JP4759518B2 - Polycarbonate having low photoelastic constant and film comprising the same - Google Patents
Polycarbonate having low photoelastic constant and film comprising the same Download PDFInfo
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- JP4759518B2 JP4759518B2 JP2006540999A JP2006540999A JP4759518B2 JP 4759518 B2 JP4759518 B2 JP 4759518B2 JP 2006540999 A JP2006540999 A JP 2006540999A JP 2006540999 A JP2006540999 A JP 2006540999A JP 4759518 B2 JP4759518 B2 JP 4759518B2
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- polycarbonate
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- 239000004417 polycarbonate Substances 0.000 title claims description 56
- 229920000515 polycarbonate Polymers 0.000 title claims description 56
- 230000009477 glass transition Effects 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000004973 liquid crystal related substance Substances 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000010408 film Substances 0.000 description 90
- 238000000034 method Methods 0.000 description 18
- -1 aromatic bisphenols Chemical class 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 11
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229960002479 isosorbide Drugs 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JJVKWFOGASBDAO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;sodium Chemical compound [Na].[Na].C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 JJVKWFOGASBDAO-UHFFFAOYSA-N 0.000 description 2
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 0 CC(CC=C1)C(C2(c(cc3*)ccc3OC(C(C)(C)C)O)c(cc3*)ccc3OC(C)(C)C)=C1c1c2cccc1 Chemical compound CC(CC=C1)C(C2(c(cc3*)ccc3OC(C(C)(C)C)O)c(cc3*)ccc3OC(C)(C)C)=C1c1c2cccc1 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HOBSGKWFTBDQCH-UHFFFAOYSA-N phenol;sodium Chemical compound [Na].[Na].OC1=CC=CC=C1 HOBSGKWFTBDQCH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
-
- 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
-
- 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
- G02F1/133637—Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本発明はポリカーボネートに関する。特に、光弾性定数の低いポリカーボネート、及び該ポリカーボネートからなる、位相差フィルムとして有用なフィルムに関する。 The present invention relates to polycarbonate. In particular, the present invention relates to a polycarbonate having a low photoelastic constant and a film comprising the polycarbonate and useful as a retardation film.
ビスフェノールＡをビスフェノール成分とする芳香族ポリカーボネートは、光ディスク基板、位相差フィルムなどの光学用途をはじめ、種々の用途に用いられている。
また、特開２０００−１６９５７３号公報及び特開２００２−３０８９７８号公報には、耐熱性に優れるポリカーボネートとして、フルオレン構造を有する芳香族ビスフェノールと脂環族ジオールとの共重合ポリカーボネートが記載されている。
ところで、近年、液晶表示装置の進歩は著しく、携帯電話、パソコンモニターといった小型及び中型のものだけでなく、テレビ用の大型のものまで広く用いられようとしている。液晶表示装置には、液晶の色補償、視野角の拡大、コントラストの向上といった表示品位の改善のために位相差フィルムが通常具備されている。この位相差フィルムのポリマー素材としてはポリカーボネート、ポリエーテルスルホン等がよく使われている。かかる位相差フィルムの中で、位相差値が波長の１／４であるλ／４板及び１／２であるλ／２板は、反射型ＬＣＤ，防眩フィルム、光ディスク用のピックアップ、液晶プロジェクター等に利用されているが、これらの用途では可視光領域である４００〜７００ｎｍの広帯域にわたって位相差がλ／４、あるいはλ／２であることが理想である。すなわち短波長ほど位相差値が小さくなるような波長分散特性を有する位相差フィルムが望ましい。
しかしながら、一般的に高分子材料の複屈折は短波長になるほど大きくなるという性質を有している。ポリカーボネート等の汎用的に用いられる高分子を素材とした位相差フィルムでこのような波長分散特性を実現するために、λ／４板とλ／２板とを貼り合わせて積層したり、あるいはアッベ数の異なる二枚の位相差フィルムを積層する方法が知られていた（特開平１０−６８８１６号公報、特開平２−２８５３０４号公報）。しかしながらかかる積層方法は、フィルムを貼り合わせる角度の調整が難しく、また生産性が高いとはいえない。近年このような特性を、積層せずに高分子フィルム１枚で実現した位相差フィルムが提案されている（特許第３３２５５６０号公報参照）。該位相差フィルムは、それぞれ複屈折の波長分散性の異なる正と負の屈折率異方性を有する高分子単位の組み合わせで構成された高分子材料からなるものである。かかる高分子材料としてフルオレン成分含有の芳香族ポリカーボネートが記載されている。
近年の液晶表示装置の用途拡大は目覚ましく、液晶表示装置に使われる光学用フィルムとして、特許第３３２５５６０号公報に記載された芳香族ポリカーボネートよりも、さらにより光弾性定数が低いものが求められている。すなわち、短波長になるほど位相差が小さいという特性を有しかつ光弾性定数の極めて小さい高分子材料からなる位相差フィルムが求められている。
例えば、特許第３１６０２０９号公報および特開平１１−２２８６８３号公報には、光弾性定数を低減したポリカーボネートとして、ビスフェノールＡのような芳香族ジオールを用いず脂環族ジオールを用いたものが提案されている。
このような脂環族ジオールから得られるポリカーボネートは芳香族ジオールを用いた場合と比較して光弾性定数が小さくなるがガラス転移点が低下することがほとんどである。特に位相差フィルムとして適用する場合には耐熱性の点で十分とは言えない。液晶表示装置用の光学フィルムには優れた耐熱安定性が望まれているからである。Aromatic polycarbonates containing bisphenol A as a bisphenol component are used in various applications including optical applications such as optical disk substrates and retardation films.
JP-A Nos. 2000-169573 and 2002-308978 describe copolymer polycarbonates of aromatic bisphenols having a fluorene structure and alicyclic diols as polycarbonates having excellent heat resistance.
By the way, in recent years, the progress of liquid crystal display devices has been remarkable, and not only small and medium-sized devices such as mobile phones and personal computer monitors but also large-sized devices for televisions are being used widely. A liquid crystal display device is usually provided with a retardation film in order to improve display quality such as color compensation of liquid crystal, expansion of viewing angle, and improvement of contrast. Polycarbonate, polyethersulfone and the like are often used as the polymer material for the retardation film. Among such retardation films, a λ / 4 plate having a retardation value of ¼ of a wavelength and a λ / 2 plate having a retardation value of ½ are reflective LCDs, antiglare films, optical disk pickups, and liquid crystal projectors. In these applications, it is ideal that the phase difference is λ / 4 or λ / 2 over a wide band of 400 to 700 nm, which is the visible light region. That is, a retardation film having a wavelength dispersion characteristic such that the retardation value becomes smaller as the wavelength becomes shorter is desirable.
