JP2004237451A - Polyester film for releasing polarizing plate - Google Patents
Polyester film for releasing polarizing plate Download PDFInfo
- Publication number
- JP2004237451A JP2004237451A JP2003025811A JP2003025811A JP2004237451A JP 2004237451 A JP2004237451 A JP 2004237451A JP 2003025811 A JP2003025811 A JP 2003025811A JP 2003025811 A JP2003025811 A JP 2003025811A JP 2004237451 A JP2004237451 A JP 2004237451A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polarizing plate
- polyester film
- releasing
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 37
- 239000010954 inorganic particle Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 75
- 239000010410 layer Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- 239000000314 lubricant Substances 0.000 claims description 28
- -1 polyethylene terephthalate Polymers 0.000 claims description 27
- 229920000728 polyester Polymers 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 2
- 238000007689 inspection Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 239000010419 fine particle Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002987 primer (paints) Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 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 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は偏光板離形用ポリエステルフィルムに関する。更に詳しくは透明性、滑り性、巻取り性、検査性、耐スクラッチ性に優れた偏光板離形用ポリエステルフィルムに関する。
【0002】
【従来の技術】
近年、携帯電話、携帯用ゲーム機、車載用テレビ、電気機器、パソコン等の表示部に液晶表示装置が急速に普及しつつあり、特に携帯電話やノート型および省スペースデスクトップ型パソコンの需要が増加している。それに伴い、液晶ディスプレイの需要増と大画面化が進行している。液晶表示装置においては、液晶膜の両面に偏光軸が互いに直交するように偏光膜が貼り合わせてある。貼り合わせるまでの間は、偏光膜の片面に離形フィルムが貼り合わせてある。
【0003】
離形フィルムは、偏光膜の表面傷防止の保護フィルムであり、最終製品には剥離されており、用いられることはないが、偏光膜を検品するため透明性であること、配向角が小さいこと、フライスペック(光学的異物)が少ないこと、離形性を得るためシリコーン層を塗設するがシリコーン易接性であること、加工作業性が良いこと等が要求される。また、上述のように、偏光板用離形フィルムは、最終製品において剥離されるものであるが、その剥離作業において、偏光板表面に、擦傷痕が付かないようにしなければならない。これらの要求特性を満たしたフィルムが、特許公開2002−207119号公報に例示されている。
【0004】
【特許文献1】
特開2002−207119号公報
【0005】
【発明が解決しようとする課題】
上述のフィルム製品は、一般的に、フィルム製造工程、離形剤塗工その他の加工工程を通して、ウェブ状物としてロール搬送されることがほとんどである。このロール搬送工程において、主にフィルムと搬送ロールとの擦過により、フィルム表面に傷がついてしまう、いわゆるスクラッチが発生すると、上述の偏光膜検品工程において大きな支障となる。従来は、このスクラッチが全工程において発生しないような偏光板離形フィルムは見当たらないのが現状であった。
【0006】
本発明は、かかる従来技術の課題を解消し、透明性で配向角が小さいこと、シリコ−ン易接性、フライスペック(光学的異物)が少ないこと、加工作業性が良いこと、偏光板表面に傷がつきにくいこと、さらにフィルム製造から、後加工までの全工程を通してフィルムにスクラッチの発生しないことを同時に満足する偏光板離形用フィルムを提供することを課題とするものである。
【0007】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、特定の滑剤粒子を特定量含有し、その滑剤粒子の含有量の異なる少なくとも2層からなるポリエステルフィルムを用い、加工作業性、特に耐スクラッチ性を保持しながら高透明、低異物、低配向角を実現することにより、要求特性を満足する偏光板離形フィルムが得られることを見出し、本発明を完成するに至った。
【0008】
すなわち本発明の偏光板離形用ポリエステルフィルムは、共押出し法で製造された多層ポリエステルフィルムであって、フィルムのヘーズ値が6%以下、配向角が10度以下、長径90μm以上のフライスペックが0.3m2当り5個以下であり、フィルム中の少なくとも1つ以上の層中にモース硬度7以上の不活性無機粒子を0.001〜1.0重量%含有することを特徴とする。
【0009】
好ましくは、該不活性無機粒子が酸化アルミニウム粒子であり、さらに好ましくは、該酸化アルミニウム粒子の結晶系が、γ、δ、θ型のうちから選ばれる少なくとも1種類以上のものである。また好ましくは、中心線表面粗さRaが20nm以上60nm以下、10点平均粗さRzが500nm以上である偏光板離形用ポリエステルフィルムである。また好ましくは、フィルムの厚みが15μm以上75μm以下である偏光板離形用ポリエステルフィルムである。また好ましくは、平均粒径の異なる少なくとも2種以上の滑剤粒子を含有する偏光板離形用ポリエステルフィルムである。また好ましくは、シリコーンに対し易接着性の塗布層を有する偏光板離形用ポリエステルフィルムである。
【0010】
<ポリエステル>
本発明のフィルムを構成するポリエステルは、ポリエチレンテレフタレートまたはエチレンテレフタレートを主たる繰り返し単位とする共重合物であることが好ましい。ポリエチレンテレフタレートは、ホモポリマーとしては高透明で偏光板離形用フィルムに適しており、特に機械的強度が大きい点が特長である。
【0011】
本発明において、共重合ポリエステルの場合の共重合成分は、ジカルボン酸成分でもジオール成分でもよい。このジカルボン酸成分としてはイソフタル酸、ナフタレンジカルボン酸等の如き芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸、シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸等が例示でき、またジオール成分としては1,4−ブタンジオール、1,6−ヘキサンジオール、ジエチレングリコール等の如き脂肪族ジオール、1,4−シクロヘキサンジメタノールの如き脂環族ジオール、ビスフェノールAの如き芳香族ジオールが例示できる。これらは単独または二種以上を使用することができる。これらの中では、イソフタル酸が透明性、引裂き強度が共に高く、特に好ましい。
【0012】
共重合成分の割合は、その種類にもよるが結果として、ポリマー融点が245℃〜258℃(ホモポリマーの融点)の範囲になる割合である。融点が245℃未満では耐熱性が劣ることになる。また熱収縮率が大きく、フィルムの平面性が低下する。ここで、ポリエステルの融点測定は、Du Pont Instruments 910 DSCを用い、昇温速度20℃/分で融解ピークを求める方法による。なおサンプル量は約20mgとする。
【0013】
ポリエチレンテレフタレートまたは共重合ポリエステルの固有粘度(オルトクロロフェノール、35℃)は0.52〜1.50であることが好ましく、さらに好ましくは0.57〜1.00、特に好ましくは0.60〜0.80である。この固有粘度が0.52未満の場合には引裂き強度が不足することがあり、好ましくない。他方、固有粘度が1.50を超える場合には、原料製造工程およびフィルム製膜工程における生産性が損なわれる。
【0014】
