JP2004300379A - Readily adhering polyester film for optical use - Google Patents
Readily adhering polyester film for optical use Download PDFInfo
- Publication number
- JP2004300379A JP2004300379A JP2003098103A JP2003098103A JP2004300379A JP 2004300379 A JP2004300379 A JP 2004300379A JP 2003098103 A JP2003098103 A JP 2003098103A JP 2003098103 A JP2003098103 A JP 2003098103A JP 2004300379 A JP2004300379 A JP 2004300379A
- Authority
- JP
- Japan
- Prior art keywords
- polyester film
- film
- polyester
- coating layer
- coating
- 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 39
- 230000003287 optical effect Effects 0.000 title claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 40
- 239000010419 fine particle Substances 0.000 claims abstract description 27
- 239000002952 polymeric resin Substances 0.000 claims abstract description 9
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims description 39
- 230000001070 adhesive effect Effects 0.000 claims description 35
- -1 polyethylene terephthalate Polymers 0.000 claims description 28
- 229920000728 polyester Polymers 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- 229920001225 polyester resin Polymers 0.000 claims description 11
- 239000004645 polyester resin Substances 0.000 claims description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 37
- 239000011248 coating agent Substances 0.000 abstract description 35
- 239000010410 layer Substances 0.000 abstract description 14
- 239000010408 film Substances 0.000 description 68
- 239000001993 wax Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000012788 optical film Substances 0.000 description 5
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 4
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004203 carnauba wax Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 239000004094 surface-active agent Substances 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 1
- DBXOZIGKCLFPQZ-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)cyclohexane-1,3-diamine Chemical compound C1OC1CN(C1CC(CCC1)N(CC1OC1)CC1OC1)CC1CO1 DBXOZIGKCLFPQZ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical group C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- PBYIFPWEHGSUEY-UHFFFAOYSA-N 2-ethenyl-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C=C)=N1 PBYIFPWEHGSUEY-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical class CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical compound OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-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、光学用易接着性ポリエステルフィルムに関し、更に詳しくは、優れた接着性、透明性、易滑性、塗膜均一性を有する光学用易接着性ポリエステルフィルムに関する。
【０００２】
【従来の技術】
ポリエステルフィルム、特にポリエチレンテレフタレートやポリエチレンナフタレートの二軸延伸フィルムは、優れた機械的性質、耐熱性、耐薬品性を有するため、磁気テープ、強磁性薄膜テープ、写真フィルム、包装用フィルム、電子部品用フィルム、電気絶縁フィルム、金属板ラミネート用フィルム、ガラスディスプレイ等の表面に貼るフィルム、各種部材の保護用フィルム等の素材として広く用いられている。
【０００３】
ポリエステルフィルムは、近年、特に各種光学用フィルムに多く用いられ、液晶表示装置の部材のプリズムレンズシート、タッチパネル、バックライト等のベースフィルムや反射防止用フィルムのベースフィルムやディスプレイの防爆用ベースフィルム等の用途に用いられている。このような光学用フィルムに用いられるベースフィルムは優れた透明性が要求される。さらにプリズムレンズ層、ハードコート、粘着剤、反射防止処理、スパッタ層等に対する優れた易接着性が要求される。
【０００４】
光学用フィルムは、透明性が要求されるため、通常内添フィラーを最小限にする必要がある。また、易接着層の接着力を向上させるには易接着層にガラス転移点の低い樹脂が用いられる。このように光学用フィルムでは内添フィラーを必要最小限にするか、もしくは内添フィラーを全く用いないのでフィルム表面が平坦になっており、更にガラス転移点の低い樹脂を易接着層に用いるとフィルムを巻いたり、重ね合わせた時に貼付きが発生し、フィルム同士が滑らずハンドリング性が悪化したり、滑りにくいために製膜や加工工程で表面に傷が入り易くなる。また、光学用フィルムは透明性が高いため易接着層の透明性が低いと発泡や振動等による塗布の不均一性が目立ちやすい。
【０００５】
ところで、二軸配向ポリエステルフィルムは一般的に他の材料、例えばアクリル系樹脂を主成分とするプリズムレンズ層やハードコートとの接着性が悪いため、ポリエステルフィルムの表面に、ポリエステル樹脂やアクリル樹脂やウレタン樹脂等の易接着層を積層して用いることが提案されている（例えば、特開平１０−１１９２１５号公報、特開２０００−２４６８５５号公報）。しかし、これら樹脂からなる易接着層を形成したものでは、接着力が不足する場合がある。例えば、ＣＲＴ用のフィルムではハードコート層への接着力は良好だが反対面の粘着層への接着力が不十分であり、汎用性に乏しい。
【０００６】
【特許文献１】
特開平１０−１１９２１５号公報
【０００７】
【特許文献２】
特開２０００−２４６８５５号公報
【０００８】
【発明が解決しようとする課題】
本発明は、かかる従来技術の問題点を解消し、透明性、易滑性、耐傷性、塗膜均一性に優れ、しかも種々の光学用途に用いられる層との接着力に優れた光学用易接着性ポリエステルフィルムを提供することを目的とする。
【０００９】
【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、ポリエステルフィルムの少なくとも片面に、塗布層を有し、その表面の正反射光（Ａ）と１５°での反射光（Ｂ）の強度比（Ａ／Ｂ）が０．５〜２の範囲であり、該塗布層を有し、高分子樹脂及び微粒子から主に構成される易接着性塗膜を形成すれば、上記課題を解決できることを見出し、本発明を完成するに至った。
【００１０】
すなわち本発明は、ポリエステルフィルムの少なくとも片面に、高分子樹脂及び微粒子からなる塗布層を有し、表面の正反射光（Ａ）と１５°での反射光（Ｂ）の強度比（Ａ／Ｂ）が０．５〜２であることを特徴とする、光学用易接着性ポリエステルフィルムである。
【００１１】
本発明は、好ましい態様として、以下の態様を取る。
【００１２】
高分子樹脂がポリエステル樹脂である態様。
【００１３】
微粒子が平均粒子径２０〜１５０ｎｍの無機もしくは有機微粒子である態様。
【００１４】
塗布層が塗布層の全重量に対して０．５〜３０重量％の脂肪族ワックスを含有する態様。
【００１５】
表面ヘーズ値が０．５％以下である態様。
【００１６】
ポリエステルフィルムのポリエステルがポリエチレンテレフタレートまたはポリエチレン−２，６−ナフタレートである態様。
【００１７】
以下、本発明を詳細に説明する。
【００１８】
［ポリエステルフィルム］
本発明においてポリエステルフィルムを構成するポリエステルは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから合成される線状飽和ポリエステルである。
【００１９】
ポリエステルとして、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−ナフタレートを例示することができる。ポリエステルは、これらの共重合体またはこれと少割合の他樹脂とのブレンド物であってもよい。これらのポリエステルのうち、特にポリエチレンテレフタレート、ポリエチレン−２，６−ナフタレートが力学的物性や光学物性等のバランスが良いので好ましい。
