KR20220029387A - Retardation film and polarizing plate - Google Patents
Retardation film and polarizing plate Download PDFInfo
- Publication number
- KR20220029387A KR20220029387A KR1020210107052A KR20210107052A KR20220029387A KR 20220029387 A KR20220029387 A KR 20220029387A KR 1020210107052 A KR1020210107052 A KR 1020210107052A KR 20210107052 A KR20210107052 A KR 20210107052A KR 20220029387 A KR20220029387 A KR 20220029387A
- Authority
- KR
- South Korea
- Prior art keywords
- retardation film
- film
- retardation
- bis
- dihydroxy compound
- Prior art date
Links
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 10
- 239000004417 polycarbonate Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 9
- 230000002087 whitening effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 95
- 125000002723 alicyclic group Chemical group 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 230000008859 change Effects 0.000 description 15
- 229920005668 polycarbonate resin Polymers 0.000 description 15
- 239000004431 polycarbonate resin Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 description 13
- -1 diester carbonate Chemical class 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 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 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229960002479 isosorbide Drugs 0.000 description 7
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000004292 cyclic ethers Chemical group 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 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 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- DNTHXHASNDRODE-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]cyclohexyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)CCCCC1 DNTHXHASNDRODE-UHFFFAOYSA-N 0.000 description 2
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- RVIZJROSQMQZCG-UHFFFAOYSA-N adamantane-1,2-diol Chemical compound C1C(C2)CC3CC1C(O)C2(O)C3 RVIZJROSQMQZCG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- KLDXJTOLSGUMSJ-BXKVDMCESA-N (3s,3as,6s,6as)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@H]2[C@@H](O)CO[C@H]21 KLDXJTOLSGUMSJ-BXKVDMCESA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- BABJMFGHXVXNKB-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-1,5-diol Chemical compound OC1CCCC2C(O)CCCC21 BABJMFGHXVXNKB-UHFFFAOYSA-N 0.000 description 1
- WTIPFYCAMXYLQJ-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-2,3-diol Chemical compound C1CCCC2CC(O)C(O)CC21 WTIPFYCAMXYLQJ-UHFFFAOYSA-N 0.000 description 1
- OIXGILBUABDWRY-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-2,6-diol Chemical compound C1C(O)CCC2CC(O)CCC21 OIXGILBUABDWRY-UHFFFAOYSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-UHFFFAOYSA-N 0.000 description 1
- MUULEEXYBWFOAQ-UHFFFAOYSA-N 2-[2-[2-[2-(2-hydroxyethoxy)-3-propan-2-ylphenyl]propan-2-yl]-6-propan-2-ylphenoxy]ethanol Chemical compound CC(C)C1=CC=CC(C(C)(C)C=2C(=C(C(C)C)C=CC=2)OCCO)=C1OCCO MUULEEXYBWFOAQ-UHFFFAOYSA-N 0.000 description 1
- LFEXGRKRPALUFH-UHFFFAOYSA-N 2-[2-bromo-4-[2-[3-bromo-4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C(Br)=CC=1C(C)(C)C1=CC=C(OCCO)C(Br)=C1 LFEXGRKRPALUFH-UHFFFAOYSA-N 0.000 description 1
- YBHWVDKCKDWQBX-UHFFFAOYSA-N 2-[2-cyclohexyl-4-[9-[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C2CCCCC2)C=C1C1CCCCC1 YBHWVDKCKDWQBX-UHFFFAOYSA-N 0.000 description 1
- DONOMPLAOYHIGR-UHFFFAOYSA-N 2-[2-tert-butyl-4-[2-[3-tert-butyl-4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C1=C(OCCO)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(OCCO)=CC=2)C(C)(C)C)=C1 DONOMPLAOYHIGR-UHFFFAOYSA-N 0.000 description 1
- CUPZWXCTZHAVPP-UHFFFAOYSA-N 2-[2-tert-butyl-4-[9-[3-tert-butyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=C(OCCO)C(C(C)(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C(C)(C)C)=C1 CUPZWXCTZHAVPP-UHFFFAOYSA-N 0.000 description 1
- JTLKXEMTIVAKJG-UHFFFAOYSA-N 2-[2-tert-butyl-4-[9-[5-tert-butyl-4-(2-hydroxyethoxy)-2-methylphenyl]fluoren-9-yl]-5-methylphenoxy]ethanol Chemical compound CC1=CC(OCCO)=C(C(C)(C)C)C=C1C1(C=2C(=CC(OCCO)=C(C=2)C(C)(C)C)C)C2=CC=CC=C2C2=CC=CC=C21 JTLKXEMTIVAKJG-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- JHWYZCNTNCSPFU-UHFFFAOYSA-N 2-[4-[1-[3-[2-[4-(2-hydroxyethoxy)phenyl]propyl]phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)CC(C=1)=CC=CC=1CC(C)C1=CC=C(OCCO)C=C1 JHWYZCNTNCSPFU-UHFFFAOYSA-N 0.000 description 1
- GPLGAPZOFUAGQL-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]-1-phenylethyl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C=1C=CC(OCCO)=CC=1)(C)C1=CC=CC=C1 GPLGAPZOFUAGQL-UHFFFAOYSA-N 0.000 description 1
- RAPDSRFNGPRVPV-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]-3,3,5-trimethylcyclohexyl]phenoxy]ethanol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(OCCO)=CC=1)C1=CC=C(OCCO)C=C1 RAPDSRFNGPRVPV-UHFFFAOYSA-N 0.000 description 1
- IGLFRWDFPLPJHA-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]cyclopentyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)CCCC1 IGLFRWDFPLPJHA-UHFFFAOYSA-N 0.000 description 1
- TZIYYPHSIYMLQN-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]ethyl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)C1=CC=C(OCCO)C=C1 TZIYYPHSIYMLQN-UHFFFAOYSA-N 0.000 description 1
- AMOWUNDRFWJYHD-UHFFFAOYSA-N 2-[4-[1-[4-[2-[4-(2-hydroxyethoxy)phenyl]propyl]phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)CC(C=C1)=CC=C1CC(C)C1=CC=C(OCCO)C=C1 AMOWUNDRFWJYHD-UHFFFAOYSA-N 0.000 description 1
- DDEMAGHDTBWGLX-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]propan-2-yl]-2,6-dimethylphenoxy]ethanol Chemical compound CC1=C(OCCO)C(C)=CC(C(C)(C)C=2C=C(C)C(OCCO)=C(C)C=2)=C1 DDEMAGHDTBWGLX-UHFFFAOYSA-N 0.000 description 1
- WURUICCPWMHUFA-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)-3-methylphenyl]propan-2-yl]-2-methylphenoxy]ethanol Chemical compound C1=C(OCCO)C(C)=CC(C(C)(C)C=2C=C(C)C(OCCO)=CC=2)=C1 WURUICCPWMHUFA-UHFFFAOYSA-N 0.000 description 1
- ZMKBETOAFQAZNU-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)phenyl]-4-methylpentan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)(CC(C)C)C1=CC=C(OCCO)C=C1 ZMKBETOAFQAZNU-UHFFFAOYSA-N 0.000 description 1
- RYFDAZYNMLFWKG-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)phenyl]butan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)(CC)C1=CC=C(OCCO)C=C1 RYFDAZYNMLFWKG-UHFFFAOYSA-N 0.000 description 1
- FKJIXBPMPGRKIX-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)phenyl]octan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)(CCCCCC)C1=CC=C(OCCO)C=C1 FKJIXBPMPGRKIX-UHFFFAOYSA-N 0.000 description 1
- VUXCJJQXZXRORH-UHFFFAOYSA-N 2-[4-[3-[4-(2-hydroxyethoxy)phenyl]-5,7-dimethyl-1-adamantyl]phenoxy]ethanol Chemical compound C1C(C)(C2)CC(C3)(C)CC1(C=1C=CC(OCCO)=CC=1)CC23C1=CC=C(OCCO)C=C1 VUXCJJQXZXRORH-UHFFFAOYSA-N 0.000 description 1
- JDOGLHRXPDOFJQ-UHFFFAOYSA-N 2-[4-[3-[4-(2-hydroxyethoxy)phenyl]cyclohexyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1CC(C=2C=CC(OCCO)=CC=2)CCC1 JDOGLHRXPDOFJQ-UHFFFAOYSA-N 0.000 description 1
- XUWHBHOYULRMIA-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]phenoxy]ethanol Chemical group C1=CC(OCCO)=CC=C1C1=CC=C(OCCO)C=C1 XUWHBHOYULRMIA-UHFFFAOYSA-N 0.000 description 1
- UFXJMCPOUORUQC-UHFFFAOYSA-N 2-[4-[4-[4-(2-hydroxyethoxy)phenyl]cyclohexyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1CCC(C=2C=CC(OCCO)=CC=2)CC1 UFXJMCPOUORUQC-UHFFFAOYSA-N 0.000 description 1
- IRTFFZWZLVOXMG-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluoren-9-yl]-2,6-dimethylphenoxy]ethanol Chemical compound CC1=C(OCCO)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(OCCO)=C(C)C=2)=C1 IRTFFZWZLVOXMG-UHFFFAOYSA-N 0.000 description 1
- HBTONAMIPDVQRI-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-phenylphenyl]fluoren-9-yl]-2-phenylphenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 HBTONAMIPDVQRI-UHFFFAOYSA-N 0.000 description 1
- WXNRFPMJYZGKSS-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-propan-2-ylphenyl]fluoren-9-yl]-2-propan-2-ylphenoxy]ethanol Chemical compound C1=C(OCCO)C(C(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C(C)C)=C1 WXNRFPMJYZGKSS-UHFFFAOYSA-N 0.000 description 1
- DFKLRRVOFXYLFN-UHFFFAOYSA-N 2-[4-[[4-(2-hydroxyethoxy)phenyl]-diphenylmethyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C(C=1C=CC(OCCO)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DFKLRRVOFXYLFN-UHFFFAOYSA-N 0.000 description 1
- MFBRWKCKAGAJAJ-UHFFFAOYSA-N 2-[4-[[4-(2-hydroxyethoxy)phenyl]methyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1CC1=CC=C(OCCO)C=C1 MFBRWKCKAGAJAJ-UHFFFAOYSA-N 0.000 description 1
- LYZMKCWNBRTLTJ-UHFFFAOYSA-N 2-methylcyclohexane-1,4-diol Chemical compound CC1CC(O)CCC1O LYZMKCWNBRTLTJ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RKSBPFMNOJWYSB-UHFFFAOYSA-N 3,3-Bis(4-hydroxyphenyl)pentane Chemical compound C=1C=C(O)C=CC=1C(CC)(CC)C1=CC=C(O)C=C1 RKSBPFMNOJWYSB-UHFFFAOYSA-N 0.000 description 1
- HZGJTATYGAJRAL-UHFFFAOYSA-N 3,4,4a,5,6,7,8,8a-octahydro-2h-naphthalene-1,1-diol Chemical compound C1CCCC2C(O)(O)CCCC21 HZGJTATYGAJRAL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- DTOMAXGIWFLDMR-UHFFFAOYSA-N 4-[(4-hydroxy-3-nitrophenyl)methyl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1CC1=CC=C(O)C([N+]([O-])=O)=C1 DTOMAXGIWFLDMR-UHFFFAOYSA-N 0.000 description 1
- XAIZOTQTRJYNHC-UHFFFAOYSA-N 4-[2-(3,5-diethyl-4-hydroxyphenyl)propan-2-yl]-2,6-diethylphenol Chemical compound CCC1=C(O)C(CC)=CC(C(C)(C)C=2C=C(CC)C(O)=C(CC)C=2)=C1 XAIZOTQTRJYNHC-UHFFFAOYSA-N 0.000 description 1
- ACWKCNYOCGALDS-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-diphenylphenyl)propan-2-yl]-2,6-diphenylphenol Chemical compound C=1C(C=2C=CC=CC=2)=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=C(C=1O)C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 ACWKCNYOCGALDS-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- KBKLXLYSUOMJQE-UHFFFAOYSA-N 4-[9-(4-hydroxy-2-methylphenyl)fluoren-9-yl]-3-methylphenol Chemical compound CC1=CC(O)=CC=C1C1(C=2C(=CC(O)=CC=2)C)C2=CC=CC=C2C2=CC=CC=C21 KBKLXLYSUOMJQE-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RABVYVVNRHVXPJ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-adamantyl]methanol Chemical compound C1C(C2)CC3CC1(CO)CC2(CO)C3 RABVYVVNRHVXPJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- AZJUMRZVLRZXPD-UHFFFAOYSA-N adamantane methanol Chemical compound OC.OC.C1C(C2)CC3CC1CC2C3 AZJUMRZVLRZXPD-UHFFFAOYSA-N 0.000 description 1
- MOLCWHCSXCKHAP-UHFFFAOYSA-N adamantane-1,3-diol Chemical compound C1C(C2)CC3CC1(O)CC2(O)C3 MOLCWHCSXCKHAP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- NNYOSLMHXUVJJH-UHFFFAOYSA-N heptane-1,5-diol Chemical compound CCC(O)CCCCO NNYOSLMHXUVJJH-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- GROIHDHFSBIQKH-UHFFFAOYSA-N phenyl 3-[9-[[9-(3-oxo-3-phenoxypropyl)fluoren-9-yl]methyl]fluoren-9-yl]propanoate Chemical compound C=1C=CC=CC=1OC(=O)CCC1(C2=CC=CC=C2C2=CC=CC=C21)CC1(C2=CC=CC=C2C2=CC=CC=C21)CCC(=O)OC1=CC=CC=C1 GROIHDHFSBIQKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
Abstract
Description
본 발명은 위상차 필름 및 편광판에 관한 것이다.The present invention relates to a retardation film and a polarizing plate.
최근, 박형 디스플레이의 보급과 함께, 유기 EL 패널을 탑재한 화상 표시 장치(유기 EL 표시 장치)가 제안되어 있다. 유기 EL 패널은 반사성이 높은 금속층을 갖고 있고, 외광 반사나 배경의 비쳐듬 등의 문제를 발생하기 쉽다. 그래서, 위상차 필름을 시인측에 설치함으로써, 이들 문제를 방지하는 것이 알려져 있다. 그러나, 종래의 위상차 필름에 있어서는, 필름의 반송 중의 꺽임, 주름, 타흔 등의 공정 불량이 발생할 경우가 있고, 또한 필름의 압입시에 휘점이 발생할 경우가 있다. 또한, 종래의 위상차 필름을 화상 표시 장치의 시인측에 사용할 경우, 사용과 함께 백화 및/또는 크랙이 발생할 경우가 있고, 색상 불균일이 발생하는 경우가 있으며, 또한 굴곡성이 불충분한 경우가 있다. DESCRIPTION OF RELATED ART In recent years, with the spread of a thin display, the image display apparatus (organic electroluminescent display apparatus) in which the organic electroluminescent panel was mounted is proposed. An organic EL panel has a highly reflective metal layer, and it is easy to generate|occur|produce problems, such as external light reflection and background reflection. Then, it is known to prevent these problems by providing retardation film on the visual recognition side. However, in the conventional retardation film, process defects, such as a wrinkle, a wrinkle, and a dent, during conveyance of a film, may generate|occur|produce, and a luminescent point may generate|occur|produce at the time of press-fitting of a film. Moreover, when the conventional retardation film is used for the visual recognition side of an image display apparatus, whitening and/or a crack may generate|occur|produce with use, and a color nonuniformity may generate|occur|produce, and also flexibility may be insufficient.