However, generally, the birefringence of a polymer material has a property that it increases as the wavelength becomes shorter. In order to achieve such wavelength dispersion characteristics with a retardation film made of a general-purpose polymer such as polycarbonate, a λ / 4 plate and a λ / 2 plate are laminated together or laminated. A method of laminating two retardation films having different numbers has been known (Japanese Patent Laid-Open Nos. 10-68816 and 2-285304). However, in such a lamination method, it is difficult to adjust the angle at which the films are bonded, and the productivity is not high. In recent years, there has been proposed a retardation film that realizes such characteristics with a single polymer film without being laminated (see Japanese Patent No. 3325560). The retardation film is made of a polymer material composed of a combination of polymer units having positive and negative refractive index anisotropies having different birefringence wavelength dispersion properties. As such a polymer material, an aromatic polycarbonate containing a fluorene component is described.
In recent years, the use of liquid crystal display devices has been remarkably expanded, and an optical film used in the liquid crystal display device is required to have an even lower photoelastic constant than the aromatic polycarbonate described in Japanese Patent No. 3325560. . That is, there is a demand for a retardation film made of a polymer material having a property that the retardation is smaller as the wavelength is shorter and the photoelastic constant is extremely small.
For example, Japanese Patent No. 3160209 and Japanese Patent Application Laid-Open No. 11-228683 propose a polycarbonate having a reduced photoelastic constant and using an alicyclic diol instead of an aromatic diol such as bisphenol A. Yes.
The polycarbonate obtained from such an alicyclic diol has a smaller photoelastic constant than the case of using an aromatic diol, but the glass transition point is almost lowered. In particular, when applied as a retardation film, it cannot be said that heat resistance is sufficient. This is because excellent heat stability is desired for optical films for liquid crystal display devices.
本発明の主たる目的は、光弾性定数の低い新規なポリカーボネートを提供することにある。
本発明の他の目的は、耐熱性が高く、かつ光弾性定数の低いポリカーボネートからなるフィルムを提供することにある。
本発明の他の目的は、耐熱性が高く、光弾性定数の低いポリカーボネートからなり、短波長ほど位相差値が小さくなるような波長分散特性を有する新規な位相差フィルムを提供することにある。
本発明の他の目的は、上記位相差フィルムを具備する液晶表示装置を提供することにある。
本発明の他の目的および利点は以下の説明から明らかになろう。
本発明によれば、本発明の目的および利点は、下記式（Ａ）
で表される繰り返し単位と、下記式（Ｂ）
で表される繰り返し単位とを含んでなり、上記繰り返し単位（Ａ），（Ｂ）及び（Ｃ）の合計を基準として、繰り返し単位（Ａ）が５〜３０モル％、繰り返し単位（Ｂ）が１０〜９０モル％、繰り返し単位（Ｃ）が５〜８５モル％の割合を占めるポリカーボネート、によって達成される。
本発明者は、側鎖にフルオレン環を有する芳香族ビスフェノールと脂環族ジオールとをジオール成分とする共重合ポリカーボネートについて、その分子構造および共重合組成、ならびに該共重合ポリカーボネートからなる位相差フィルムおよびその波長分散特性を検討した。その結果、ある特定の組成及び構造の共重合ポリカーボネートからなる位相差フィルムは、位相差が短波長になるほど小さくなる逆波長分散性を示し、かつ光学弾性定数が極めて小さなることを見出した。また上記特性に加えてガラス転移温度が１２０□以上の耐熱性の高いフィルムが得られることを見出し、本発明を完成するに至った。The main object of the present invention is to provide a novel polycarbonate having a low photoelastic constant.
Another object of the present invention is to provide a film made of polycarbonate having high heat resistance and low photoelastic constant.
Another object of the present invention is to provide a novel retardation film comprising a polycarbonate having a high heat resistance and a low photoelastic constant, and having a wavelength dispersion characteristic such that the retardation value decreases as the wavelength becomes shorter.
Another object of the present invention is to provide a liquid crystal display device comprising the retardation film.
Other objects and advantages of the present invention will become apparent from the following description.
According to the present invention, the objects and advantages of the present invention are as follows:
A repeating unit represented by the following formula (B):
The repeating unit (A) is 5 to 30 mol% and the repeating unit (B) is based on the total of the repeating units (A), (B) and (C). 10 to 90 mol%, achieved by a polycarbonate in which the repeating unit (C) occupies a proportion of 5 to 85 mol%.