【００２０】
ポリエステルには、必要に応じて適当なフィラーを含有させてもよいが、透明性を良好する観点から、ポリエステル中のフィラーは少ないほうがよく、フィラーを実質的に含有しないことが好ましい。
【００２１】
フィラーを用いる場合、フィラーとしては、従来からポリエステルフィルムの滑り性付与剤として知られているものを用いることができる。例えば、炭酸カルシウム、酸化カルシウム、酸化アルミニウム、カオリン、酸化珪素、酸化亜鉛、カーボンブラック、炭化珪素、酸化錫、架橋アクリル樹脂粒子、架橋ポリスチレン樹脂粒子、メラミン樹脂粒子、架橋シリコーン樹脂粒子を挙げることができる。
【００２２】
ポリエステルには、着色剤、帯電防止剤、酸化防止剤、有機滑剤、触媒を必要に応じて添加してもよい。
【００２３】
本発明おけるポリエステルフィルムは、上述のポリエステルを、例えばフィルム状に溶融押出し、キャスティングドラムで冷却固化させて未延伸フィルムとし、この未延伸フィルムをＴｇ〜（Ｔｇ＋６０）℃で長手方向に１回もしくは２回以上合計の倍率が３倍〜６倍になるよう延伸し、その後Ｔｇ〜（Ｔｇ＋６０）℃で幅方向に倍率が３〜５倍になるように延伸し、必要に応じて更に１８０〜２３０℃で１〜６０秒間熱処理を行い、熱処理温度より１０〜２０℃低い温度で幅方向に０〜２０％収縮させながら再熱処理を行うことにより得ることができる。
【００２４】
本発明におけるポリエステルフィルムの厚みは、ハードコート、タッチパネル、防眩処理等の支持体として使用する場合に必要な強度を得るために２５〜３００μｍであることが好ましく、特に５０〜２５０μｍであることが好ましい。
【００２５】
［塗布層］
本発明のフィルムは塗布層を備える。この塗布層は、表面の正反射光（Ａ）と１５°での反射光（Ｂ）の強度比（Ａ／Ｂ）が０．５〜２の範囲である。０．５よりも小さいと散乱光が増え、光線透過率が低くなる。２よりも大きくなると正反射光が強くなり、光による観察では塗布層の不均一性が目立つ。
【００２６】
この条件を満たす塗布層は、次に説明する高分子樹脂と微粒子からなる塗布層をフィルムの表面に設けることにより形成することができる。
【００２７】
［高分子樹脂］
塗布層に用いる高分子樹脂は、ポリエステル樹脂であることが好ましく、水（多少の有機溶剤を含有していても良い）に可溶性または分散性のものが好ましい。
かかるポリエステル樹脂として、以下に示す多塩基酸またはそのエステル形成誘導体とポリオールまたはそのエステル形成誘導体から得られるポリエステルを挙げることができる。
【００２８】
ポリエステル樹脂の多塩基酸成分としては、例えば、テレフタル酸、イソフタル酸、フタル酸、無水フタル酸、２、６−ナフタレンジカルボン酸、１、４−シクロヘキサンジカルボン酸、アジピン酸、セバシン酸、トリメリット酸、ピロメリット酸、ダイマー酸、５−ナトリウムスルホイソフタル酸を挙げることができる。
【００２９】
ポリエステル樹脂は、これら酸成分を２種以含有する共重合ポリエステルであることが好ましい。ポリエステル樹脂には、若干量であればマレイン酸、イタコン酸等の不飽和多塩基酸成分が、或いはｐ−ヒドロキシ安息香酸等の如きヒドロキシカルボン酸成分が含まれていてもよい。
【００３０】
ポリエステル樹脂のポリオール成分としては、例えばエチレングリコール、１、４−ブタンジオール、ジエチレングリコール、ジプロピレングリコール、１、６−ヘキサンジオール、１、４−シクロヘキサンジメタノール、キシレングリコール、ジメチロールプロパン等や、ポリ（エチレンオキシド）グリコール、ポリ（テトラメチレンオキシド）グリコールやこれらモノマーを挙げることができる。
【００３１】
［微粒子］
塗布層に用いる微粒子は平均粒子径が２０〜１５０ｎｍの無機もしくは有機微粒子であることが好ましい。微粒子は１種類を用いてもよいが、２種類以上を用ることが好ましい。
【００３２】
微粒子は、平均粒子径が６０〜１５０ｎｍの微粒子と平均粒子径が２０〜６０ｎｍの微粒子を合わせて使用することが好ましい。この場合、塗布層中の微粒子の含有量は、平均粒子径が６０〜１５０ｎｍの微粒子が０．０５〜５重量％、平均粒子径が２０〜６０ｎｍの微粒子が１〜１０重量％であることが好ましい。このような微粒子を塗布層に含有させることによりフィルムに滑性及び耐傷性を向上させることができる。
【００３３】
無機微粒子としては、例えば炭酸カルシウム、炭酸マグネシウム、酸化カルシウム、酸化亜鉛、酸化マグネシウム、酸化ケイ素、ケイ酸ソーダ、酸化アルミニウム、酸化鉄、酸化ジルコニウム、硫酸バリウム、酸化チタン、酸化錫、三酸化アンチモン、カーボンブラック、二硫化モリブデンを挙げることができる。
【００３４】
有機微粒子としては、アクリル系架橋重合体、スチレン系架橋重合体、シリコーン樹脂、フッ素樹脂、ベンゾグアナミン樹脂、フェノール樹脂、ナイロン樹脂等の有機微粒子を挙げることができる。
【００３５】
微粒子は、水分散液中で沈降するのを避けるため、比重が３を超えない微粒子を選ぶことが好ましい。
【００３６】
［架橋剤］
塗布層には、さらに耐擦過性を上げるために、架橋剤を添加することが好ましい。架橋剤は、好ましくは、オキサゾリン、エポキシ、メラミン、イソシアネート、カップリング剤、特に好ましくはオキサゾリンを用いる。
【００３７】
塗布層が架橋剤を含有する場合、塗布層中の含有される架橋剤は、塗布層の全重量の好ましくは１〜４０重量％、さらに好ましくは５〜３０重量％である。
【００３８】
［オキサゾリン］
オキサゾリンとしては、オキサゾリン基を含有する重合体が好ましい。これは、付加重合性オキサゾリン基含有モノマー単独もしくは他のモノマーとの重合によって作成できる。付加重合性オキサゾリン基含有モノマーは、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−エチル−２−オキサゾリンを挙げることができ、これらの１種または２種以上の混合物を使用することができる。これらの中でも２−イソプロペニル−２−オキサゾリンが工業的にも入手しやすく好適である。
【００３９】
他のモノマーは、付加重合性オキサゾリン基含有モノマーと共重合可能なモノマーであれば制限なく、例えばアルキルアクリレート、アルキルメタクリレート（アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２ーエチルヘキシル基、シクロヘキシル基）等のア（メタ）クリル酸エステル類；アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸、クロトン酸、スチレンスルホン酸及びその塩（ナトリウム塩、カリウム塩、アンモニウム塩、第三級アミン塩等）等の不飽和カルボン酸類；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル類；アクリルアミド、メタクリルアミド、Ｎ−アルキルアクリルアミド、Ｎ−アルキルメタクリルアミド、Ｎ、Ｎ−ジアルキルアクリルアミド、Ｎ、Ｎ−ジアルキルメタクリレート（アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２−エチルヘキシル基、シクロヘキシル基等）等の不飽和アミド類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル類；エチレン、プロピレン等のα−オレフィン類；塩化ビニル、塩化ビニリデン、フッ化ビニル等の含ハロゲンα、β−不飽和モノマー類；スチレン、α−メチルスチレン、等のα、β−不飽和芳香族モノマーを挙げることができる。これらを用いる場合１種を用いてもよく、２種以上を用いてもよい。
【００４０】
オキサゾリンとしては、ポリアルキレンオキシド鎖を有する共重合体が特に好ましい。ポリエステル樹脂との相溶性が良いためである。
【００４１】
ポリアルキレンオキシド鎖は、ポリアルキレンオキシド鎖を有するモノマーに由来するが、このモノマーとしては、アクリル酸、メタクリル酸のエステル部にポリアルキレンオキシドを付加させたものを挙げることができる。
【００４２】
ポリアルキレンオキシド鎖としては、例えばポリメチレンオキシド、ポリエチレンオキシド、ポリプロピレンオキシド、ポリブチレンオキシドを挙げることができる。ポリアルキレンオキシド鎖の繰り返し単位は３〜１００であることが好ましい。ポリアルキレンオキシド鎖の繰り返し単位が３より少ないとポリエステル樹脂とアクリル樹脂との相溶性が悪く塗布層の透明性が悪くなり好ましくなく、１００より大きいと塗布層の耐湿熱性が下がり、高湿度、高温下でハードコート等との密着性が悪化して好ましくない。
【００４３】
ポリアルキレンオキシド鎖を有するアクリル樹脂は好ましい態様であるが、これを用いると、塗布層中のポリエステル樹脂とアクリル樹脂の相溶性がポリアルキレンオキシド連鎖を含有しないアクリル樹脂と比較し良くなり、塗布層の透明性を向上させることができる。
【００４４】
［エポキシ］
エポキシとしては、例えばポリエポキシ化合物、ジエポキシ化合物、モノエポキシ化合物、グリシジルアミン化合物を挙げることができる。
【００４５】
ポリエポキシ化合物としては、例えば、ソルビトール、ポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、トリグリシジルトリス（２−ヒドロキシエチル）イソシアネート、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテルを挙げることができる。
【００４６】
ジエポキシ化合物としては、例えば、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、レゾルシンジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテルを挙げることができる。
【００４７】
モノエポキシ化合物としては、例えば、アリルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、グリシジルアミン化合物としてはＮ，Ｎ，Ｎ’，Ｎ’，−テトラグリシジル−ｍ−キシリレンジアミン、１，３−ビス（Ｎ，Ｎ−ジグリシジルアミノ）シクロヘキサンを挙げることができる。
【００４８】
［メラミン］
メラミンとしては、メラミンとホルムアルデヒドを縮合して得られるメチロールメラミン誘導体に低級アルコールを反応させてエーテル化した化合物及びそれらの混合物が好ましい。
【００４９】
メチロールメラミン誘導体としては、例えば、モノメチロールメラミン、ジメチロールメラミン、トリメチロールメラミン、テトラメチロールメラミン、ペンタメチロールメラミン、ヘキサメチロールメラミンが挙げられる。