본 발명은 상기 종래의 과제를 해결하기 위해서 이루어진 것이고, 그 목적으로 하는 바는, 반송 중의 공정 불량의 발생이 억제되고, 필름의 압입시의 휘점의 발생이 억제되며, 백화 및/또는 크랙의 발생이 어제되고, 색상 불균일이 억제되며, 또한, 굴곡성이 우수한 위상차 필름을 제공하는 것에 있다.The present invention has been made in order to solve the above conventional problems, and the object thereof is that the occurrence of process defects during conveyance is suppressed, the occurrence of bright spots at the time of press-fitting of the film is suppressed, and the occurrence of whitening and/or cracks is suppressed. It is to provide the retardation film excellent in flexibility, which becomes this yesterday, and a color nonuniformity is suppressed.
본 발명의 실시형태에 있어서의 위상차 필름은, 폴리카보네이트계 수지를 포함하고, 면내 위상차 Re(550)는 80㎚∼190㎚이며, Re(450)/Re(550)는 0.98∼1.03이며, 돌자탄성률은 50gf/㎜ 이상이다.Retardation film in embodiment of this invention contains polycarbonate-type resin, in-plane retardation Re(550) is 80 nm - 190 nm, Re(450)/Re(550) is 0.98 - 1.03, The elastic modulus is 50 gf/mm or more.
하나의 실시형태에 있어서는, 상기 위상차 필름의 단위막두께당의 돌자강도는 10gf/㎛ 이상이다.In one embodiment, the puncture strength per unit film thickness of the retardation film is 10 gf/µm or more.
하나의 실시형태에 있어서는, 상기 위상차 필름의 파단강도는 800㎫ 이상이고, 또한, 파단신도는 3% 이상이다.In one embodiment, the breaking strength of the retardation film is 800 MPa or more, and the breaking elongation is 3% or more.
하나의 실시형태에 있어서는, 상기 위상차 필름의 두께는 40㎛ 이하이다.In one embodiment, the thickness of the said retardation film is 40 micrometers or less.
하나의 실시형태에 있어서는, 상기 위상차 필름의 폭 방향의 Re(550)의 편차는 5㎚ 이하이다.In one embodiment, the dispersion|variation of Re(550) of the width direction of the said retardation film is 5 nm or less.
본 발명의 다른 실시형태에 있어서는, 위상차층 부착 편광판이 제공된다. 이 위상차층 부착 편광판은, 편광자와, 상기 편광자의 적어도 편면에 접착제층을 개재하여 접합된 상기 위상차 필름을 포함한다.In another embodiment of the present invention, a polarizing plate with a retardation layer is provided. This polarizing plate with a retardation layer contains a polarizer and the said retardation film bonded to at least one surface of the said polarizer via an adhesive bond layer.
본 발명의 실시형태에 의하면, 특정의 폴리카보네이트계 수지를 포함하고, 돌자탄성률을 특정의 범위 내로 함으로써, 반송 중의 공정 불량의 발생 및 색상 불균일의 발생이 억제되고, 또한 굴곡성이 우수한 위상차 필름을 실현할 수 있다. 또한, 단위막두께당의 돌자강도, 파단강도 및 파단신도를 특정의 범위 내로 함으로써, 필름의 압입시의 휘점의 발생 및 색상 불균일의 발생이 억제되고, 내크랙성이 우수한 위상차 필름을 실현할 수 있다.According to the embodiment of the present invention, by containing a specific polycarbonate-based resin and making the puncture modulus within a specific range, the occurrence of process defects during transport and the occurrence of color unevenness are suppressed, and a retardation film excellent in flexibility can be realized. can In addition, by setting the puncture strength, breaking strength, and breaking elongation per unit film thickness within a specific range, the occurrence of bright spots and color unevenness during press-fitting of the film is suppressed, and a retardation film excellent in crack resistance can be realized.
이하, 본 발명의 실시형태에 대하여 설명하지만, 본 발명은 이들 실시형태에는 한정되지 않는다.EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment.
(용어 및 기호의 정의)(Definition of terms and symbols)
본 명세서에 있어서의 용어 및 기호의 정의는 하기와 같다.Definitions of terms and symbols in this specification are as follows.
(1) 굴절률(nx, ny, nz)(1) refractive index (nx, ny, nz)
「nx」는 면내의 굴절률이 최대가 되는 방향(즉, 지상축 방향)의 굴절률이며, 「ny」는 면내에서 지상축과 직교하는 방향(즉, 진상축 방향)의 굴절률이며, 「nz」는 두께 방향의 굴절률이다."nx" is the refractive index in the direction in which the in-plane refractive index is maximum (ie, slow axis direction), "ny" is the refractive index in the direction orthogonal to the slow axis in the plane (ie, fast axis direction), and "nz" is It is the refractive index in the thickness direction.
(2) 면내 위상차(Re)(2) In-plane phase difference (Re)
「Re(λ)」는 23℃에 있어서의 파장 λ㎚의 광으로 측정한 면내 위상차이다. 예를 들면, 「Re(550)」는 23℃에 있어서의 파장 550㎚의 광으로 측정한 면내 위상차이다. Re(λ)는 층(필름)의 두께를 d(㎚)라고 했을 때, 식: Re(λ)=(nx-ny)×d에 의해 구해진다."Re(λ)" is the in-plane retardation measured with the light of wavelength λnm in 23 degreeC. For example, "Re(550)" is the in-plane retardation measured with the light of wavelength 550nm in 23 degreeC. Re(λ) is obtained by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (film) is d(nm).
A. 위상차 필름A. Retardation film
본 발명의 실시형태에 의한 위상차 필름은 폴리카보네이트 수지를 포함한다. 본 발명의 실시형태에 의한 위상차 필름은, 대표적으로는 폴리카보네이트 수지 필름의 연신 필름이다.The retardation film according to an embodiment of the present invention contains a polycarbonate resin. The retardation film according to the embodiment of the present invention is typically a stretched film of a polycarbonate resin film.
상기 위상차 필름의 면내 위상차 Re(550)는 80㎚∼190㎚이며, 바람직하게는 10㎚∼160㎚이다. 즉, 위상차 필름은 λ/4 위상차판으로서 기능할 수 있다.The in-plane retardation Re (550) of the retardation film is 80 nm to 190 nm, preferably 10 nm to 160 nm. That is, the retardation film can function as a λ/4 retardation plate.
상기 위상차 필름은, 위상차값이 측정광의 파장에 의해서도 거의 변화되지 않는 플랫한 파장 분산 특성을 나타낸다. 위상차 필름의 Re(450)/Re(550)는 0.98∼1.03이며, 바람직하게는 0.99∼1.03이며, 보다 바람직하게는 1.00∼1.03이다. 이러한 Re(450)/Re(550)를 갖는 폴리카보네이트계 수지를 사용함으로써 뛰어난 반사 방지 특성을 실현할 수 있다.The retardation film exhibits a flat wavelength dispersion characteristic in which the retardation value hardly changes depending on the wavelength of the measurement light. Re(450)/Re(550) of retardation film is 0.98-1.03, Preferably it is 0.99-1.03, More preferably, it is 1.00-1.03. By using such a polycarbonate-based resin having Re(450)/Re(550), excellent antireflection properties can be realized.
상기 위상차 필름의 돌자탄성률은 50gf/㎜ 이상이며, 바람직하게는 100gf/㎜ 이상이며, 보다 바람직하게는 150gf/㎜ 이상이다. 돌자탄성률이란, 니들(돌자 지그)을 필름의 주면에 대하여 수직으로 짤렀을 때에 상기 필름이 파단하기(또는 찢어지기) 직전의 힘(gf)을, 그 때의 변형(㎜)으로 나누어서 구한 것이다. 위상차 필름이 상기와 같은 돌자탄성률을 가짐으로써 반송 중의 공정 불량 등의 발생 및 색상 불균일의 발생이 억제되고, 또한 굴곡성이 우수한 위상차 필름이 얻어질 수 있다.The retardation film has a puncture modulus of 50 gf/mm or more, preferably 100 gf/mm or more, and more preferably 150 gf/mm or more. The puncture modulus is obtained by dividing the force (gf) immediately before the film breaks (or torn) by the deformation (mm) at that time when the needle (piercing jig) is cut perpendicularly to the main surface of the film. When the retardation film has the puncture modulus as described above, the occurrence of process defects and the like during transport and the occurrence of color unevenness are suppressed, and a retardation film excellent in flexibility can be obtained.
상기 위상차 필름의 단위막두께당의 돌자강도는, 바람직하게는 10gf/㎛ 이상이며, 보다 바람직하게는 15gf/㎛ 이상이며, 더 바람직하게는 20gf/㎛ 이상이다. 단위막두께당의 돌자강도란, 니들을 필름에 대하여 수직으로 강하시켜서 필름이 깨졌을 때의 강도를 두께로 나눈 것을 나타낸다. 위상차 필름이 상기와 같은 단위막두께당의 돌자강도를 가짐으로써, 필름의 압입시의 휘점의 발생 및 색상 불균일의 발생이 억제된 위상차 필름이 얻어질 수 있다.The puncture strength per unit film thickness of the retardation film is preferably 10 gf/μm or more, more preferably 15 gf/μm or more, and still more preferably 20 gf/μm or more. The puncture strength per unit film thickness refers to the strength when the film is broken by dropping the needle vertically with respect to the film divided by the thickness. Since the retardation film has the puncture strength per unit film thickness as described above, a retardation film in which the occurrence of bright spots and color unevenness during press-fitting of the film is suppressed can be obtained.
상기 위상차 필름의 파단강도는, 바람직하게는 800㎫ 이상이며, 또한, 파단신도는 바람직하게는 3% 이상이다. 위상차 필름의 파단강도는, 보다 바람직하게는 1500㎫ 이상이며, 더 바람직하게는 2500㎫ 이상이다. 위상차 필름의 파단강도의 상한은, 예를 들면 7000㎫이다. 또한, 위상차 필름의 파단신도는, 보다 바람직하게는 4% 이상이며, 더 바람직하게는 6% 이상이다. 위상차 필름의 파단신도의 상한은, 예를 들면 300%일 수 있다. 파단강도란 인장시험에 있어서 필름이 파단했을 때의 응력을 나타낸다. 파단신도란 상기 필름이 파단했을 때의 변형(신장율)을 나타낸다.위상차 필름의 파단강도 및 파단신도가 상기와 같은 범위임으로써 색상 불균일의 발생이 억제되고, 또한 내크랙성이 우수한 위상차 필름이 얻어질 수 있다.The breaking strength of the retardation film is preferably 800 MPa or more, and the breaking elongation is preferably 3% or more. The breaking strength of retardation film becomes like this. More preferably, it is 1500 MPa or more, More preferably, it is 2500 MPa or more. The upper limit of the breaking strength of retardation film is 7000 MPa, for example. Moreover, the breaking elongation of retardation film becomes like this. More preferably, it is 4 % or more, More preferably, it is 6 % or more. The upper limit of the elongation at break of the retardation film may be, for example, 300%. Breaking strength refers to the stress when the film breaks in a tensile test. Elongation at break indicates the deformation (elongation) when the film is broken. When the breaking strength and elongation at break of the retardation film are in the same ranges as above, the occurrence of color non-uniformity is suppressed, and a retardation film having excellent crack resistance is obtained. can get
상기 위상차 필름의 두께는, 바람직하게는 40㎛ 이하이며, 보다 바람직하게는 35㎛ 이하이다. 위상차 필름의 두께의 하한은, 예를 들면 5㎛일 수 있다. 위상차 필름의 두께가 이러한 범위임으로써, 위상차 필름을 박형의 디바이스에 적합하게 적용할 수 있다.The thickness of the said retardation film becomes like this. Preferably it is 40 micrometers or less, More preferably, it is 35 micrometers or less. The lower limit of the thickness of the retardation film may be, for example, 5 μm. When the thickness of the retardation film is within such a range, the retardation film can be suitably applied to a thin device.
상기 위상차 필름의 폭 방향의 Re(550)의 편차는 바람직하게는 5㎚ 이하이며, 보다 바람직하게는 3㎚ 이하이며, 더 바람직하게는 2㎚ 이하이다. 위상차 필름의 폭 방향의 Re(550)의 편차의 하한은, 예를 들면 0.5㎚일 수 있다. Re(550)의 편차를 이러한 범위로 규정함으로써, 위상차 필름의 양호한 광학 균일성이 실현될 수 있다.The deviation of Re(550) in the width direction of the retardation film is preferably 5 nm or less, more preferably 3 nm or less, and still more preferably 2 nm or less. The lower limit of the deviation of Re (550) in the width direction of the retardation film may be, for example, 0.5 nm. By defining the deviation of Re(550) in this range, good optical uniformity of the retardation film can be realized.
상기 위상차 필름에 있어서의 온도 65℃, 습도 90% 조건 하에서 500시간 경과 후의 면내 위상차 Re(550)의 변화율의 절대값은, 바람직하게는 3% 이하이며, 보다 바람직하게는 2% 이하이다. 상기 변화율의 절대값의 하한은, 예를 들면 0.01%일 수 있다. 상기 위상차 변화율은, |(Re500-Re0)/Re0|×100(%)로 나타내어진다. Re0은 시험 개시 전의 위상차 필름의 면내 위상차(㎚)이며, Re500은 시험 후의 위상차 필름의 면내 위상차(㎚)이다. 위상차 필름의 면내 위상차 Re(550)의 변화율의 절대값이 이러한 범위임으로써, 위상차 필름을 화상 표시 장치에 적용했을 경우에 화상 표시 장치 상의 장소마다의 위상차에 의한 색상 변화가 적아져 표시 상의 색 불균일의 발생이 억제될 수 있다.The absolute value of the change rate of the in-plane retardation Re (550) after 500 hours has passed under the conditions of a temperature of 65° C. and a humidity of 90% in the retardation film is preferably 3% or less, and more preferably 2% or less. The lower limit of the absolute value of the change rate may be, for example, 0.01%. The phase difference change rate is represented by |(Re 500 -Re 0 )/Re 0 |×100 (%). Re 0 is the in-plane retardation (nm) of the retardation film before the start of the test, and Re 500 is the in-plane retardation (nm) of the retardation film after the test. Since the absolute value of the rate of change of the in-plane retardation Re (550) of the retardation film is within this range, when the retardation film is applied to an image display device, the color change due to the phase difference at each location on the image display device is reduced, so color non-uniformity on the display occurrence can be suppressed.
상기 위상차 필름의 투습도는, 바람직하게는 150g/㎡·24h 이하이며, 보다 바람직하게는 120g/㎡·24h 이하이다. 투습도의 하한은, 예를 들면 1g/㎡·24h일 수 있다. 위상차 필름의 투습도가 이러한 범위이면, 가습 환경 하에 있어서의 위상차의 변화를 억제할 수 있다.The water vapor transmission rate of the retardation film is preferably 150 g/m 2 ·24 h or less, and more preferably 120 g/m 2 ·24 h or less. The lower limit of the moisture permeability may be, for example, 1 g/m 2 ·24h. If the water vapor transmission rate of retardation film is such a range, the change of retardation in a humidified environment can be suppressed.