The present inventor has obtained a molecular structure and a copolymer composition of a copolymer polycarbonate comprising an aromatic bisphenol having a fluorene ring in the side chain and an alicyclic diol as a diol component, a retardation film comprising the copolymer polycarbonate, and The chromatic dispersion characteristics were examined. As a result, it has been found that a retardation film made of a copolymerized polycarbonate having a specific composition and structure exhibits reverse wavelength dispersion which decreases as the retardation becomes shorter, and has an extremely small optical elastic constant. Further, in addition to the above characteristics, it was found that a film having a high heat resistance having a glass transition temperature of 120 □ or more was obtained, and the present invention was completed.
第１図は、実施例１で製造したポリカーボネートの１Ｈ−ＮＭＲスペクトルのチャートである。FIG. 1 is a chart of 1 H-NMR spectrum of the polycarbonate produced in Example 1.
本発明のポリカーボネートは、上記式（Ａ），（Ｂ）及び（Ｃ）で表される繰り返し単位を含む。具体的には、フルオレン環をもつ構造と、イソソルビドから誘導された構造と、特定の脂肪族または脂環族炭化水素基を有する構造とを有する。
上記式（Ａ）において、Ｒ１およびＲ２は、同一または異なり、水素原子またはメチル基である。好ましくは、Ｒ１およびＲ２は両方ともメチル基である。
上記式（Ｂ）は、イソソルビド（１，４：３，６−ジアンハイドロ−Ｄ−グルシトール）から誘導された繰り返し単位である。かかる単位を含有することにより、耐熱性が向上し、熱に対し高い安定性を与える。またイソソルビドは天然物由来であり、自然界のバイオマスからも得られる物質であり、資源の有効利用に貢献する。この点で本発明のポリカーボネートは極めて有用である。
上記式（Ｃ）において、Ｒ３は、炭素数２〜２０の脂肪族または脂環族炭化水素基であるか、炭素数２〜２０個および酸素原子数１〜６個からなる脂肪族または脂環族炭化水素基である。かかる脂肪族または脂環族炭化水素基は、エーテル結合を含んでいてもよい。
このようなＲ３を含む上記式（Ｃ）としては、例えば下記式（Ｄ）〜（Ｇ）で表される繰り返し単位が光学特性に優れかつ経済的に有利である。
上記式（Ｅ）は、トリシクロデカンジメタノールから誘導されたカーボネート結合を有する繰り返し単位である。
上記式（Ｆ）は、シクロヘキサンジメタノールから誘導されたカーボネート結合を有する繰り返し単位である。
上記式（Ｇ）は、鎖状の脂肪族ジオールから誘導されたカーボネート結合を有する繰り返し単位である。上記式（Ｇ）において、ｍは２〜１２の整数である。具合的にはエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールから誘導されたものを好ましく挙げることが出来る。
上記式（Ｄ）〜（Ｇ）で表される繰り返し単位は、１種類であっても、またこれらの組み合わせであってもよい。
上記式（Ａ），（Ｂ）及び（Ｃ）で表される繰り返し単位の割合としては、上記繰り返し単位（Ａ），（Ｂ）及び（Ｃ）の合計を基準として、すなわち、上記式（Ａ），（Ｂ）及び（Ｃ）の和を１００モル％として、繰り返し単位（Ａ）が５〜３０モル％、繰り返し単位（Ｂ）が１０〜９０モル％、繰り返し単位（Ｃ）が５〜８５モル％の割合を占める。このような割合とすることにより、耐熱性が高くかつ光弾性定数の低いという特性を兼ね備えたポリカーボネートを与える。さらに、フィルムの成形性に優れ、延伸により位相差を発現するフィルムを与えることができる。さらには短波長ほど位相差値が小さくなるような波長分散特性を有する位相差フィルムを提供することができる。
上記繰り返し単位（Ａ）の割合としては、好ましくは８〜２５モル％であり、より好ましくは１０〜２５モル％である。
上記繰り返し単位（Ｂ）の割合としては、好ましくは２０〜８５モル％であり、より好ましくは２５〜８０モル％である。
上記繰り返し単位（Ｃ）の割合としては、好ましくは５〜７５モル％であり、より好ましくは８〜７０モル％である。
本発明のポリカーボネートは、上記式（Ａ），（Ｂ）及び（Ｃ）で表される繰り返し単位が上記割合を満足すればよい。したがって、本発明のポリカーボネートとしては共重合ポリマーが好ましいが、光学特性、特に透明性が良好であれば、２種類以上のポリマーの混合物であっても、共重合組成比の異なる１種または２種以上の混合物であっても、またそれらの組み合わせてあってもよい。混合物の場合は相溶性が高いポリマー同士の組み合わせであれば透明性が良好である。
本発明のポリカーボネートは、耐熱性を大きく損ねたり、光弾性定数が大きくなったり、位相差の波長分散特性を損ねない範囲で、下記式（Ｈ）
上記式（Ｈ）中、Ｒ１１〜Ｒ１８はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基から選ばれる少なくとも１種の基であり、Ｘは下記式で表される基である。
本発明のポリカーボネートは、上記式（Ａ），（Ｂ）及び（Ｃ）で表される繰り返し単位から実質的に構成されてなる共重合ポリマーが好ましい。
実質的にとは、上記式（Ｈ）で表される芳香族ジオールからなる繰り返し単位を全繰り返し単位の１０モル％以下で含んでいてもよいという意味である。上記式（Ｈ）の説明については上記したとおりである。
本発明のポリカーボネートは、その分子量が、フェノール／１，１，２，２−テトラクロロエタン（体積比５０／５０）の混合溶媒中、濃度０．５ｇ／ｄＬ、３０℃で測定した還元粘度（ηｓｐ／ｃ）で０．１〜１０ｄＬ／ｇの範囲にあることが好ましく、より好ましくは０．３０〜８ｄＬ／ｇ、さらに好ましくは０．４０〜５ｄＬ／ｇである。還元粘度が０．１ｄＬ／ｇよりも小さいとフィルムの靭性が保たれず、また１０ｄＬ／ｇよりも大きいとポリマーおよびフィルムの製造面で困難となる。
本発明のポリカーボネートは、耐熱性が高く、熱に対して安定性が良好である。耐熱性の指標として、かかるポリカーボネートは１２０〜２００℃の範囲にあるガラス転移温度（Ｔｇ）を持っていることが好適である。より好ましいＴｇは１３０〜１７０℃の範囲である。
本発明のポリカーボネートは、光弾性定数が小さいことが特徴である。光弾性定数の絶対値としては、２５×１０−１２Ｐａ−１以下であることが好ましい。特に、液晶表示装置に用いる位相差フィルムに適用するには、フィルムにかかる応力に対する位相差の変化が少なく表示安定性を保つため、この光弾性定数が低いことが望まれる。より好ましい光弾性定数の絶対値としては０〜２０×１０−１２Ｐａ−１である。
本発明のポリカーボネートの製造方法としては、上記式（Ａ）、（Ｂ）及び（Ｃ）で表される繰り返し単位を誘導するジオール、具体的には、フルオレン環含有ビスフェノール、イソソルビド、及び脂肪族または脂環族ジオールを原料として、これらと炭酸ジエステルとを用いて、溶融重合法により重合する方法を好ましく挙げることが出来る。
かかる溶融重合の際に用いる炭酸ジエステルとして、具体的にはジフェニルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート等を挙げることが出来るが、なかでも反応性、コスト面からジフェニルカーボネートが好ましい。
溶融重合反応は、好ましくは重合触媒の存在下、原料であるジオールと炭酸ジエステルとを常圧で加熱し、予備反応させた後、減圧下で２８０℃以下の温度で加熱しながら撹拌して、生成するフェノールを留出させる。反応系は窒素などの、原料、反応混合物および反応生成物に対し不活性なガスの雰囲気に保つことが好ましい。窒素以外の不活性ガスとしては、アルゴンなどを挙げることができる。
特に、本発明のポリカーボネートが共重合体である場合には、反応初期には常圧で加熱反応させることが好ましい。これはオリゴマー化反応を進行させ、反応後期に減圧してフェノール等の芳香族アルコールまたは脂肪族アルコールを留去する際、未反応のモノマーが留出してモルバランスが崩れ、重合度が低下することを防ぐためである。このような製造方法においては、芳香族アルコールまたは脂肪族アルコールを適宜系（反応器）から除去することにより反応を進めることができる。そのためには、減圧することが効果的である。
重合温度としては、１８０℃以上２８０℃以下の範囲であることが好ましく、より好ましくは２３０〜２７０□の範囲である。共重合体の着色を抑制する観点からは出来るだけ低温にすることが好ましいが、重合反応を適切に進め共重合体の組成がランダムな構造となるためにはある程度温度を高くする必要がある。