【００５０】
低級アルコールとしては、メチルアルコール、エチルアルコール、イソプロピルアルコールを挙げることができる。
【００５１】
［イソシアネート］
イソシアネートとしては、例えば、トリレンジイソシアネート、ジフェニルメタン−４，４´−ジイソシアネート、メタキシリレンジイソシアネート、ヘキサメチレン−１，６−ジイソシアネート、１，６−ジイソシアネートヘキサン、トリレンジイソシアネートとヘキサントリオールの付加物、トリレンジイソシアネートとトリメチロールプロパンの付加物、ポリオール変性ジフェニルメタン−４，４´−ジイソシアネート、カルボジイミド変性ジフェニルメタン−４，４´−ジイソシアネート、イソホロンジイソシアネート、１，５−ナフタレンジイソシアネート、３，３´−ビトリレン−４，４´ジイソシアネート、３，３´ジメチルジフェニルメタン−４，４´−ジイソシアネート、メタフェニレンジイソシアネートが挙げられる。
【００５２】
［カップリング剤］
カップリング剤としては、例えばシランカップリング剤が挙げられる。これは一般式ＹＲＳｉＸ３で示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、メルカプト基の如き有機官能基、Ｒはメチレン、エチレン、プロピレン基の如きアルキレン基、Ｘはメトキシ基、エトキシ基の如き加水分解基及びアルキル基である。Ｙ部分がエポキシ基であることが特に好ましい。
【００５３】
好ましいシランカップリング剤は、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である。
【００５４】
［有機金属化合物］
架橋剤として、他にはジルコニウム、チタン、アルミニウム等の金属を含む有機金属化合物で、アルコキシド、キレート、アシレートに分類されるものを用いてもよい。
【００５５】
具体例を挙げると、例えばジルコニウムテトラアセチルアセトネート、ジルコニウムアセテート、チタンアセチルアセトネート、トリエタノールアミンチタネート、チタンラクテートである。
【００５６】
［脂肪族ワックス］
塗布層は、脂肪族ワックスを含有することが好ましい。含有量は、塗布層の全重量に対して、好ましくは０．５〜３０重量％、さらに好ましくは１重量％〜１０重量％である。この割合が０．５重量％より少ないとフィルム表面の滑性が得られないことがあり好ましくない。３０重量％を超えるとポリエステルフィルム基材への密着やハードコートや粘着剤等に対する易接着性が不足する場合があり好ましくない。
【００５７】
脂肪族ワックスとしては、例えばカルナバワックス、キャンデリラワックス、ライスワックス、木ロウ、ホホバ油、パームワックス、ロジン変性ワックス、オウリキュリーワックス、サトウキビワックス、エスパルトワックス、バークワックス等の植物系ワックス、ミツロウ、ラノリン、鯨ロウ、イボタロウ、セラックワックス等の動物系ワックス、モンタンワックス、オゾケライト、セレシンワックス等の鉱物系ワックス、パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタム等の石油系ワックス、フィッシャートロプッシュワックス、ポリエチレンワックス、酸化ポリエチレンワックス、ポリプロピレンワックス、酸化ポリプロピレンワックス等の合成炭化水素系ワックスを挙げることができる。これらの中でも、ハードコートや粘着剤等に対する易接着性と滑性が良好なことから、カルナバワックス、パラフィンワックス、ポリエチレンワックスが好ましい。これらは、環境負荷の低減や、取扱のし易さから、水分散体として用いることが好ましい。
【００５８】
［ヘーズ］
本発明の光学用易接着性ポリエステルフィルムは、表面ヘーズ値０．５％以下であることが好ましい。０．５％より高い表面ヘーズであるとフィルム全体のヘーズが高くなり透明性の悪化や塗布斑等の表面欠点が見えやすくなる問題があり好ましくない。このような光学易接着性ポリエステルフィルムは、前記の組成物からなる塗布層を形成させることにより得ることができる。
【００５９】
［塗布層の形成］
塗布層の塗設に用いられる上記組成物は、塗布層（以下『塗膜』いうことがある）を形成させるために、水溶液、水分散液或いは乳化液等の水性塗液の形態で使用されることが好ましい。塗膜を形成するために、必要に応じて、前記組成物以外の他の樹脂、例えば帯電防止剤、着色剤、界面活性剤、紫外線吸収剤を添加してもよい。
【００６０】
水性塗液の固形分濃度は、通常１〜２０重量％、好ましくは１〜１０重量％である。この割合が１重量％未満であると、ポリエステルフィルムへの塗れ性が不足することがあり、２０重量％を超えると塗液の安定性や塗布層の外観が悪化することがあり好ましくない。
【００６１】
水性塗液のポリエステルフィルムへの塗布は、任意の段階で実施することができるが、ポリエステルフィルムの製造過程で実施するのが好ましく、更には配向結晶化が完了する前のポリエステルフィルムに塗布するのが好ましい。
【００６２】
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、未延伸フィルム、未延伸フィルムを縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、更には縦方向およ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）を含むものである。
【００６３】
なかでも、未延伸フィルムまたは一方向に配向せしめた一軸延伸フィルムに、上記組成物の水性塗液を塗布し、そのまま縦延伸および／または横延伸と熱固定とを施すのが好ましい。
【００６４】
水性塗液をフィルムに塗布する際には、塗布性を向上させるための予備処理としてフィルム表面にコロナ表面処理、火炎処理、プラズマ処理等の物理処理を施すか、あるいは組成物と共にこれと化学的に不活性な界面活性剤を併用することが好ましい。
【００６５】
かかる界面活性剤は、フィルムへの水性塗液の濡れを促進機能や塗液の安定性を向上させるものであり、例えば、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等のアニオン型、ノニオン型界面活性剤を挙げることができる。界面活性剤は、塗膜を形成する組成物中に、１〜１０重量％含まれていることが好ましい。
【００６６】
塗液の塗布量は、塗膜の厚さが、通常０．０１〜０．３μｍ、好ましくは０．０２〜０．２５μｍの範囲となるような量とすることが好ましい。塗膜の厚さが薄過ぎると、接着力が不足し、逆に厚過ぎると、ブロッキングを起こしたり、ヘーズ値が高くなったりする可能性があり好ましくない。
【００６７】
塗布方法としては、公知の任意の塗工法が適用できる。例えばロールコート法、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、含浸法、カーテンコート法を適用することができる。こられは単独または組合せて用いることができる。尚、塗膜は、必要に応じ、フィルムの片面のみに形成してもよいし、両面に形成してもよい。
【００６８】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。なお、評価は以下の方法で行なった。
（１）角度別反射光強度
変角光度計（ＧＰ−２００ 株式会社村上色彩技術研究所製）を用いて、フィルムの面に垂直に水銀ランプの光を当て、＋４５°〜−４５℃の範囲でスキャンして反射光の強度を測定した。正反射光（０°での反射光）（Ａ）と１５°での反射光（Ｂ）の強度比を算出した。強度比は次式（１）より求めることができる。
強度比＝Ａ／Ｂ （１）
【００６９】
（２）塗布層均一性
三波長の蛍光灯の光をフィルム表面に当て、正反射光で塗布状況を観察した。
◎：塗布層が均一である。
△：弱い斑がある。
×：強い斑がある。
【００７０】
（３）耐傷性
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
【００７１】
（４）表面ヘーズ値
ＪＩＳ Ｋ７１３６に準じ、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を一枚、二枚、三枚とフィルムを重ねた箇所はセダー油を間に入れて表面ヘーズをキャンセルさせ測定した。一枚、二枚、三枚のフィルムヘーズから概算して表面ヘーズを求めた。尚、フィルムの表面ヘーズを下記の基準で評価した。
◎： 表面ヘーズ値≦０．３％ ……表面ヘーズ極めて良好
○：０．３％＜表面ヘーズ値≦０．５％ ……表面ヘーズ良好
×：０．５％＜表面ヘーズ値 ……表面ヘーズ不良
【００７２】
（５）接着性
・ハードコート
易接着性ポリエステルフィルムの塗膜形成面に厚さ１０μｍのハードコート層を形成して碁盤目のクロスカット（１ｍｍ２のマス目を１００個）を施し、その上に２４ｍｍ幅のセロハンテープ（ニチバン社製）を貼り付け、１８０°の剥離角度で急激に剥がした後、剥離面を観察し、下記の基準で評価した。
５：剥離面積が１０％未満 ……接着力極めて良好
４：剥離面積が１０％以上２０％未満 ……接着力良好
３：剥離面積が２０％以上３０％未満 ……接着力やや良好
２：剥離面積が３０％以上４０％未満 ……接着力不良
１：剥離面積が４０％を超えるもの ……接着力極めて不良
・粘着剤（ＰＳＡ）
易接着性ポリエステルフィルムの塗膜形成面に厚さ２０μｍの粘着剤（ＰＳＡ）層を形成してフロートガラスに粘着剤層面を貼付、２３℃、６５％ＲＨの雰囲気下で１日経時させ、９０°の剥離角度にて剥離し、ガラス表面に粘着剤（ＰＳＡ）の残留状態を観察し、下記の基準で評価した。
【００７３】
尚、粘着剤（ＰＳＡ：Ｐｒｅｓｓｕｒｅ−Ｓｅｎｓｉｔｉｖｅ−Ａｄｈｅｓｉｖｅ）には、ウレタン含有アクリレート共重合体（アクリル成分はｎ−ブチルアクリレート（８６モル％）、メチルアクリレート（１４モル％））を用いた。
５：粘着剤（ＰＳＡ）残留面積が１０％未満 ……接着力極めて良好
４：粘着剤（ＰＳＡ）残留面積が１０％以上２０％未満……接着力良好
３：粘着剤（ＰＳＡ）残留面積が２０％以上３０％未満……接着力やや良好
２：粘着剤（ＰＳＡ）残留面積が３０％以上４０％未満……接着力不良
１：粘着剤（ＰＳＡ）残留面積が４０％を超えるもの ……接着力極めて不良
【００７４】
（６）耐ブロッキング性
２枚のフィルムを、塗膜形成面同士が接するように重ね合せ、これに、６０℃、８０％ＲＨの雰囲気下で１７時間にわたって０．６ｋｇ／ｃｍ２の圧力をかけ、その後、剥離して、その剥離力により耐ブロッキング性を下記の基準で評価した。
（７）ガラス転移温度
サンプル約１０ｍｇを測定用のアルミニウム製パンに封入して示差熱量計（デュポン社製・Ｖ４．ＯＢ２０００型ＤＳＣ）に装着し、２５℃から２０℃／分の速度で３００℃まで昇温させ、３００℃で５分間保持した後取出し、直ちに氷の上に移して急冷した。このパンを再度示差熱量計に装着し、２５℃から２０℃／分の速度で昇温させてガラス転移温度（Ｔｇ：℃）を測定した。