상기 위상차 필름의 광탄성계수의 절대값은, 바람직하게는 2×10-11㎡/N 이하이며, 보다 바람직하게는 2.0×10-13㎡/N∼1.5×10-11㎡/N이며, 더 바람직하게는 1.0×10-12㎡/N∼1.2×10-11㎡/N이다. 위상차 필름의 광탄성계수의 절대값이 이러한 범위이면, 가열시의 수축응력이 발생했을 경우에 위상차 변화가 생기기 어렵다. 그 결과, 위상차 필름을 화상 표시 장치에 적용했을 경우에, 화상 표시 장치의 열 불균일이 양호하게 방지될 수 있다.The absolute value of the photoelastic coefficient of the retardation film is preferably 2×10 -11 m2/N or less, more preferably 2.0×10 -13 m2/N to 1.5×10 -11 m2/N, further preferably Usually it is 1.0×10 -12 m2/N to 1.2×10 -11 m2/N. If the absolute value of the photoelastic coefficient of the retardation film is within such a range, it is difficult to cause a change in retardation when a shrinkage stress during heating occurs. As a result, when the retardation film is applied to an image display apparatus, thermal unevenness of the image display apparatus can be prevented favorably.
본 발명의 실시형태에 의하면, 상기와 같이, 소망의 면내 위상차, 파장 분산 특성 및 두께를 만족하고, 또한, 반송 중의 공정 불량의 발생이 억제되고, 필름의 압입시의 휘점의 발생이 억제되어, 백화 및/또는 크랙의 발생이 억제되고, 색상 불균일이 억제되고, 또한 굴곡성이 우수한 위상차 필름이 얻어질 수 있다. 이러한 위상차 필름은, 텔레비젼, 절곡 가능 및/또는 절첩 가능한 화상 표시 장치, 퍼블릭 인포메이션 디스플레이(PID)에 적합하게 사용될 수 있다.According to the embodiment of the present invention, as described above, the desired in-plane retardation, wavelength dispersion characteristics and thickness are satisfied, and the occurrence of process defects during transport is suppressed, and the occurrence of bright spots at the time of press-fitting of the film is suppressed, The retardation film which whitening and/or generation|occurrence|production of a crack is suppressed, color nonuniformity is suppressed, and is also excellent in flexibility can be obtained. Such retardation film can be suitably used for a television, a bendable and/or foldable image display apparatus, and a public information display (PID).
B. 구성 재료B. Construction Materials
위상차 필름은, 상기와 같이, 대표적으로는 폴리카보네이트 수지 필름의 연신 필름이다.As mentioned above, retardation film is a stretched film of a polycarbonate resin film typically.
(폴리카보네이트 수지)(polycarbonate resin)
본 발명에 따른 폴리카보네이트 수지는, 하기 구조식(1)으로 나타내어지는 결합 구조를 갖는 디히드록시 화합물에 유래하는 구성단위를 적어도 포함하는 것이며, 분자 내에 적어도 하나의 결합 구조 -CH2-O-를 갖는 디히드록시 화합물을 적어도 포함하는 디히드록시 화합물과, 탄산 디에스테르를 중합촉매의 존재 하 반응시킴으로써 제조된다.The polycarbonate resin according to the present invention contains at least a structural unit derived from a dihydroxy compound having a bonding structure represented by the following structural formula (1), and contains at least one bonding structure -CH 2 -O- in the molecule It is produced by reacting a dihydroxy compound containing at least a dihydroxy compound having a dihydroxy compound and a diester carbonate in the presence of a polymerization catalyst.
여기에서, 구조식(1)으로 나타내어지는 결합 구조를 갖는 디히드록시 화합물로서는, 2개의 알콜성 수산기를 가지고, 분자 내에 연결기 -CH2-O-를 갖는 구조를 포함하고, 중합촉매의 존재 하, 탄산 디에스테르와 반응해서 폴리카보네이트를 생성할 수 있는 화합물이면 어떠한 구조의 화합물이여도 사용하는 것이 가능하고, 복수종 병용해도 관계없다. 또한, 본 발명에 따른 폴리카보네이트 수지에 사용하는 디히드록시 화합물로서, 구조식(1)으로 나타내어지는 결합 구조를 갖지 않는 디히드록시 화합물을 병용해도 관계없다. 이하, 구조식(1)으로 나타내어지는 결합 구조를 갖는 디히드록시 화합물을 디히드록시 화합물(A), 구조식(1)으로 나타내어지는 결합 구조를 갖지 않는 디히드록시 화합물을 디히드록시 화합물(B)로 약기할 경우가 있다.Here, the dihydroxy compound having a bonding structure represented by the structural formula (1) includes a structure having two alcoholic hydroxyl groups and a linking group -CH 2 -O- in the molecule, and in the presence of a polymerization catalyst, If it is a compound which reacts with diester carbonate and can produce|generate a polycarbonate, even if it is a compound of any structure, it is possible to use it, and it does not matter even if it uses multiple types together. Moreover, as a dihydroxy compound used for the polycarbonate resin which concerns on this invention, you may use together the dihydroxy compound which does not have the bonding structure represented by Structural formula (1). Hereinafter, the dihydroxy compound having the bonding structure represented by Structural Formula (1) is referred to as the dihydroxy compound (A), and the dihydroxy compound not having the bonding structure represented by the Structural Formula (1) is referred to as the dihydroxy compound (B). may be abbreviated as
(디히드록시 화합물(A))(dihydroxy compound (A))
디히드록시 화합물(A)에 있어서의 「연결기 -CH2-O-」란, 수소원자 이외의 원자와 서로 결합해서 분자를 구성하는 구조를 의미한다. 이 연결기에 있어서, 적어도 산소원자가 결합할 수 있는 원자 또는 탄소원자와 산소원자가 동시에 결합할 수 있는 원자로서는, 탄소원자가 가장 바람직하다. 디히드록시 화합물(A) 중의 「연결기 -CH2-O-」의 수는, 바람직하게는 1 이상, 보다 바람직하게는 2∼4이다.The "linking group -CH 2 -O-" in the dihydroxy compound (A) means a structure in which it bonds to atoms other than a hydrogen atom to form a molecule. In this coupling group, at least as an atom to which an oxygen atom can bond or an atom to which a carbon atom and an oxygen atom can bond simultaneously, a carbon atom is most preferable. The number of "linking groups -CH 2 -O-" in the dihydroxy compound (A) is preferably 1 or more, more preferably 2 to 4.
더욱 구체적으로는, 디히드록시 화합물(A)로서는, 예를 들면 9,9-비스(4-(2-히드록시에톡시)페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-메틸페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-이소프로필페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-이소부틸페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-tert-부틸페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-시클로헥실페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-페닐페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3,5-디메틸페닐)플루오렌, 9,9-비스(4-(2-히드록시에톡시)-3-tert-부틸-6-메틸페닐)플루오렌, 9,9-비스(4-(3-히드록시-2,2-디메틸프로폭시)페닐)플루오렌으로 예시하는 바와 같은, 측쇄에 방향족기를 갖고, 주쇄에 방향족기에 결합한 에테르기를 갖는 화합물, 비스[4-(2-히드록시에톡시)페닐]메탄, 비스[4-(2-히드록시에톡시)페닐]디페닐메탄, 1,1-비스[4-(2-히드록시에톡시)페닐]에탄, 1,1-비스[4-(2-히드록시에톡시)페닐]-1-페닐에탄, 2,2-비스[4-(2-히드록시에톡시)페닐]프로판, 2,2-비스[4-(2-히드록시에톡시)-3-메틸페닐]프로판, 2,2-비스[3,5-디메틸-4-(2-히드록시에톡시)페닐]프로판, 1,1-비스[4-(2-히드록시에톡시)페닐]-3,3,5-트리메틸시클로 헥산, 1,1-비스[4-(2-히드록시에톡시)페닐]시클로헥산, 1,4-비스[4-(2-히드록시에톡시)페닐]시클로헥산, 1,3-비스[4-(2-히드록시에톡시)페닐]시클로헥산, 2,2-비스[4-(2-히드록시에톡시)-3-페닐페닐]프로판, 2,2-비스[(2-히드록시에톡시)-3-이소프로필페닐]프로판, 2,2-비스[3-tert-부틸-4-(2-히드록시에톡시)페닐]프로판, 2,2-비스[4-(2-히드록시에톡시)페닐]부탄, 2,2-비스[4-(2-히드록시에톡시)페닐]-4-메틸 펜탄, 2,2-비스[4-(2-히드록시에톡시)페닐]옥탄, 1,1-비스[4-(2-히드록시에톡시)페닐]데칸, 2,2-비스[3-브로모-4-(2-히드록시에톡시)페닐]프로판, 2,2-비스[3-시클로헥실-4-(2-히드록시에톡시)페닐]프로판으로 예시하는 바와 같은, 비스(히드록시알콕시아릴)알칸류, 1,1-비스[4-(2-히드록시에톡시)페닐]시클로헥산, 1,1-비스[3-시클로헥실-4-(2-히드록시에톡시)페닐]시클로헥산, 1,1-비스[4-(2-히드록시에톡시)페닐]시클로펜탄으로 예시되는 바와 같은, 비스(히드록시알콕시아릴)시클로알칸류, 4,4'-비스(2-히드록시에톡시)디페닐에테르, 4,4'-비스(2-히드록시에톡시)-3,3'-디메틸디페닐에테르로 예시되는 바와 같은, 디히드록시알콕시디아릴에테르류, 4,4'-비스(2-히드록시에톡시페닐)술피드, 4,4'-비스[4-(2-디히드록시에톡시)-3-메틸페닐]술피드로 예시되는 바와 같은, 비스히드록시알콕시아릴술피드류, 4,4'-비스(2-히드록시에톡시페닐)술폭시드, 4,4'-비스[4-(2-디히드록시에톡시)-3-메틸페닐]술폭시드로 예시되는 바와 같은, 비스히드록시알콕시아릴술폭시드류, 4,4'-비스(2-히드록시에톡시페닐)술폰, 4,4'-비스[4-(2-디히드록시에톡시)-3-메틸페닐]술폰으로 예시되는 바와 같은, 비스히드록시알콕시아릴술폰류, 1,4-비스히드록시에톡시벤젠, 1,3-비스히드록시에톡시벤젠, 1,2-비스히드록시에톡시벤젠, 1,3-비스[2-[4-(2-히드록시에톡시)페닐]프로필]벤젠, 1,4-비스[2-[4-(2-히드록시에톡시)페닐]프로필]벤젠, 4,4'-비스(2-히드록시에톡시)비페닐, 1,3-비스[4-(2-히드록시에톡시)페닐]-5,7-디메틸아다만탄, 하기 식(4)으로 나타내어지는 디히드록시 화합물로 대표되는 무수 당알콜, 및 하기 일반식(6)으로 나타내어지는 스피로글리콜 등의 환상 에테르 구조를 갖는 화합물을 들 수 있고, 이것들은 단독으로 사용해도 좋고, 2종 이상을 조합시켜서 사용해도 좋다.More specifically, as the dihydroxy compound (A), for example, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyl) Roxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxy) Roxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-( 2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4- (2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, 9 A compound having an aromatic group in a side chain and an ether group bonded to an aromatic group in the main chain, as exemplified by ,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene, bis[4 -(2-hydroxyethoxy)phenyl]methane, bis[4-(2-hydroxyethoxy)phenyl]diphenylmethane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]ethane , 1,1-bis[4-(2-hydroxyethoxy)phenyl]-1-phenylethane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis [4-(2-hydroxyethoxy)-3-methylphenyl]propane, 2,2-bis[3,5-dimethyl-4-(2-hydroxyethoxy)phenyl]propane, 1,1-bis[ 4-(2-hydroxyethoxy)phenyl]-3,3,5-trimethylcyclohexane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,4-bis[ 4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,3-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 2,2-bis[4-(2-hydroxyethane) Toxy)-3-phenylphenyl]propane, 2,2-bis[(2-hydroxyethoxy)-3-isopropylphenyl]propane, 2,2-bis[3-tert-butyl-4-(2- Hydroxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]butane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]-4- Methyl pentane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]octane, 1,1-bis[4-(2-hydroxyethane) Toxy)phenyl]decane, 2,2-bis[3-bromo-4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[3-cyclohexyl-4-(2-hydroxyethane) Bis(hydroxyalkoxyaryl)alkanes, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,1-bis[3- as exemplified by oxy)phenyl]propane bis(hydroxyalkoxyaryl) as exemplified by cyclohexyl-4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclopentane ) cycloalkanes, 4,4'-bis(2-hydroxyethoxy)diphenyl ether, and 4,4'-bis(2-hydroxyethoxy)-3,3'-dimethyldiphenyl ether As such, dihydroxyalkoxydiaryl ethers, 4,4'-bis(2-hydroxyethoxyphenyl)sulfide, 4,4'-bis[4-(2-dihydroxyethoxy)-3 Bishydroxyalkoxyarylsulfides, 4,4'-bis(2-hydroxyethoxyphenyl)sulfoxide, 4,4'-bis[4-(2-) as exemplified by -methylphenyl]sulfide bishydroxyalkoxyarylsulfoxides, 4,4'-bis(2-hydroxyethoxyphenyl)sulfone, 4,4'- as exemplified by dihydroxyethoxy)-3-methylphenyl]sulfoxide Bishydroxyalkoxyarylsulfones, 1,4-bishydroxyethoxybenzene, 1,3-bishydrone, as exemplified by bis[4-(2-dihydroxyethoxy)-3-methylphenyl]sulfone Roxyethoxybenzene, 1,2-bishydroxyethoxybenzene, 1,3-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl]benzene, 1,4-bis[2-[ 4-(2-hydroxyethoxy)phenyl]propyl]benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, 1,3-bis[4-(2-hydroxyethoxy)phenyl ]-5,7-dimethyladamantane, anhydrous sugar alcohols represented by dihydroxy compounds represented by the following formula (4), and spiroglycol represented by the following formula (6), compounds having a cyclic ether structure These are mentioned, These may be used independently and may be used in combination of 2 or more type.
이들 디히드록시 화합물(A)은, 단독으로 사용해도 좋고, 2종 이상을 조합시켜서 사용해도 좋다. 본 발명에 있어서, 상기 식(4)으로 나타내어지는 디히드록시 화합물로서는, 입체 이성체의 관계에 있는, 이소소르비드, 이소만니드, 이소이데트를 들 수 있고, 이것들은 1종을 단독으로 사용해도 좋고, 2종 이상을 조합시켜서 사용해도 좋다.These dihydroxy compounds (A) may be used independently and may be used in combination of 2 or more type. In the present invention, examples of the dihydroxy compound represented by the formula (4) include isosorbide, isomannide, and isoidet, which have a stereoisomer relationship, and these compounds may be used alone It is good, and you may use it in combination of 2 or more type.