かかる重合の際の重合触媒としては（ｉ）含窒素塩基性化合物、（ｉｉ）アルカリ金属化合物および（ｉｉｉ）アルカリ土類金属化合物などの公知のものが挙げられる。これらは単独で使用しても、二種類以上を併用してもよいが、（ｉ）と（ｉｉ）、（ｉ）と（ｉｉｉ）あるいは（ｉ）と（ｉｉ）と（ｉｉｉ）の組み合わせで併用することが好ましい場合が多い。
具体的には（ｉ）含窒素塩基性化合物の例として、テトラメチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリエチルアミン、２−メチルイミダゾール、テトラメチルアンモニウムボロハイドライドなどを挙げることが出来る。
（ｉｉ）アルカリ金属化合物の具体的な例として、水酸化ナトリウム、水酸化リチウム、炭酸水素ナトリウム、炭酸水素カリウム、酢酸ナトリウム、りん酸水素ニナトリウム、ビスフェノールＡのニナトリウム塩、ニカリウム塩、ニリチウム塩、フェノールのニナトリウム塩、ニカリウム塩、ニリチウム塩などが挙げられる。
（ｉｉｉ）アルカリ土類金属化合物の具体的な例として、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、炭酸水素カルシウム、炭酸水素マグネシウム、炭酸カルシウム、酢酸カルシウム、ステアリン酸カルシウムなどを挙げることが出来る。
本発明のポリカーボネートには、必要に応じて各種の添加剤が含有されていてもよい。かかる添加剤としては、例えば熱安定化剤、安定化助剤、可塑剤、酸化防止剤、光安定剤、重金属不活性化剤、難燃剤、滑剤、帯電防止剤、界面活性化剤、紫外線吸収剤、抗菌剤が挙げられる。
本発明のポリカーボネートは、成形性および透明性に優れるので、例えばフィルム、シート、各種成形品として有用である。具体的な用途としては、例えば、光学フィルム、レンズ、自動車用部品、透明容器、光ディスク基板を挙げることができる。特に本発明のポリカーボネートからなるフィルムは延伸することができ、延伸により得られた配向フィルムは複屈折を有するので、位相差フィルムとして好適である。
以下、本発明のポリカーボネートから形成されるフィルムについて詳細に説明する。
フィルムの製造方法としては、例えば溶液キャスト法、溶融押し出し法、熱プレス法、カレンダー法等公知の方法を挙げることが出来る。
本発明で用いるポリカーボネート（特に共重合ポリカーボネート）は有機溶媒に対する溶解性が良好なので、溶液キャスト法を適用することができる。溶液キャスト法の場合、溶媒としては塩化メチレン、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン、ジオキソラン、ジオキサン等が好適に用いられる。溶液キャスト法で得られるフィルム中の残留溶媒量は２重量％以下であることが好ましく、より好ましくは１重量％以下である。２重量％以上と残留溶媒量が多いとフィルムのガラス転移温度の低下が著しくなり耐熱性の点で好ましくない。
本発明のフィルムの製造法としては溶融押し出し法が生産性の点から好ましい。溶融押し出し法においては、Ｔダイを用いて樹脂を押し出し冷却ロールに送る方法が好ましく用いられる。このときの温度はポリカーボネートの分子量、Ｔｇ、溶融流動特性などから決められるが、１８０℃〜３５０℃の範囲であり、２００℃〜３２０℃の範囲がより好ましい。該温度が低すぎると粘度が高くなりポリマーの配向、応力歪みが残りやすいことがある。該温度が高すぎると熱劣化、着色、Ｔダイからのダイライン（筋）などの問題が起きやすくなる。
本発明のフィルムの厚みとしては、３０〜４００μｍの範囲が好ましく、より好ましくは４０〜３００μｍの範囲である。かかるフィルムをさらに延伸して位相差フィルムとする場合には、該位相差フィルムの所望の位相差値、厚みを勘案して上記範囲内で適宜決めればよい。
かくして得られた未延伸のフィルムは延伸配向されることにより、本発明の位相差フィルムを得ることができる。延伸方法としては縦一軸延伸、テンター等を用いる横一軸延伸、あるいはそれらを組み合わせた同時ニ軸延伸、逐次ニ軸延伸など公知の方法を用いることが出来る。好ましくは縦一軸延伸である。また連続で行うことが生産性の点で好ましいが、バッチ式で行ってもよい。延伸温度はポリカーボネートのガラス転移温度（Ｔｇ）に対して、（Ｔｇ−２０℃）〜（Ｔｇ＋３０℃）の範囲内であり、好ましくは（Ｔｇ−１０℃）〜（Ｔｇ＋２０℃）の範囲内である。延伸倍率は目的とする位相差値により決められるが、縦、横それぞれ、１．０５〜４倍、より好ましくは１．１〜３倍である。なお、溶液キャスト法により得たフィルムを延伸する場合の上記Ｔｇとは、該フィルム中に微量の溶媒を含むガラス転移温度を言う。
本発明の位相差フィルムは波長４００〜７００ｎｍの可視光領域において、フィルム面内の位相差が短波長になるほど小さくなるという特徴を有する。すなわち、波長４５０ｎｍ、５５０ｎｍ、６５０ｎｍにおけるフィルム面内の位相差値Ｒ（４５０）、Ｒ（５５０）、Ｒ（６５０）で表現した位相差の波長分散特性が、下記式（１）および（２）
Ｒ（４５０）／Ｒ（５５０）＜１ （１）
Ｒ（６５０）／Ｒ（５５０）＞１ （２）
を満たすことを特徴とする。ここでフィルム面内の位相差値Ｒとは下記式（３）で定義されるものであり、フィルムに垂直方向に透過する光の位相の遅れを表す特性である。
Ｒ＝（ｎｘ−ｎｙ）×ｄ （３）
上記式（３）において、ｎｘはフィルム面内の遅相軸（最も屈折率が高い軸）の屈折率であり、ｎｙはフィルム面内でｎｘと垂直方向の屈折率であり、ｄはフィルムの厚みである。
位相差の波長分散特性として、好ましくは
０．６０＜Ｒ（４５０）／Ｒ（５５０）＜０．９７ （１）−１
かつ
１．０１＜Ｒ（６５０）／Ｒ（５５０）＞１．４０ （２）−１
であり、より好ましくは
０．６５＜Ｒ（４５０）／Ｒ（５５０）＜０．９２ （１）−２
かつ
１．０１＜Ｒ（６５０）／Ｒ（５５０）＞１．３０ （２）−２
の範囲である。
また波長５５０ｎｍにおけるフィルム面内の位相差値Ｒ（５５０）としては、Ｒ（５５０）＞５０ｎｍであることが好ましい。本発明の位相差フィルムは積層することなく１枚で広帯域のλ／４板またはλ／２板として使用できるものである。かかる用途ではさらに、λ／４板の場合は１００ｎｍ＜Ｒ（５５０）＜１８０ｎｍ、λ／２板の場合は２２０ｎｍ＜Ｒ（５５０）＜３３０ｎｍ、であることが望ましい。
また本発明の位相差フィルムの厚みは、目的とする位相差値と関連するが２０〜２００μｍの範囲であり、より好ましくは３０〜１５０μｍである。
本発明の位相差フィルムは、これを構成するポリカーボネートの光弾性定数が低い。したがって、応力に対する位相差の変化が少なく、かかる位相差フィルムを具備した液晶表示装置は表示安定性に優れたものとなる。
本発明の位相差フィルムは透明性が高いことが必要であり、全光線透過率で８５％以上であることが望ましく、より望ましくは８８％以上である。またヘイズ値は好ましくは５％以下であり、より好ましくは３％以下である。The polycarbonate of the present invention contains repeating units represented by the above formulas (A), (B) and (C). Specifically, it has a structure having a fluorene ring, a structure derived from isosorbide, and a structure having a specific aliphatic or alicyclic hydrocarbon group.
In the above formula (A), R 1 and R 2 are the same or different and are a hydrogen atom or a methyl group. Preferably R 1 and R 2 are both methyl groups.
The above formula (B) is a repeating unit derived from isosorbide (1,4: 3,6-dianhydro-D-glucitol). By containing such a unit, heat resistance is improved and high heat stability is imparted. Isosorbide is derived from natural products and is a substance obtained from natural biomass, contributing to the effective use of resources. In this respect, the polycarbonate of the present invention is extremely useful.
In the above formula (C), R 3 is an aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, or an aliphatic or aliphatic group having 2 to 20 carbon atoms and 1 to 6 oxygen atoms. A cyclic hydrocarbon group; Such an aliphatic or alicyclic hydrocarbon group may contain an ether bond.