【００７６】
（８）固有粘度
固有粘度（［η］ｄｌ／ｇ）は、２５℃のｏ−クロロフェノール溶液で測定した。
【００７７】
（９）総合評価
下記の基準で評価を実施した。
◎：反射光強度比が０．５〜２の範囲内であり、塗布層均一性が◎で耐傷性が５で表面ヘーズが◎で、ハードコートおよび粘着剤に対する接着性が両方とも３以上、かつ耐ブロッキング性が◎である（総合評価・極めて良好）
○：反射光強度比が０．５〜２の範囲内であり、塗布層均一性が◎で耐傷性が４以上で表面ヘーズが○以上、ハードコートおよび粘着剤に対する接着性が両方とも３以上、かつ耐ブロッキング性が○である（総合評価・良好）
△：反射光強度比が０．５〜２の範囲内であり、塗布層均一性が△以上で耐傷性が３以上で表面ヘーズが○以上、ハードコートおよび粘着剤に対する接着性が両方とも３以上、かつ耐ブロッキング性が△である（総合評価・やや良好）
×：反射光強度比が０．５〜２の範囲外であり、塗布層均一性が×で耐傷性が２以下で表面ヘーズが×、ハードコートおよび粘着剤に対する接着性が両方とも２以下、かつ耐ブロッキング性が×である（総合評価・不良）
塗液を組成する成分として以下の成分を用いた。
【００７８】
ポリエステル：
酸成分がテレフタル酸９２モル％／イソフタル酸３モル％／５−ナトリウムスルホイソフタル酸５モル％、グリコール成分がエチレングリコール９０モル％／ジエチレングリコール１０モル％で構成されている（Ｔｇ＝６５℃、平均分子量１４０００）
【００７９】
尚、ポリエステルは、特開平０６−１１６４８７号公報の実施例１に記載の方法に準じて下記の通り製造した。即ち、テレフタル酸ジメチル５５部、イソフタル酸ジメチル２部、５−ナトリウムスルホイソフタル酸ジメチル５部、エチレングリコール３６部、ジエチレングリコール３部を反応器に仕込み、これにテトラブトキシチタン０．０５部を添加して窒素雰囲気下で温度を２３０℃にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に２５５℃まで上昇させ系内を１ｍｍＨｇの減圧にして重縮合反応を行い、ポリエステルを得た。
【００８０】
架橋剤１：
メチルメタクリレート３０モル％／２−イソプロペニル−２−オキサゾリン３０モル％／ポリエチレンオキシド（ｎ＝１０）メタクリレート１０モル％／アクリルアミド３０モル％で構成されている（Ｔｇ＝５０℃）。
【００８１】
尚、架橋剤１は、特開昭６３−３７１６７号公報の製造例１〜３に記載の方法に準じて下記の通り製造した。即ち、四つ口フラスコに、イオン交換水３０２部を仕込んで窒素気流中で６０℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム０．５部、亜硝酸水素ナトリウム０．２部を添加し、更にモノマー類である、メタクリル酸メチル２３．３部、２−イソプロペニル−２−オキサゾリン２２．６部、ポリエチレンオキシド（ｎ＝１０）メタクリル酸４０．７部、アクリルアミド１３．３部の混合物を３時間にわたり、液温が６０〜７０℃になるよう調整しながら滴下した。滴下終了後も同温度範囲に２時間保持しつつ、撹拌下に反応を継続させ、次いで冷却して固形分が２５％のアクリルの水分散体を得た。
【００８２】
架橋剤２：
メチロール化メラミン （株式会社三和ケミカル製 商品名ＭＸ−０３５）
微粒子１：
アクリルフィラー（平均粒径：１００ｎｍ）（株式会社日本触媒製 商品名エポスターＭＸ−１００Ｗ）
微粒子２：
アクリルフィラー（平均粒径：４０ｎｍ）（株式会社日本触媒製 商品名エポスターＭＸ−０３０Ｗ）添加剤：カルナバワックス（中京油脂株式会社製 商品名セロゾール５２４）
濡れ剤：
ポリオキシエチレン（ｎ＝７）ラウリルエーテル（三洋化成株式会社製 商品名ナロアクティーＮ−７０）
添加剤：
パラフィンワックス（中京油脂株式会社製 商品名ナロアクティーＮ−７０）
【００８３】
［実施例１〜３、比較例１〜３］
溶融ポリエチレンテレフタレート（［η］＝０．６２ｄｌ／ｇ、Ｔｇ＝７８℃）をダイより押出し、常法により冷却ドラムで冷却して未延伸フィルムとし、次いで縦方向に３．２倍に延伸した後、その両面に表２に示す塗剤（塗液１〜６の組成は下記表１に示す塗膜用組成物である）の濃度８％の水性塗液をロールコーターで均一に塗布した。
【００８４】
【表１】
次いで、この塗布フィルムを引き続いて９５℃で乾燥し、横方向に１２０℃で３．５倍に延伸し、２２０℃で幅方向に３％収縮させ熱固定し、厚さ１８８μｍの易接着性フィルムを得た。尚、塗膜の厚さは０．１μｍであった。
【００８６】
［実施例４］
溶融ポリエチレン−２，６−ナフタレート（［η］＝０．６５ｄｌ／ｇ、Ｔｇ＝１２１℃）をダイより押出し、常法により冷却ドラムで冷却して未延伸フィルムとし、次いで縦方向に３．６倍に延伸した後、その両面に塗膜用組成物（表１の塗液１）の濃度８％の水性塗液をロールコーターで均一に塗布した。次いで、この塗布フィルムを引き続いて１０５℃で乾燥し、横方向に１４０℃で３．８倍に延伸し、２３０℃で幅方向に３％収縮させ熱固定し、厚さ１８８μｍの易接着性フィルムを得た。尚、塗膜の厚さは０．１μｍであった。
【００８７】
【表２】
【発明の効果】
本発明によれば、透明性、易滑性、耐傷性、塗膜均一性に優れ、しかも種々の光学用途に用いられる層との接着力に優れた光学用易接着性ポリエステルフィルムを提供することができる。
【００８９】
本発明の光学用易接着性ポリエステルフィルムは、各種光学用途の特にプリズムレンズシート、タッチパネル、バックライト等のベースフィルムや、反射防止用フィルムのベースィルム、ディスプレイの防爆用ベースフィルムに有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an optically-adhesive polyester film for optical use, and more particularly, to an optically-adhesive polyester film having excellent adhesiveness, transparency, lubricity, and coating uniformity.
[0002]
[Prior art]
Polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, have excellent mechanical properties, heat resistance, and chemical resistance. Therefore, magnetic tapes, ferromagnetic thin tapes, photographic films, packaging films, and electronic components It is widely used as a material for films for use, electrical insulating films, films for laminating metal plates, films to be pasted on the surface of glass displays, etc., and films for protecting various members.
[0003]
In recent years, polyester films have been widely used in various optical films in recent years, such as prism lens sheets for liquid crystal display devices, base films for touch panels and backlights, base films for antireflection films, and explosion-proof base films for displays. It is used for applications. The base film used for such an optical film is required to have excellent transparency. Further, excellent easy adhesion to a prism lens layer, a hard coat, an adhesive, an antireflection treatment, a sputter layer, and the like is required.
[0004]
Since the optical film is required to be transparent, it is usually necessary to minimize the amount of the internal filler. In order to improve the adhesive strength of the easy-adhesion layer, a resin having a low glass transition point is used for the easy-adhesion layer. As described above, in the optical film, the internal filler is minimized or the internal filler is not used at all, so that the film surface is flat, and a resin having a low glass transition point is used for the easy-adhesion layer. When the films are wound or overlapped, sticking occurs, and the films do not slip each other, resulting in poor handling properties. In addition, since the optical film has high transparency, if the transparency of the easy-adhesion layer is low, nonuniformity of application due to foaming, vibration, or the like tends to be conspicuous.
[0005]