또, 디히드록시 화합물(A) 중, 자원으로서 풍부하게 존재하고, 용이하게 입수 가능한 여러가지 전분으로부터 제조되는 소르비톨을 탈수 축합해서 얻어지는 이소소르비드가, 입수 및 제조의 용이함, 광학 특성, 성형성의 면으로부터 가장 바람직하다. 본원 발명에 있어서는, 디히드록시 화합물(A)로서 이소소르비드가 적합하게 사용된다.In addition, among the dihydroxy compounds (A), isosorbide obtained by dehydration condensation of sorbitol produced from various starches, which is abundantly present as a resource and is readily available, is easy to obtain and manufacture, optical properties, and moldability. most preferred from In this invention, isosorbide is used suitably as a dihydroxy compound (A).
(디히드록시 화합물(B))(dihydroxy compound (B))
본 발명에 있어서는, 디히드록시 화합물로서 디히드록시 화합물(A) 이외의 디히드록시 화합물인 디히드록시 화합물(B)을 사용해도 좋다. 디히드록시 화합물(B)로서는, 예를 들면 지환식 디히드록시 화합물, 지방족 디히드록시 화합물, 옥시알킬렌글리콜류, 방향족 디히드록시 화합물, 환상 에테르 구조를 갖는 디올류를, 폴리카보네이트의 구성단위로 되는 디히드록시 화합물로서, 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물과 함께 사용할 수 있다.In the present invention, as the dihydroxy compound, a dihydroxy compound (B) which is a dihydroxy compound other than the dihydroxy compound (A) may be used. As the dihydroxy compound (B), for example, an alicyclic dihydroxy compound, an aliphatic dihydroxy compound, an oxyalkylene glycol, an aromatic dihydroxy compound, or a diol having a cyclic ether structure is used in the composition of the polycarbonate. As a dihydroxy compound used as a unit, it can be used together with a dihydroxy compound (A), for example, the dihydroxy compound represented by Formula (4).
본 발명에 사용할 수 있는 지환식 디히드록시 화합물로서는, 특별하게 한정되지 않지만, 바람직하게는, 통상 5원환 구조 또는 6원환 구조를 포함하는 화합물을 사용한다. 또한, 6원환 구조는 공유결합에 의해 의자형 또는 배형으로 고정되어 있어도 좋다. 지환식 디히드록시 화합물이 5원환 또는 6원환 구조임으로써, 얻어지는 폴리카보네이트의 내열성을 높게 할 수 있다. 지환식 디히드록시 화합물에 포함되는 탄소원자수는 통상 70 이하이며, 바람직하게는 50 이하, 보다 바람직하게는 30 이하이다. 이 값이 커질수록 내열성이 높아지지만, 합성이 곤란해지거나, 정제가 곤란해지거나, 비용이 고가이거나 한다. 탄소원자수가 작아질수록 정제하기 쉬워, 입수하기 쉬워진다.Although it does not specifically limit as an alicyclic dihydroxy compound which can be used for this invention, Preferably, the compound containing a 5-membered ring structure or a 6-membered ring structure is used normally. In addition, the 6-membered ring structure may be fixed in a chair shape or an embryo shape by a covalent bond. When the alicyclic dihydroxy compound has a 5-membered ring or 6-membered ring structure, the heat resistance of the obtained polycarbonate can be increased. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. Although heat resistance becomes high, so that this value becomes large, synthesis|combination becomes difficult, refinement|purification becomes difficult, or cost becomes expensive. It becomes easy to refine|purify and it becomes easy to obtain, so that the number of carbon atoms becomes small.
본 발명에서 사용할 수 있는 5원환 구조 또는 6원환 구조를 포함하는 지환식 디히드록시 화합물로서는, 구체적으로는, 하기 일반식 (II) 또는 (III)으로 나타내어지는 지환식 디히드록시 화합물을 들 수 있다.Specific examples of the alicyclic dihydroxy compound having a 5-membered ring structure or a 6-membered ring structure that can be used in the present invention include an alicyclic dihydroxy compound represented by the following general formula (II) or (III). there is.
HOCH2-R1-CH2OH (II)HOCH 2 -R 1 -CH 2 OH (II)
HO-R2-OH (III)HO-R 2 -OH (III)
(식 (II), (III) 중, R1, R2는 각각, 탄소수 4∼20의 시클로알킬렌기를 나타낸다.)(In formulas (II) and (III), R 1 and R 2 each represent a cycloalkylene group having 4 to 20 carbon atoms.)
상기 일반식(II)으로 나타내어지는 지환식 디히드록시 화합물인 시클로헥산디메탄올로서는, 일반식(II)에 있어서, R1이 하기 일반식(IIa)(식 중, R3은 탄소수 1∼12의 알킬기 또는 수소원자를 나타낸다.)으로 나타내어지는 여러가지의 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 1,2-시클로헥산디메탄올, 1,3-시클로헥산디메탄올, 1,4-시클로헥산디메탄올 등을 들 수 있다.As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the said general formula (II), in general formula (II), R< 1 > is following general formula (IIa) (wherein, R< 3 > is C1-C12) represents an alkyl group or a hydrogen atom of)). Specific examples of such substances include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.
상기 일반식(II)으로 나타내어지는 지환식 디히드록시 화합물인 트리시클로데칸디메탄올, 펜타시클로펜타데칸디메탄올로서는, 일반식(II)에 있어서, R1이 하기 일반식(IIb)(식 중, n은 0 또는 1을 나타낸다.)으로 나타내어지는 여러가지의 이성체를 포함한다.As tricyclodecanedimethanol and pentacyclopentadecanedimethanol which are alicyclic dihydroxy compounds represented by the general formula (II), in the general formula (II), R 1 is the following general formula (IIb) (wherein , n represents 0 or 1.).
상기 일반식(II)으로 나타내어지는 지환식 디히드록시 화합물인 데칼린디메탄올 또는, 트리시클로테트라데칸디메탄올로서는, 일반식(II)에 있어서, R1이 하기 일반식(IIc)(식 중, m은 0, 또는 1을 나타낸다.)으로 나타내어지는 여러가지의 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 2,6-데칼린디메탄올, 1,5-데칼린디메탄올, 2,3-데칼린디메탄올 등을 들 수 있다.As decalindimethanol or tricyclotetradecanedimethanol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), R 1 is the following general formula (IIc) (wherein, m represents 0 or 1.) and includes various isomers. Specific examples of such substances include 2,6-decalin dimethanol, 1,5-decalin dimethanol, and 2,3-decalin dimethanol.
또한, 상기 일반식(II)으로 나타내어지는 지환식 디히드록시 화합물인 노보네인디메탄올로서는, 일반식(II)에 있어서, R1이 하기 일반식(IId)으로 나타내어지는 여러가지의 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 2,3-노보네인디메탄올, 2,5-노보네인디메탄올 등을 들 수 있다.Moreover, as norbornein dimethanol which is an alicyclic dihydroxy compound represented by the said general formula (II), in general formula (II), R< 1 > includes various isomers represented by the following general formula (IId). . Specific examples of such substances include 2,3-norbornein dimethanol and 2,5-norbornein dimethanol.
일반식(II)으로 나타내어지는 지환식 디히드록시 화합물인 아다만탄디메탄올로서는, 일반식(II)에 있어서, R1이 하기 일반식(IIe)으로 나타내어지는 여러가지 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 1,3-아다만탄디메탄올 등을 들 수 있다.As adamantane dimethanol which is an alicyclic dihydroxy compound represented by general formula (II), in general formula (II), R< 1 > includes various isomers represented by the following general formula (IIe). Specific examples of this include 1,3-adamantane dimethanol and the like.
또한, 상기 일반식(III)으로 나타내어지는 지환식 디히드록시 화합물인 시클로헥산디올은, 일반식(III)에 있어서, R2가 하기 일반식(IIIa)(식 중, R3은 탄소수 1∼12의 알킬기 또는 수소원자를 나타낸다.)으로 나타내어지는 여러가지 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 1,2-시클로헥산디올, 1,3-시클로헥산디올, 1,4-시클로헥산디올, 2-메틸-1,4-시클로헥산디올 등을 들 수 있다.Moreover, in the cyclohexanediol which is an alicyclic dihydroxy compound represented by the said general formula (III), in general formula (III), R< 2 > is the following general formula (IIIa) (wherein, R< 3 > is C1-C10) 12 is an alkyl group or a hydrogen atom.) Specific examples of such substances include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.
상기 일반식(III)으로 나타내어지는 지환식 디히드록시 화합물인 트리시클로데칸디올, 펜타시클로펜타데칸디올로서는, 일반식(III)에 있어서, R2가 하기 일반식(IIIb)(식 중, n은 0 또는 1을 나타낸다.)으로 나타내어지는 여러가지 이성체를 포함한다.As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the general formula (III), in the general formula (III), R 2 is the following general formula (IIIb) (wherein n represents 0 or 1.).
상기 일반식(III)으로 나타내어지는 지환식 디히드록시 화합물인 데칼린디올 또는 트리시클로테트라데칸디올로서는, 일반식(III)에 있어서, R2가 하기 일반식(IIIc)(식 중, m은 0, 또는 1을 나타낸다.)으로 나타내어지는 여러가지 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 2,6-데칼린디올, 1,5-데칼린디올, 2,3-데칼린디올 등이 사용된다.As decalindiol or tricyclotetradecanediol which is an alicyclic dihydroxy compound represented by the general formula (III), in the general formula (III), R 2 is the following general formula (IIIc) (wherein m is 0) , or 1 is represented.) As such, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol, etc. are specifically used.
상기 일반식(III)으로 나타내어지는 지환식 디히드록시 화합물인 노보네인디올로서는, 일반식(III)에 있어서, R2가 하기 일반식(IIId)으로 나타내어지는 여러가지 이성체를 포함한다. 이러한 것으로서는, 구체적으로는 2,3-노보네인디올, 2,5-노보네인디올 등이 사용된다.As norborneindiol which is an alicyclic dihydroxy compound represented by the said general formula (III), in general formula (III), R< 2 > includes various isomers represented by the following general formula (IIId). As such, 2,3-norborneindiol, 2,5-norborneindiol, etc. are specifically used.
상기 일반식(III)으로 나타내어지는 지환식 디히드록시 화합물인 아다만탄디올로서는, 일반식(III)에 있어서, R2가 하기 일반식(IIIe)으로 나타내어지는 여러가지 이성체를 포함한다. 이러한 것으로서는 구체적으로는, 1,3-아다만탄디올 등이 사용된다.As adamantanediol which is an alicyclic dihydroxy compound represented by the said general formula (III), in general formula (III), R< 2 > includes various isomers represented by the following general formula (IIIe). As such, 1,3-adamantanediol or the like is specifically used.
상술한 지환식 디히드록시 화합물의 구체예 중, 특히, 시클로헥산디메탄올류, 트리시클로데칸디메탄올류, 아다만탄디올류, 펜타시클로펜타데칸디메탄올류가 바람직하고, 입수의 용이함, 취급의 용이함이라고 하는 관점으로부터, 1,4-시클로헥산디메탄올, 1,3-시클로헥산디메탄올, 1,2-시클로헥산디메탄올, 트리시클로데칸디메탄올이 바람직하다. 본원 발명에 있어서는, 디히드록시 화합물(B)로서 트리시클로데칸디메탄올이 적합하게 사용된다.Among the specific examples of the above-mentioned alicyclic dihydroxy compound, cyclohexanedimethanols, tricyclodecanedimethanols, adamantanediols, and pentacyclopentadecanedimethanols are preferable, and availability and handling are particularly preferred. 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecanedimethanol are preferable from a viewpoint of the ease of In the present invention, tricyclodecanedimethanol is preferably used as the dihydroxy compound (B).
본 발명에 사용할 수 있는 지방족 디히드록시 화합물로서는, 예를 들면, 에틸렌글리콜, 1,3-프로판디올, 1,2-프로판디올, 1,4-부탄디올, 1,3-부탄디올, 1,2-부탄디올, 1,5-헵탄디올, 1,6-헥산디올을 들 수 있다. 본 발명에 사용할 수 있는 옥시알킬렌글리콜류로서는, 예를 들면, 디에틸렌글리콜, 트리에틸렌글리콜, 테트라에틸렌글리콜, 폴리에틸렌글리콜을 들 수 있다.Examples of the aliphatic dihydroxy compound usable in the present invention include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2- butanediol, 1,5-heptanediol, and 1,6-hexanediol are mentioned. Examples of the oxyalkylene glycols usable in the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol.
본 발명에 사용할 수 있는 방향족 디히드록시 화합물로서는, 예를 들면, 2,2-비스(4-히드록시페닐)프로판[=비스페놀A], 2,2-비스(4-히드록시-3,5-디메틸페닐)프로판, 2,2-비스(4-히드록시-3,5-디에틸페닐)프로판, 2,2-비스(4-히드록시-(3,5-디페닐)페닐)프로판, 2,2-비스(4-히드록시-3,5-디브로모페닐)프로판, 2,2-비스(4-히드록시페닐)펜탄, 2,4'-디히드록시-디페닐메탄, 비스(4-히드록시페닐)메탄, 비스(4-히드록시-5-니트로페닐)메탄, 1,1-비스(4-히드록시페닐)에탄, 3,3-비스(4-히드록시페닐)펜탄, 1,1-비스(4-히드록시페닐)시클로헥산, 비스(4-히드록시페닐)술폰, 2,4'-디히드록시디페닐술폰, 비스(4-히드록시페닐)술피드, 4,4'-디히드록시디페닐에테르, 4,4'-디히드록시-3,3'-디클로로디페닐에테르, 4,4'-디히드록시-2,5-디에톡시디페닐에테르, 9,9-비스[4-(2-히드록시에톡시)페닐]플루오렌, 9,9-비스[4-(2-히드록시에톡시-2-메틸)페닐]플루오렌, 9,9-비스(4-히드록시페닐)플루오렌, 9,9-비스(4-히드록시-2-메틸페닐)플루오렌을 들 수 있다.Examples of the aromatic dihydroxy compound usable in the present invention include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5). -dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane , 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 4 ,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 9 ,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy-2-methyl)phenyl]fluorene, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are mentioned.
본 발명에 사용할 수 있는 환상 에테르 구조를 갖는 디올류로서는, 예를 들면, 스피로글리콜류, 디옥산글리콜류를 들 수 있다. 또, 상기 예시 화합물은, 본 발명에 사용할 수 있는 지환식 디히드록시 화합물, 지방족 디히드록시 화합물, 옥시알킬렌글리콜류, 방향족 디히드록시 화합물, 환상 에테르 구조를 갖는 디올류의 일례이며, 조금도 이것들에 한정되는 것은 아니다. 이들 화합물은, 1종 또는 2종 이상을 식(4)으로 나타내어지는 디히드록시 화합물과 함께 사용할 수 있다.Examples of the diols having a cyclic ether structure that can be used in the present invention include spiroglycols and dioxane glycols. In addition, the above exemplary compound is an example of an alicyclic dihydroxy compound, an aliphatic dihydroxy compound, an oxyalkylene glycol, an aromatic dihydroxy compound, and a diol having a cyclic ether structure that can be used in the present invention. It is not limited to these. These compounds can be used 1 type, or 2 or more types together with the dihydroxy compound represented by Formula (4).
