爐 100‧‧‧ oven
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