By the way, the biaxially oriented polyester film generally has poor adhesion to other materials, for example, a prism lens layer or a hard coat containing an acrylic resin as a main component. It has been proposed to stack and use an easily adhesive layer such as a urethane resin (for example, JP-A-10-119215 and JP-A-2000-246855). However, when an easy-adhesion layer made of these resins is formed, the adhesive strength may be insufficient. For example, a CRT film has good adhesion to the hard coat layer, but has insufficient adhesion to the adhesive layer on the opposite side, and is poor in versatility.
[0006]
[Patent Document 1]
JP-A-10-119215
[Patent Document 2]
JP 2000-246855 A
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of the prior art, and is excellent in transparency, lubricity, scratch resistance, coating uniformity, and excellent in adhesion to layers used for various optical applications. An object is to provide an adhesive polyester film.
[0009]
[Means for Solving the Problems]
The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, the polyester film has a coating layer on at least one surface, and the regular reflection light (A) on the surface and the reflection light (B) at 15 ° are reflected on the surface. )) Is in the range of 0.5 to 2, and the above-mentioned problem is caused by forming an easily adhesive coating film having the coating layer and mainly composed of a polymer resin and fine particles. And found that the present invention was completed.
[0010]
That is, the present invention has a coating layer composed of a polymer resin and fine particles on at least one surface of a polyester film, and has an intensity ratio (A / B) of regular reflection light (A) on the surface and reflection light (B) at 15 °. ) Is from 0.5 to 2, which is an easily adhesive polyester film for optical use.
[0011]
The present invention takes the following aspects as preferred aspects.
[0012]
An embodiment in which the polymer resin is a polyester resin.
[0013]
An embodiment in which the fine particles are inorganic or organic fine particles having an average particle diameter of 20 to 150 nm.
[0014]
An embodiment in which the coating layer contains 0.5 to 30% by weight of the aliphatic wax based on the total weight of the coating layer.
[0015]
An embodiment in which the surface haze value is 0.5% or less.
[0016]
An embodiment in which the polyester of the polyester film is polyethylene terephthalate or polyethylene-2,6-naphthalate.
[0017]
Hereinafter, the present invention will be described in detail.
[0018]
[Polyester film]
In the present invention, the polyester constituting the polyester film is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
[0019]
Examples of the polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), and polyethylene-2,6-naphthalate. The polyester may be a copolymer of these or a blend thereof with a small proportion of another resin. Of these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferred because of their good balance of mechanical properties and optical properties.
[0020]
The polyester may contain an appropriate filler if necessary, but from the viewpoint of improving transparency, it is preferable that the amount of the filler in the polyester is small, and it is preferable that the polyester contains substantially no filler.
[0021]
When a filler is used, a filler conventionally known as a slipperiness imparting agent for a polyester film can be used. For example, calcium carbonate, calcium oxide, aluminum oxide, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, and crosslinked silicone resin particles. it can.
[0022]
If necessary, a colorant, an antistatic agent, an antioxidant, an organic lubricant, and a catalyst may be added to the polyester.
[0023]
The polyester film in the present invention is obtained by, for example, melt-extruding the above-mentioned polyester into a film shape, cooling and solidifying the polyester with a casting drum to form an unstretched film, and subjecting the unstretched film to Tg to (Tg + 60) ° C once or twice in the longitudinal direction. The film is stretched so that the total magnification becomes 3 to 6 times or more, and then stretched at Tg to (Tg + 60) ° C. so that the magnification becomes 3 to 5 times in the width direction, and further 180 to 230 ° C. if necessary. At a temperature lower by 10 to 20 ° C. than the heat treatment temperature while shrinking the film by 0 to 20% in the width direction.
[0024]
The thickness of the polyester film in the present invention is preferably from 25 to 300 μm, particularly preferably from 50 to 250 μm, in order to obtain the necessary strength when used as a support for a hard coat, touch panel, anti-glare treatment and the like. preferable.