이들 디히드록시 화합물(B)을 사용함으로써, 용도에 따른 유연성의 개선, 내열성의 향상, 성형성의 개선 등의 효과를 얻을 수 있다. 본 발명에 따른 폴리카보네이트 수지를 구성하는 전체 디히드록시 화합물에 대한 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물의 비율은 특별하게 한정되지 않지만, 바람직하게는 10몰% 이상, 보다 바람직하게는 40몰% 이상, 더 바람직하게는 60몰% 이상, 바람직하게는 90몰% 이하, 보다 바람직하게는 80몰% 이하, 더 바람직하게는 70몰% 이하이다. 다른 디히드록시 화합물에 유래하는 구성단위의 함유 비율이 지나치게 많으면, 광학 특성 등의 성능을 저하시키거나 할 경우가 있다.By using these dihydroxy compounds (B), effects such as improvement of flexibility, improvement of heat resistance and improvement of moldability according to the use can be obtained. The ratio of the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4) to the total dihydroxy compounds constituting the polycarbonate resin according to the present invention is not particularly limited, but preferably is 10 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less. . When there is too much content rate of the structural unit derived from another dihydroxy compound, performance, such as an optical characteristic, may fall.
상기 다른 디히드록시 화합물 중에서, 지환식 디히드록시 화합물을 사용할 경우, 폴리카보네이트를 구성하는 전체 디히드록시 화합물에 대한 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물과 지환식 디히드록시 화합물의 합계의 비율은 특별하게 한정되지 않지만, 바람직하게는 80몰% 이상, 보다 바람직하게는 90몰% 이상, 더 바람직하게는 95몰% 이상이다.Among the other dihydroxy compounds, when an alicyclic dihydroxy compound is used, the dihydroxy compound (A) relative to all the dihydroxy compounds constituting the polycarbonate, for example, the dihydroxy compound represented by the formula (4) Although the ratio of the total of a hydroxy compound and an alicyclic dihydroxy compound is not specifically limited, Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more.
또한, 본 발명에 따른 폴리카보네이트 수지에 있어서의, 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위와 지환식 디히드록시 화합물에 유래하는 구성단위의 함유 비율에 대해서는, 임의의 비율로 선택할 수 있지만, 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위:지환식 디히드록시 화합물에 유래하는 구성단위=1:99∼99:1(몰%)이 바람직하고, 특히 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위:지환식 디히드록시 화합물에 유래하는 구성단위=10:90∼90:10(몰%)인 것이 바람직하다. 상기 범위보다 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위가 많고 지환식 디히드록시 화합물에 유래하는 구성단위가 적으면 착색하기 쉬워지고, 반대로 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위가 적고 지환식 디히드록시 화합물에 유래하는 구성단위가 많으면 분자량이 많아지기 어려워지는 경향이 있다.Further, in the polycarbonate resin according to the present invention, the dihydroxy compound (A), for example, a structural unit derived from a dihydroxy compound represented by formula (4) and an alicyclic dihydroxy compound derived from The content ratio of the structural unit can be selected at any ratio, but the structural unit derived from the dihydroxy compound represented by formula (4): the structural unit derived from the alicyclic dihydroxy compound = 1:99 to 99 :1 (mol%) is preferable, and in particular, structural unit derived from the dihydroxy compound represented by formula (4): structural unit derived from an alicyclic dihydroxy compound = 10:90 to 90:10 (mol%) ) is preferred. If there are more structural units derived from the dihydroxy compound represented by formula (4) than the above range and fewer constitutional units derived from the alicyclic dihydroxy compound, coloration becomes easier, and conversely, the dihydroxy compound represented by formula (4) When the number of structural units derived from the hydroxy compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight tends to be difficult to increase.
또한, 지방족 디히드록시 화합물, 옥시알킬렌글리콜류, 방향족 디히드록시 화합물, 환상 에테르 구조를 갖는 디올류를 사용할 경우, 폴리카보네이트를 구성하는 전체 디히드록시 화합물에 대한 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물과 이것들의 각 디히드록시 화합물의 합계의 비율은 특별하게 한정되지 않고, 임의의 비율로 선택할 수 있다. 또한, 디히드록시 화합물(A), 예를 들면 식(4)으로 나타내어지는 디히드록시 화합물에 유래하는 구성단위와 이것들의 각 디히드록시 화합물에 유래하는 구성단위의 함유 비율도 특별하게 한정되지 않고, 임의의 비율로 선택할 수 있다.In addition, when an aliphatic dihydroxy compound, oxyalkylene glycol, aromatic dihydroxy compound, or diol having a cyclic ether structure is used, the dihydroxy compound (A) relative to all the dihydroxy compounds constituting the polycarbonate , For example, the ratio of the sum total of the dihydroxy compound represented by Formula (4) and each dihydroxy compound of these is not specifically limited, It can select by arbitrary ratios. In addition, the content ratio of the structural unit derived from the dihydroxy compound (A), for example, the dihydroxy compound represented by Formula (4), and the structural units derived from each of these dihydroxy compounds is not particularly limited. and may be selected at any ratio.
폴리카보네이트계 수지의 상세는, 예를 들면 일본 특허공개 2012-31370호 공보(일본 특허 제5448264호)에 기재되어 있다. 상기 특허문헌의 기재는, 본 명세서에 참고로서 원용된다.The detail of polycarbonate-type resin is described in Unexamined-Japanese-Patent No. 2012-31370 (Japanese Patent No. 5448264), for example. The description of the said patent document is taken in in this specification as a reference.
C. 위상차 필름의 제조 방법C. Manufacturing method of retardation film
본 발명의 실시형태에 의한 위상차 필름의 제조 방법은, 수지 필름을 연신 처리하는 것을 포함한다. 수지 필름은, 상기 C항에서 설명한 폴리카보네이트 수지로부터 형성된 필름이다.The manufacturing method of the retardation film by embodiment of this invention includes the extending|stretching process of a resin film. The resin film is a film formed from the polycarbonate resin described in the above section C.
하나의 실시형태에 있어서는, 위상차 필름은 2축 연신에 의해 제작될 수 있다. 2축 연신은 동시 2축 연신이라도 좋고, 축차 2축 연신이라도 좋다. 길이 방향의 연신 배율은, 바람직하게는 1.0배를 초과하고 2.0배 이하이며, 보다 바람직하게는 1.1배∼1.5배이다. 폭 방향의 연신 배율은, 바람직하게는 1.6배∼2.2배이며, 보다 바람직하게는 1.8배∼2.0배이다. 상기 폴리카보네이트 수지로부터 형성된 필름을 이러한 연신 배율로 연신함으로써, 소망의 광학 특성 뿐만 아니라, 매우 우수한 기계적 특성(예를 들면, 굴곡성, 내크랙성)을 실현할 수 있다.In one embodiment, the retardation film can be produced by biaxial stretching. Simultaneous biaxial stretching may be sufficient as biaxial stretching, and sequential biaxial stretching may be sufficient as it. The draw ratio of the longitudinal direction becomes like this. Preferably it exceeds 1.0 time and is 2.0 times or less, More preferably, they are 1.1 times - 1.5 times. The draw ratio of the width direction becomes like this. Preferably they are 1.6 times - 2.2 times, More preferably, they are 1.8 times - 2.0 times. By stretching the film formed from the polycarbonate resin at such a draw ratio, not only desired optical properties but also extremely excellent mechanical properties (eg, flexibility and crack resistance) can be realized.
상기 수지 필름의 연신 온도는, 바람직하게는 Tg-30℃∼Tg+30℃이며, 보다 바람직하게는 Tg-10℃∼Tg+25℃이며, 더 바람직하게는 Tg+8℃∼Tg+20℃이다. 이러한 온도로 연신함으로써, 본 발명에 있어서 적절한 특성을 갖는 위상차 필름이 얻어질 수 있다. 또, Tg는 필름의 구성 재료의 유리전이온도이다.The stretching temperature of the resin film is preferably Tg-30°C to Tg+30°C, more preferably Tg-10°C to Tg+25°C, still more preferably Tg+8°C to Tg+20°C. am. By stretching at such a temperature, a retardation film having suitable properties in the present invention can be obtained. In addition, Tg is the glass transition temperature of the constituent material of a film.
D. 위상차층 부착 편광판D. Polarizing plate with retardation layer
상기 A항∼C항에 기재된 위상차 필름은, 다른 위상차 필름 및/또는 광학 부재와의 적층체로서 제공될 수 있다. 하나의 실시형태에 있어서는, 위상차 필름은 편광판과의 적층체(위상차층 부착 편광판)로서 제공될 수 있다. 따라서, 본 발명은 상기 위상차 필름을 갖는 위상차층 부착 편광판을 포함한다. 위상차 필름에 있어서, 편광판의 편광자의 흡수축과 위상차 필름의 지상축이 이루는 각도는, 용도 및 목적에 따라 적절하게 설정될 수 있다. 하나의 실시형태에 있어서는, 상기 각도는, 바람직하게는 40°∼50°이며, 보다 바람직하게는 42°∼48°이며, 더 바람직하게는 약 45°이다.The retardation film according to the above items A to C may be provided as a laminate with another retardation film and/or an optical member. In one embodiment, retardation film can be provided as a laminated body with a polarizing plate (polarizing plate with retardation layer). Accordingly, the present invention includes a polarizing plate with a retardation layer having the retardation film. In the retardation film, the angle between the absorption axis of the polarizer of the polarizing plate and the slow axis of the retardation film may be appropriately set according to the purpose and use. In one embodiment, the angle is preferably 40° to 50°, more preferably 42° to 48°, still more preferably about 45°.
위상차층 부착 편광판은, 대표적으로는, 편광자와, 편광자의 적어도 편면에 접착제층을 개재해서 접합된 상기 위상차 필름을 갖는다. 상기 편광자에 있어서는, 편광자의 적어도 편면에 보호층을 갖고 있어도 좋다. 또한, 상기 편광판의 시인측과 반대측의 면에 점착제층 및 세퍼레이터를 갖고 있어도 좋다.A polarizing plate with a retardation layer typically has a polarizer and the said retardation film bonded by the at least single side|surface of a polarizer via an adhesive bond layer. In the said polarizer, you may have a protective layer on at least single side|surface of a polarizer. Moreover, you may have an adhesive layer and a separator in the surface on the opposite side to the visual recognition side of the said polarizing plate.
편광자로서는, 임의의 적절한 편광자가 채용될 수 있다. 예를 들면, 편광자를 형성하는 수지 필름은 단층의 수지 필름이라도 좋고, 2층 이상의 적층체라도 좋다.As the polarizer, any suitable polarizer may be employed. For example, a single-layered resin film may be sufficient as the resin film which forms a polarizer, and the laminated body of two or more layers may be sufficient as it.
단층의 수지 필름으로 구성되는 편광자의 구체예로서는, 폴리비닐알콜(PVA)계 필름, 부분 포르말화 PVA계 필름, 에틸렌·아세트산 비닐 공중합체계 부분 비누화 필름 등의 친수성 고분자 필름에, 요오드나 이색성 염료 등의 이색성 물질에 의한 염색 처리 및 연신 처리가 실시된 것, PVA의 탈수 처리물이나 폴리염화비닐의 탈염산 처리물 등 폴리엔계 배향 필름 등을 들 수 있다. 바람직하게는, 광학 특성이 뛰어난 것으로부터, PVA계 필름을 요오드로 염색하여 1축 연신해서 얻어진 편광자가 사용된다.As a specific example of a polarizer composed of a single-layer resin film, a polyvinyl alcohol (PVA)-based film, a partially formalized PVA-based film, and a hydrophilic polymer film such as an ethylene/vinyl acetate copolymer-based partially saponified film, iodine, dichroic dye, etc. polyene-based oriented films such as those subjected to the dyeing treatment and stretching treatment with a dichroic substance of PVA and dehydrochloric acid treatment products of PVA and polyvinyl chloride. Preferably, since it is excellent in an optical characteristic, the polarizer obtained by dyeing a PVA-type film with iodine and carrying out uniaxial stretching is used.
상기 요오드에 의한 염색은, 예를 들면 PVA계 필름을 요오드 수용액에 침지시킴으로써 행하여진다. 상기 1축 연신의 연신 배율은, 바람직하게는 3∼7배이다. 연신은 염색 처리 후에 행해도 좋고, 염색하면서 행해도 좋다. 또한, 연신하고나서 염색해도 좋다. 필요에 따라서, PVA계 필름에, 팽윤 처리, 가교 처리, 세정 처리, 건조 처리 등이 실시된다. 예를 들면, 염색 전에 PVA계 필름을 물에 침지해서 수세 함으로써 PVA계 필름 표면의 오염이나 블록킹 방지제를 세정할 수 있을 뿐 아니라, PVA계 필름을 팽윤시켜서 염색 불균일 등을 방지할 수 있다.The dyeing with the iodine is performed, for example, by immersing the PVA-based film in an aqueous iodine solution. The draw ratio of the said uniaxial stretching becomes like this. Preferably it is 3 to 7 times. Extending|stretching may be performed after a dyeing process, and may be performed, dyeing|staining. Moreover, after extending|stretching, you may dye|dye. A swelling process, a crosslinking process, a washing process, a drying process, etc. are given to a PVA-type film as needed. For example, by immersing the PVA-based film in water and washing with water before dyeing, it is possible to not only wash the surface of the PVA-based film from stains and anti-blocking agents, but also to swell the PVA-based film to prevent uneven coloring.
적층체를 이용하여 얻어지는 편광자의 구체예로서는, 수지 기재와 상기 수지 기재에 적층된 PVA계 수지층(PVA계 수지 필름)의 적층체, 또는, 수지 기재와 상기 수지 기재에 도포 형성된 PVA계 수지층의 적층체를 이용하여 얻어지는 편광자를 들 수 있다. 이러한 편광자의 제조 방법의 상세는, 예를 들면, 일본 특허공개 2012-73580호 공보(일본 특허 제5414738호) 등에 기재되어 있다. 상기 특허문헌의 기재는 본 명세서에 참고로서 원용된다. 상기 공보는 그 전체의 기재가 본 명세서에 참고로서 원용된다.As a specific example of a polarizer obtained using a laminate, a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and a PVA-based resin layer coated on the resin substrate. The polarizer obtained using a laminated body is mentioned. The detail of the manufacturing method of such a polarizer is described in Unexamined-Japanese-Patent No. 2012-73580 (Japanese Patent No. 5414738) etc., for example. The description of the above patent document is incorporated herein by reference. The above publication is incorporated herein by reference in its entirety.
하나의 실시형태에 있어서는, 편광자의 두께는, 바람직하게는 1㎛∼25㎛이며, 보다 바람직하게는 3㎛∼10㎛이며, 더 바람직하게는 3㎛∼8㎛이다. 편광자의 두께가 이러한 범위이면, 가열시의 컬을 양호하게 억제할 수 있고, 및, 양호한 가열시의 외관 내구성이 얻어진다.In one embodiment, the thickness of a polarizer becomes like this. Preferably they are 1 micrometer - 25 micrometers, More preferably, they are 3 micrometers - 10 micrometers, More preferably, they are 3 micrometers - 8 micrometers. Curl|Karl at the time of a heating can be suppressed favorably as the thickness of a polarizer is such a range, and favorable external appearance durability at the time of a heating is acquired.