本発明におけるポリエチレンテレフタレートまたは共重合ポリエステルは、その製法により限定されることはないが、テレフタル酸、エチレングリコール、共重合ポリエステルの場合は更に共重合成分を加えてエステル化反応させ、次いで得られた反応生成物を目的とする重合度になるまで重縮合反応させてポリエチレンテレフタレート、または共重合ポリエチレンテレフタレートとする方法がある。あるいはテレフタル酸ジメチルエステル、エチレングリコールを、共重合ポリエステルの場合は更に共重合成分を加えてエステル交換反応させ、ついで得られた反応生成物を目的とする重合度になるまで重縮合反応させてポリエチレンテレフタレート、または共重合ポリエチレンテレフタレートとする方法を好ましく挙げることができる。また、上記の方法(溶融重合)により得られたポリエチレンテレフタレートまたは共重合ポリエチレンテレフタレートは、必要に応じて固相状態での重合方法(固相重合)により、さらに重合度の高いポリマーとすることができる。
【0015】
前記共重合ポリエステルには、必要に応じて、酸化防止剤、熱安定剤、粘度調整剤、可塑剤、色相改良剤、滑剤、核剤などの添加剤を加えることができる。また前記重縮合反応に使用する触媒としては、チタン化合物(Ti化合物)、ゲルマニウム化合物(Ge化合物)などが好ましく挙げられる。
【0016】
<添加微粒子>
本発明の偏光板離形用ポリエステルフィルムには、滑剤微粒子を添加してフィルムの作業性(滑り性)を確保し、同時に、さらにフィルム製造から、後加工までの全工程を通してフィルムにスクラッチが発生しないようにすることが重要であり、透明性をも維持するために各層の滑剤微粒子の平均粒径および添加量を最適範囲に調整することが好ましい。
【0017】
特に、滑剤微粒子として、上述の耐スクラッチ性を発揮させるために、フィルム中の少なくとも1つ以上の層中にモース硬度7以上の不活性無機粒子を0.001〜1.0重量%含有させる必要がある。モース硬度7以上の不活性無機粒子の含有量は、0.001重量%未満では耐スクラッチ性が発揮しえず、1.0重量%を越えると、ヘーズ値が6%を超えることが多く好ましくない。
【0018】
モース硬度7以上の不活性無機粒子としては任意のものが選べるが、中でも、酸化アルミニウム粒子が耐スクラッチ性の点からは好ましく、特に、その結晶系がγ、δ、θ型の酸化アルミニウム粒子である場合に、耐スクラッチ性が最も顕著に発揮されるので好ましい。
【0019】
フィルム中に、その他の滑剤微粒子を共存させてもよい。この場合、平均粒径の異なる少なくとも2種以上の滑剤粒子を含有していることが好ましい。滑剤微粒子としては任意のものが選べるが、無機系滑剤としては、シリカ、二酸化チタン、炭酸カルシウム、硫酸バリウム等が例示でき、有機系滑剤としては球状シリコーン樹脂粒子、架橋ポリスチレン粒子等が例示できる。
【0020】
本発明のフィルムは、少なくとも2層以上からなる共押出しフィルムである。そしてその各層に添加する滑剤粒子の平均粒径は、偏光膜に接する側は大粒径のものとしては1000〜3000nm、好ましくは1000〜2500nm、更に好ましくは1000〜2000nmの範囲である。また小粒径のものは、好ましくは50〜800nm、更に好ましくは100〜700nmの範囲である。
【0021】
大粒径粒子の平均粒径が3000nmを超えると、この面に塗設されたシリコーン層と偏光膜面との剥離強度が軽くなりすぎ、自然剥離が発生して実用性が低下する場合がある。また、ロールに巻いた時突起が転写して面の欠点となることがある。平均粒径1000nm未満の場合では、この面に塗設されたシリコーン層と偏光膜面との剥離強度が重くなりすぎ、剥離作業性が低下し、偏光膜の表面に剥離痕のような欠点を生じる場合がある。
【0022】
小粒径粒子の平均粒径が800nmを超えると耐擦傷性が発現し難い場合がある。一方、50nm未満では耐擦傷性を得るためには添加量を多くせねばならず、フィルムのヘーズ値が6%を超える場合がある。
【0023】
外面側(偏光膜面に接しない側)では、2層の場合と3(または3以上)層の場合で異なる。3(または3以上)層の場合は偏光膜面に接する層と大略同様である。但し、塗工されないので、大粒径粒子の平均粒径の下限は500nmである。この場合、中間層の滑剤粒子は作業性には寄与せず、透明性を低下させるので、少ないほど良い。しかし、回収部分の再利用を考慮し、0%としないのが好ましい。中間層の滑剤粒子の含有量は、偏光膜と接する層の含有量の70%以下、更には50%以下であることが好ましい。含有量が70%を超えると、透明性が低下し、偏光板の欠点検査に際して欠点を隠してしまうので好ましくない。2層の場合には、外面側にも作業性を付与するため、滑剤粒子の含有量は、偏光膜と接する層の含有量の70%以下、20%以上であることが好ましい。20%未満では滑り性が悪く、作業性が悪い。
【0024】
また、粗大粒子やフライスペックの個数を減らすには、製膜時のフィルターとして線径15μm以下のステンレス鋼細線よりなる平均目開き10〜30μm、好ましくは15〜25μmの不織布型フィルターを用い、溶融ポリマーを濾過することが推奨される。この方法により、粒径20μm以上の粗大粒子や長径90μm以上のフライスペックをほぼ除去できる。
【0025】
モース硬度7以上の不活性無機粒子を含有させる他は、滑剤粒子の材質は特定するものではないが、平均粒径200〜3000nmの粒子としては上に例示した中で特に、球状シリコーン樹脂、球状シリカが好ましく、粒径分布がシャープであり、モース硬度が5以上の粒子が粒子の変形が小さいので好ましい。50〜800nmの粒子としては上述の酸化アルミニウムの他、シリカ、酸化チタン、酸化ジルコニウムやこれらの複合酸化物が好ましく、2種以上併用してもよい。
【0026】
滑剤粒子は、通常、ポリエステルを製造するための反応時、例えばエステル交換法による場合、エステル交換反応中ないし重縮合反応中の任意の時期、または直接重合法による場合の任意の時期に、反応系中に添加(好ましくはグリコール中のスラリーとして)される。特に、重縮合反応の初期、例えば固有粘度が約0.3に至るまでの期間に粒子を反応系中に添加するのが好ましい。
【0027】
<フィルム厚み>
本発明のフィルムの厚みは15μm以上、75μm以下であることが好ましい。更には20μm以上70μm以下、特に25μm以上65μmの範囲内であることが好ましい。75μmを超えるとヘーズ値が6%を超えることがあり、検査精度が低下する上に、コスト高になるので好ましくない。厚み15μm未満では強度、いわゆる腰が不足し、離形時に剥し難くなる。
【0028】
各層の厚みは、偏光膜に接する側は全厚みの3%以上50%以下、好ましくは4%以上40%以下、更に好ましくは5%以上30%以下である。2層の場合、他の層が全厚みの50%以上97%以下、好ましくは60%以上96%以下、更に好ましくは70%以上95%以下である。偏光膜に接する側即ち粗面側が50%を超えるとヘーズ値が6%を超えることがあり、3%未満であるとフィルムの巻取り性が悪く、製品歩留まりが低くなる。3(以上)層の場合、偏光膜に接する側の反対面の表層の厚みは全厚みの3〜20%が好ましい。3%未満では効果が小さく、20%を超えるとヘーズ値が大きくなり易い。
【0029】
<フライスペック>
本発明のポリエステルフィルム中に存在する長径90μm以上のフライスペックは、0.3m2中に5個以下であることを要する。長径90μm以上のフライスペックは、光の直進を妨げ、画像の歪みの原因となるので少ないほど良い。フライスペックは異物、未溶融ポリマーや粗大粒子を核に生じるので、前述の不織布型フィルターの使用により、粗大粒子や異物を除去することが好ましい。更には、フライスペックの原因物を多くは含まない滑剤粒子を用いることが好ましい。
【0030】
<配向角>
本発明のフィルムの配向角は10度以下である。配向角が10度を超えると偏光膜を検品するに際し、視野が暗くなり、異物の検知精度が低下する。配向角が10度以下のフィルムを得るには、製膜機幅の中央部20%程度のみを用いるのが好ましい。残りの部分は他の用途に用いる。なおここで配向角とは、延伸による配向主軸の幅(横)方向となす角である。縦横逐次延伸による通常のポリエステルフィルムは、製膜時の幅方向の中央部では弱い横配向または均等配向であり、この配向角を0度とする。
【0031】
枚葉フィルムの形態で供給することが可能な場合、打ち抜き機の一辺の方向を配向角に相当する角度だけ横方向から傾けて打ち抜くことにより、端部品も使用できるがロスが端程多くなる。
【0032】
全幅フィルムの両端を把持具で把持し、入口幅と出口幅をほぼ等しくして熱処理ができる装置を有する場合、製膜法で述べる熱処理工程で、処理温度をより低くし、中央部の移動量を通常の半分程度にして製膜する。移動量は横延伸機に入る前のフィルムに、墨縄等で横(幅)方向に直線を描き、横延伸機から出た後の直線が円弧状に曲がる量で求める。このフィルムを、把持具を持つ熱処理機であって入口幅と出口幅をほぼ等しくできる装置に通して200〜245℃で熱処理する。このとき、製膜時と該熱処理時とは走行方向が逆になるように処理することが肝要であり、前記円弧状の線がほぼ直線状に戻るように条件設定する。この処理により、両端部の異方性は矯正され、全幅に亘り、配向角10度以内が実現できる。しかし、生産性の減少(工程が増える)や把持具部分の廃棄による歩留まりの低下が避けられず、不利益もある。設備対応できる場合に限り、採用できる方法である。
【0033】
<表面粗さ>
本発明のフィルムの中心線表面粗さRaは、20nm以上60nm以下であることが好ましい。20nm未満であるとフィルム面が互いに密着する傾向があり、巻き姿や作業性が悪く、表面に傷がつき易い。60nmを超えると、透明性が低下し、検品性が低下する。10点平均表面粗さRzはシリコーン塗布側では500nm以上であることが好ましい。Rzが500nm未満であるとシリコーン塗布層の表面に突起が非常に少なくなり、偏光膜との剥離が重くなる。上限は特定できないが、Raが60nmを超えなければよい。このような表面粗さを得るためには、前述の滑剤粒子の添加による。