[0025]
[Coating layer]
The film of the present invention has a coating layer. In this coating layer, the intensity ratio (A / B) of the specular reflected light (A) on the surface and the reflected light (B) at 15 ° is in the range of 0.5 to 2. If it is smaller than 0.5, the scattered light increases, and the light transmittance decreases. When it is larger than 2, the specular reflection light becomes strong, and the non-uniformity of the coating layer is conspicuous in observation by light.
[0026]
The coating layer that satisfies this condition can be formed by providing a coating layer composed of a polymer resin and fine particles described below on the surface of the film.
[0027]
[Polymer resin]
The polymer resin used for the coating layer is preferably a polyester resin, and is preferably soluble or dispersible in water (which may contain some organic solvent).
Examples of such polyester resins include polyesters obtained from the following polybasic acids or their ester-forming derivatives and polyols or their ester-forming derivatives.
[0028]
As the polybasic acid component of the polyester resin, for example, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid , Pyromellitic acid, dimer acid and 5-sodium sulfoisophthalic acid.
[0029]
The polyester resin is preferably a copolymerized polyester containing two or more of these acid components. The polyester resin may contain an unsaturated polybasic acid component such as maleic acid or itaconic acid, or a hydroxycarboxylic acid component such as p-hydroxybenzoic acid in a small amount.
[0030]
Examples of the polyol component of the polyester resin include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, dimethylolpropane, and the like. Examples thereof include (ethylene oxide) glycol, poly (tetramethylene oxide) glycol, and these monomers.
[0031]
[Fine particles]
The fine particles used for the coating layer are preferably inorganic or organic fine particles having an average particle diameter of 20 to 150 nm. One type of fine particles may be used, but two or more types are preferably used.
[0032]
The fine particles are preferably used in combination of fine particles having an average particle diameter of 60 to 150 nm and fine particles having an average particle diameter of 20 to 60 nm. In this case, the content of the fine particles in the coating layer is such that the fine particles having an average particle diameter of 60 to 150 nm are 0.05 to 5% by weight, and the fine particles having an average particle diameter of 20 to 60 nm are 1 to 10% by weight. preferable. By including such fine particles in the coating layer, the lubricity and scratch resistance of the film can be improved.
[0033]
As the inorganic fine particles, for example, calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum oxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, Examples thereof include carbon black and molybdenum disulfide.
[0034]
Examples of the organic fine particles include organic fine particles such as an acrylic crosslinked polymer, a styrene crosslinked polymer, a silicone resin, a fluororesin, a benzoguanamine resin, a phenol resin, and a nylon resin.
[0035]
As the fine particles, it is preferable to select fine particles having a specific gravity not exceeding 3 in order to avoid settling in the aqueous dispersion.
[0036]
[Crosslinking agent]
It is preferable to add a crosslinking agent to the coating layer in order to further increase the scratch resistance. As the cross-linking agent, oxazoline, epoxy, melamine, isocyanate, and a coupling agent, particularly preferably oxazoline, are used.
[0037]
When the coating layer contains a crosslinking agent, the amount of the crosslinking agent contained in the coating layer is preferably 1 to 40% by weight, more preferably 5 to 30% by weight based on the total weight of the coating layer.
[0038]
[Oxazoline]
As the oxazoline, a polymer containing an oxazoline group is preferable. This can be prepared by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer. The addition-polymerizable oxazoline group-containing monomer is 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline, and one or a mixture of two or more of these can be used. Among these, 2-isopropenyl-2-oxazoline is easily available industrially and is preferable.
[0039]
The other monomer is not limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer, and examples thereof include an alkyl acrylate and an alkyl methacrylate (as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as styrenesulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, methacrylamide, N-alkyl Acrylamide, N-alkyl methacrylamide , N, N-dialkylacrylamide, N, N-dialkylmethacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl Amides, cyclohexyl group, etc.); vinyl esters, such as vinyl acetate and vinyl propionate; vinyl ethers, such as methyl vinyl ether and ethyl vinyl ether; α-olefins, such as ethylene and propylene; vinyl chloride, vinylidene chloride And halogen-containing α, β-unsaturated monomers such as vinyl fluoride; and α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene. When these are used, one type may be used or two or more types may be used.
[0040]
As oxazoline, a copolymer having a polyalkylene oxide chain is particularly preferred. This is because the compatibility with the polyester resin is good.
[0041]
The polyalkylene oxide chain is derived from a monomer having a polyalkylene oxide chain. Examples of the monomer include those obtained by adding a polyalkylene oxide to an ester portion of acrylic acid or methacrylic acid.
[0042]
Examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide. The repeating unit of the polyalkylene oxide chain preferably has 3 to 100. If the number of repeating units of the polyalkylene oxide chain is less than 3, the compatibility between the polyester resin and the acrylic resin is poor, and the transparency of the coating layer is poor. Under this condition, the adhesion to a hard coat or the like deteriorates, which is not preferable.
[0043]
The acrylic resin having a polyalkylene oxide chain is a preferred embodiment, but when this is used, the compatibility between the polyester resin and the acrylic resin in the coating layer is better than that of an acrylic resin containing no polyalkylene oxide chain, and the coating layer Can be improved in transparency.
[0044]
[Epoxy]
Examples of the epoxy include a polyepoxy compound, a diepoxy compound, a monoepoxy compound, and a glycidylamine compound.
[0045]
Examples of the polyepoxy compound include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylol Propane polyglycidyl ether can be mentioned.
[0046]
Examples of the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Glycidyl ether and polytetramethylene glycol diglycidyl ether can be exemplified.
[0047]
As the monoepoxy compound, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and as the glycidylamine compound, N, N, N ′, N ′,-tetraglycidyl-m-xylylenediamine, 1,3 -Bis (N, N-diglycidylamino) cyclohexane.
[0048]
[melamine]
As melamine, a compound obtained by reacting a methylol melamine derivative obtained by condensing melamine and formaldehyde with a lower alcohol and etherifying the compound and a mixture thereof are preferable.
[0049]
Examples of the methylol melamine derivative include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.
[0050]
Examples of the lower alcohol include methyl alcohol, ethyl alcohol, and isopropyl alcohol.
[0051]
[Isocyanate]
Examples of the isocyanate include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, an adduct of tolylene diisocyanate and hexanetriol, Adduct of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-vitrilene- 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and metaphenylene diisocyanate.
[0052]
[Coupling agent]
Examples of the coupling agent include a silane coupling agent. This is a compound represented by the general formula YRSiX 3. Here, Y is an organic functional group such as a vinyl group, an epoxy group, an amino group, or a mercapto group, R is an alkylene group such as a methylene, ethylene, or propylene group, X is a hydrolyzing group such as a methoxy group or an ethoxy group, and an alkyl group. It is. It is particularly preferred that the Y moiety is an epoxy group.
[0053]
Preferred silane coupling agents are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.
[0054]
[Organic metal compound]
As the crosslinking agent, an organometallic compound containing a metal such as zirconium, titanium, or aluminum, which is classified into alkoxide, chelate, and acylate, may be used.
[0055]
Specific examples include zirconium tetraacetylacetonate, zirconium acetate, titanium acetylacetonate, triethanolamine titanate, and titanium lactate.
[0056]
[Aliphatic wax]
The coating layer preferably contains an aliphatic wax. The content is preferably 0.5 to 30% by weight, more preferably 1% to 10% by weight, based on the total weight of the coating layer. If this proportion is less than 0.5% by weight, the film surface may not have lubricity, which is not preferred. If the content exceeds 30% by weight, the adhesion to the polyester film substrate and the easy adhesion to a hard coat or an adhesive may be insufficient, which is not preferable.
[0057]
Examples of the aliphatic wax include carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, ouriculi wax, sugarcane wax, esparto wax, bark wax, and other vegetable waxes, and beeswax. , Waxes such as lanolin, whale wax, wax wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, fisher tropush wax, polyethylene Examples include synthetic hydrocarbon waxes such as wax, polyethylene oxide wax, polypropylene wax, and polypropylene oxide wax. Among them, carnauba wax, paraffin wax, and polyethylene wax are preferable because they have good adhesiveness to a hard coat or a pressure-sensitive adhesive and good lubricity. These are preferably used as an aqueous dispersion from the viewpoint of reduction of environmental load and ease of handling.