As the above formula (C) containing R 3 , for example, repeating units represented by the following formulas (D) to (G) are excellent in optical properties and economically advantageous.
The above formula (E) is a repeating unit having a carbonate bond derived from tricyclodecane dimethanol.
The above formula (F) is a repeating unit having a carbonate bond derived from cyclohexanedimethanol.
The above formula (G) is a repeating unit having a carbonate bond derived from a chain aliphatic diol. In said formula (G), m is an integer of 2-12. Specific examples include those derived from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
The repeating units represented by the above formulas (D) to (G) may be one type or a combination thereof.
The ratio of the repeating units represented by the above formulas (A), (B) and (C) is based on the total of the above repeating units (A), (B) and (C), that is, the above formula (A ), (B) and (C) as 100 mol%, the repeating unit (A) is 5 to 30 mol%, the repeating unit (B) is 10 to 90 mol%, and the repeating unit (C) is 5 to 85 mol%. Occupies a percentage by mole. By setting such a ratio, a polycarbonate having the characteristics of high heat resistance and low photoelastic constant is provided. Furthermore, it is possible to give a film that is excellent in film formability and develops a phase difference by stretching. Furthermore, it is possible to provide a retardation film having a wavelength dispersion characteristic such that the retardation value becomes smaller as the wavelength becomes shorter.
As a ratio of the said repeating unit (A), Preferably it is 8-25 mol%, More preferably, it is 10-25 mol%.
As a ratio of the said repeating unit (B), Preferably it is 20-85 mol%, More preferably, it is 25-80 mol%.
As a ratio of the said repeating unit (C), Preferably it is 5-75 mol%, More preferably, it is 8-70 mol%.
In the polycarbonate of the present invention, the repeating units represented by the above formulas (A), (B) and (C) may satisfy the above ratio. Accordingly, the polycarbonate of the present invention is preferably a copolymer, but if the optical properties, particularly transparency, is good, even if it is a mixture of two or more polymers, one or two different copolymer composition ratios. It may be a mixture of the above or a combination thereof. In the case of a mixture, transparency is good if it is a combination of highly compatible polymers.
The polycarbonate of the present invention has the following formula (H) as long as the heat resistance is not significantly impaired, the photoelastic constant is increased, and the wavelength dispersion characteristic of the retardation is not impaired.
In the formula (H), R 11 to R 18 are each independently at least one group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, X is a group represented by the following formula.
The polycarbonate of the present invention is preferably a copolymer composed substantially of repeating units represented by the above formulas (A), (B) and (C).
“Substantially” means that the repeating unit composed of the aromatic diol represented by the above formula (H) may be contained in an amount of 10 mol% or less of all repeating units. The description of the formula (H) is as described above.
The polycarbonate of the present invention has a molecular weight of reduced viscosity (η measured in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (volume ratio 50/50) at a concentration of 0.5 g / dL and 30 ° C. sp / c) is preferably in the range of 0.1 to 10 dL / g, more preferably 0.30 to 8 dL / g, and still more preferably 0.40 to 5 dL / g. If the reduced viscosity is less than 0.1 dL / g, the toughness of the film cannot be maintained, and if it is more than 10 dL / g, it is difficult to produce the polymer and the film.
The polycarbonate of the present invention has high heat resistance and good stability against heat. As an index of heat resistance, it is preferable that the polycarbonate has a glass transition temperature (Tg) in the range of 120 to 200 ° C. A more preferable Tg is in the range of 130 to 170 ° C.
The polycarbonate of the present invention is characterized by a small photoelastic constant. The absolute value of the photoelastic constant is preferably 25 × 10 −12 Pa −1 or less. In particular, in order to apply to a retardation film used in a liquid crystal display device, it is desired that the photoelastic constant is low in order to maintain a display stability with little change in retardation due to stress applied to the film. A more preferable absolute value of the photoelastic constant is 0 to 20 × 10 −12 Pa −1 .
As a method for producing the polycarbonate of the present invention, a diol that induces a repeating unit represented by the above formulas (A), (B), and (C), specifically, a fluorene ring-containing bisphenol, isosorbide, and aliphatic or A preferred example is a method in which an alicyclic diol is used as a raw material and polymerized by a melt polymerization method using these and a carbonic acid diester.
Specific examples of the carbonic acid diester used in the melt polymerization include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. From the aspect, diphenyl carbonate is preferred.
In the melt polymerization reaction, the diol and carbonic acid diester as raw materials are heated at normal pressure, preferably in the presence of a polymerization catalyst, pre-reacted, and then stirred while heating at a temperature of 280 ° C. or lower under reduced pressure. The resulting phenol is distilled off. The reaction system is preferably maintained in an atmosphere of a gas, such as nitrogen, which is inert with respect to the raw materials, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon.
In particular, when the polycarbonate of the present invention is a copolymer, it is preferable to carry out a heating reaction at normal pressure at the initial stage of the reaction. This is because the oligomerization reaction proceeds, the pressure is reduced in the latter stage of the reaction, and when the aromatic alcohol or aliphatic alcohol such as phenol is distilled off, unreacted monomers are distilled out, the molar balance is lost, and the degree of polymerization is reduced. Is to prevent. In such a production method, the reaction can be advanced by appropriately removing the aromatic alcohol or aliphatic alcohol from the system (reactor). For this purpose, it is effective to reduce the pressure.
As polymerization temperature, it is preferable that it is the range of 180 degreeC or more and 280 degrees C or less, More preferably, it is the range of 230-270 □. Although it is preferable to make the temperature as low as possible from the viewpoint of suppressing the coloration of the copolymer, it is necessary to raise the temperature to some extent in order to appropriately proceed the polymerization reaction and have a random copolymer composition.
Examples of the polymerization catalyst in the polymerization include known compounds such as (i) a nitrogen-containing basic compound, (ii) an alkali metal compound, and (iii) an alkaline earth metal compound. These may be used singly or in combination of two or more, but in combination of (i) and (ii), (i) and (iii) or (i) and (ii) and (iii) In many cases, it is preferable to use them in combination.
Specifically, examples of (i) nitrogen-containing basic compounds include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine, 2-methylimidazole, tetramethylammonium borohydride, and the like. I can do it.
(Ii) Specific examples of the alkali metal compound include sodium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, disodium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, and dilithium salt. , Phenol disodium salt, dipotassium salt, dilithium salt and the like.
(Iii) Specific examples of the alkaline earth metal compound include calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydrogen carbonate, magnesium hydrogen carbonate, calcium carbonate, calcium acetate, calcium stearate and the like.
The polycarbonate of the present invention may contain various additives as necessary. Such additives include, for example, heat stabilizers, stabilizing aids, plasticizers, antioxidants, light stabilizers, heavy metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, UV absorbers. Agents and antibacterial agents.
Since the polycarbonate of this invention is excellent in a moldability and transparency, it is useful as a film, a sheet | seat, and various molded articles, for example. Specific examples include optical films, lenses, automotive parts, transparent containers, and optical disk substrates. In particular, a film made of the polycarbonate of the present invention can be stretched, and an oriented film obtained by stretching has birefringence, and therefore is suitable as a retardation film.