【0034】
<易接層>
本発明のポリエステルフィルムの片面即ち偏光膜と接する面に、シリコーン易接性の塗膜を形成させることが好ましい。シリコーンは偏光膜表面保護のために用いる本発明のフィルムを偏光膜から離形するために塗布するものであるが、ポリエステルフィルムとシリコーンは接着性が良くないので何らかの易接性の処理を要する。本発明においては、下記のプライマー層を形成することが好ましい。
【0035】
プライマー層を構成するシランカップリング剤は、一般式YRSiX3で表わされる化合物である。ここで、Yはビニル基、エポキシ基、アミノ基、メルカプト基等の如き有機官能基、Rはメチレン、エチレン、プロピレン等の如きアルキレン基、Xはメトキシ基、エトキシ基等の如き加水分解基及びアルキル基である。具体的化合物としては、例えばビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、N−β(アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等を挙げることができる。好ましいシランカップリング剤としては、水溶性又は水分散性を有するカップリング剤である。
【0036】
前記シランカップリング剤と共にプライマー層を構成するアルカリ性無機微粒子としては、例えば酸化鉄ゾル、アルミナゾル、酸化スズゾル、酸化ジルコニウムゾル、シリカゾル等を挙げることができるが、特にアルミナゾル、シリカゾルが好ましい。就中シランカップリング剤の初期反応性(ダイマー化、トリマー化等)を促進する点から、シリカゾルが好ましい。
【0037】
アルカリ性無機微粒子は表面積の大きい小粒径のものが良く、平均粒径が1〜150nm、さらには2〜100nm、特に3〜50nmであるものが好ましい。平均粒径が150nmより大きくなると、表面積が小さくなりすぎ、シランカップリング剤の反応促進作用が低下し、かつプライマー層の表面が粗面化するため好ましくない。他方、平均粒径が1nmより小さくなると、表面積が大きすぎ、シランカップリング剤の反応制御が困難となり好ましくない。
【0038】
アルカリ性無機微粒子の量は、シランカップリング剤の量に対して、1〜50重量%、さらには2〜20重量%であることが好ましい。この量が1重量%未満であると、架橋反応が進まず、他方50重量%を超えると塗布液の安定性に欠け、例えば無機微粒子の添加後短時間で塗布液中に沈澱が発生し、好ましくない。
【0039】
シランカップリング剤及びアルカリ性無機微粒子を含有するプライマー塗布液、特に水性塗布液は、そのpHを4.0〜7.0、好ましくは5.0〜6.7に調整する。このpHが4.0未満になると、無機微粒子の触媒活性が失われ、他方7.0を超えると塗液が不安定となり、沈澱が生じるので好ましくない。このpHを調整する酸としては塩酸、硝酸、硫酸等の無機酸や蓚酸、蟻酸、クエン酸、酢酸等の有機酸が用いられるが、特に有機酸が好ましい。
【0040】
かかる塗布後、特に水性液には、アニオン界面活性剤、カチオン型界面活性剤、ノニオン型界面活性等の界面活性剤を必要量添加して用いることができる。かかる界面活性剤としては塗布液の表面張力を0.5N/m以下、好ましくは0.4N/m以下に降下でき、ポリエステルフィルムヘの濡れを促進するものが好ましく、例えばポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン−脂肪酸エステルソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、脂肪酸金属石鹸、アルキル硫酸塩、アルキルスルホン酸塩、アルキルスルホコハク酸塩、第4級アンモニウムクロライド塩、アルキルアミン塩酸等を挙げることができる。更に本発明の効果を消失させない範囲において、例えば帯電防止剤、紫外線吸収剤、顔料、有機フィラー、潤滑剤、ブロッキング防止剤等の他の添加剤を混合することができる。
【0041】
かかるプライマー塗布液をポリエステルフィルムの片面に塗布し、次いで乾燥、熱架橋させることで、架橋プライマー層を設けることができる。塗布は、通常のプライマー塗布工程、すなわち二軸延伸熱固定したポリエステルフィルムに、該フィルムの製造工程と切離して塗布する工程で行ってもよい。しかし、この工程では、芥、塵挨などを巻込み易いから、クリーンな雰囲気での塗工が望ましい。かかる観点よりポリエステルフィルム製造工程での塗工が好ましい。特に、この工程中で結晶配向が完了する前のポリエステルフィルムの片面又は両面に水性塗布液として塗布することが好ましい。
【0042】
ここで、結晶配向が完了する前のポリエステルフィルムとは、ポリエステルを熱溶融してそのままフィルム状となした未延伸フィルム、未延伸フィルムを縦方向(長手方向)または横方向(幅方向)の何れか一方に配向せしめた一軸延伸フィルム、さらには縦方向及び横方向の二方向に低倍率延伸配向せしめたもの(最終的に縦方向または横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム)等を含むものである。通常の工程においては縦方向に一軸延伸後に塗布するのが好ましい。
【0043】
上記塗布液の固形分濃度は、通常30重量%以下であり、10重量%以下が更に好ましい。塗布量は走行しているフィルム1m2当り0.5〜20g、さらに1〜10gが好ましい。
【0044】
塗布方法としては、公知の任意の塗工法が適用できる。例えば、キスコート法、バーコート法、ダイコート法、リバースコート法、オフセットグラビアコート法、マイヤバーコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、合浸法及びカーテンコート法などを単独又は組み合わせて適用するとよい。
【0045】
塗液を塗布した、結晶配向完了する前のポリエステルフィルムは、乾燥され、延伸、熱固定等の工程に導かれる。例えば水性液を塗布した縦一軸延伸ポリエステルフィルムは、ステンターに導かれて横延伸及び熱固定される。この間、塗布液は乾燥され熱架橋される。かかる処理は、従来から当業界に蓄積された条件で行うことができる。好ましい条件としては、例えば乾燥条件は90〜130℃×2〜10秒であり、延伸温度は90〜130℃、延伸倍率は縦方向3〜5倍、横方向3〜5倍、必要ならば再縦方向1〜3倍であり、熱固定する場合は180〜240℃×2〜20秒である。かかる処理後の塗膜の厚さは20〜1000nm、更には40〜500nmであることが好ましい。
【0046】
<製膜法>
本発明における偏光板離形用ポリエステルフィルムは、基本的には従来から知られている、あるいは当業界に蓄積されている方法で製造することができる。しかし、本発明の要件を満足するため細心の注意が肝要である。例えば、先ず未配向積層フィルムを製造し、次いで該フィルムを二軸配向させることで得ることができる。この未配向積層フィルムは、従来から蓄積された積層フィルムの製造法で製造することができる。例えば、ポリエステルA層と、反対面を形成するポリエステルB層(必要に応じてC層)とを、ポリエステルの溶融状態又は冷却固化された状態で積層する方法を用いることができる。さらに具体的には、例えば共押出やエクストルージョンラミネート等の方法で製造できる。本発明は共押出し法を採る。
【0047】
各層の厚み配分に配慮し、上述の方法で積層されたフィルムは、更に従来から蓄積された二軸配向フィルムの製造法に準じて縦および横方向に延伸し、二軸配向フィルムとすることができる。例えば、融点(Tm:℃)ないし(Tm+70)℃の温度でポリエステルを溶融・共押出して未延伸積層フィルムを得、該未延伸積層フィルムを一軸方向(縦方向又は横方向)に(Tg−10)〜(Tg+70)℃の温度(但し、Tg:ポリエステルのガラス転移温度)で2.5倍以上、好ましくは3倍以上の倍率で延伸し、次いで上記延伸方向と直角方向にTg〜(Tg+70)℃の温度で2.5倍以上、好ましくは3倍以上の倍率で延伸するのが好ましい。さらに必要に応じて縦方向および/又は横方向に再度延伸してもよい。このようにして全延伸倍率は、面積延伸倍率として9倍以上が好ましく、12〜35倍がさらに好ましく、15〜30倍が特に好ましい。
【0048】
さらにまた、二軸配向フィルムは、(Tg+70)℃〜(Tm−10)℃の温度で熱固定することができ、例えばポリエチレンテレフタレートの場合は180〜235℃で熱固定するのが好ましい。偏光膜との貼合せ時等において熱収縮率が問題になる場合には、熱固定温度を225〜235℃とし、問題がなければ180〜210℃とするほうが配向角10度以下の範囲が広く、好ましい。熱固定時間は1〜60秒が好ましい。
【0049】
上記工程中、例えば縦延伸後にフィルムの片面(偏光膜に接する側)に、水分散性の塗剤を塗布し、フィルムにシリコーン易接性の乾燥後5〜200nmの皮膜を形成させることが好ましい。塗工法は限定されないが、リバースロールコーターによる塗工が好ましい。その他の条件は前項で述べた通りである。
【0050】
【実施例】
本発明における種々の物性値および特性は、以下の如く測定して評価することができる。
【0051】
(1)ヘーズ値
日本電色工業社製のヘーズ測定器(NDH−2000)を使用してフィルムのヘーズ値をJIS K−7136に準拠して測定する。評価基準は次ぎの通りである。