보호층은 편광자를 보호하는 필름으로서 사용할 수 있는 임의의 적절한 보호 필름으로 형성된다. 상기 보호 필름의 주성분이 되는 재료의 구체예로서는, 트리아세틸셀룰로오스(TAC) 등의 셀룰로오스계 수지나, 폴리에스테르계, 폴리비닐알콜계, 폴리카보네이트계, 폴리아미드계, 폴리이미드계, 폴리에테르술폰계, 폴리술폰계, 폴리스티렌계, 폴리노보넨계, 폴리올레핀계, (메타)아크릴계, 아세테이트계 등의 투명 수지 등을 들 수 있다. 또한, (메타)아크릴계, 우레탄계, (메타)아크릴우레탄계, 에폭시계, 실리콘계 등의 열경화형 수지 또는 자외선 경화형 수지 등도 들 수 있다. 이 밖에도, 예를 들면, 실록산계 폴리머 등의 유리질계 폴리머도 들 수 있다. 또한, 일본 특허공개 2001-343529호 공보(WO01/37007)에 기재된 폴리머 필름도 사용할 수 있다. 이 필름의 재료로서는, 예를 들면, 측쇄에 치환 또는 비치환의 이미드기를 갖는 열가소성 수지와, 측쇄에 치환 또는 비치환의 페닐기 및 니트릴기를 갖는 열가소성 수지를 함유하는 수지 조성물을 사용할 수 있고, 예를 들면, 이소부텐과 N-메틸말레이미드로 이루어지는 교호 공중합체와, 아크릴로니트릴·스티렌 공중합체를 갖는 수지 조성물을 들 수 있다. 상기 폴리머 필름은, 예를 들면 상기 수지 조성물의 압출 성형물일 수 있다.The protective layer is formed of any suitable protective film that can be used as a film for protecting the polarizer. Specific examples of the material used as the main component of the protective film include cellulose resins such as triacetyl cellulose (TAC), polyester, polyvinyl alcohol, polycarbonate, polyamide, polyimide, and polyethersulfone. and transparent resins such as polysulfone-based, polystyrene-based, polynorbornene-based, polyolefin-based, (meth)acrylic-based and acetate-based resins. Moreover, thermosetting resins, such as (meth)acrylic type, a urethane type, (meth)acrylic type urethane type, an epoxy type, a silicone type, or ultraviolet curable resin, etc. are mentioned. In addition, for example, glassy polymers, such as a siloxane type polymer, are mentioned. Moreover, the polymer film described in Unexamined-Japanese-Patent No. 2001-343529 (WO01/37007) can also be used. As a material for this film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used, for example, , a resin composition comprising an alternating copolymer comprising isobutene and N-methylmaleimide and an acrylonitrile/styrene copolymer. The polymer film may be, for example, an extrusion molding of the resin composition.
보호층의 두께는, 바람직하게는 10㎛∼100㎛이다. 보호층은 접착층(구체적으로는, 접착제층, 점착제층)을 개재해서 편광자에 적층되어 있어도 되고, 편광자에 밀착(접착층을 개재하지 않고) 적층되어 있어도 된다. 필요에 따라서, 위상차층 부착 편광판의 최표면에 배치되는 보호층에는, 하드코트층, 방현층 및 반사 방지층 등의 표면 처리층이 형성될 수 있다.The thickness of the protective layer is preferably 10 µm to 100 µm. The protective layer may be laminated on the polarizer via an adhesive layer (specifically, an adhesive layer, an adhesive layer), or may be laminated on the polarizer in close contact (without interposing an adhesive layer). Surface treatment layers, such as a hard-coat layer, a glare-proof layer, and an antireflection layer, may be formed in the protective layer arrange|positioned at the outermost surface of a polarizing plate with a retardation layer as needed.
상기 위상차층 부착 편광판은 화상 표시 장치의 시인측에 사용될 수 있다. 또한, 상기 위상차층 부착 편광판에 있어서의 위상차층은, 시인측에 배치되어도 좋고, 표시셀측에 배치되어도 좋다.The polarizing plate with a retardation layer may be used on the viewing side of an image display device. In addition, the retardation layer in the said polarizing plate with a retardation layer may be arrange|positioned at the visual recognition side, and may be arrange|positioned at the display cell side.
점착제층을 형성하는 점착제로서는, 임의의 적절한 점착제가 채용될 수 있다. 점착제의 베이스 수지로서는, 예를 들면 아크릴계 수지, 스티렌계 수지, 실리콘계 수지, 우레탄계 수지, 고무계 수지를 들 수 있다. 이러한 베이스 수지는, 예를 들면, 일본 특허공개 2015-120337호 공보(일본 특허 제6457789호) 또는 일본 특허공개 2011-201983호 공보에 기재되어 있다. 이들 공보의 기재는, 본 명세서에 참고로서 원용된다. 점착제에 포함될 수 있는 가교제로서는, 예를 들면, 이소시아네이트 화합물, 에폭시 화합물, 아지리딘 화합물을 들 수 있다. 점착제는, 예를 들면, 실란커플링제를 포함하고 있어도 좋다. 점착제의 배합 처방은, 목적 및 소망의 특성에 따라 적절하게 설정될 수 있다.As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, any suitable pressure-sensitive adhesive may be employed. As base resin of an adhesive, an acrylic resin, a styrene resin, a silicone resin, a urethane resin, and a rubber-type resin are mentioned, for example. Such a base resin is described in, for example, Japanese Patent Application Laid-Open No. 2015-120337 (Japanese Patent No. 6457789) or Japanese Patent Application Laid-Open No. 2011-201983. The description of these publications is incorporated herein by reference. As a crosslinking agent which can be contained in an adhesive, an isocyanate compound, an epoxy compound, and an aziridine compound are mentioned, for example. The pressure-sensitive adhesive may contain, for example, a silane coupling agent. The formulation of the pressure-sensitive adhesive may be appropriately set according to the purpose and desired characteristics.
점착제층의 저장탄성률은, 바람직하게는 1.0×104Pa∼1.0×107Pa이며, 보다 바람직하게는 2.0×104Pa∼5.0×106Pa이다. 점착제층의 저장탄성률이 이러한 범위이면, 롤 형성시의 블록킹을 억제할 수 있다. 또, 저장탄성률은, 예를 들면, 온도 23℃ 및 각속도 0.1rad/s에서의 동적 점탄성 측정으로부터 구할 수 있다.The storage modulus of the pressure-sensitive adhesive layer is preferably 1.0×10 4 Pa to 1.0×10 7 Pa, more preferably 2.0×10 4 Pa to 5.0×10 6 Pa. Blocking at the time of roll formation can be suppressed as the storage modulus of an adhesive layer is this range. In addition, the storage modulus can be calculated|required from the dynamic viscoelasticity measurement at a temperature of 23 degreeC and angular velocity of 0.1 rad/s, for example.
점착제층의 두께는, 바람직하게는 1㎛∼60㎛이며, 보다 바람직하게는 3㎛∼30㎛이다. 두께가 지나치게 얇으면 점착성이 불충분하게 되고, 점착 계면에 기포 등이 들어갈 경우가 있다. 두께가 지나치게 두꺼우면 점착제가 밀려나오는 등의 불량이 생기기 쉬워진다.The thickness of an adhesive layer becomes like this. Preferably they are 1 micrometer - 60 micrometers, More preferably, they are 3 micrometers - 30 micrometers. When thickness is too thin, adhesiveness will become inadequate, and a bubble etc. may enter into an adhesion interface. When thickness is too thick, it will become easy to produce defects, such as an adhesive protruding.
실용적으로는, 위상차 필름이 실제로 사용되기까지의 동안, 점착제층 표면에 세퍼레이터가 박리 가능하게 가부착되어 있다. 세퍼레이터로서는, 예를 들면, 실리콘계 박리제, 불소계 박리제, 장쇄 알킬아크릴레이트계 박리제 등의 박리제에 의해 표면 코트된 플라스틱(예를 들면, 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌, 폴리프로필렌) 필름, 부직포 또는 종이 등을 들 수 있다. 세퍼레이터의 두께는, 목적에 따라서 임의의 적절한 두께를 채용할 수 있다. 세퍼레이터의 두께는, 예를 들면 10㎛∼100㎛이다.Practically, while the retardation film is actually used, the separator is temporarily affixed to the pressure-sensitive adhesive layer surface so that peeling is possible. As the separator, for example, a plastic (e.g., polyethylene terephthalate (PET), polyethylene, polypropylene) film, nonwoven fabric or paper coated with a release agent such as a silicone-based release agent, a fluorine-based release agent, or a long-chain alkyl acrylate-based release agent. and the like. Any appropriate thickness can be employ|adopted for the thickness of a separator according to the objective. The thickness of the separator is, for example, 10 µm to 100 µm.
(실시예)(Example)
이하, 실시예에 의해 본 발명을 구체적으로 설명하지만, 본 발명은 이들 실시예에 의해 한정되는 것은 아니다. 또, 각 특성의 측정 방법 및 평가 방법은 하기와 같다.Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In addition, the measuring method and evaluation method of each characteristic are as follows.
(1) 면내 위상차 및 파장 분산 특성(1) In-plane retardation and wavelength dispersion characteristics
실시예 및 비교예에서 얻어진 위상차 필름을 길이 4㎝ 및 폭 4㎝로 잘라내어 측정 시료로 했다. 상기 측정 시료에 대해서, Axometrics사제, 제품명「Axoscan」 을 이용하여 면내 위상차 Re(550)를 측정했다. 또한, Re(450)도 측정하고, Re(450)/Re(550)를 산출했다.The retardation film obtained by the Example and the comparative example was cut out to 4 cm in length and 4 cm in width, and it was set as the measurement sample. About the said measurement sample, the in-plane retardation Re (550) was measured using the Axometrics company make and product name "Axoscan". Moreover, Re(450) was also measured, and Re(450)/Re(550) was computed.
(2) 두께(2) thickness
10㎛ 이하의 두께는, 간섭 막후계(오츠카 덴시사제, 제품명「MCPD-3000」)를 사용해서 측정했다. 10㎛를 초과하는 두께는 디지털 마이크로미터(안리쓰사제, 제품명「KC-351C」)를 이용하여 측정했다.The thickness of 10 µm or less was measured using an interference film thickness meter (manufactured by Otsuka Denshi Corporation, product name “MCPD-3000”). The thickness exceeding 10 µm was measured using a digital micrometer (manufactured by Anritsu Corporation, product name “KC-351C”).
(3) 투습도(3) moisture permeability
실시예 및 비교예에서 얻어진 위상차 필름에 대해서, JIS Z0208의 투습도 시험(컵법)에 준거하여, 온도 40℃, 습도 92% RH의 분위기 중, 면적 1㎡의 시료를 24시간에 통과하는 수증기량(g)을 측정했다.Regarding the retardation films obtained in Examples and Comparative Examples, based on the water vapor transmission rate test (cup method) of JIS Z0208, in an atmosphere at a temperature of 40° C. and a humidity of 92% RH, the amount of water vapor passing through a sample having an area of 1 m 2 in 24 hours (g ) was measured.
(4) 위상차 변화(4) Phase difference change
실시예 및 비교예에서 얻어진 위상차 필름을, 5㎝×5㎝로 잘라내고, 한쪽의 면에 점착제를 핸드 롤러로 붙이고, 점착제면을 알칼리 유리의 편면에 붙여서 시험편을 얻었다. 시험편을 온도 65℃ 또한 습도 90%의 오븐에 500시간 보존(가습 시험)하고, 시험 개시 전 및 시험 후의 위상차 변화(%)를 산출했다.The retardation film obtained in the Example and the comparative example was cut out to 5 cm x 5 cm, the adhesive was affixed on one side with a hand roller, the adhesive side was pasted on the single side|surface of alkali glass, and the test piece was obtained. The test piece was stored in an oven at a temperature of 65°C and a humidity of 90% for 500 hours (humidification test), and the phase difference change (%) before the start of the test and after the test was calculated.
(5) 위상차의 편차(5) Deviation of phase difference
(1)과 마찬가지로, 실시예 및 비교예에서 얻어진 위상차 필름의 면내 위상차 Re(550)를 측정했다. 위상차 필름의 폭 방향에 대하여 9점 측정을 행하고, 위상차값의 최대값과 최소값의 차를 위상차의 편차로 했다.Similarly to (1), the in-plane retardation Re(550) of the retardation films obtained in Examples and Comparative Examples was measured. 9 points|pieces were measured with respect to the width direction of retardation film, and the difference of the maximum value and minimum value of retardation value was made into the dispersion|variation of retardation.
(6) 돌자탄성률(6) stony elastic modulus
돌자탄성률은, 니들(돌자 지그)을 위상차 필름의 주면에 대하여 수직으로 찔렀을 때에, 실시예 및 비교예에서 얻어진 위상차 필름이 파단되기(또는 찢어지기) 직전의 힘(gf)을, 그 때의 변형(㎜)으로 나누어서 구했다. 니들로서는, 선단지름이 1㎜φ, 0.5R인 것을 사용했다. 니들을 찌르는 속도는 0.33㎝/초로 했다. 상기 측정은 온도 23℃의 환경 하에서 행하였다.The puncture elastic modulus is the force (gf) immediately before the retardation film obtained in Examples and Comparative Examples is broken (or torn) when a needle (piercing jig) is punctured perpendicularly to the main surface of the retardation film, at that time It was obtained by dividing by the strain (mm). As the needle, one having a tip diameter of 1 mmφ and 0.5R was used. The needle piercing speed was set to 0.33 cm/sec. The said measurement was performed in the environment of the temperature of 23 degreeC.
(7) 돌자강도(7) piercing strength
선단지름 1㎜φ, 0.5R의 니들을 장착한 시험기를 사용했다. 중앙에 원형의 구멍이 뚫린 2개의 지그로 위상차 필름을 끼워서, 위상차 필름을 시험기에 고정했다. 니들을 위상차 필름에 대하여, 상기 지그의 구멍을 지나도록 수직으로 강하시켜서, 위상차 필름이 깨졌을 때의 강도를 측정했다. 시험 조건은, 온도 23±3℃의 환경 하, 돌자속도 0.33㎝/초로 했다. 시험 12개에 대하여 돌자 시험을 행하고, 그 평균값을 위상차 필름의 두께로 나눔으로써, 위상차 필름의 단위막두께당의 돌자강도를 구했다.A testing machine equipped with a needle having a tip diameter of 1 mmφ and 0.5R was used. The retardation film was sandwiched by two jigs with a circular hole in the center, and the retardation film was fixed to the testing machine. The needle was vertically lowered with respect to the retardation film so as to pass through the hole of the jig, and the strength when the retardation film was broken was measured. The test conditions were an environment with a temperature of 23±3°C, and a piercing speed of 0.33 cm/sec. The puncture test was performed about 12 tests, and the puncture strength per unit film thickness of retardation film was calculated|required by dividing the average value by the thickness of retardation film.