[0058]
[Haze]
The easily adhesive polyester film for optical of the present invention preferably has a surface haze value of 0.5% or less. If the surface haze is higher than 0.5%, the haze of the whole film becomes high, and there is a problem that surface defects such as deterioration of transparency and uneven coating are easily seen, which is not preferable. Such an optically-adhesive polyester film can be obtained by forming a coating layer composed of the above composition.
[0059]
[Formation of coating layer]
The composition used for coating the coating layer is used in the form of an aqueous coating solution such as an aqueous solution, an aqueous dispersion, or an emulsion to form a coating layer (hereinafter sometimes referred to as a “coating film”). Is preferred. In order to form a coating film, a resin other than the above-mentioned composition, for example, an antistatic agent, a coloring agent, a surfactant, or an ultraviolet absorber may be added as necessary.
[0060]
The solid content concentration of the aqueous coating solution is usually 1 to 20% by weight, preferably 1 to 10% by weight. If the proportion is less than 1% by weight, the coatability on the polyester film may be insufficient, and if it exceeds 20% by weight, the stability of the coating solution and the appearance of the coating layer may be undesirably deteriorated.
[0061]
The application of the aqueous coating liquid to the polyester film can be carried out at any stage, but is preferably carried out in the process of producing the polyester film, and further applied to the polyester film before the orientation crystallization is completed. Is preferred.
[0062]
Here, the polyester film before the completion of the crystal orientation refers to an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further, in two directions, the longitudinal direction and the transverse direction. And a low-magnification stretch-oriented film (a biaxially stretched film before being finally re-stretched in the machine direction or the cross direction to complete the oriented crystallization).
[0063]
In particular, it is preferable to apply an aqueous coating solution of the above composition to an unstretched film or a uniaxially stretched film which is oriented in one direction, and to perform longitudinal stretching and / or transverse stretching and heat fixing as it is.
[0064]
When applying the aqueous coating liquid to the film, the film surface is subjected to a physical treatment such as a corona surface treatment, a flame treatment, a plasma treatment, or a chemical treatment together with the composition as a preliminary treatment for improving the coatability. It is preferable to use an inert surfactant in combination.
[0065]
Such surfactants are those that promote the function of promoting the wetting of the aqueous coating liquid on the film and the stability of the coating liquid, and include, for example, polyoxyethylene-fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, and fatty acid metal soaps. And anionic and nonionic surfactants such as alkyl sulfates, alkyl sulfonates and alkyl sulfosuccinates. The surfactant is preferably contained at 1 to 10% by weight in the composition forming the coating film.
[0066]
The amount of the coating liquid applied is preferably such that the thickness of the coating film is usually in the range of 0.01 to 0.3 μm, preferably 0.02 to 0.25 μm. If the thickness of the coating film is too thin, the adhesive strength becomes insufficient, while if it is too thick, blocking may occur or the haze value may increase, which is not preferable.
[0067]
As a coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brushing method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be applied. These can be used alone or in combination. The coating film may be formed on only one side of the film or on both sides as necessary.
[0068]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation was performed by the following method.
(1) A mercury lamp was irradiated perpendicularly to the surface of the film using a reflected light intensity variable angle photometer (GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.) in the range of + 45 ° to -45 ° C. And the intensity of the reflected light was measured. The intensity ratio between the specularly reflected light (reflected light at 0 °) (A) and the reflected light at 15 ° (B) was calculated. The intensity ratio can be obtained from the following equation (1).
Intensity ratio = A / B (1)
[0069]
(2) Uniformity of Coating Layer Light from a three-wavelength fluorescent lamp was applied to the film surface, and the coating state was observed with regular reflection light.
A: The coating layer is uniform.
Δ: There are weak spots.
×: There are strong spots.
[0070]
(3) 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 the pin is fixed at a constant speed (20 mm / s). The film was slid up to evaluate the degree of scratches entering the film surface.
5: No scratch at all 4: 0% <Scratch area ≦ 10% with respect to 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
(4) Surface haze value According to JIS K7136, using a haze measuring device (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd. The surface haze was canceled with oil in between to measure. The surface haze was determined by estimating the film haze of one, two or three sheets. In addition, the surface haze of the film was evaluated based on the following criteria.
◎: Surface haze value ≦ 0.3%… extremely good surface haze ：: 0.3% <surface haze value ≦ 0.5%… good surface haze X: 0.5% <surface haze value …… surface haze Defective
(5) Adhesive / Hard Coat A hard coat layer having a thickness of 10 μm is formed on the coating film forming surface of the easily adhesive polyester film, and a cross-cut of a grid (100 squares of 1 mm 2 ) is performed. Then, a cellophane tape (manufactured by Nichiban Co.) having a width of 24 mm was applied thereto, and was peeled off rapidly at a peeling angle of 180 °. The peeled surface was observed and evaluated according to the following criteria.
5: Peeling area is less than 10% ... adhesive strength is extremely good 4: Peeling area is 10% or more and less than 20% ... Good adhesive strength 3: Peeling area is 20% or more and less than 30% ... Slightly good 2: Peeling strength Area is 30% or more and less than 40%… Adhesive strength defect 1: Peeling area exceeds 40% …… Adhesive strength is extremely poor, PSA (PSA)
An adhesive (PSA) layer having a thickness of 20 μm is formed on the coating film forming surface of the easily-adhesive polyester film, and the adhesive layer surface is adhered to the float glass, and aged at 23 ° C. and 65% RH for 1 day. The adhesive was peeled at a peel angle of °, the residual state of the pressure-sensitive adhesive (PSA) was observed on the glass surface, and evaluated according to the following criteria.
[0073]
The pressure-sensitive adhesive (PSA: Pressure-Sensitive-Adhesive) used was a urethane-containing acrylate copolymer (acrylic components were n-butyl acrylate (86 mol%) and methyl acrylate (14 mol%)).
5: Residual area of PSA (PSA) is less than 10% .... Excellent adhesive strength. 4: Residual area of PSA (PSA) is 10% or more and less than 20% .... Good adhesive strength. 3: Residual area of PSA (PSA). 20% or more and less than 30% ... Slightly good adhesive strength 2: Adhesive (PSA) residual area is 30% or more and less than 40% ... Poor adhesive strength 1: Adhesive (PSA) residual area exceeds 40% ... Extremely poor adhesive strength
(6) Blocking resistance The two films are superimposed so that the coating film forming surfaces are in contact with each other, and a pressure of 0.6 kg / cm 2 is applied thereto for 17 hours in an atmosphere of 60 ° C. and 80% RH. Thereafter, the film was peeled off, and the blocking resistance was evaluated by the peeling force according to the following criteria.
(7) About 10 mg of the glass transition temperature sample was sealed in an aluminum pan for measurement, mounted on a differential calorimeter (V4.OB2000 type DSC manufactured by DuPont), and was heated from 25 ° C to 300 ° C at a rate of 20 ° C / min. And kept at 300 ° C. for 5 minutes, taken out, immediately transferred to ice and rapidly cooled. The pan was attached to the differential calorimeter again, and the temperature was raised from 25 ° C. at a rate of 20 ° C./min to measure the glass transition temperature (Tg: ° C.).
[0076]
(8) Intrinsic viscosity Intrinsic viscosity ([η] dl / g) was measured with an o-chlorophenol solution at 25 ° C.
[0077]
(9) Comprehensive evaluation Evaluation was performed based on the following criteria.
◎: the reflected light intensity ratio is in the range of 0.5 to 2, the uniformity of the coating layer is ◎, the scratch resistance is 5, the surface haze is 接着, and the adhesion to the hard coat and the adhesive is 3 or more. And the blocking resistance is ◎ (overall evaluation, extremely good)
：: The reflected light intensity ratio is in the range of 0.5 to 2, the uniformity of the coating layer is ◎, the scratch resistance is 4 or more, the surface haze is 以上 or more, and the adhesion to the hard coat and the adhesive is 3 or more. , And the blocking resistance is ○ (overall evaluation, good)
Δ: The reflected light intensity ratio is in the range of 0.5 to 2, the uniformity of the coating layer is Δ or more, the scratch resistance is 3 or more, the surface haze is 以上 or more, and the adhesiveness to both the hard coat and the adhesive is 3 Above, and the blocking resistance is △ (Comprehensive evaluation, slightly good)
×: The reflected light intensity ratio is out of the range of 0.5 to 2, the uniformity of the coating layer is ×, the scratch resistance is 2 or less, the surface haze is ×, and the adhesiveness to the hard coat and the adhesive is 2 or less. And the blocking resistance is x (Comprehensive evaluation / defective)
The following components were used as components for forming the coating liquid.
[0078]
polyester:
The acid component is composed of 92 mol% of terephthalic acid / 3 mol% of isophthalic acid / 5 mol% of 5-sodium sulfoisophthalic acid, and the glycol component is composed of 90 mol% of ethylene glycol / 10 mol% of diethylene glycol (Tg = 65 ° C., average Molecular weight 14000)
[0079]
The polyester was produced as follows according to the method described in Example 1 of JP-A-06-116487. That is, 55 parts of dimethyl terephthalate, 2 parts of dimethyl isophthalate, 5 parts of dimethyl 5-sodium sulfoisophthalate, 36 parts of ethylene glycol and 3 parts of diethylene glycol were charged into a reactor, and 0.05 part of tetrabutoxytitanium was added thereto. The mixture was heated under a nitrogen atmosphere while controlling the temperature at 230 ° C., and the produced methanol was distilled off to carry out a transesterification reaction. Then, the temperature of the reaction system was gradually raised to 255 ° C., and the pressure inside the system was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester.
[0080]
Crosslinking agent 1:
It is composed of 30 mol% of methyl methacrylate / 2 30 mol% of 2-isopropenyl-2-oxazoline / polyethylene oxide (n = 10) 10 mol% of methacrylate / 30 mol% of acrylamide (Tg = 50 ° C.).
[0081]
In addition, the crosslinking agent 1 was manufactured as follows according to the method of the manufacture examples 1-3 of Unexamined-Japanese-Patent No. 63-37167. That is, in a four-necked flask, 302 parts of ion-exchanged water was charged and heated to 60 ° C. in a nitrogen stream, and then 0.5 part of ammonium persulfate and 0.2 part of sodium hydrogen nitrite were added as a polymerization initiator. Further, a mixture of 23.3 parts of methyl methacrylate, 22.6 parts of 2-isopropenyl-2-oxazoline, 40.7 parts of polyethylene oxide (n = 10) methacrylic acid and 13.3 parts of acrylamide, which are monomers. The solution was added dropwise over 3 hours while adjusting the solution temperature to 60 to 70 ° C. The reaction was continued with stirring while maintaining the same temperature range for 2 hours after the completion of the dropwise addition, and then cooled to obtain an aqueous dispersion of acrylic having a solid content of 25%.
[0082]
Crosslinking agent 2:
Methylolated melamine (trade name: MX-035, manufactured by Sanwa Chemical Co., Ltd.)
Fine particles 1:
Acrylic filler (average particle size: 100 nm) (Nippon Shokubai Co., Ltd., trade name: Eposter MX-100W)
Fine particles 2:
Acrylic filler (average particle size: 40 nm) (Nippon Shokubai Co., Ltd., trade name: Eposter MX-030W) Additive: carnauba wax (Chukyo Yushi Co., Ltd., trade name Cersol 524)
Wetting agent:
Polyoxyethylene (n = 7) lauryl ether (Naroacty N-70, manufactured by Sanyo Chemical Industries, Ltd.)
Additive:
Paraffin wax (product name: NAROACTY N-70 manufactured by Chukyo Yushi Co., Ltd.)
[0083]
[Examples 1 to 3, Comparative Examples 1 to 3]
Molten polyethylene terephthalate ([η] = 0.62 dl / g, Tg = 78 ° C.) is extruded from a die, cooled with a cooling drum by a conventional method to form an unstretched film, and then stretched 3.2 times in the machine direction. An aqueous coating liquid having a concentration of 8% of a coating agent shown in Table 2 (the composition of coating liquids 1 to 6 is a coating composition shown in Table 1 below) was uniformly applied to both surfaces thereof by a roll coater.
[0084]
[Table 1]
Next, the applied film is subsequently dried at 95 ° C., stretched 3.5 times at 120 ° C. in the transverse direction, shrunk 3% at 220 ° C. in the width direction, and heat-fixed, and a 188 μm-thick easily adhesive film. Got. In addition, the thickness of the coating film was 0.1 μm.
[0086]
[Example 4]
Molten polyethylene-2,6-naphthalate ([η] = 0.65 dl / g, Tg = 121 ° C.) was extruded from a die, cooled by a cooling drum by a conventional method to form an unstretched film, and then 3.6 in the longitudinal direction. After stretching the film twice, an aqueous coating liquid having a concentration of 8% of the coating film composition (coating liquid 1 in Table 1) was uniformly applied to both surfaces by a roll coater. Next, the coated film is subsequently dried at 105 ° C., stretched 3.8 times in the transverse direction at 140 ° C., shrunk 3% in the width direction at 230 ° C., and heat-fixed, and a 188 μm-thick easily adhesive film. Got. In addition, the thickness of the coating film was 0.1 μm.
[0087]
[Table 2]
【The invention's effect】
According to the present invention, there is provided an easily adhesive polyester film for optical use which is excellent in transparency, lubricity, scratch resistance and coating uniformity, and which has excellent adhesive strength to layers used for various optical applications. Can be.
[0089]
The easily adhesive polyester film for optical use of the present invention is useful for various optical applications, particularly for base films such as prism lens sheets, touch panels, and backlights, base films for antireflection films, and explosion-proof base films for displays.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003098103A JP2004300379A (en) | 2003-04-01 | 2003-04-01 | Readily adhering polyester film for optical use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003098103A JP2004300379A (en) | 2003-04-01 | 2003-04-01 | Readily adhering polyester film for optical use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004300379A true JP2004300379A (en) | 2004-10-28 |
Family
ID=33409720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003098103A Pending JP2004300379A (en) | 2003-04-01 | 2003-04-01 | Readily adhering polyester film for optical use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004300379A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006198938A (en) * | 2005-01-21 | 2006-08-03 | Unitika Ltd | Laminate |
| US20110157525A1 (en) * | 2008-07-29 | 2011-06-30 | Nitto Denko Corporation | Polarizer-protecting film, and polarizing plate and image display apparatus each comprising polarizer-protecting film |
| US20140356618A1 (en) * | 2012-03-23 | 2014-12-04 | Fujifilm Corporation | Multilayer film and optical sheet |
| KR101848452B1 (en) * | 2016-03-21 | 2018-04-13 | 에스케이씨 주식회사 | Multilayer white porous polyester film |
| JP2018154027A (en) * | 2017-03-17 | 2018-10-04 | 三菱ケミカル株式会社 | Coated film |
-
2003
- 2003-04-01 JP JP2003098103A patent/JP2004300379A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006198938A (en) * | 2005-01-21 | 2006-08-03 | Unitika Ltd | Laminate |
| US20110157525A1 (en) * | 2008-07-29 | 2011-06-30 | Nitto Denko Corporation | Polarizer-protecting film, and polarizing plate and image display apparatus each comprising polarizer-protecting film |
| US8854577B2 (en) * | 2008-07-29 | 2014-10-07 | Nitto Denko Corporation | Polarizer-protecting film comprising an easy-adhesion layer composition, and polarizing plate and image display apparatus each comprising the polarizing-protecting film |
| US20140356618A1 (en) * | 2012-03-23 | 2014-12-04 | Fujifilm Corporation | Multilayer film and optical sheet |
| KR101848452B1 (en) * | 2016-03-21 | 2018-04-13 | 에스케이씨 주식회사 | Multilayer white porous polyester film |
| JP2018154027A (en) * | 2017-03-17 | 2018-10-04 | 三菱ケミカル株式会社 | Coated film |
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