Hereinafter, the film formed from the polycarbonate of the present invention will be described in detail.
Examples of the method for producing the film include known methods such as a solution casting method, a melt extrusion method, a hot pressing method, and a calendar method.
Since the polycarbonate (particularly copolymerized polycarbonate) used in the present invention has good solubility in an organic solvent, a solution casting method can be applied. In the case of the solution casting method, methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dioxolane, dioxane and the like are preferably used as the solvent. The amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. When the amount of residual solvent is 2% by weight or more, the glass transition temperature of the film is remarkably lowered, which is not preferable from the viewpoint of heat resistance.
As a method for producing the film of the present invention, the melt extrusion method is preferred from the viewpoint of productivity. In the melt extrusion method, a method of extruding a resin using a T die and feeding it to a cooling roll is preferably used. The temperature at this time is determined from the molecular weight of the polycarbonate, Tg, melt flow characteristics, etc., but is in the range of 180 ° C to 350 ° C, more preferably in the range of 200 ° C to 320 ° C. If the temperature is too low, the viscosity increases, and polymer orientation and stress strain may remain. If the temperature is too high, problems such as thermal degradation, coloring, and die lines (stripe) from the T-die are likely to occur.
As thickness of the film of this invention, the range of 30-400 micrometers is preferable, More preferably, it is the range of 40-300 micrometers. In the case where such a film is further stretched to obtain a retardation film, a desired retardation value and thickness of the retardation film may be taken into consideration and appropriately determined within the above range.
The unstretched film thus obtained is stretched and oriented, whereby the retardation film of the present invention can be obtained. As the stretching method, a known method such as longitudinal uniaxial stretching, lateral uniaxial stretching using a tenter or the like, or simultaneous biaxial stretching and sequential biaxial stretching in combination thereof can be used. Longitudinal uniaxial stretching is preferred. Moreover, although it is preferable from a point of productivity to perform continuously, you may carry out by a batch type. The stretching temperature is in the range of (Tg-20 ° C) to (Tg + 30 ° C), preferably in the range of (Tg-10 ° C) to (Tg + 20 ° C) with respect to the glass transition temperature (Tg) of the polycarbonate. . Although the draw ratio is determined by the target retardation value, it is 1.05 to 4 times, more preferably 1.1 to 3 times for each of the length and width. In addition, said Tg in the case of extending | stretching the film obtained by the solution cast method means the glass transition temperature which contains a trace amount solvent in this film.
The retardation film of the present invention is characterized in that in the visible light region having a wavelength of 400 to 700 nm, the retardation in the film plane becomes smaller as the wavelength becomes shorter. That is, the chromatic dispersion characteristics of retardation expressed by retardation values R (450), R (550), and R (650) in the film plane at wavelengths of 450 nm, 550 nm, and 650 nm are expressed by the following formulas (1) and (2).
R (450) / R (550) <1 (1)
R (650) / R (550)> 1 (2)
It is characterized by satisfying. Here, the retardation value R in the film plane is defined by the following formula (3), and is a characteristic representing the phase delay of light transmitted in the direction perpendicular to the film.
R = (n x -n y) × d (3)
In the above formula (3), n x is a refractive index in a slow axis in the film plane (highest refractive index axis), n y is a refractive index of n x and the vertical direction in the film plane, d Is the thickness of the film.
The wavelength dispersion characteristic of the phase difference is preferably 0.60 <R (450) / R (550) <0.97 (1) -1
And 1.01 <R (650) / R (550)> 1.40 (2) -1
And more preferably 0.65 <R (450) / R (550) <0.92 (1) -2
And 1.01 <R (650) / R (550)> 1.30 (2) -2
Range.
The retardation value R (550) in the film plane at a wavelength of 550 nm is preferably R (550)> 50 nm. The retardation film of the present invention can be used as a wide-band λ / 4 plate or λ / 2 plate without being laminated. In such applications, it is further desirable that 100 nm <R (550) <180 nm for a λ / 4 plate and 220 nm <R (550) <330 nm for a λ / 2 plate.
Moreover, although the thickness of the retardation film of this invention is related with the target retardation value, it is the range of 20-200 micrometers, More preferably, it is 30-150 micrometers.
The retardation film of the present invention has a low photoelastic constant of the polycarbonate constituting it. Therefore, the change of the phase difference with respect to stress is small, and the liquid crystal display device provided with such a retardation film has excellent display stability.
The retardation film of the present invention needs to have high transparency, and is desirably 85% or more in total light transmittance, and more desirably 88% or more. The haze value is preferably 5% or less, more preferably 3% or less.
以下に実施例により本発明をより具体的に説明するが、本発明はこれら実施例のみに限定されるのではない。
実施例、比較例における物性測定は以下の方法で行った。
（１）ガラス転移温度（Ｔｇ）：ＴＡＩｎｓｔｒｕｍｅｎｔｓ製２９２０型ＤＳＣを使用し、昇温速度は２０℃／分で測定した。
（２）共重合体の分子量：フェノール／１，１，２，２−テトラクロロエタン（体積比＝５０／５０）の混合溶媒からなる濃度０．５ｇ／ｄＬの溶液での、３０℃における還元粘度ηｓｐ／ｃ（ｄＬ／ｇ）を測定した。
（３）共重合体の１Ｈ−ＮＭＲ測定：日本電子製ＪＮＭ−α４００型のＮＭＲ装置を使用した。重クロロホルム溶媒に溶解し、化学シフトの基準としてテトラメチルシランを用いて測定した。
（４）フィルムの全光線透過率およびヘイズ値：日本電色工業（株）製濁度計ＮＤＨ−２０００型を用いて測定した。
（５）フィルムの面内位相差値Ｒ：日本分光（株）製分光エリプソメーターＭ１５０を使用して波長４００〜８００ｎｍの範囲で測定した。面内位相差値Ｒは、入射光線がフィルム面に垂直な状態で測定した。
（６）フィルムの厚み：アンリツ社製の電子マイクロ膜厚計で測定した。
（７）フィルムの光弾性定数：日本分光（株）製分光エリプソメーターＭ１５０にて測定した。測定波長５５０ｎｍにてフィルムに応力を与えたときの位相差値の変化から算出した。
実施例１
トリシクロデカンジメタノール１１．７８ｇ（０．０６モル）とイソソルビド９．８６ｇ（０．０６７５モル）、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン（＝ビスクレゾールフルオレン、以下ＢＣＦと記す）８．５２ｇ（０．０２２５モル）、ジフェニルカーボネート３２．４５ｇ（０．１５１５モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを１．３７ｍｇ（１５μモル）、および２，２−ビス（４−ヒドロキシフェニル）プロパン二ナトリウム塩を２０．４２μｇ（０．０７５μモル）仕込んで窒素雰囲気下１８０℃で溶融させた。
撹拌下、反応槽内を１．３３×１０−２ＭＰａに減圧し、生成するフェノールを留去しながら２０分間反応させた。次に２００℃に昇温した後、徐々に減圧し、フェノールを留去しながら３．９９×１０−３ＭＰａで２０分間反応させ、さらに、２１５℃に昇温して２０分間反応させた。ついで２３０℃に昇温して１０分間反応させ、２．６６×１０−３ＭＰａに減圧して１０分間反応を続行し、２５０℃に昇温して１０分間反応させた。この後、１．３３×１０−３ＭＰａに減圧して１０分間、さらに減圧して最終的に１．３３×１０−４ＭＰａ以下にして１．５時間反応させて重合反応を終了した。得られたポリマーの還元粘度ηｓｐ／ｃは０．７２ｄＬ／ｇ、ガラス転移温度は１４２℃であった。また重クロロホルム溶媒を用いてポリマーの１Ｈ−ＮＭＲ測定を行い、モノマー仕込み比通りの組成の共重合ポリカーボネートが得られていることを確認した（第１図参照）。該樹脂を塩化メチレンに溶解して１５ｗｔ％溶液を作成し、溶液キャスト法によりキャストフィルムを作成した。該未延伸フィルムを用いてフィルム端をチャックで固定するバッチ式の二軸延伸装置にて延伸を行った。横方向は自由として温度１４７℃にて１．５倍縦一軸延伸を行い、延伸後のフィルム中央部分の膜厚、位相差Ｒ（５５０）、およびその波長分散、全光線透過率、ヘイズ、光弾性定数、ガラス転移温度を測定した。結果を表１に示す。
実施例２
ジオールとして、トリシクロデカンジメタノール１４．７２ｇ（０．０７５モル）、イソソルビド６．５８ｇ（０．０４５モル）およびＢＣＦ１１．３６ｇ（０．０３モル）を用いた他は実施例１と同様にして共重合ポリカーボネートの溶融重合を行った。得られたポリマーの還元粘度は０．４７ｄＬ／ｇ、ガラス転移温度は１４３℃であった。実施例１と同様にして未延伸フィルムを作成し、温度１４８℃にて１．５倍で縦一軸延伸を行った。該延伸フィルムの物性を表１に示す。
実施例３
ジオールとして、スピログリコール２４．２０ｇ（０．０７９５モル）、イソソルビド７．６７ｇ（０．０５２５モル）およびＢＣＦ６．８１ｇ（０．０１８モル）を用いた他は実施例１と同様にして共重合ポリカーボネートの溶融重合を行った。得られたポリマーの還元粘度は０．９０ｄＬ／ｇ、ガラス転移温度は１３８℃であった。実施例１と同様にして未延伸フィルムを作成し、温度１４３℃にて１．５倍で縦一軸延伸を行った。該延伸フィルムの物性を表１に示す。さらにこの位相差フィルムを使い、偏光板透過軸と位相差フィルム遅相軸の角度を４５度ずらして偏光板／延伸フィルム／アルミ反射板の構成の光学積層フィルムを作成した。各フィルム間は粘着剤を用いた。この積層フィルムを目視したところ着色のない黒であり、かかる位相差フィルムは反射型ＴＦＴや半透過型ＴＦＴに用いられるλ／４板として、優れた特性を有していることが分かった。
実施例４
ジオールとして、シクロヘキサンジメタノール６．４９ｇ（０．０４５モル）、イソソルビド１２．０６ｇ（０．０８２５モル）およびＢＣＦ８．５２ｇ（０．０２２５モル）を用いた他は実施例１と同様にして共重合ポリカーボネートの溶融重合を行った。得られたポリマーの還元粘度は０．６６ｄＬ／ｇ、ガラス転移温度は１５８℃であった。実施例１と同様にして未延伸フィルムを作成し、温度１６２℃にて１．５倍で縦一軸延伸を行った。該延伸フィルムの物性を表１に示す。
実施例５
ジオールとして、１，３−プロパンジオール１３６．８ｇ（１．８モル）、イソソルビド１０５２ｇ（７．２モル）およびＢＣＦ３７８．５ｇ（１．０モル）を用い、ジフェニルカーボネートを２１６３ｇ（１０．１モル）、重合触媒としてテトラメチルアンモニウムヒドロキシドを９２．１ｍｇ（１．０１ｍモル）および２，２−ビス（４−ヒドロキシフェニル）プロパン二ナトリウム塩を１．３６ｍｇ（５．０μモル）を用いて、仕込み手順、反応条件は実施例１と同様にして共重合ポリカーボネートの溶融重合を行った。得られたポリマーの還元粘度は０．５９ｄＬ／ｇ、ガラス転移温度は１４７℃であった。該ポリマーを２軸押し出し機（日本製鋼所製ＴＥＸ３０ＳＳ−４２ＢＷ−３Ｖ）を用いて、幅１５ｃｍのＴダイから溶融押し出しし、冷却ドラムで連続的に巻き取ることにより製膜した。製膜はシリンダーおよびＴダイ温度２５０℃、冷却ドラム温度１４０℃、製膜速度１ｍ／分で行い、透明性、均質性に優れた厚み１０４μｍのフィルムを得た。このフィルムを実施例１と同様の延伸設備で温度１５２℃にて１．５倍縦一軸延伸を行った。該延伸フィルムの物性を表１に示す。
The physical properties in Examples and Comparative Examples were measured by the following methods.
(1) Glass transition temperature (Tg): A TA Instruments 2920 type DSC was used, and the temperature elevation rate was measured at 20 ° C./min.
(2) Molecular weight of copolymer: reduced viscosity at 30 ° C. in a solution having a concentration of 0.5 g / dL composed of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (volume ratio = 50/50) η sp / c (dL / g) was measured.
(3) 1 H-NMR measurement of copolymer: JNM-α400 type NMR apparatus manufactured by JEOL Ltd. was used. It was dissolved in deuterated chloroform solvent and measured using tetramethylsilane as a standard for chemical shift.
(4) Total light transmittance and haze value of the film: Measured using a turbidimeter NDH-2000 model manufactured by Nippon Denshoku Industries Co., Ltd.
(5) In-plane retardation value R of film: Measured in a wavelength range of 400 to 800 nm using a spectroscopic ellipsometer M150 manufactured by JASCO Corporation. The in-plane retardation value R was measured in a state where the incident light beam was perpendicular to the film surface.
(6) Film thickness: Measured with an electronic micro film thickness meter manufactured by Anritsu Corporation.
(7) Photoelastic constant of film: Measured with a spectroscopic ellipsometer M150 manufactured by JASCO Corporation. It was calculated from the change in retardation value when stress was applied to the film at a measurement wavelength of 550 nm.
Example 1
11.78 g (0.06 mol) of tricyclodecane dimethanol, 9.86 g (0.0675 mol) of isosorbide, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (= biscresol fluorene, hereinafter referred to as BCF) 8.52 g (0.0225 mol), 32.45 g (0.1515 mol) of diphenyl carbonate, and 1.37 mg (15 μmol) of tetramethylammonium hydroxide as a polymerization catalyst, and 2 , 2-bis (4-hydroxyphenyl) propane disodium salt was charged in an amount of 20.42 μg (0.075 μmol) and melted at 180 ° C. in a nitrogen atmosphere.
While stirring, the inside of the reaction vessel was depressurized to 1.33 × 10 −2 MPa, and the reaction was carried out for 20 minutes while distilling off the produced phenol. Next, after heating up to 200 degreeC, it pressure-reduced gradually, it was made to react at 3.99 * 10 < -3 > MPa for 20 minutes, distilling phenol off, and also it heated up to 215 degreeC and made it react for 20 minutes. Next, the temperature was raised to 230 ° C. and reacted for 10 minutes, the pressure was reduced to 2.66 × 10 −3 MPa, the reaction was continued for 10 minutes, the temperature was raised to 250 ° C. and reacted for 10 minutes. Thereafter, the pressure was reduced to 1.33 × 10 −3 MPa for 10 minutes, and the pressure was further reduced to 1.33 × 10 −4 MPa or less for 1.5 hours to complete the polymerization reaction. The polymer obtained had a reduced viscosity η sp / c of 0.72 dL / g and a glass transition temperature of 142 ° C. Further, 1 H-NMR measurement of the polymer was performed using deuterated chloroform solvent, and it was confirmed that a copolymerized polycarbonate having a composition according to the monomer charge ratio was obtained (see FIG. 1). The resin was dissolved in methylene chloride to prepare a 15 wt% solution, and a cast film was prepared by a solution casting method. The unstretched film was stretched by a batch type biaxial stretching apparatus in which the film end was fixed with a chuck. The horizontal direction is freely 1.5 times longitudinal uniaxial stretching at a temperature of 147 ° C., the film thickness at the center of the film after stretching, retardation R (550), and its wavelength dispersion, total light transmittance, haze, light Elastic constants and glass transition temperatures were measured. The results are shown in Table 1.
Example 2
As Example 1, except that 14.72 g (0.075 mol) of tricyclodecane dimethanol, 6.58 g (0.045 mol) of isosorbide and 11.36 g (0.03 mol) of BCF were used as the diol. The copolymerized polycarbonate was melt polymerized. The polymer obtained had a reduced viscosity of 0.47 dL / g and a glass transition temperature of 143 ° C. An unstretched film was prepared in the same manner as in Example 1, and longitudinally uniaxially stretched 1.5 times at a temperature of 148 ° C. Table 1 shows the physical properties of the stretched film.
Example 3
Copolycarbonate as in Example 1 except that 24.20 g (0.0795 mol) spiroglycol, 7.67 g (0.0525 mol) isosorbide and 6.81 g (0.018 mol) BCF were used as the diol. Was melt polymerized. The polymer obtained had a reduced viscosity of 0.90 dL / g and a glass transition temperature of 138 ° C. An unstretched film was prepared in the same manner as in Example 1, and longitudinally uniaxially stretched 1.5 times at a temperature of 143 ° C. Table 1 shows the physical properties of the stretched film. Furthermore, using this retardation film, the angle between the polarizing plate transmission axis and the retardation film slow axis was shifted by 45 degrees to prepare an optical laminated film having a configuration of polarizing plate / stretched film / aluminum reflector. An adhesive was used between the films. When this laminated film was visually observed, it was black without coloration, and it was found that such a retardation film had excellent characteristics as a λ / 4 plate used for a reflective TFT or a transflective TFT.
Example 4
Copolymerization was carried out in the same manner as in Example 1 except that 6.49 g (0.045 mol) of cyclohexanedimethanol, 12.06 g (0.0825 mol) of isosorbide and 8.52 g (0.0225 mol) of BCF were used as the diol. Polycarbonate was melt polymerized. The polymer obtained had a reduced viscosity of 0.66 dL / g and a glass transition temperature of 158 ° C. An unstretched film was prepared in the same manner as in Example 1, and longitudinally uniaxially stretched 1.5 times at a temperature of 162 ° C. Table 1 shows the physical properties of the stretched film.
Example 5
As the diol, 136.8 g (1.8 mol) of 1,3-propanediol, 1052 g (7.2 mol) of isosorbide and 378.5 g (1.0 mol) of BCF were used, and 2163 g (10.1 mol) of diphenyl carbonate was used. , 92.1 mg (1.01 mmol) of tetramethylammonium hydroxide and 1.36 mg (5.0 μmol) of 2,2-bis (4-hydroxyphenyl) propane disodium salt were charged as a polymerization catalyst. The procedure and reaction conditions were the same as in Example 1, and the copolymerized polycarbonate was melt polymerized. The polymer obtained had a reduced viscosity of 0.59 dL / g and a glass transition temperature of 147 ° C. The polymer was melt-extruded from a T-die having a width of 15 cm using a twin-screw extruder (TEX30SS-42BW-3V manufactured by Nippon Steel), and continuously formed by a cooling drum. Film formation was performed at a cylinder and T-die temperature of 250 ° C., a cooling drum temperature of 140 ° C., and a film formation speed of 1 m / min. This film was stretched 1.5 times longitudinally and uniaxially at a temperature of 152 ° C. using the same stretching equipment as in Example 1. Table 1 shows the physical properties of the stretched film.
本発明のポリカーボネートは、耐熱性が高く、光弾性定数が低い。また透明性が良好なフィルムを得ることができる。したがって、位相差フィルムなど光学用途のポリマーとして極めて有用である。 The polycarbonate of the present invention has high heat resistance and low photoelastic constant. Moreover, a film with good transparency can be obtained. Therefore, it is extremely useful as a polymer for optical applications such as a retardation film.
Claims (10)
で表される繰り返し単位と、下記式（Ｂ）
で表される繰り返し単位とを含んでなり、上記繰り返し単位（Ａ），（Ｂ）及び（Ｃ）の合計を基準として、繰り返し単位（Ａ）が５〜３０モル％、繰り返し単位（Ｂ）が１０〜９０モル％、繰り返し単位（Ｃ）が５〜８５モル％の割合を占め、かつ分子量が、フェノール／１，１，２，２−テトラクロロエタン（体積比５０／５０）の混合溶媒中、濃度０．５ｇ／ｄＬ、３０℃で測定した還元粘度（η ｓｐ ／ｃ）で０．１〜１０ｄＬ／ｇの範囲にあるポリカーボネート。The following formula (A)
A repeating unit represented by the following formula (B):
The repeating unit (A) is 5 to 30 mol% and the repeating unit (B) is based on the total of the repeating units (A), (B) and (C). 10 to 90 mol%, repeating unit (C) occupies a proportion of 5 to 85 mol% , and the molecular weight is a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (volume ratio 50/50), A polycarbonate having a reduced viscosity (η sp / c) measured at 30 ° C. of 0.1 to 10 dL / g at a concentration of 0.5 g / dL .
Ｒ（４５０）／Ｒ（５５０）＜１ （１）
Ｒ（６５０）／Ｒ（５５０）＞１ （２）
を満たす請求項７記載の位相差フィルム。In-plane retardation values R (450), R (550), and R (650) at wavelengths of 450 nm, 550 nm, and 650 nm are represented by the following formulas (1) and (2).
R (450) / R (550) <1 (1)
R (650) / R (550)> 1 (2)
The retardation film of Claim 7 which satisfy | fills.
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2006041190A1 (en) | 2006-04-20 |
| TW200628511A (en) | 2006-08-16 |
| JPWO2006041190A1 (en) | 2008-05-22 |
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