(8) 파단강도 및 파단신도(8) Breaking strength and breaking elongation
실시예 및 비교예에서 얻어진 위상차 필름을, 폭 1㎝×길이 13㎝로 절단한 후, 인장시험기로서 「오토그래프 ASG-50D형」(시마즈 세이사쿠쇼제)을 사용하고, 인장속도 200㎜/min, 척간 거리 50㎜, 실온(23℃)에서 인장시험을 행하여, 위상차 필름이 파단했을 때의 응력을 구해서 파단강도로 하고, 위상차 필름이 파단했을 때의 변형(신장율)을 구해서 파단강도로 했다.After the retardation films obtained in Examples and Comparative Examples were cut to width 1 cm x length 13 cm, "Autograph ASG-50D type" (manufactured by Shimadzu Corporation) was used as a tensile tester, and a tensile rate of 200 mm/min. , a tensile test was performed at a distance between chucks of 50 mm and room temperature (23 ° C.), the stress when the retardation film was broken was determined as the breaking strength, and the strain (elongation) when the retardation film was broken was determined as the breaking strength.
(9) 접착성(9) Adhesiveness
실시예 및 비교예에서 얻어진 위상차 필름과 편광자를 접합하여 적층체를 얻었다. 얻어진 적층체를, 편광자의 연신 방향과 평행하게 200㎜, 직교 방향으로 15㎜의 크기로 잘라내고, 상기 적층체를 유리판에 접합했다. 그리고 위상차 필름과 편광자 사이에 커터 나이프로 절개를 넣고, 텐시론 만능 시험기 RTC(가부시키가이샤 에이 앤드 디사제)에 의해, 90도 방향으로 위상차 필름과 편광자를 박리속도 1000㎜/min으로 박리하고, 그 박리강도(N/15㎜)를 측정했다. 박리강도가 1N/15㎜ 이상일 경우를 양호, 1N/15㎜ 미만일 경우를 불량으로 했다.The retardation film and the polarizer obtained by the Example and the comparative example were bonded together, and the laminated body was obtained. The obtained laminated body was cut out in the magnitude|size of 200 mm in parallel to the extending|stretching direction of a polarizer, and 15 mm in an orthogonal direction, and the said laminated body was bonded to the glass plate. Then, an incision is made between the retardation film and the polarizer with a cutter knife, and the retardation film and the polarizer are peeled off at a peeling rate of 1000 mm/min in a 90 degree direction by a Tenshiron universal testing machine RTC (manufactured by A&D Corporation), The peel strength (N/15 mm) was measured. The case where the peeling strength was 1N/15mm or more was considered good, and the case where it was less than 1N/15mm was made into bad.
(10) 주행성(반송시의 공정 불량의 평가)(10) Runability (evaluation of process defects at the time of conveyance)
실시예 및 비교예에서 얻어진 위상차 필름을, 가이드 롤에 의해 5m/min∼40m/min 속도로 반송할 때에, 꺽임, 상처, 타흔 등 결점의 발생이 없으면(문제 없이 반송할 수 있으면) 양호, 꺽임, 상처, 타흔 등이 발생하는 경우에는 불량으로 했다.When the retardation film obtained in Examples and Comparative Examples is conveyed at a speed of 5 m/min to 40 m/min by a guide roll, if defects such as creases, scratches, and dents do not occur (if it can be conveyed without problems), good, wrinkled , it was set as defective when a wound, a dent, etc. generate|occur|produced.
(11) 굴곡성(MIT 시험)(11) Flexibility (MIT test)
MIT 시험은 JIS P 8115에 준거해 행하였다. 구체적으로는, 실시예 및 비교예에서 얻어진 위상차 필름을 길이 15㎝ 및 폭 1.5㎝로 잘라내어 측정 시료로 했다. 측정 시료를 MIT 내절 피로시험기 BE-202형(테스터 산교(주)제)에 부착하고(하중 1.0kgf, 클램프의 R: 0.38㎜), 시험 속도 90cpm 및 절곡 각도 90°로 반복해서 절곡을 행하여, 측정 시료가 파단했을 때의 절곡 횟수를 시험값으로 했다. 경험값이 500회 이상인 것을 양호, 500회 미만인 것을 불량으로 했다.The MIT test was performed based on JIS P 8115. Specifically, the retardation films obtained in Examples and Comparative Examples were cut out to a length of 15 cm and a width of 1.5 cm to obtain a measurement sample. Attach the measurement sample to the MIT bending fatigue tester BE-202 (manufactured by Tester Sangyo Co., Ltd.) (load 1.0 kgf, clamp R: 0.38 mm), and bend repeatedly at a test speed of 90 cpm and a bending angle of 90 °, The number of times of bending when the measurement sample fracture|ruptures was made into the test value. The thing of 500 or more times of an experience value was made into favorable, and the thing of less than 500 times was made defective.
(12) 색상 불균일(12) color unevenness
실시예 및 비교예에서 얻어진 위상차 필름과 편광자를 접합하여 적층체를 얻었다. 상기 적층체를 소정 사이즈로 잘라내고, 위상차 필름 표면에 코로나 처리를 실시했다. 적층체의 상기 코로나 처리면을, 아크릴계 점착제(20㎛)를 개재해서 무알칼리 유리판에 접합하여 시험 샘플을 제작했다. 이 시험 샘플을, 유리판면이 대향하도록 해서 유기 EL 장치 대체품에 적재하고, 색상 불균일(라인 불균일)을 형광등 아래에서 육안에 의해 관찰하여, 하기의 기준으로 평가했다.The retardation film and the polarizer obtained by the Example and the comparative example were bonded together, and the laminated body was obtained. The said laminate was cut out to predetermined size, and corona-treated on the retardation film surface. The said corona-treated surface of the laminated body was bonded to the alkali-free-glass plate via an acrylic adhesive (20 micrometers), and the test sample was produced. This test sample was placed on an organic EL device substitute so that the glass plate faces were opposed to each other, and color unevenness (line unevenness) was visually observed under a fluorescent lamp, and evaluated on the basis of the following criteria.
양호: 색상 불균일은 실질적으로 확인되지 않았다Good: The color unevenness was not confirmed substantially.
불량: 색상 불균일이 현저해서 실용상 허용 불가능했다Poor: The color non-uniformity was significant and was practically unacceptable.
(13) 압입시의 휘점의 평가(13) Evaluation of bright spots at the time of press-fitting
돌자강도 시험에서 평가한 샘플과 같은 샘플을 편광자와 접착하고, 필름측을 돌자 시험기에서 10gf/㎛의 힘으로 밀어넣었다. 그 후, 상기 편광판과 90°의 축을 이루도록 편광판을 1매 준비하고, 크로스니콜의 상태에서 투과광을 돌자 시험을 한 필름의 반대측으로부터 투과시켜, 휘점이 보이지 않으면 양호, 보인 것을 불량으로 했다.The same sample as the sample evaluated in the puncture strength test was adhered to the polarizer, and the film side was pushed with a force of 10 gf/μm in the puncture tester. Thereafter, one polarizing plate was prepared so as to form an axis of 90° with the polarizing plate, and transmitted light was transmitted from the opposite side of the tested film in the state of cross nicol.
(14) 내크랙성(14) crack resistance
실시예 및 비교예에서 얻어진 위상차 필름을, -40℃∼80℃의 히트 쇼크 시험에 300사이클 투입 후, 300㎛ 이상의 크랙의 발생이 없을 경우를 양호, 300㎛ 이상의 크랙의 발생이 있을 경우를 불량으로 했다.After 300 cycles of the retardation films obtained in Examples and Comparative Examples were subjected to a heat shock test at -40°C to 80°C, good when no cracks of 300 μm or more were generated, and poor when cracks of 300 μm or more were generated. did it with
[실시예 1][Example 1]
1. 수지 필름의 제작1. Preparation of resin film
이소소르비드(이하 「ISB」라고 약기할 경우가 있다) 81.98질량부에 대하여, 트리시클로데칸디메탄올(이하 「TCDDM」이라고 약기할 경우가 있다) 47.19질량부, 디페닐카보네이트(이하 「DPC」라고 약기할 경우가 있다) 175.1질량부, 및 촉매로서, 탄산세슘 0.2질량% 수용액 0.979질량부를 반응용기에 투입하고, 질소분위기 하에서, 반응의 제1단째의 공정으로서, 가열탱크 온도를 150℃로 가열하고, 필요에 따라서 교반하면서 원료를 용해시켰다(약 15분). 이어서, 압력을 상압으로부터 13.3kPa로 하고, 가열탱크 온도를 190℃까지 1시간으로 상승시키면서, 발생하는 페놀을 반응용기 밖으로 뽑아냈다. 반응용기 전체를 190℃에서 15분 유지한 후, 제2단째의 공정으로서, 반응용기 내의 압력을 6.67kPa로 하고, 가열탱크 온도를 230℃까지 15분으로 상승시켜, 발생하는 페놀을 반응용기 밖으로 뽑아냈다. 교반기의 교반 토크가 상승해 오므로, 8분으로 250℃까지 승온하고, 또한 발생하는 페놀을 제거하기 위해서 반응용기 내의 압력을 0.200kPa 이하로 도달시켰다. 소정의 교반 토크에 도달 후 반응을 종료하고, 생성한 반응물을 수중에 압출하여 폴리카보네이트 수지의 펠릿을 얻었다. 얻어진 폴리카보네이트 수지를 80℃에서 5시간 진공건조를 한 후, 단축 압출기(도시바 기카이사제, 실린더 설정 온도: 250℃), T다이(폭 300㎜, 설정 온도: 250℃), 칠 롤(설정 온도: 120∼130℃) 및 권취기를 구비한 필름 제막 장치를 이용하여, 두께 90㎛의 폴리카보네이트 수지 필름을 제작했다. To 81.98 parts by mass of isosorbide (hereinafter sometimes abbreviated as "ISB"), 47.19 parts by mass of tricyclodecanedimethanol (hereinafter sometimes abbreviated as "TCDDM"), diphenyl carbonate (hereinafter, "DPC") 175.1 parts by mass, and 0.979 parts by mass of a 0.2 mass % cesium carbonate aqueous solution as a catalyst are put into a reaction vessel, and in a nitrogen atmosphere, as the first step of the reaction, the heating tank temperature is set to 150 ° C. The raw material was dissolved by heating and stirring if necessary (about 15 minutes). Then, the generated phenol was taken out of the reaction vessel while the pressure was set to 13.3 kPa from the normal pressure and the heating tank temperature was raised to 190° C. in 1 hour. After maintaining the entire reaction vessel at 190° C. for 15 minutes, as the second step, the pressure in the reaction vessel is set to 6.67 kPa, the heating tank temperature is raised to 230° C. for 15 minutes, and the generated phenol is removed from the reaction vessel. pulled out Since the stirring torque of the stirrer increased, the temperature was raised to 250°C in 8 minutes, and the pressure in the reaction vessel was reached to 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the resulting reactant was extruded into water to obtain polycarbonate resin pellets. After vacuum drying the obtained polycarbonate resin at 80 ° C. for 5 hours, a single screw extruder (manufactured by Toshiba Kikai, cylinder set temperature: 250 ° C), T-die (width 300 mm, set temperature: 250 ° C), chill roll (set Temperature: 120-130 degreeC) and the 90-micrometer-thick polycarbonate resin film was produced using the film film forming apparatus provided with and a winder.
2. 위상차 필름의 제작2. Preparation of retardation film
미연신의 상기 폴리카보네이트 수지 필름을, 동시 2축 연신기를 이용하여 예열 처리, 동시 2축 연신에 제공하여 위상차 필름을 얻었다. 예열 온도는 133℃로 하고, 연신 온도는 135℃로 하고, 길이 방향의 연신 배율을 1.2배, 축 방향의 연신 배율을 1.9배로 했다. 얻어진 위상차 필름의 파장분산값은 1.025이며, 면내 위상차 Re(550)는 118㎚이며, 두께는 30㎛이며, 투습도는 110g/㎡·24h이며, 위상차 변화는 1%이며, 면내 위상차의 편차는 2㎚이었다. 또한, 위상차 필름의 돌자탄성률은 435gf/㎜이며, 돌자강도는 27.8gf/㎛이며, 파단강도는 2480㎫이며, 파단신도는 5.8%이었다. 얻어진 위상차 필름을, 상기 (9)∼(14)의 평가에 제공했다. 결과를 표 1에 나타낸다.The unstretched polycarbonate resin film was subjected to preheat treatment and simultaneous biaxial stretching using a simultaneous biaxial stretching machine to obtain a retardation film. The preheating temperature was 133°C, the stretching temperature was 135°C, the draw ratio in the longitudinal direction was 1.2 times, and the draw ratio in the axial direction was 1.9 times. The obtained retardation film had a wavelength dispersion value of 1.025, an in-plane retardation Re (550) of 118 nm, a thickness of 30 μm, a moisture permeability of 110 g/m 2 ·24 h, a phase difference change of 1%, and a deviation of the in-plane retardation of 2 was nm. In addition, the retardation film had a puncture modulus of 435 gf/mm, a piercing strength of 27.8 gf/㎛, a breaking strength of 2480 MPa, and an elongation at break of 5.8%. The obtained retardation film was used for evaluation of said (9)-(14). A result is shown in Table 1.
[실시예 2][Example 2]
예열 온도는 137℃로, 연신 온도는 140℃로 하고, 길이 방향의 연신 배율을 1.2배, 폭 방향의 연신 배율을 1.9배로 한 것 이외는 실시예 1과 마찬가지로 해서 위상차 필름을 얻었다. 얻어진 위상차 필름의 파장분산값은 1.022이며, 면내 위상차 Re(550)는 144㎚이며, 두께는 30㎛이며, 투습도 82g/㎡·24h이며, 위상차 변화는 0.8%이며, 면내 위상차의 편차는 2㎚이었다. 또한, 위상차 필름의 돌자탄성률은 446gf/㎜이며, 돌자강도는 28gf/㎛이며, 파단강도는 2480㎫이며, 파단신도는 5.8%이었다. 얻어진 위상차 필름을, 실시예 1과 같은 평가에 제공했다. 결과를 표 1에 나타낸다.A retardation film was obtained in the same manner as in Example 1, except that the preheating temperature was 137 ° C., the stretching temperature was 140 ° C., the draw ratio in the longitudinal direction was 1.2 times, and the draw ratio in the width direction was 1.9 times. The obtained retardation film had a wavelength dispersion value of 1.022, an in-plane retardation Re (550) of 144 nm, a thickness of 30 μm, a moisture permeability of 82 g/m 2 ·24 h, a phase difference change of 0.8%, and a deviation of the in-plane retardation of 2 nm it was In addition, the retardation film had a puncture modulus of 446 gf/mm, a piercing strength of 28 gf/㎛, a breaking strength of 2480 MPa, and an elongation at break of 5.8%. The obtained retardation film was subjected to the same evaluation as in Example 1. A result is shown in Table 1.