○:ヘーズ値6%以下
×:ヘーズ値6%超。
【0052】
(2)配向角
偏光顕微鏡を用い、試料がない状態で暗視野の状態にする。検光子の偏光軸の方向と試料の横方向を合わせて試料を挿入する。配向角が0度であると、暗視野のままであり、その他の場合視野が明るくなる。試料を回転して暗視野とする。回転角が試料の配向角である。評価基準は次ぎの通りである。
○:配向角が10度以下
×:配向角が10度超。
【0053】
(3)フライスペック
面光源、直交偏光板、拡大鏡を持つ装置の偏光板の上に試料を置いて、観察する。試料を回転させて暗視野にするとフライスペックが明るく見える。試料面積0.3m2当たり長径90μm以上の個数で表す。評価基準は次ぎの通りである。
○:長径90μm以上のフライスペックの個数が0.3m2当たり5個以下
×:長径90μm以上のフライスペックの個数が0.3m2当たり6個以上。
【0054】
(4)表面粗さ
a. 中心線表面粗さ(Ra)
フィルムの表裏両面をそれぞれ表面粗さ計(東京精密(株)サーフコム111A)で測定し平均値を算出して各表面の表面粗さとする。
b. 10点平均粗さ(Rz)
ピークの高い方から5点(Hp1,Hp2,Hp3,Hp4,Hp5)と谷の低い方から5点(Hv1,Hv2,Hv3,Hv4,Hv5)をとり、その平均粗さをRzとする。すなわち Rz=[(Hp1+Hp2+Hp3+Hp4+Hp5)−(Hv1+Hv2+Hv3+Hv4+Hv5)]/5 によって求めることができる。
【0055】
(5)粒子の平均粒径
a. 粒子が一次粒子の場合
(株)島津製作所製CP−50型セントリフューグル パーティクルサイズアナライザー(Centrifugal Particle Analyzer)を用いて測定する。得られた遼心沈降曲線を基に算出した各粒径の粒子とその残存量との積算曲線から、50マスパーセントに相当する粒径を読みとり、この値を上記平均粒径とする(「粒度測定技術」日刊工業新聞社発行、1975年、頁242〜247参照)。
【0056】
b. 粒子が凝集粒子の場合
添加した滑剤としての不活性微粒子が1次粒子の凝集による2次粒子である場合は、上記方法での平均粒径測定で得られた粒径は、実際の平均粒径より小さくなる場合があるため、次の方法を採用する。まず、粒子を含有したフィルムを断面方向に厚さ100nmの超薄切片とし、透過電子顕微鏡(例えば日本電子製JEM−1200EX)を用いて、1万倍程度の倍率で粒子を観察し、凝集粒子(2次粒子)を観察する。この写真を用いて、個々の粒子の円面積相当の直径を画像解析装置等を用いて粒子1000個について測定し、数平均した粒子径を平均2次粒径とする。なお、粒子種の同定はSEM−XMA、ICPによる金属元素の定量分析などを使用して行うことができる。平均1次粒径は透過電子顕微鏡の倍率を10万〜100万倍にて撮影するほかは平均2次粒径粒径測定の方法に準じて測定する。
【0057】
(6)フィルム厚み
外付マイクロメータで100点測定し、平均値を求めてフィルムの厚みとする。
【0058】
(7)融点
示差走査熱量測定装置(Du Pont Instruments 910 DSC)を用い、昇温速度20℃/分で融解ピークを求める方法によった。なお、サンプル量は約20mgとする。
【0059】
(8)耐スクラッチ性
直径6mmの硬質クロムメッキしたピンを固定し、長手方向に20cm、幅方向に15mmにカットしたフィルムをピンに対して90°で接触させ、一定速度(20mm/s)でピン上を滑らせて、フィルム表面に入る傷の度合を評価した。
5:まったく傷が入らない
4:0%<全体面積に対する傷の面積≦10%
3:10%<全体面積に対する傷の面積≦25%
2:25%<全体面積に対する傷の面積≦50%
1:50%<全体面積に対する傷の面積。
得られた評価結果から、下記のように耐スクラッチ性を判定した。
○:「傷の度合」評点が3点以上
×:「傷の度合」評点が2点以下。
【0060】
[実施例1]
ジメチルテレフタレートとエチレングリコールとを、エステル交換触煤として酢酸マンガンを、重合触媒として酸化ゲルマニウムを、安定剤として亜燐酸を、さらに滑剤として平均粒径1200nmの球状シリコーン粒子をポリマーに対して0.01重量%、平均粒径600nmの球状炭酸カルシウムをポリマーに対して0.2重量%、平均粒径400nmのθ型アルミナをポリマーに対して0.2重量%になるように添加して常法により重合し、固有粘度(オルソクロロフェノール、35℃)0.65のポリエチレンテレフタレートを得た。このポリエチレンテレフタレートのペレットを170℃で3時間乾燥後、押出機に供給し、溶融温度295℃で溶融し、線径13μmのステンレス細線よりなる平均目開き24μmの不織布型フィルターで濾過し、T形3層ダイの両表層から押出した。別の押出機に、滑剤粒子の量を無滑剤のポリマーで希釈し、表1に示す添加量としたポリマーを供給し、上記と同条件で上記T形3層ダイの中間層から押出した。この3層溶融物を表面仕上げ0.3s程度、表面温度20℃の回転冷却ドラム上に押出し、全厚み534μm、各層厚み70/394/70μmの未延伸フィルムを得た。
【0061】
このようにして得られた未延伸フィルムを75℃に予熱し、低速ローラーと高速ローラーの間で15mm上方より800℃の表面温度の赤外線ヒーター1本にて加熱して3.6倍に延伸し、縦延伸終了後のフィルムの片面にシリコーン易接性塗剤として次の成分の塗液を乾燥横延伸後40nmになるように塗布した。ここで用いた塗液は、シランカップリング剤(γ−グリシドプロピルトリメトキシシラン)83重量部、無機微粒子(平均粒径6nm、20%分散液pH9.5シリカゾル)2重量部、ノニオン界面活性剤(ポリオキシエチレンノニルフェニルエーテル)15重量部、を含み、クエン酸でpH6.3に調整した水性塗布液である。
【0062】
続いてステンターに供給し、120℃にて横方向に3.9倍に延伸した。得られた二軸配向フィルムを200℃の温度で5秒間熱固定し、38μm厚みの二軸配向ポリエステルフィルムを得た。
【0063】
表1には、作成したフィルムの塗布層を除く最終的な層厚みの構成、各層に添加した滑剤の材質とその平均粒径、さらに滑剤の添加量を示す。そしてこうして得られたフィルムの全幅の中央付近から採取した試料の評価結果を表2に示す。表2の結果が示すように、いずれの特性も良好なものであった。
【0064】
[実施例2〜3、比較例1〜6]
実施例1に準じて、ポリエチレンテレフタレートからなるポリエステルフィルムを作成した。ただし、各実施例および比較例においては、表1に示すように層厚みの構成や、滑剤添加の条件を変えてある。こうして得られたフィルムの特性を表2に示す。なお、比較例1はフィルム全幅の端の部分から採取した。この結果から、本発明のフィルムは要求特性を満足していることが明白である。
【0065】
【表1】
【0066】
【表2】
【0067】
【発明の効果】
本発明によれば、小配向角、高透明性、および、巻取、貼り合わせ、検品、剥離、搬送などの作業性をスクラッチを発生させることなく同時に満足する偏光板離形フィルムを提供することができ、その工業的価値は高い。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyester film for releasing a polarizing plate. More specifically, the present invention relates to a polyester film for releasing a polarizing plate, which is excellent in transparency, slipperiness, winding property, inspection property, and scratch resistance.
[0002]
[Prior art]
2. Description of the Related Art In recent years, liquid crystal display devices have been rapidly spreading in display units of mobile phones, portable game machines, in-vehicle televisions, electric devices, personal computers, and the like. In particular, demand for mobile phones, notebook computers, and space-saving desktop personal computers has increased. are doing. Accordingly, the demand for liquid crystal displays is increasing and the screen size is increasing. In a liquid crystal display device, a polarizing film is attached to both surfaces of a liquid crystal film such that polarizing axes are orthogonal to each other. Before the bonding, the release film is bonded to one side of the polarizing film.
[0003]
The release film is a protective film that prevents surface damage of the polarizing film.It is peeled off from the final product and is not used.However, it must be transparent to inspect the polarizing film, and its orientation angle must be small. In addition, it is required that fly specifications (optical contaminants) are small, a silicone layer is applied to obtain releasability, but the silicone is easy to contact, and that workability is good. In addition, as described above, the release film for a polarizing plate is peeled off from the final product. In the peeling work, it is necessary to prevent scratches on the polarizing plate surface. A film satisfying these required characteristics is exemplified in Japanese Patent Application Publication No. 2002-207119.
[0004]
[Patent Document 1]
JP-A-2002-207119
[0005]
[Problems to be solved by the invention]
In most cases, the above-mentioned film products are generally roll-conveyed as a web through a film production process, a release agent coating process, and other processing processes. In the roll transporting process, if scratches occur on the film surface, mainly due to abrasion between the film and the transporting rolls, so-called scratches will be a major obstacle in the polarizing film inspection process described above. Conventionally, there has been no polarizing plate release film in which this scratch does not occur in all steps.
[0006]
The present invention solves the problems of the prior art, and is transparent, has a small orientation angle, has easy silicon contact, has few fly specs (optical foreign matter), has good workability, and has a polarizing plate surface. It is an object of the present invention to provide a polarizing plate release film that simultaneously satisfies that the film is hardly damaged and that the film is free from scratches throughout the entire process from film production to post-processing.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, using a polyester film comprising at least two layers containing specific lubricant particles in a specific amount and having different contents of the lubricant particles, processing workability. In particular, they have found that a polarizing plate release film satisfying the required characteristics can be obtained by realizing high transparency, low foreign matter, and low orientation angle while maintaining scratch resistance, and have completed the present invention.
[0008]
That is, the polyester film for releasing a polarizing plate of the present invention is a multilayer polyester film produced by a co-extrusion method, and has a haze value of 6% or less, an orientation angle of 10 ° or less, and a fly spec of 90 μm or more in major axis. 0.3m 2 The film is characterized in that the film contains 0.001 to 1.0% by weight of inert inorganic particles having a Moh's hardness of 7 or more in at least one layer in the film.
[0009]
Preferably, the inert inorganic particles are aluminum oxide particles, and more preferably, the crystal system of the aluminum oxide particles is at least one selected from γ, δ, and θ types. Also preferably, a polyester film for releasing a polarizing plate having a center line surface roughness Ra of 20 nm or more and 60 nm or less and a 10-point average roughness Rz of 500 nm or more. Also preferably, it is a polyester film for releasing a polarizing plate having a thickness of 15 μm or more and 75 μm or less. Also preferably, a polyester film for polarizing plate release contains at least two or more kinds of lubricant particles having different average particle diameters. Also preferred is a polyester film for releasing a polarizing plate, which has a coating layer that easily adheres to silicone.
[0010]
<Polyester>
The polyester constituting the film of the present invention is preferably polyethylene terephthalate or a copolymer containing ethylene terephthalate as a main repeating unit. Polyethylene terephthalate is highly transparent as a homopolymer and is suitable for a film for releasing a polarizing plate, and is characterized by a particularly high mechanical strength.
[0011]
In the present invention, the copolymer component in the case of the copolymerized polyester may be a dicarboxylic acid component or a diol component. Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the diol component include aliphatic diols such as 1,4-butanediol, 1,6-hexanediol, and diethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; and bisphenol A. An aromatic diol can be exemplified. These can be used alone or in combination of two or more. Among these, isophthalic acid is particularly preferable because of high transparency and high tear strength.
[0012]
The proportion of the copolymer component depends on the type, and as a result, the polymer melting point is in the range of 245 ° C to 258 ° C (the melting point of the homopolymer). If the melting point is lower than 245 ° C., the heat resistance will be poor. Further, the heat shrinkage is large, and the flatness of the film is reduced. Here, the melting point of the polyester is measured by a method using a Du Pont Instruments 910 DSC to obtain a melting peak at a heating rate of 20 ° C./min. The sample amount is about 20 mg.
[0013]
The intrinsic viscosity (orthochlorophenol, 35 ° C.) of polyethylene terephthalate or copolymerized polyester is preferably 0.52 to 1.50, more preferably 0.57 to 1.00, and particularly preferably 0.60 to 0. .80. If the intrinsic viscosity is less than 0.52, the tear strength may be insufficient, which is not preferable. On the other hand, when the intrinsic viscosity exceeds 1.50, productivity in the raw material production step and the film formation step is impaired.
[0014]
The polyethylene terephthalate or the copolymerized polyester in the present invention is not limited by the production method, but in the case of terephthalic acid, ethylene glycol, and the copolymerized polyester, a copolymerization component is further added and an esterification reaction is performed, and then the obtained product is obtained. There is a method in which the reaction product is subjected to a polycondensation reaction until a desired degree of polymerization is obtained to obtain polyethylene terephthalate or copolymerized polyethylene terephthalate. Alternatively, terephthalic acid dimethyl ester and ethylene glycol, in the case of a copolymerized polyester, are further subjected to a transesterification reaction by adding a copolymerization component, and then a polycondensation reaction is performed on the resulting reaction product until the desired degree of polymerization is reached. A preferred method is terephthalate or copolymerized polyethylene terephthalate. In addition, the polyethylene terephthalate or copolymerized polyethylene terephthalate obtained by the above method (melt polymerization) may be converted into a polymer having a higher degree of polymerization by a polymerization method in the solid state (solid state polymerization) if necessary. it can.
[0015]
If necessary, additives such as an antioxidant, a heat stabilizer, a viscosity modifier, a plasticizer, a hue improver, a lubricant and a nucleating agent can be added to the copolymerized polyester. Preferred examples of the catalyst used in the polycondensation reaction include a titanium compound (Ti compound) and a germanium compound (Ge compound).
[0016]
<Additional fine particles>
In the polyester film for releasing a polarizing plate of the present invention, fine particles of a lubricant are added to ensure the workability (slipperiness) of the film, and at the same time, the film is scratched throughout the entire process from film production to post-processing. It is important not to do so, and in order to also maintain transparency, it is preferable to adjust the average particle size and the added amount of the lubricant fine particles in each layer to optimal ranges.
[0017]
In particular, in order to exert the above-mentioned scratch resistance as lubricant fine particles, it is necessary to contain 0.001 to 1.0% by weight of inert inorganic particles having a Mohs hardness of 7 or more in at least one or more layers in the film. There is. If the content of inert inorganic particles having a Mohs' hardness of 7 or more is less than 0.001% by weight, scratch resistance cannot be exhibited, and if it exceeds 1.0% by weight, the haze value often exceeds 6%, and is preferably used. Absent.
[0018]
As the inert inorganic particles having a Mohs hardness of 7 or more, arbitrary ones can be selected. Among them, aluminum oxide particles are preferable from the viewpoint of scratch resistance. In particular, the crystal system is γ, δ, θ type aluminum oxide particles. In some cases, it is preferable because scratch resistance is most remarkably exhibited.
[0019]
Other lubricant fine particles may coexist in the film. In this case, it is preferable to contain at least two or more types of lubricant particles having different average particle sizes. As the lubricant fine particles, any one can be selected. Examples of the inorganic lubricant include silica, titanium dioxide, calcium carbonate, barium sulfate, and the like. Examples of the organic lubricant include spherical silicone resin particles and cross-linked polystyrene particles.
[0020]
The film of the present invention is a coextruded film comprising at least two layers. The average particle size of the lubricant particles added to each layer is in the range of 1000 to 3000 nm, preferably 1000 to 2500 nm, and more preferably 1000 to 2000 nm as a large particle size on the side in contact with the polarizing film. Further, those having a small particle diameter are preferably in the range of 50 to 800 nm, more preferably 100 to 700 nm.
[0021]
When the average particle diameter of the large-diameter particles exceeds 3,000 nm, the peel strength between the silicone layer coated on this surface and the polarizing film surface becomes too light, spontaneous peeling may occur, and the practicability may decrease. . In addition, when wound on a roll, the projections may be transferred to cause a surface defect. When the average particle size is less than 1000 nm, the peel strength between the silicone layer applied on this surface and the polarizing film surface becomes too heavy, the peeling workability is reduced, and defects such as peeling marks on the polarizing film surface are caused. May occur.
[0022]
If the average particle size of the small-sized particles exceeds 800 nm, it may be difficult to develop abrasion resistance. On the other hand, if it is less than 50 nm, the addition amount must be increased in order to obtain scratch resistance, and the haze value of the film may exceed 6% in some cases.
[0023]
On the outer surface side (the side not in contact with the polarizing film surface), the case of two layers and the case of three (or more) layers are different. In the case of three (or three or more) layers, it is substantially the same as the layer in contact with the polarizing film surface. However, since the coating is not performed, the lower limit of the average particle diameter of the large particle diameter is 500 nm. In this case, the lubricant particles in the intermediate layer do not contribute to the workability and reduce the transparency. However, considering the reuse of the recovered portion, it is preferable not to set it to 0%. The content of the lubricant particles in the intermediate layer is preferably 70% or less, more preferably 50% or less, of the content of the layer in contact with the polarizing film. If the content exceeds 70%, the transparency is lowered, and the defect is hidden when inspecting the defect of the polarizing plate. In the case of two layers, the content of the lubricant particles is preferably 70% or less and 20% or more of the content of the layer in contact with the polarizing film in order to impart workability to the outer surface side. If it is less than 20%, the sliding property is poor and the workability is poor.
[0024]
Further, in order to reduce the number of coarse particles and fly specs, a non-woven fabric type filter having an average opening of 10 to 30 μm, preferably 15 to 25 μm made of stainless steel fine wire having a wire diameter of 15 μm or less is used as a filter at the time of film formation. It is recommended that the polymer be filtered. According to this method, coarse particles having a particle diameter of 20 μm or more and fly specs having a long diameter of 90 μm or more can be almost removed.
[0025]
Except for containing inert inorganic particles having a Moh's hardness of 7 or more, the material of the lubricant particles is not specified, but as the particles having an average particle diameter of 200 to 3000 nm, the spherical silicone resin and the spherical particles are particularly exemplified. Silica is preferred, and particles having a sharp particle size distribution and a Mohs hardness of 5 or more are preferred because of small deformation of the particles. In addition to the above-described aluminum oxide, silica, titanium oxide, zirconium oxide, and composite oxides thereof are preferably used as the particles having a particle size of 50 to 800 nm, and two or more kinds thereof may be used in combination.
[0026]
The lubricant particles are usually used during the reaction for producing the polyester, for example, by the transesterification method, at any time during the transesterification reaction or the polycondensation reaction, or at any time when the direct polymerization method is used. (Preferably as a slurry in glycol). In particular, it is preferable to add particles to the reaction system at the beginning of the polycondensation reaction, for example, during a period until the intrinsic viscosity reaches about 0.3.
[0027]
<Film thickness>
The thickness of the film of the present invention is preferably 15 μm or more and 75 μm or less. Further, it is preferably in the range of 20 μm or more and 70 μm or less, particularly preferably in the range of 25 μm or more and 65 μm. If it exceeds 75 μm, the haze value may exceed 6%, which lowers the inspection accuracy and increases the cost, which is not preferable. If the thickness is less than 15 μm, the strength, that is, the so-called waist, is insufficient, and it is difficult to peel off at the time of release.
[0028]
The thickness of each layer on the side in contact with the polarizing film is 3% to 50%, preferably 4% to 40%, more preferably 5% to 30% of the total thickness. In the case of two layers, the other layer accounts for 50% or more and 97% or less of the total thickness, preferably 60% or more and 96% or less, and more preferably 70% or more and 95% or less. If the side in contact with the polarizing film, that is, the rough surface side exceeds 50%, the haze value may exceed 6%, and if it is less than 3%, the winding property of the film is poor and the product yield is low. In the case of three (or more) layers, the thickness of the surface layer on the side opposite to the side in contact with the polarizing film is preferably 3 to 20% of the total thickness. If it is less than 3%, the effect is small, and if it exceeds 20%, the haze value tends to increase.
[0029]
<Fly specs>
The fly specification having a major axis of 90 μm or more present in the polyester film of the present invention is 0.3 m 2 It is necessary that there be no more than five. Fly specifications having a major axis of 90 μm or more hinder straight traveling of light and cause distortion of an image. Since fly specs generate foreign matter, unmelted polymer and coarse particles in the nucleus, it is preferable to remove coarse particles and foreign matters by using the above-mentioned nonwoven fabric type filter. Further, it is preferable to use lubricant particles that do not contain many fly specs.
[0030]
<Orientation angle>
The orientation angle of the film of the present invention is 10 degrees or less. When the orientation angle exceeds 10 degrees, when inspecting the polarizing film, the visual field becomes dark, and the detection accuracy of foreign substances is reduced. In order to obtain a film having an orientation angle of 10 degrees or less, it is preferable to use only about 20% of the center of the film forming machine width. The rest is used for other purposes. Here, the orientation angle is an angle formed with the width (lateral) direction of the orientation main axis by stretching. A normal polyester film formed by longitudinal and transverse sequential stretching has weak horizontal orientation or uniform orientation at the center in the width direction at the time of film formation, and the orientation angle is set to 0 degree.
[0031]
When the sheet can be supplied in the form of a single-wafer film, by punching by inclining the direction of one side of the punching machine from the lateral direction by an angle corresponding to the orientation angle, end parts can also be used, but the loss increases more at the end.
[0032]
If you have a device that can perform heat treatment by holding both ends of the full-width film with a gripper and making the entrance width and exit width almost equal, in the heat treatment step described in the film forming method, lower the processing temperature and move the center part Is formed to about half of the normal thickness. The moving amount is determined by drawing a straight line in the horizontal (width) direction with ink rope or the like on the film before entering the horizontal stretching machine, and calculating the amount of the straight line bent out of the horizontal stretching machine in an arc shape. The film is heat-treated at 200 to 245 ° C. through a heat treatment machine having a gripper and capable of making the entrance width and the exit width substantially equal. At this time, it is important to perform processing so that the running direction is reversed between the time of film formation and the time of the heat treatment, and conditions are set such that the arc-shaped line returns to a substantially straight line. By this processing, the anisotropy at both ends is corrected, and an orientation angle of 10 degrees or less can be realized over the entire width. However, a decrease in yield due to a decrease in productivity (increase in the number of steps) and a discard of the gripping tool part cannot be avoided, and there is a disadvantage. This is a method that can be adopted only when equipment can be handled.
[0033]
<Surface roughness>
The center line surface roughness Ra of the film of the present invention is preferably 20 nm or more and 60 nm or less. If it is less than 20 nm, the film surfaces tend to adhere to each other, the winding appearance and workability are poor, and the surface is easily scratched. If it exceeds 60 nm, the transparency is reduced, and the inspection property is reduced. The ten-point average surface roughness Rz is preferably 500 nm or more on the silicone coating side. When Rz is less than 500 nm, projections on the surface of the silicone coating layer become very small, and the separation from the polarizing film becomes heavy. Although the upper limit cannot be specified, it is sufficient that Ra does not exceed 60 nm. In order to obtain such surface roughness, the aforementioned lubricant particles are added.
[0034]
<Easy contact layer>
It is preferable to form a coating film that is easily contactable with silicone on one surface of the polyester film of the present invention, that is, on the surface in contact with the polarizing film. Silicone is applied to release the film of the present invention used for protecting the polarizing film surface from the polarizing film. However, since the polyester film and the silicone have poor adhesiveness, some treatment for easy adhesion is required. In the present invention, it is preferable to form the following primer layer.
[0035]
The silane coupling agent constituting the primer layer is a compound represented by the general formula YRSix3. Here, Y is an organic functional group such as a vinyl group, an epoxy group, an amino group, and a mercapto group; R is an alkylene group such as methylene, ethylene, and propylene; X is a hydrolytic group such as a methoxy group and an ethoxy group; It is an alkyl group. Specific compounds include, for example, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropyl Examples include trimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. Preferred silane coupling agents are water-soluble or water-dispersible coupling agents.
[0036]
Examples of the alkaline inorganic fine particles constituting the primer layer together with the silane coupling agent include iron oxide sol, alumina sol, tin oxide sol, zirconium oxide sol, silica sol, and the like, and alumina sol and silica sol are particularly preferable. Among them, silica sol is preferred from the viewpoint of promoting the initial reactivity (dimerization, trimerization, etc.) of the silane coupling agent.
[0037]
The alkaline inorganic fine particles preferably have a small particle diameter having a large surface area, and preferably have an average particle diameter of 1 to 150 nm, more preferably 2 to 100 nm, particularly preferably 3 to 50 nm. If the average particle size is larger than 150 nm, the surface area becomes too small, the reaction promoting action of the silane coupling agent is reduced, and the surface of the primer layer is unfavorably roughened. On the other hand, when the average particle size is smaller than 1 nm, the surface area is too large, and it is difficult to control the reaction of the silane coupling agent, which is not preferable.
[0038]
The amount of the alkaline inorganic fine particles is preferably 1 to 50% by weight, more preferably 2 to 20% by weight, based on the amount of the silane coupling agent. If the amount is less than 1% by weight, the crosslinking reaction does not proceed, while if it exceeds 50% by weight, the stability of the coating solution is lacking. For example, precipitation occurs in the coating solution in a short time after addition of the inorganic fine particles, Not preferred.
[0039]
The pH of a primer coating solution containing a silane coupling agent and alkaline inorganic fine particles, particularly an aqueous coating solution, is adjusted to 4.0 to 7.0, preferably 5.0 to 6.7. When the pH is less than 4.0, the catalytic activity of the inorganic fine particles is lost. On the other hand, when the pH is more than 7.0, the coating solution becomes unstable and precipitates, which is not preferable. Examples of the acid for adjusting the pH include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as oxalic acid, formic acid, citric acid, and acetic acid. Organic acids are particularly preferable.
[0040]
After the application, a necessary amount of a surfactant such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be added to the aqueous liquid. As such a surfactant, those capable of lowering the surface tension of the coating solution to 0.5 N / m or less, preferably 0.4 N / m or less and promoting wetting to a polyester film are preferable. For example, polyoxyethylene alkyl phenyl ether And polyoxyethylene-fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid metal soaps, alkyl sulfates, alkyl sulfonates, alkyl sulfosuccinates, quaternary ammonium chloride salts, and alkylamine hydrochlorides. Further, other additives such as an antistatic agent, an ultraviolet absorber, a pigment, an organic filler, a lubricant, and an anti-blocking agent can be mixed as long as the effects of the present invention are not lost.
[0041]
Such a primer coating solution is applied to one surface of a polyester film, and then dried and thermally crosslinked to provide a crosslinked primer layer. The application may be carried out in a usual primer application step, that is, a step of applying to a polyester film which has been biaxially stretched and heat-set, separated from the production step of the film. However, in this step, it is desirable to apply the coating in a clean atmosphere because refuse, dust and the like are easily involved. From such a viewpoint, coating in the polyester film production process is preferable. In particular, it is preferable to apply an aqueous coating solution to one or both sides of the polyester film before the crystal orientation is completed in this step.
[0042]
Here, the polyester film before the completion of the crystal orientation refers to an unstretched film in which the polyester is thermally melted and formed into a film as it is, or an unstretched film in either the longitudinal direction (longitudinal direction) or the transverse direction (width direction). A uniaxially stretched film oriented in one direction, and further a film stretched and oriented in a low ratio in two directions of a longitudinal direction and a transverse direction (before final stretching in the longitudinal direction or the transverse direction to complete orientation crystallization) Biaxially stretched film). In a usual process, it is preferable to apply the film after uniaxial stretching in the longitudinal direction.
[0043]
The solid content concentration of the coating solution is usually 30% by weight or less, and more preferably 10% by weight or less. Coating amount is 1m of running film 2 It is preferably 0.5 to 20 g, more preferably 1 to 10 g.
[0044]
As a coating method, any known coating method can be applied. For example, kiss coat method, bar coat method, die coat method, reverse coat method, offset gravure coat method, myrbar coat method, gravure coat method, roll brush method, spray coat method, air knife coat method, infiltration method and curtain coat method These may be applied alone or in combination.
[0045]
The polyester film to which the coating liquid has been applied and before the completion of the crystal orientation is dried, and guided to steps such as stretching and heat setting. For example, a vertically uniaxially stretched polyester film to which an aqueous liquid has been applied is guided to a stenter and is horizontally stretched and thermally fixed. During this time, the coating solution is dried and thermally crosslinked. Such processing can be performed under conditions conventionally accumulated in the art. Preferred conditions include, for example, drying conditions of 90 to 130 ° C. × 2 to 10 seconds, a stretching temperature of 90 to 130 ° C., a stretching ratio of 3 to 5 times in the machine direction, 3 to 5 times in the transverse direction, and The length is 1 to 3 times in the vertical direction, and 180 to 240 ° C. × 2 to 20 seconds when heat-fixed. The thickness of the coating film after such treatment is preferably 20 to 1000 nm, more preferably 40 to 500 nm.
[0046]
<Film forming method>
The polyester film for releasing a polarizing plate in the present invention can be basically produced by a conventionally known method or a method accumulated in the art. However, great care is needed to satisfy the requirements of the present invention. For example, it can be obtained by first producing an unoriented laminated film and then biaxially orienting the film. This unoriented laminated film can be produced by a conventionally accumulated method for producing a laminated film. For example, a method of laminating a polyester A layer and a polyester B layer (C layer if necessary) forming the opposite surface can be used in a state where the polyester is melted or cooled and solidified. More specifically, it can be manufactured by a method such as coextrusion or extrusion lamination. The present invention employs a co-extrusion method.
[0047]
In consideration of the thickness distribution of each layer, the film laminated by the above method may be further stretched in the vertical and horizontal directions according to a conventionally accumulated manufacturing method of a biaxially oriented film to form a biaxially oriented film. it can. For example, polyester is melted and co-extruded at a temperature of melting point (Tm: ° C) to (Tm + 70) ° C to obtain an unstretched laminated film, and the unstretched laminated film is uniaxially (longitudinal or transverse) (Tg-10). ) To (Tg + 70) ° C. (however, Tg: glass transition temperature of polyester) at a stretching ratio of 2.5 times or more, preferably 3 times or more, and then Tg to (Tg + 70) in a direction perpendicular to the stretching direction. It is preferable that the film is stretched at a temperature of ° C. at a magnification of 2.5 times or more, preferably 3 times or more. Further, if necessary, the film may be stretched again in the machine direction and / or the cross direction. Thus, the total stretching ratio is preferably 9 times or more, more preferably 12 to 35 times, particularly preferably 15 to 30 times, as the area stretching ratio.
[0048]
Furthermore, the biaxially oriented film can be heat-set at a temperature of (Tg + 70) ° C to (Tm-10) ° C. For example, in the case of polyethylene terephthalate, it is preferable to heat-set at 180 to 235 ° C. When the heat shrinkage rate becomes a problem at the time of lamination with a polarizing film or the like, the heat setting temperature is set to 225 to 235 ° C., and if there is no problem, the range of 180 to 210 ° C. or less for the orientation angle of 10 ° or less is wider. ,preferable. The heat setting time is preferably 1 to 60 seconds.
[0049]
In the above step, for example, it is preferable that a water-dispersible coating agent is applied to one surface (the side in contact with the polarizing film) of the film after longitudinal stretching, and a film having a thickness of 5 to 200 nm is formed on the film after drying with easy silicone contact. . The coating method is not limited, but coating by a reverse roll coater is preferable. Other conditions are as described in the previous section.
[0050]
【Example】
Various physical properties and characteristics in the present invention can be measured and evaluated as follows.
[0051]
(1) Haze value
The haze value of the film is measured using a haze measuring device (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K-7136. The evaluation criteria are as follows.
○: Haze value 6% or less
X: Haze value more than 6%.
[0052]
(2) Orientation angle
Using a polarizing microscope, place in a dark field state without any sample. The sample is inserted so that the direction of the polarization axis of the analyzer is aligned with the lateral direction of the sample. When the orientation angle is 0 degrees, the visual field remains dark, and in other cases, the visual field becomes bright. Rotate sample to dark field. The rotation angle is the orientation angle of the sample. The evaluation criteria are as follows.
:: orientation angle of 10 degrees or less
X: The orientation angle exceeds 10 degrees.
[0053]
(3) Fly specifications
A sample is placed on a polarizing plate of a device having a surface light source, a crossed polarizing plate, and a magnifying glass and observed. When the sample is rotated to a dark field, the fly specs appear bright. Sample area 0.3m 2 It is represented by the number of major diameters of 90 μm or more. The evaluation criteria are as follows.
:: The number of fly specs having a major axis of 90 μm or more is 0.3 m. 2 5 or less per
×: The number of fly specs having a major axis of 90 μm or more is 0.3 m. 2 6 or more per.
[0054]
(4) Surface roughness
a. Center line surface roughness (Ra)
Both the front and back surfaces of the film are measured with a surface roughness meter (Surfcom 111A, Tokyo Seimitsu Co., Ltd.), and the average value is calculated to be the surface roughness of each surface.
b. 10-point average roughness (Rz)
Five points (Hp1, Hp2, Hp3, Hp4, Hp5) from the higher peak and five points (Hv1, Hv2, Hv3, Hv4, Hv5) from the lower valley are taken, and the average roughness is Rz. That is, Rz = [(Hp1 + Hp2 + Hp3 + Hp4 + Hp5)-(Hv1 + Hv2 + Hv3 + Hv4 + Hv5)] / 5.
[0055]
(5) Average particle size
a. When the particle is a primary particle
It is measured using a CP-50 type centrifugal particle size analyzer (Centrifugal Particle Analyzer) manufactured by Shimadzu Corporation. From the integrated curve of the particles of each particle size and the residual amount calculated based on the obtained Liaoshin sedimentation curve, the particle size corresponding to 50 mass% is read, and this value is defined as the above average particle size ("particle size" Measurement Techniques ", published by Nikkan Kogyo Shimbun, 1975, pp. 242 to 247).
[0056]
b. When the particles are agglomerated particles
When the inert fine particles as the added lubricant are secondary particles due to aggregation of the primary particles, the particle size obtained by the average particle size measurement by the above method may be smaller than the actual average particle size. Therefore, the following method is adopted. First, the film containing the particles is cut into ultrathin sections having a thickness of 100 nm in the cross-sectional direction, and the particles are observed at a magnification of about 10,000 times using a transmission electron microscope (for example, JEM-1200EX manufactured by JEOL Ltd.). (Secondary particles) are observed. Using this photograph, the diameter equivalent to the circular area of each particle is measured for 1000 particles using an image analyzer or the like, and the number averaged particle diameter is defined as the average secondary particle diameter. The identification of the particle type can be performed using SEM-XMA, quantitative analysis of a metal element by ICP, or the like. The average primary particle size is measured in accordance with the method of measuring the average secondary particle size except that the transmission electron microscope is used at a magnification of 100,000 to 1,000,000 times.
[0057]
(6) Film thickness
100 points are measured with an external micrometer, and the average value is determined to be the thickness of the film.
[0058]
(7) Melting point
Using a differential scanning calorimeter (Du Pont Instruments 910 DSC), the melting peak was determined at a heating rate of 20 ° C./min. The sample amount is about 20 mg.
[0059]
(8) Scratch resistance
A hard chrome-plated pin having a diameter of 6 mm is fixed, and a film cut to a length of 20 cm and a width of 15 mm is brought into contact with the pin at 90 ° and slid on the pin at a constant speed (20 mm / s). The degree of scratches entering the film surface was evaluated.
5: No damage at all
4: 0% <Scratch area ≦ 10% of total area
3: 10% <Scratch area ≦ 25% of the total area
2: 25% <wound area ≤50% of total area
1: 50% <wound area relative to total area.
From the obtained evaluation results, the scratch resistance was determined as follows.
:: “Scratch degree” score of 3 or more
X: The score of "degree of scratch" is 2 or less.
[0060]
[Example 1]
Dimethyl terephthalate and ethylene glycol, manganese acetate as a transesterification catalyst, germanium oxide as a polymerization catalyst, phosphorous acid as a stabilizer, and spherical silicone particles having an average particle diameter of 1200 nm as a lubricant 0.01% to the polymer. % By weight, spherical calcium carbonate having an average particle diameter of 600 nm was added to the polymer in an amount of 0.2% by weight, and θ-type alumina having an average particle diameter of 400 nm was added to the polymer in an amount of 0.2% by weight, and the conventional method was used. Polymerization yielded polyethylene terephthalate having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65. The polyethylene terephthalate pellets were dried at 170 ° C. for 3 hours, fed to an extruder, melted at a melting temperature of 295 ° C., and filtered through a nonwoven fabric type filter having an average opening of 24 μm consisting of stainless fine wires having a diameter of 13 μm. Extruded from both surfaces of a three-layer die. To another extruder, the amount of the lubricant particles was diluted with a lubricant-free polymer, and the polymer having the addition amount shown in Table 1 was supplied, and extruded from the intermediate layer of the T-type three-layer die under the same conditions as above. The three-layer melt was extruded onto a rotary cooling drum having a surface finish of about 0.3 s and a surface temperature of 20 ° C. to obtain an unstretched film having a total thickness of 534 μm and a layer thickness of 70/394/70 μm.
[0061]
The unstretched film thus obtained is preheated to 75 ° C. and heated by a single infrared heater having a surface temperature of 800 ° C. from 15 mm above the low-speed roller and the high-speed roller and stretched 3.6 times. On the one surface of the film after the completion of the longitudinal stretching, a coating liquid of the following components was applied as a silicone-friendly coating agent to a thickness of 40 nm after the dry transverse stretching. The coating liquid used here was 83 parts by weight of a silane coupling agent (γ-glycidopropyltrimethoxysilane), 2 parts by weight of inorganic fine particles (average particle diameter 6 nm, 20% dispersion pH 9.5 silica sol), nonionic surfactant An aqueous coating solution containing 15 parts by weight of an agent (polyoxyethylene nonylphenyl ether) and adjusted to pH 6.3 with citric acid.
[0062]
Subsequently, it was supplied to a stenter and stretched 3.9 times in the transverse direction at 120 ° C. The obtained biaxially oriented film was heat-set at a temperature of 200 ° C. for 5 seconds to obtain a 38 μm thick biaxially oriented polyester film.
[0063]
Table 1 shows the composition of the final layer thickness excluding the coating layer of the formed film, the material of the lubricant added to each layer, the average particle size thereof, and the amount of the lubricant added. Table 2 shows the evaluation results of the samples obtained from the vicinity of the center of the entire width of the film thus obtained. As shown in the results of Table 2, all the characteristics were good.
[0064]
[Examples 2 to 3, Comparative Examples 1 to 6]
A polyester film made of polyethylene terephthalate was prepared according to Example 1. However, in each of Examples and Comparative Examples, as shown in Table 1, the composition of the layer thickness and the conditions for adding the lubricant were changed. Table 2 shows the properties of the film thus obtained. In Comparative Example 1, the film was collected from the end portion of the entire width of the film. From these results, it is clear that the film of the present invention satisfies the required characteristics.
[0065]
[Table 1]
[0066]
[Table 2]
[0067]
【The invention's effect】
According to the present invention, there is provided a polarizing plate release film that simultaneously satisfies small orientation angles, high transparency, and workability such as winding, bonding, inspection, peeling, and conveyance without generating scratches. And its industrial value is high.
Claims (8)
Priority Applications (1)
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JP2003025811A JP2004237451A (en) | 2003-02-03 | 2003-02-03 | Polyester film for releasing polarizing plate |
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JP2003025811A JP2004237451A (en) | 2003-02-03 | 2003-02-03 | Polyester film for releasing polarizing plate |
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JPH0253735A (en) * | 1988-08-12 | 1990-02-22 | Nippon Chemiphar Co Ltd | Agent for alleviating dementia |
JP2006171707A (en) * | 2004-11-18 | 2006-06-29 | Nitto Denko Corp | Polarizing plate and image display using same |
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US9798189B2 (en) | 2010-06-22 | 2017-10-24 | Toyobo Co., Ltd. | Liquid crystal display device, polarizer and protective film |
US10503016B2 (en) | 2010-06-22 | 2019-12-10 | Toyobo Co., Ltd. | Liquid crystal display device, polarizer and protective film |
US9897857B2 (en) | 2010-06-22 | 2018-02-20 | Toyobo Co., Ltd. | Liquid crystal display device, polarizer and protective film |
US10180597B2 (en) | 2011-05-18 | 2019-01-15 | Toyobo Co., Ltd. | Liquid crystal display device, polarizing plate, and polarizer protection film |
US10175494B2 (en) | 2011-05-18 | 2019-01-08 | Toyobo Co., Ltd. | Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device |
JPWO2013100044A1 (en) * | 2011-12-28 | 2015-05-11 | 東洋紡株式会社 | Liquid crystal display device, polarizing plate and polarizer protective film |
WO2013100044A1 (en) * | 2011-12-28 | 2013-07-04 | 東洋紡株式会社 | Liquid crystal display device, polarizing plate, and polarizer protective film |
JPWO2014021242A1 (en) * | 2012-07-30 | 2016-07-21 | 東洋紡株式会社 | Liquid crystal display device, polarizing plate and polarizer protective film |
WO2014021242A1 (en) * | 2012-07-30 | 2014-02-06 | 東洋紡株式会社 | Liquid crystal display device, polarizing plates, and polarizer protection film |
JP2014233899A (en) * | 2013-06-01 | 2014-12-15 | 三菱樹脂株式会社 | Polyester film for release film |
JP2015145077A (en) * | 2014-02-03 | 2015-08-13 | 三菱樹脂株式会社 | Polyester film for release film |
JP2015189118A (en) * | 2014-03-28 | 2015-11-02 | 三菱樹脂株式会社 | Polyester film for mold releasing film |
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