[실시예 3][Example 3]
예열 온도는 137℃로, 연신 온도는 140℃로 하고, 길이 방향의 연신 배율을 1.2배, 폭 방향의 연신 배율을 1.9배로 한 것 이외는 실시예 1과 마찬가지로 해서 위상차 필름을 얻었다. 얻어진 위상차 필름의 파장분산값은 1.026이며, 면내 위상차 Re(550)는 157㎚이며, 두께는 30㎛이며, 투습도는 81g/㎡·24h이며, 위상차 변화는 0.9%이며, 면내 위상차의 편차는 2㎚이었다. 또한, 위상차 필름의 돌자탄성률은 457gf/㎜이며, 돌자강도는 29gf/㎛이며, 파단강도는 2480㎫이며, 파단신도는 5.8%이었다. 얻어진 위상차 필름을, 실시예 1과 같은 평가에 제공했다. 결과를 표 1에 나타낸다.A retardation film was obtained in the same manner as in Example 1, except that the preheating temperature was 137 ° C., the stretching temperature was 140 ° C., the draw ratio in the longitudinal direction was 1.2 times, and the draw ratio in the width direction was 1.9 times. The obtained retardation film had a wavelength dispersion value of 1.026, an in-plane retardation Re (550) of 157 nm, a thickness of 30 μm, a moisture permeability of 81 g/m 2 ·24 h, a phase difference change of 0.9%, and a deviation of the in-plane retardation of 2 was nm. In addition, the puncture modulus of the retardation film was 457 gf/mm, the piercing strength was 29 gf/㎛, the breaking strength was 2480 MPa, and the breaking elongation was 5.8%. The obtained retardation film was subjected to the same evaluation as in Example 1. A result is shown in Table 1.
[비교예 1][Comparative Example 1]
수지 필름으로서 시판의 시클로올레핀계 수지 필름(니폰 제온사제, 상품명 「제오노아」)을 이용하여, 예열 온도 140℃, 연신 온도 143℃로 하고, 길이 방향의 연신 배율을 1.2배, 폭 방향의 연신 배율을 1.9배로 함으로서 연신을 행한 것 이외는 실시예 1과 마찬가지로 해서 위상차 필름을 얻었다. 얻어진 위상차 필름의 파장분산값은 1.01이며, 면내 위상차 Re(550)는 140㎚이며, 두께는 52㎛이며, 투습도는 6g/㎡·24h이며, 위상차 변화는 0.6%이며, 면내 위상차의 편차는 2㎚이었다. 또한, 위상차 필름의 돌자탄성률은 304gf/㎜이며, 돌자강도는 17gf/㎛이며, 파단강도는 2150㎫이며, 파단신도는 0.7%이었다. 얻어진 위상차 필름을, 실시예 1과 같은 평가에 제공했다. 결과를 표 1에 나타낸다.As the resin film, using a commercially available cycloolefin-based resin film (manufactured by Nippon Zeon, trade name “Zeonoa”), a preheating temperature of 140° C. and a stretching temperature of 143° C., the stretching ratio in the longitudinal direction is 1.2 times, and stretching in the transverse direction. A retardation film was obtained in the same manner as in Example 1 except that stretching was performed by increasing the magnification to 1.9. The obtained retardation film had a wavelength dispersion value of 1.01, an in-plane retardation Re (550) of 140 nm, a thickness of 52 μm, a water vapor transmission rate of 6 g/m 2 ·24 h, a phase difference change of 0.6%, and a deviation of the in-plane retardation of 2 was nm. In addition, the retardation film had a puncture modulus of 304 gf/mm, a piercing strength of 17 gf/㎛, a breaking strength of 2150 MPa, and an elongation at break of 0.7%. The obtained retardation film was subjected to the same evaluation as in Example 1. A result is shown in Table 1.
[비교예 2][Comparative Example 2]
(폴리에스테르카보네이트계 수지의 중합)(Polymerization of polyester carbonate-based resin)
교반날개 및 100℃로 제어된 환류 냉각기를 구비한 종형 반응기 2기로 이루어지는 배치 중합 장치를 이용하여 중합을 행하였다. 비스[9-(2-페녹시카르보닐에틸)플루오렌-9-일]메탄 29.60질량부(0.046mol), 이소소르비드(ISB) 29.21질량부(0.200mol), 스피로글리콜(SPG) 42.28질량부(0.139mol), 디페닐카보네이트(DPC) 63.77질량부(0.298mol) 및 촉매로서 아세트산 칼슘 1수화물 1.19×10-2질량부(6.78×10-5mol)를 투입했다. 반응기 내를 감압 질소 치환한 후, 열매로 가온을 행하고, 내부온도가 100℃로 된 시점에서 교반을 개시했다. 승온 개시 40분 후에 내부온도를 220℃에 도달시키고, 이 온도를 유지하도록 제어함과 동시에 감압을 개시하고, 220℃에 도달하고나서 90분으로 13.3㎪로 했다. 중합 반응과 함께 부생하는 페놀 증기를 100℃의 환류 냉각기에 안내하고, 페놀 증기 중에 약간량 포함되는 모노머 성분을 반응기에 되돌리고, 응축하지 않는 페놀 증기는 45℃의 응축기에 안내해서 회수했다. 제1반응기에 질소를 도입해서 일단 대기압까지 복압시킨 후, 제1반응기 내의 올리고머화된 반응액을 제2반응기에 옮겼다. 이어서, 제2반응기 내의 승온 및 감압을 개시하여 50분으로 내부온도 240℃, 압력 0.2㎪로 했다. 그 후, 소정의 교반 동력으로 될 때까지 중합을 진행시켰다. 소정 동력에 도달한 시점에서 반응기에 질소를 도입해서 복압하고, 생성한 폴리에스테르카보네이트계 수지를 수중으로 압출하여 스트랜드를 커팅해서 펠릿을 얻었다.Polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors equipped with stirring blades and a reflux condenser controlled at 100°C. Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane 29.60 parts by mass (0.046 mol), isosorbide (ISB) 29.21 parts by mass (0.200 mol), spiroglycol (SPG) 42.28 mass Parts (0.139 mol), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC), and 1.19×10 -2 parts by mass (6.78×10 -5 mol) of calcium acetate monohydrate were added as a catalyst. After the inside of the reactor was purged with reduced pressure nitrogen, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100°C. The internal temperature was made to reach 220 degreeC 40 minutes after the start of temperature increase, and while controlling so that this temperature might be maintained, pressure reduction was started, and it was 13.3 kPa in 90 minutes after reaching 220 degreeC. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 100° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the phenol vapor that did not condensed was collected by introducing it to a condenser at 45° C. After nitrogen was introduced into the first reactor and returned to atmospheric pressure, the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was 240°C and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was reached. When a predetermined power was reached, nitrogen was introduced into the reactor and the pressure was restored, and the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.
(위상차 필름의 제작)(Production of retardation film)
얻어진 폴리에스테르카보네이트계 수지(펠릿)를 80℃에서 5시간 진공건조를 한 후, 단축 압출기(도시바 기카이사제, 실린더 설정 온도: 250℃), T다이(폭 200㎜, 설정 온도: 250℃), 칠 롤(설정 온도: 120∼130℃) 및 권취기를 구비한 필름 제막 장치를 이용하여, 두께 130㎛의 장척 형상의 수지 필름을 제작했다. 얻어진 장척 형상의 수지 필름을, 소정의 위상차가 얻어지도록 조정하면서 연신하여, 두께 57㎛의 위상차 필름을 얻었다. 연신 조건은, 폭 방향으로 연신 온도 145℃, 연신 배율 1.2배이었다. 얻어진 위상차 필름의 파장분산값은 0.855이며, 면내 위상차 Re(550)는 140㎚이며, 투습도는 74g/㎡·24h이며, 위상차 변화는 1.7%이며, 면내 위상차의 편차는 2㎚이었다. 또한, 위상차 필름의 돌자탄성률은 770gf/㎜이며, 돌자강도는 33gf/㎛이며, 파단강도는 2820㎫이며, 파단신도는 1.5%이었다. 얻어진 위상차 필름을, 실시예 1과 같은 평가에 제공했다. 결과를 표 1에 나타낸다.After vacuum drying the obtained polyester carbonate-based resin (pellet) at 80 ° C. for 5 hours, a single screw extruder (manufactured by Toshiba Kikai, cylinder set temperature: 250 ° C), T-die (width 200 mm, set temperature: 250 ° C) , a long resin film having a thickness of 130 µm was produced using a film film forming apparatus equipped with , a chill roll (set temperature: 120 to 130° C.) and a winder. The obtained elongate resin film was extended|stretched, adjusting so that a predetermined|prescribed retardation might be obtained, and the retardation film of 57 micrometers in thickness was obtained. The stretching conditions were a stretching temperature of 145°C and a stretching ratio of 1.2 times in the width direction. The obtained retardation film had a wavelength dispersion value of 0.855, an in-plane retardation Re (550) of 140 nm, a water vapor transmission rate of 74 g/m 2 ·24 h, a retardation change of 1.7%, and a deviation of the in-plane retardation of 2 nm. In addition, the puncture modulus of the retardation film was 770 gf/mm, the puncture strength was 33 gf/㎛, the breaking strength was 2820 MPa, and the breaking elongation was 1.5%. The obtained retardation film was subjected to the same evaluation as in Example 1. A result is shown in Table 1.
[비교예 3][Comparative Example 3]
예열 온도는 137℃로, 연신 온도는 140℃로 하고, 길이 방향의 연신 배율을 1.2배, 폭 방향의 연신 배율을 1.9배로 한 것 이외는 실시예 1과 마찬가지로 해서 위상차 필름을 얻었다. 얻어진 위상차 필름의 파장분산값은 1.022이며, 면내 위상차 Re(550)는 140㎚이며, 두께는 5㎛이며, 투습도는 165g/㎡·24h이며, 위상차 변화는 1%이며, 면내 위상차의 편차는 3㎚이었다. 또한, 위상차 필름의 돌자탄성률은 42gf/㎜이며, 돌자강도는 12gf/㎛이며, 파단강도는 700㎫이며, 파단신도는 5%이었다. 얻어진 위상차 필름을, 실시예 1과 같은 평가에 제공했다. 결과를 표 1에 나타낸다.A retardation film was obtained in the same manner as in Example 1, except that the preheating temperature was 137 ° C., the stretching temperature was 140 ° C., the draw ratio in the longitudinal direction was 1.2 times, and the draw ratio in the width direction was 1.9 times. The obtained retardation film had a wavelength dispersion value of 1.022, an in-plane retardation Re (550) of 140 nm, a thickness of 5 μm, a water vapor transmission rate of 165 g/m 2 ·24h, a phase difference change of 1%, and a deviation of the in-plane retardation of 3 was nm. In addition, the puncture modulus of the retardation film was 42 gf/mm, the piercing strength was 12 gf/㎛, the breaking strength was 700 MPa, and the breaking elongation was 5%. The obtained retardation film was subjected to the same evaluation as in Example 1. A result is shown in Table 1.
표 1로부터 분명한 바와 같이, 본 발명의 실시예의 위상차 필름은, 접착성, 주행성, 굴곡성, 색상 불균일의 억제, 압입시의 휘점 발생의 억제 및 내크랙성의 전부에 있어서 뛰어난 것을 알 수 있다. 이것은 특정의 폴리카보네이트 수지를 포함하는 위상차 필름을 사용한 것, 상기 위상차 필름의 돌자탄성률, 단위막두께당의 돌자강도, 파단강도 및 파단신도를 전부 특정의 범위 내로 함으로써 실현된다고 추찰된다.As is clear from Table 1, it can be seen that the retardation film of Examples of the present invention is excellent in adhesiveness, running property, flexibility, suppression of color unevenness, suppression of luminescent point generation at the time of press-fitting, and crack resistance. It is conjectured that this is realized by using a retardation film containing a specific polycarbonate resin, and setting the puncture modulus of the retardation film, the puncture strength per unit film thickness, the breaking strength and the breaking elongation all within specific ranges.
본 발명의 실시형태에 의한 위상차 필름은, 텔레비젼, 절곡 가능 및/또는 절첩 가능한 화상 표시 장치, 퍼블릭 인포메이션 디스플레이(PID)에 적합하게 사용된다.The retardation film by embodiment of this invention is used suitably for a television, a bendable and/or foldable image display apparatus, and a public information display (PID).
Claims (6)
단위막두께당의 돌자강도가 10gf/㎛ 이상인 위상차 필름.The method of claim 1,
A retardation film having a puncture strength of 10 gf/㎛ or more per unit film thickness.
파단강도가 800㎫ 이상이며, 또한, 파단신도가 3% 이상인 위상차 필름.The method of claim 1,
The retardation film having a breaking strength of 800 MPa or more, and a breaking elongation of 3% or more.
두께가 40㎛ 이하인 위상차 필름.The method of claim 1,
A retardation film having a thickness of 40 μm or less.
폭 방향의 Re(550)의 편차가 5㎚ 이하인 위상차 필름.The method of claim 1,
The retardation film in which the dispersion|variation of Re (550) in the width direction is 5 nm or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020146965A JP2022041639A (en) | 2020-09-01 | 2020-09-01 | Retardation film and polarizing plate |
| JPJP-P-2020-146965 | 2020-09-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20220029387A true KR20220029387A (en) | 2022-03-08 |
Family
ID=80441042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210107052A KR20220029387A (en) | 2020-09-01 | 2021-08-13 | Retardation film and polarizing plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2022041639A (en) |
| KR (1) | KR20220029387A (en) |
| CN (1) | CN114114511A (en) |
| TW (1) | TW202210562A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3325560B2 (en) | 1998-10-30 | 2002-09-17 | 帝人株式会社 | Retardation film and optical device using the same |
-
2020
- 2020-09-01 JP JP2020146965A patent/JP2022041639A/en active Pending
-
2021
- 2021-07-16 TW TW110126254A patent/TW202210562A/en unknown
- 2021-08-13 KR KR1020210107052A patent/KR20220029387A/en active Search and Examination
- 2021-08-31 CN CN202111011903.6A patent/CN114114511A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3325560B2 (en) | 1998-10-30 | 2002-09-17 | 帝人株式会社 | Retardation film and optical device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202210562A (en) | 2022-03-16 |
| JP2022041639A (en) | 2022-03-11 |
| CN114114511A (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI672532B (en) | Polarizing plate with phase difference layer and image display device | |
| KR102339860B1 (en) | Optical film for organic EL display devices, polarizing film for organic EL display devices, polarizing film with adhesive layer for organic EL display devices, and organic EL display device | |
| KR20220029385A (en) | Optical film and polarizing plate | |
| KR20220029387A (en) | Retardation film and polarizing plate | |
| KR20220029386A (en) | Retardation film and polarizing plate | |
| TWI840521B (en) | Phase difference film and polarizing plate with phase difference layer | |
| JP2024149635A (en) | Optical films and polarizing plates | |
| JP7543250B2 (en) | Polarizing plate with retardation layer | |
| JP7323602B2 (en) | Retardation film and polarizing plate with retardation layer | |
| KR20220033422A (en) | Retardation film, polarizing plate with retardation layer, and method for producing retardation film | |
| JP2024145561A (en) | Laminated Film | |
| JP2023073124A (en) | Polarizer with phase difference layer and image display device with the same | |
| JP2024145562A (en) | LAMINATED FILM AND METHOD FOR PRODUCING LAMINATED FILM | |
| JP2024145560A (en) | Laminated Film | |
| KR20220033421A (en) | Optical film, polarizing plate, and method for producing optical film | |
| JP2020034673A (en) | Retardation film, polarizing plate with retardation layer, and method for manufacturing retardation film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination |