JP2022018374A - Polyimide film, laminate of polyimide film and inorganic substrate, and flexible electronic device - Google Patents
Polyimide film, laminate of polyimide film and inorganic substrate, and flexible electronic device Download PDFInfo
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- JP2022018374A JP2022018374A JP2020121443A JP2020121443A JP2022018374A JP 2022018374 A JP2022018374 A JP 2022018374A JP 2020121443 A JP2020121443 A JP 2020121443A JP 2020121443 A JP2020121443 A JP 2020121443A JP 2022018374 A JP2022018374 A JP 2022018374A
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- film
- polyimide film
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- acid
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 116
- 239000000758 substrate Substances 0.000 title claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000011787 zinc oxide Substances 0.000 claims abstract description 29
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 14
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 13
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 25
- 239000011256 inorganic filler Substances 0.000 claims description 25
- 238000002834 transmittance Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 abstract description 36
- 230000000694 effects Effects 0.000 abstract description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 13
- 239000009719 polyimide resin Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000002087 whitening effect Effects 0.000 abstract description 5
- 150000003755 zirconium compounds Chemical class 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000003698 laser cutting Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 75
- -1 alicyclic tetracarboxylic acid Chemical class 0.000 description 46
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 235000014692 zinc oxide Nutrition 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 229920005575 poly(amic acid) Polymers 0.000 description 24
- 239000011521 glass Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 4
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BDWOQDZGSYLSCZ-UHFFFAOYSA-N [1,3]oxazolo[4,5-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1OC=N2 BDWOQDZGSYLSCZ-UHFFFAOYSA-N 0.000 description 3
- PMJNNCUVWHTTMV-UHFFFAOYSA-N [1,3]oxazolo[5,4-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1N=CO2 PMJNNCUVWHTTMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- ZIXLDMFVRPABBX-UHFFFAOYSA-N 2-methylcyclopentan-1-one Chemical compound CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 2
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 2
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
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- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 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
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- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 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
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- PHPTWVBSQRENOR-UHFFFAOYSA-N (3-amino-4-phenoxyphenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C(C=C1N)=CC=C1OC1=CC=CC=C1 PHPTWVBSQRENOR-UHFFFAOYSA-N 0.000 description 1
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- HFAMSBMTCKNPRG-UHFFFAOYSA-N (4-amino-3-phenoxyphenyl)-(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(OC=3C=CC=CC=3)C(N)=CC=2)=C1 HFAMSBMTCKNPRG-UHFFFAOYSA-N 0.000 description 1
- NILYJZJYFZUPPO-UHFFFAOYSA-N (4-amino-3-phenoxyphenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C(OC=2C=CC=CC=2)=C1 NILYJZJYFZUPPO-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、無色であり、透明性に優れるポリイミドフィルム、該ポリイミドフィルムと無機基板の積層体、さらに該ポリイミドフィルムを部材に用いたフレキシブルな電子デバイスに関する。 The present invention relates to a polyimide film that is colorless and has excellent transparency, a laminate of the polyimide film and an inorganic substrate, and a flexible electronic device using the polyimide film as a member.
ポリイミドフィルムは優れた耐熱性、良好な機械特性を有し、なおかつフレキシブルな素材として電気および電子分野にて広く使用されている。しかしながら、一般のポリイミドフィルムは黄褐色に着色しているため、表示装置などの光透過が必要な部分に適用することはできない。
一方で表示装置は薄型化、軽量化が進み、さらにフレキシブル化が求められてきている。そのため基板材料をガラス基板からフレキシブルな高分子フィルム基板に代えようという試みが進められているが、着色しているポリイミドフィルムは、光線透過をON/OFFすることによって表示を行う液晶ディスプレイの基板材料としては使用できず、表示装置の駆動回路が搭載されるTAB,COFなどの周辺回路や、反射型表示方式ないし自発光型表示装置における背面側など、ごく一部にしか適用することができない。
Polyimide film has excellent heat resistance and good mechanical properties, and is widely used in the electric and electronic fields as a flexible material. However, since a general polyimide film is colored yellowish brown, it cannot be applied to a part such as a display device that requires light transmission.
On the other hand, display devices are becoming thinner and lighter, and further flexibility is required. Therefore, attempts are being made to replace the substrate material from a glass substrate with a flexible polymer film substrate, but the colored polyimide film is a substrate material for a liquid crystal display that displays by turning on / off light transmission. It cannot be used as a peripheral circuit such as a TAB or COF on which a drive circuit of a display device is mounted, or can be applied only to a small part such as the back side of a reflective display system or a self-luminous display device.
かかる背景から、無色透明のポリイミドフィルムの開発が進められている。代表的な例としてフッ素化ポリイミド樹脂や半脂環型もしくは全脂環型ポリイミド樹脂などを用いた無色透明ポリイミドフィルムを開発する試みがある(特許文献1~3)。これらのフィルムは着色が少なく、かつ透明性を有している。またこれらの無色ポリイミドを、酸素含有量を規定した気体を噴きつけながら加熱処理する方法が提案されており(特許文献4)、さらに着色が抑制されることが示されている。 Against this background, the development of colorless and transparent polyimide films is underway. As a typical example, there is an attempt to develop a colorless transparent polyimide film using a fluorinated polyimide resin, a semi-lipid ring type or a full alicyclic polyimide resin (Patent Documents 1 to 3). These films are less colored and have transparency. Further, a method of heat-treating these colorless polyimides while spraying a gas having an oxygen content has been proposed (Patent Document 4), and it has been shown that coloring is further suppressed.
着色しているポリイミドは紫外域に吸収があるためUVレーザーでの加工が容易である。しかしながら、先に示したような無色ポリイミドは吸光度が低いため、UVレーザーでの加工には過剰なエネルギーが必要となり、加工時にスミアが発生しやすくなり、切断面の変色が生じる場合がある。また、かかる無色のポリイミドフィルムがフレキシブルなディスプレイやタッチセンサーなどの電子デバイスの部材に使用された場合には、外界の紫外線を直接浴びることになる。従来の着色されたポリイミドは原則として電子電気機器の筐体内で用いられてきたためポリイミドフィルム自身の紫外線劣化が問題として顕在化することは無かった。しかしながら無色のポリイミドフィルムを部材に用いた場合には、ポリイミドフィルム自身、あるいはフィルム近傍に使用されている他の部材に紫外線劣化が生じる問題が顕在化する。 Since the colored polyimide has absorption in the ultraviolet region, it is easy to process with a UV laser. However, since the colorless polyimide as shown above has a low absorbance, excessive energy is required for processing with a UV laser, smearing is likely to occur during processing, and discoloration of the cut surface may occur. Further, when such a colorless polyimide film is used for a member of an electronic device such as a flexible display or a touch sensor, it is directly exposed to ultraviolet rays of the outside world. Since the conventional colored polyimide has been used in the housing of electronic and electrical equipment in principle, the deterioration of the polyimide film itself by ultraviolet rays has not become a problem. However, when a colorless polyimide film is used as a member, the problem that ultraviolet deterioration occurs in the polyimide film itself or other members used in the vicinity of the film becomes apparent.
本発明者らは、かかる問題を解決するために鋭意研究を続けた結果、特定の無機成分を特定量配合することで、フィルムの無色性、透明性を維持しつつ高い紫外線遮蔽性を有するポリイミドフィルムを開発し、さらに該ポリイミドフィルムをフレキシブル電子デバイスに適用することで高い耐光性が期待できる電子デバイスを実現するに至った。
すなわち本発明は以下の構成である。
[1]
イエローインデックスが10以下、全光線透過率が85%以上、引張弾性率が3GPa以上、CTEが-5ppm/℃~+55ppm/℃であり、無機フィラーとして下記(a)および(b)を含むことを特徴とするポリイミドフィルム。
(a)625ppm以上20000ppm以下の酸化亜鉛粒子、および/または、750ppm以上20000ppm以下の硫化亜鉛粒子
(b)680ppm以上10000ppm以下の酸化ジルコニウム粒子、および/または、1000ppm以上10000ppm以下のケイ酸ジルコニウム粒子
[2]
前記無機フィラーの粒子径が400nm以下であることを特徴とする[1]に記載のポリイミドフィルム。
[3]
前記[1]または[2]に記載のポリイミドフィルムと無機基板を含む積層体であり、ポリイミドフィルムと無機基板が直接接していることを特徴とする積層体。
[4]
前記[1]または[2]に記載のポリイミドフィルムと無機基板を含む積層体であり、ポリイミドフィルムと無機基板がシランカップリング剤の縮合物層を介して接着していることを特徴とする積層体。
[5]
前記[1]または[2]に記載のポリイミドフィルムを部材とするフレキシブル電子デバイス。
As a result of diligent research to solve such a problem, the present inventors have made a polyimide having a high ultraviolet shielding property while maintaining the colorlessness and transparency of the film by blending a specific amount of a specific inorganic component. By developing a film and applying the polyimide film to a flexible electronic device, we have realized an electronic device that can be expected to have high light resistance.
That is, the present invention has the following configuration.
[1]
The yellow index is 10 or less, the total light transmittance is 85% or more, the tensile elastic modulus is 3 GPa or more, the CTE is -5 ppm / ° C. to + 55 ppm / ° C., and the following (a) and (b) are included as inorganic fillers. A characteristic polyimide film.
(A) Zinc oxide particles of 625 ppm or more and 20000 ppm or less, and / or zinc sulfide particles of 750 ppm or more and 20000 ppm or less (b) Zinc oxide particles of 680 ppm or more and 10000 ppm or less, and / or zirconium silicate particles of 1000 ppm or more and 10000 ppm or less [ 2]
The polyimide film according to [1], wherein the inorganic filler has a particle size of 400 nm or less.
[3]
A laminate containing the polyimide film and the inorganic substrate according to the above [1] or [2], wherein the polyimide film and the inorganic substrate are in direct contact with each other.
[4]
It is a laminate containing the polyimide film and the inorganic substrate according to the above [1] or [2], and is characterized in that the polyimide film and the inorganic substrate are adhered to each other via a condensate layer of a silane coupling agent. body.
[5]
A flexible electronic device using the polyimide film according to the above [1] or [2] as a member.
本発明は好ましくは、さらに以下の構成を有する。
[6]
前記[3]または[4]に記載の積層体のポリイミドフィルム面上に電子デバイスを形成し、次いで積層体から電子デバイスをポリイミドフィルムごと剥離することを特徴とするフレキシブルな電子デバイスの製造方法。
[7]
前記[3]または[4]に記載の積層体のポリイミドフィルム面上に電子デバイスを形成し、次いで積層体の無機基板側からレーザー光を照射した後に、電子デバイスをポリイミドフィルムごと剥離することを特徴とするフレキシブルな電子デバイスの製造方法。
The present invention preferably has the following configuration.
[6]
A method for manufacturing a flexible electronic device, which comprises forming an electronic device on the polyimide film surface of the laminate according to the above [3] or [4], and then peeling the electronic device from the laminate together with the polyimide film.
[7]
An electronic device is formed on the polyimide film surface of the laminate according to the above [3] or [4], and then laser light is irradiated from the inorganic substrate side of the laminate, and then the electronic device is peeled off together with the polyimide film. A method for manufacturing flexible electronic devices.
本発明は、無機フィラーとして酸化亜鉛粒子および/または硫化亜鉛粒子と、酸化ジルコニウム粒子および/またはケイ酸ジルコニウム粒子を所定量含む無色で透明性の高いポリイミドフィルムである。酸化亜鉛に紫外線吸収効果があることは一般に知られている。よって酸化亜鉛をフィルムに添加して紫外線遮蔽効果を得ることは公知である。が、十分な紫外線遮蔽効果を得るためには相当量の酸化亜鉛を添加する必要がある。酸化亜鉛の屈折率はポリイミド樹脂に比較すると高いために、添加量を増やすと、光線散乱効果のためにフィルムの白化が避けられず、フィルムのヘイズ値が上昇し透明性が低下してしまう。
一方の酸化ジルコニウム(ジルコニア)は酸化亜鉛より高い屈折率を有し、またケイ酸ジルコニウム(ジルコン)は、酸化亜鉛と同程度の屈折率ながら、複屈折効果を有する。そのため、いずれも少量の添加で光線散乱効果を発現し、両者を組み合わせることでフィルムの白化が顕著にならない程度の添加量で十分な紫外線吸収能を得ることが可能となる。
微粒子の光線散乱効果は粒子径に依存するため、粒子径を散乱させたい光線波長に整合させることで目的とする波長の散乱効果を高めることができる。したがって、酸化亜鉛の紫外線吸収領域と、光散乱効果を担う酸化ジルコニウムおよび/またはケイ酸ジルコニウムの粒子を整合させることで、さらに高い紫外線吸収能を得ることが可能となる。
The present invention is a colorless and highly transparent polyimide film containing zinc oxide particles and / or zinc sulfide particles as an inorganic filler and zirconium oxide particles and / or zirconium silicate particles in a predetermined amount. It is generally known that zinc oxide has an ultraviolet absorbing effect. Therefore, it is known that zinc oxide is added to a film to obtain an ultraviolet shielding effect. However, it is necessary to add a considerable amount of zinc oxide in order to obtain a sufficient UV shielding effect. Since the refractive index of zinc oxide is higher than that of the polyimide resin, when the addition amount is increased, whitening of the film is unavoidable due to the light scattering effect, the haze value of the film increases, and the transparency decreases.
On the other hand, zirconium oxide (zirconia) has a higher refractive index than zinc oxide, and zirconium silicate (zircone) has a double refractive index while having a refractive index similar to that of zinc oxide. Therefore, in each case, the light scattering effect is exhibited by adding a small amount, and by combining the two, it is possible to obtain a sufficient ultraviolet absorbing ability with an addition amount such that the whitening of the film is not noticeable.
Since the light scattering effect of fine particles depends on the particle size, it is possible to enhance the scattering effect of the target wavelength by matching the particle size with the desired light wavelength. Therefore, by matching the ultraviolet absorbing region of zinc oxide with the particles of zirconium oxide and / or zirconium silicate that are responsible for the light scattering effect, it is possible to obtain a higher ultraviolet absorbing ability.
<ポリイミドフィルム>
本発明のポリイミドフィルムは、好ましくは厚さ3μm以上120μm以下である。機械特性が良好となることから好ましくは4μm以上であり、より好ましくは5μm以上であり、さらに好ましくは8μm以上である。また、透明性が良好となることから100μm以下であることが好ましく、より好ましくは80μm以下であり、さらに好ましくは60μm以下である。
<Polyimide film>
The polyimide film of the present invention preferably has a thickness of 3 μm or more and 120 μm or less. It is preferably 4 μm or more, more preferably 5 μm or more, and further preferably 8 μm or more because the mechanical properties are good. Further, it is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 60 μm or less because the transparency becomes good.
本発明のポリイミドフィルムは、イエローインデックスが10以下である。透明性が良好となることから好ましくは4以下であり、より好ましくは3.5以下であり、さらに好ましくは3以下である。イエローインデックスは低い方が良いため下限は特に限定されないが、工業的には0.1以上であれば良く、0.2以上であっても差し支えない。 The polyimide film of the present invention has a yellow index of 10 or less. It is preferably 4 or less, more preferably 3.5 or less, and further preferably 3 or less because the transparency is good. Since the lower the yellow index is, the lower limit is not particularly limited, but industrially, it may be 0.1 or more, and 0.2 or more may be used.
本発明のポリイミドフィルムは、全光線透過率が85%以上である。透明性が良好となることから好ましくは87%以上であり、より好ましくは88%以上であり、さらに好ましくは89%以上である。上限は特に限定されないが、工業的には99%以下であれば良く、98%以下であっても差し支えない。 The polyimide film of the present invention has a total light transmittance of 85% or more. It is preferably 87% or more, more preferably 88% or more, and further preferably 89% or more because the transparency becomes good. The upper limit is not particularly limited, but industrially, it may be 99% or less, and may be 98% or less.
本発明のポリイミドフィルムのヘイズは、2以下であることが好ましく、より好ましくは1.5以下であり、さらに好ましくは1以下であり、より一層好ましくは0.8以下である。ヘイズの下限は特に限定されないが、工業的には0.01以上であれば十分であり、0.05以上であっても差し支えない。 The haze of the polyimide film of the present invention is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and even more preferably 0.8 or less. The lower limit of the haze is not particularly limited, but industrially, 0.01 or more is sufficient, and 0.05 or more may be sufficient.
本発明のポリイミドフィルムはMD方向およびTD方向の両方の引張弾性率が3GPa以上であり、好ましくは3.5GPa以上であり、より好ましくは4GPa以上である。また、8GPa以下が好ましく、より好ましくは7.5GPa以下であり、さらに好ましくは7GPa以下である。 The polyimide film of the present invention has a tensile elastic modulus in both the MD direction and the TD direction of 3 GPa or more, preferably 3.5 GPa or more, and more preferably 4 GPa or more. Further, it is preferably 8 GPa or less, more preferably 7.5 GPa or less, and further preferably 7 GPa or less.
本発明のポリイミドフィルムはMD方向およびTD方向の両方のCTEが-5ppm/℃~+55ppm/℃であり、好ましくは0ppm/℃~+50ppm/℃であり、さらに好ましくは5ppm/℃~+45ppm/℃である。 The polyimide film of the present invention has a CTE of −5 ppm / ° C. to +55 ppm / ° C. in both the MD and TD directions, preferably 0 ppm / ° C. to + 50 ppm / ° C., and more preferably 5 ppm / ° C. to + 45 ppm / ° C. be.
<ポリイミドフィルムの化学組成>
ポリイミドは、テトラカルボン酸無水物とジアミンとの縮重合反応によって得られる。
本発明では以下の組成を有するポリイミドからなるフィルムが好ましい。
・全酸成分を100質量%としたとき、脂環族テトラカルボン酸無水物を70質量%以上含有するテトラカルボン酸無水物と、全アミン成分を100質量%としたとき、分子内にアミド結合を有するジアミンを70質量%以上含有するジアミンとの縮重合により得られる化学構造からなるポリイミド
・全酸成分を100質量%としたとき、脂環族テトラカルボン酸無水物を70質量%以上含有するテトラカルボン酸無水物と、トリフルオロメチル基を分子内に有するジアミンを70質量%以上含有するジアミンとの縮重合により得られる化学構造からなるポリイミド
・全酸成分を100質量%としたとき、芳香族テトラカルボン酸無水物を70質量%以上含有するテトラカルボン酸無水物と、全アミン成分を100質量%としたとき、少なくとも分子内にイオウ原子を有するジアミンを70質量%以上含有するジアミンから得られる化学構造からなるポリイミド
・全酸成分を100質量%としたとき、少なくともトリフルオロメチル基を分子内に含有するテトラカルボン酸を30質量%以上含有するテトラカルボン酸無水物と、少なくともトリフルオロメチル基を分子内に有するジアミンを70質量%以上含有するジアミンとの縮重合により得られる化学構造からなるポリイミド
<Chemical composition of polyimide film>
The polyimide is obtained by a polycondensation reaction between a tetracarboxylic acid anhydride and a diamine.
In the present invention, a film made of polyimide having the following composition is preferable.
When the total acid component is 100% by mass, the tetracarboxylic acid anhydride containing 70% by mass or more of the alicyclic tetracarboxylic acid anhydride and when the total amine component is 100% by mass, an amide bond is formed in the molecule. When the total acid component of the polyimide having a chemical structure obtained by condensation polymerization with a diamine containing 70% by mass or more of the diamine having is 100% by mass, the alicyclic tetracarboxylic acid anhydride is contained in 70% by mass or more. Aroma when 100% by mass of the polyimide / total acid component having a chemical structure obtained by condensate of tetracarboxylic acid anhydride and diamine containing 70% by mass or more of a diamine having a trifluoromethyl group in the molecule. Obtained from a tetracarboxylic acid anhydride containing 70% by mass or more of a group tetracarboxylic acid anhydride and a diamine containing at least 70% by mass of a diamine having a sulfur atom in the molecule when the total amine component is 100% by mass. When the total acid component of the polyimide having the above chemical structure is 100% by mass, a tetracarboxylic acid anhydride containing at least 30% by mass of a tetracarboxylic acid containing a trifluoromethyl group in the molecule and at least trifluoromethyl. A polyimide having a chemical structure obtained by condensation polymerization with a diamine containing 70% by mass or more of a diamine having a group in the molecule.
本発明における脂環族テトラカルボン酸無水物としては、1,2,3,4-シクロブタンテトラカルボン酸、1,2,3,4-シクロペンタンテトラカルボン酸、1,2,3,4-シクロヘキサンテトラカルボン酸、1,2,4,5-シクロヘキサンテトラカルボン酸、3,3’,4,4’-ビシクロヘキシルテトラカルボン酸、ビシクロ[2,2、1]ヘプタン-2,3,5,6-テトラカルボン酸、ビシクロ[2,2,2]オクタン-2,3,5,6-テトラカルボン酸、ビシクロ[2,2,2]オクト-7-エン-2,3,5,6-テトラカルボン酸、テトラヒドロアントラセン-2,3,6,7-テトラカルボン酸、テトラデカヒドロ-1,4:5,8:9,10-トリメタノアントラセン-2,3,6,7-テトラカルボン酸、デカヒドロナフタレン-2,3,6,7-テトラカルボン酸、デカヒドロ-1,4:5,8-ジメタノナフタレン-2,3,6,7-テトラカルボン酸、デカヒドロ-1,4-エタノ-5,8-メタノナフタレン-2,3,6,7-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸(別名「ノルボルナン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸」)、メチルノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-(メチルノルボルナン)-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロヘキサノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸(別名「ノルボルナン-2-スピロ-2’-シクロヘキサノン-6’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸」)、メチルノルボルナン-2-スピロ-α-シクロヘキサノン-α’-スピロ-2’’-(メチルノルボルナン)-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロプロパノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロブタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロヘプタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロオクタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロノナノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロウンデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロドデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロトリデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロテトラデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-シクロペンタデカノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-(メチルシクロペンタノン)-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、ノルボルナン-2-スピロ-α-(メチルシクロヘキサノン)-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸、などのテトラカルボン酸及びこれらの酸無水物が挙げられる。これらの中でも、2個の酸無水物構造を有する二無水物が好適であり、特に、1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2,3,4-シクロヘキサンテトラカルボン酸二無水物、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物が好ましく、1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物がより好ましく、1,2,3,4-シクロブタンテトラカルボン酸二無水物がさらに好ましい。なお、これらは単独で用いてもよいし、二種以上を併用してもよい。 Examples of the alicyclic tetracarboxylic acid anhydride in the present invention include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid and 1,2,3,4-cyclohexane. Tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3', 4,4'-bicyclohexyltetracarboxylic acid, bicyclo [2,2,1] heptane-2,3,5,6 -Tetracarboxylic acid, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic acid, bicyclo [2,2,2] octo-7-en-2,3,5,6-tetra Carboxylic acid, tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3,6,7-tetracarboxylic acid, Decahydronaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1,4-ethano- 5,8-methanonaphthalene-2,3,6,7-tetracarboxylic acid, norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornan-5,5'',6 6''-Tetracarboxylic acid (also known as "norbornan-2-spiriro-2'-cyclopentanone-5'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid" ), Methylnorbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornan) -5,5'',6,6''-tetracarboxylic acid, norbornan-2-spiro -Α-Cyclohexanone-α'-Spiro-2''-Norbornane-5,5'', 6,6''-Tetracarboxylic acid (also known as "norbornan-2-spiriro-2'-cyclohexanone-6'-spiro-" 2''-norbornan-5,5'', 6,6''-tetracarboxylic acid "), methylnorbornan-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornan) -5 , 5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclopropanol-α'-spiro-2''-norbornan-5,5'', 6,6''- Tetracarboxylic acid, norbornan-2-spiro-α-cyclobutanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclo Heptanone- α'-Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornan- 5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclononanonone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetra Carboxylic acid, norbornan-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclounde Cannon-α'-Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclododecanone-α'-spiro-2''- Norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornan-5,5'', 6,6 '' -Tetracarboxylic acid, norbornan-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2 -Spiro-α-cyclopentadecanone-α'-Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α- (methylcyclopentanone) ) -Α'-Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid, norbornan-2-spiro-α- (methylcyclohexanone) -α'-spiro-2'' -Norbornane-5,5'', 6,6''-Tetracarboxylic acids such as tetracarboxylic acids, and acid anhydrides thereof. Among these, dianhydride having two acid anhydride structures is preferable, and in particular, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2,3,4-cyclohexanetetracarboxylic acid are preferable. Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is even more preferred. These may be used alone or in combination of two or more.
本発明における芳香族テトラカルボン酸無水物としては、4,4’-(2,2-ヘキサフルオロイソプロピリデン)ジフタル酸、4,4’-オキシジフタル酸、ビス(1,3-ジオキソ-1,3-ジヒドロ-2-ベンゾフラン-5-カルボン酸)1,4-フェニレン、ビス(1,3-ジオキソ-1,3-ジヒドロ-2-ベンゾフラン-5-イル)ベンゼン-1,4-ジカルボキシレート、4,4’-[4,4’-(3-オキソ-1,3-ジヒドロ-2-ベンゾフラン-1,1-ジイル)ビス(ベンゼン-1,4-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、4,4’-[(3-オキソ-1,3-ジヒドロ-2-ベンゾフラン-1,1-ジイル)ビス(トルエン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[(3-オキソ-1,3-ジヒドロ-2-ベンゾフラン-1,1-ジイル)ビス(1,4-キシレン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[4,4’-(3-オキソ-1,3-ジヒドロ-2-ベンゾフラン-1,1-ジイル)ビス(4-イソプロピル―トルエン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[4,4’-(3-オキソ-1,3-ジヒドロ-2-ベンゾフラン-1,1-ジイル)ビス(ナフタレン-1,4-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[4,4’-(3H-2,1-ベンズオキサチオール-1,1-ジオキシド-3,3-ジイル)ビス(ベンゼン-1,4-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-ベンゾフェノンテトラカルボン酸、4,4’-[(3H-2,1-ベンズオキサチオール-1,1-ジオキシド-3,3-ジイル)ビス(トルエン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[(3H-2,1-ベンズオキサチオール-1,1-ジオキシド-3,3-ジイル)ビス(1,4-キシレン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[4,4’-(3H-2,1-ベンズオキサチオール-1,1-ジオキシド-3,3-ジイル)ビス(4-イソプロピル―トルエン-2,5-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、4,4’-[4,4’-(3H-2,1-ベンズオキサチオール-1,1-ジオキシド-3,3-ジイル)ビス(ナフタレン-1,4-ジイルオキシ)]ジベンゼン-1、2-ジカルボン酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、2,3,3’,4’-ビフェニルテトラカルボン酸、ピロメリット酸、4,4’-[スピロ(キサンテン-9,9’-フルオレン)-2,6-ジイルビス(オキシカルボニル)]ジフタル酸、4,4’-[スピロ(キサンテン-9,9’-フルオレン)-3,6-ジイルビス(オキシカルボニル)]ジフタル酸、などのテトラカルボン酸及びこれらの酸無水物が挙げられる。なお、芳香族テトラカルボン酸類は単独で用いてもよいし、二種以上を併用してもよい。 Examples of the aromatic tetracarboxylic acid anhydride in the present invention include 4,4'-(2,2-hexafluoroisopropyridene) diphthalic acid, 4,4'-oxydiphthalic acid, and bis (1,3-dioxo-1,3). -Dihydro-2-benzofuran-5-carboxylic acid) 1,4-phenylene, bis (1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl) benzene-1,4-dicarboxylate, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl) bis (benzene-1,4-diyloxy)] dibenzene-1,2-dicarboxylic acid Acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 4,4'-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl) bis (toluene-2, 5-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl) bis (1,4-xylene-2) , 5-Diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl) bis (4) -Isopropyl-toluene-2,5-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[4,4'-(3-oxo-1,3-dihydro-2-benzofuran-1,1) -Diyl) bis (naphthalene-1,4-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[4,4'-(3H-2,1-benzoxathiol-1,1-dioxide) -3,3-diyl) bis (benzene-1,4-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-benzophenonetetracarboxylic acid, 4,4'-[(3H-2,1-) Benzoxathiol-1,1-dioxide-3,3-diyl) bis (toluene-2,5-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[(3H-2,1-benz) Oxathiol-1,1-dioxide-3,3-diyl) bis (1,4-xylene-2,5-diyloxy)] dibenzene-1,2-dicarboxylic acid, 4,4'-[4,4'- (3H-2,1-benzoxathiol-1,1-dioxide-3,3-diyl) Bis (4-isopropyl-toluene-2,5-diyloxy)] Dibenzene-1,2-dicarboxylic acid, 4,4 '-[4,4'-(3H-2,1-benzoxathio) Lu-1,1-dioxide-3,3-diyl) bis (naphthalen-1,4-diyloxy)] dibenzene-1,2-dicarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3. 3', 4'-biphenyltetracarboxylic acid, pyromellitic acid, 4,4'-[spiro (xanthene-9,9'-fluorene) -2,6-diylbis (oxycarbonyl)] diphthalic acid, 4,4' -[Spiro (xanthene-9,9'-fluorene) -3,6-diylbis (oxycarbonyl)] Tetracarboxylic acids such as diphthalic acid, and acid anhydrides thereof. The aromatic tetracarboxylic acids may be used alone or in combination of two or more.
本発明では、テトラカルボン酸無水物に加えてトリカルボン酸、ジカルボン酸を用いても良い。
トリカルボン酸類としては、トリメリット酸、1,2,5-ナフタレントリカルボン酸、ジフェニルエーテル-3,3’,4’-トリカルボン酸、ジフェニルスルホン-3,3’,4’-トリカルボン酸などの芳香族トリカルボン酸、或いはヘキサヒドロトリメリット酸などの上記芳香族トリカルボン酸の水素添加物、エチレングリコールビストリメリテート、プロピレングリコールビストリメリテート、1,4-ブタンジオールビストリメリテート、ポリエチレングリコールビストリメリテートなどのアルキレングリコールビストリメリテート、及びこれらの一無水物、エステル化物が挙げられる。これらの中でも、1個の酸無水物構造を有する一無水物が好適であり、特に、トリメリット酸無水物、ヘキサヒドロトリメリット酸無水物が好ましい。尚、これらは単独で使用してもよいし複数を組み合わせて使用してもよい。
In the present invention, a tricarboxylic acid or a dicarboxylic acid may be used in addition to the tetracarboxylic acid anhydride.
Examples of tricarboxylic acids include aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, diphenyl ether-3,3', 4'-tricarboxylic acid, and diphenylsulfone-3,3', 4'-tricarboxylic acid. An acid or an alkylene such as a hydrogenated additive of the above aromatic tricarboxylic acid such as hexahydrotrimellitic acid, ethylene glycol bistrimerite, propylene glycol bistrimerite, 1,4-butanediol bistrimerite, polyethylene glycol bistrimerite. Glycolbitrimeritate and these monoanhydrides and esterified products can be mentioned. Among these, monoanhydride having one acid anhydride structure is preferable, and in particular, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride are preferable. These may be used alone or in combination of two or more.
ジカルボン酸類としては、テレフタル酸、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、4、4’-オキシジベンゼンカルボン酸などの芳香族ジカルボン酸、或いは1,6-シクロヘキサンジカルボン酸などの上記芳香族ジカルボン酸の水素添加物、シュウ酸、コハク酸、グルタル酸、アジピン酸、ヘプタン二酸、オクタン二酸、アゼライン酸、セバシン酸、ウンデカ二酸、ドデカン二酸、2-メチルコハク酸、及びこれらの酸塩化物或いはエステル化物などが挙げられる。これらの中で芳香族ジカルボン酸及びその水素添加物が好適であり、特に、テレフタル酸、1,6-シクロヘキサンジカルボン酸、4、4’-オキシジベンゼンカルボン酸が好ましい。尚、ジカルボン酸類は単独で使用してもよいし複数を組み合わせて使用してもよい。 Examples of the dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid, and the above aromatic dicarboxylic acid such as 1,6-cyclohexanedicarboxylic acid. Hydrogen additives, oxalic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, azelaioic acid, sebacic acid, undecadioic acid, dodecanedioic acid, 2-methylsuccinic acid, and acid acidates thereof. Alternatively, an esterified product or the like can be mentioned. Among these, aromatic dicarboxylic acids and hydrogen additives thereof are preferable, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid are particularly preferable. The dicarboxylic acids may be used alone or in combination of two or more.
本発明における分子内にアミド結合を有するジアミンとしては、芳香族ジアミン、脂環族アミンを主に用いることができる。
芳香族ジアミン類としては、例えば、2,2’-ジメチル-4,4’-ジアミノビフェニル、1,4-ビス[2-(4-アミノフェニル)-2-プロピル]ベンゼン、1,4-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、4,4’-ビス(3-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]ケトン、ビス[4-(3-アミノフェノキシ)フェニル]スルフィド、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(3-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン、m-フェニレンジアミン、o-フェニレンジアミン、p-フェニレンジアミン、m-アミノベンジルアミン、p-アミノベンジルアミン、4-アミノ-N-(4-アミノフェニル)ベンズアミド、3,3’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル、2,2’-トリフルオロメチル-4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルスルフィド、3,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルスルフィド、3,3’-ジアミノジフェニルスルホキシド、3,4’-ジアミノジフェニルスルホキシド、4,4’-ジアミノジフェニルスルホキシド、3,3’-ジアミノジフェニルスルホン、3,4’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノベンゾフェノン、3,4’-ジアミノベンゾフェノン、4,4’-ジアミノベンゾフェノン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、ビス[4-(4-アミノフェノキシ)フェニル]メタン、1,1-ビス[4-(4-アミノフェノキシ)フェニル]エタン、1,2-ビス[4-(4-アミノフェノキシ)フェニル]エタン、1,1-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、1,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、1,3-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、1,1-ビス[4-(4-アミノフェノキシ)フェニル]ブタン、1,3-ビス[4-(4-アミノフェノキシ)フェニル]ブタン、1,4-ビス[4-(4-アミノフェノキシ)フェニル]ブタン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]ブタン、2,3-ビス[4-(4-アミノフェノキシ)フェニル]ブタン、2-[4-(4-アミノフェノキシ)フェニル]-2-[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン、2-[4-(4-アミノフェノキシ)フェニル]-2-[4-(4-アミノフェノキシ)-3,5-ジメチルフェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)-3,5-ジメチルフェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(4-アミノフェノキシ)フェニル]ケトン、ビス[4-(4-アミノフェノキシ)フェニル]スルフィド、ビス[4-(4-アミノフェノキシ)フェニル]スルホキシド、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、1,3-ビス[4-(4-アミノフェノキシ)ベンゾイル]ベンゼン、1,3-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,4-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、4,4’-ビス[(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,1-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、1,3-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、3,4’-ジアミノジフェニルスルフィド、2,2-ビス[3-(3-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン、ビス[4-(3-アミノフェノキシ)フェニル]メタン、1,1-ビス[4-(3-アミノフェノキシ)フェニル]エタン、1,2-ビス[4-(3-アミノフェノキシ)フェニル]エタン、ビス[4-(3-アミノフェノキシ)フェニル]スルホキシド、4,4’-ビス[3-(4-アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4’-ビス[3-(3-アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4’-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4’-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ジフェニルスルホン、ビス[4-{4-(4-アミノフェノキシ)フェノキシ}フェニル]スルホン、1,4-ビス[4-(4-アミノフェノキシ)フェノキシ-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノフェノキシ)フェノキシ-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノ-6-トリフルオロメチルフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノ-6-フルオロフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノ-6-メチルフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノ-6-シアノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、3,3’-ジアミノ-4,4’-ジフェノキシベンゾフェノン、4,4’-ジアミノ-5,5’-ジフェノキシベンゾフェノン、3,4’-ジアミノ-4,5’-ジフェノキシベンゾフェノン、3,3’-ジアミノ-4-フェノキシベンゾフェノン、4,4’-ジアミノ-5-フェノキシベンゾフェノン、3,4’-ジアミノ-4-フェノキシベンゾフェノン、3,4’-ジアミノ-5’-フェノキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジビフェノキシベンゾフェノン、4,4’-ジアミノ-5,5’-ジビフェノキシベンゾフェノン、3,4’-ジアミノ-4,5’-ジビフェノキシベンゾフェノン、3,3’-ジアミノ-4-ビフェノキシベンゾフェノン、4,4’-ジアミノ-5-ビフェノキシベンゾフェノン、3,4’-ジアミノ-4-ビフェノキシベンゾフェノン、3,4’-ジアミノ-5’-ビフェノキシベンゾフェノン、1,3-ビス(3-アミノ-4-フェノキシベンゾイル)ベンゼン、1,4-ビス(3-アミノ-4-フェノキシベンゾイル)ベンゼン、1,3-ビス(4-アミノ-5-フェノキシベンゾイル)ベンゼン、1,4-ビス(4-アミノ-5-フェノキシベンゾイル)ベンゼン、1,3-ビス(3-アミノ-4-ビフェノキシベンゾイル)ベンゼン、1,4-ビス(3-アミノ-4-ビフェノキシベンゾイル)ベンゼン、1,3-ビス(4-アミノ-5-ビフェノキシベンゾイル)ベンゼン、1,4-ビス(4-アミノ-5-ビフェノキシベンゾイル)ベンゼン、2,6-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ベンゾニトリル、4,4’-[9H-フルオレン-9,9-ジイル]ビスアニリン(別名「9,9-ビス(4-アミノフェニル)フルオレン」)、スピロ(キサンテン-9,9’-フルオレン)-2,6-ジイルビス(オキシカルボニル)]ビスアニリン、4,4’-[スピロ(キサンテン-9,9’-フルオレン)-2,6-ジイルビス(オキシカルボニル)]ビスアニリン、4,4’-[スピロ(キサンテン-9,9’-フルオレン)-3,6-ジイルビス(オキシカルボニル)]ビスアニリン、5-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(p-アミノフェニル)ベンゾオキサゾール、5-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール、6-アミノ-2-(m-アミノフェニル)ベンゾオキサゾール、2,2’-p-フェニレンビス(5-アミノベンゾオキサゾール)、2,2’-p-フェニレンビス(6-アミノベンゾオキサゾール)、1-(5-アミノベンゾオキサゾロ)-4-(6-アミノベンゾオキサゾロ)ベンゼン、2,6-(4,4’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(4,4’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール、2,6-(3,4’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(3,4’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール、2,6-(3,3’-ジアミノジフェニル)ベンゾ[1,2-d:5,4-d’]ビスオキサゾール、2,6-(3,3’-ジアミノジフェニル)ベンゾ[1,2-d:4,5-d’]ビスオキサゾール等が挙げられる。また、上記芳香族ジアミンの芳香環上の水素原子の一部もしくは全てが、ハロゲン原子、炭素数1~3のアルキル基もしくはアルコキシル基、またはシアノ基で置換されても良く、さらに前記炭素数1~3のアルキル基もしくはアルコキシル基の水素原子の一部もしくは全部がハロゲン原子で置換されても良い。
As the diamine having an amide bond in the molecule in the present invention, aromatic diamines and alicyclic amines can be mainly used.
Examples of aromatic diamines include 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, and 1,4-bis. (4-Amino-2-trifluoromethylphenoxy) benzene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'- Bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone , 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4-amino-N- (4-aminophenyl) benzamide, 3,3'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenyl Sulfur, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1 , 3-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane , 1,4-Bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) ) Phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-amino) Phenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-) Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4 -(4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4- (4-) Aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis [ (3-Aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4' -Diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] Methan, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bi Su [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4 '-Bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) Phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6) -Trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [ 4- (4-Amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3, 3'-Diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3 '-Diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'- Diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1, 3-Bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoyl) Xybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-) 4-Bifenoxybenzoyl) Benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [ 4- (4-Amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, 4,4'-[9H-fluoren-9,9-diyl] bisaniline (also known as "9,9-bis (4-aminophenyl)) Fluorene "), Spiro (xanthen-9,9'-fluorene) -2,6-diylbis (oxycarbonyl)] bisaniline, 4,4'-[spiro (xanthen-9,9'-fluoren) -2,6- Diylbis (oxycarbonyl)] bisaniline, 4,4'-[spiro (xanthen-9,9'-fluorene) -3,6-diylbis (oxycarbonyl)] bisaniline, 5-amino-2- (p-aminophenyl) Benzeneoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5-amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 2, 2'-p-phenylenebis (5-aminobenzoxazole), 2,2'-p-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6-aminobenzoxazole) Oxazolo) Benzene, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole, 2,6- (3,4-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2, 6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2,6- (3,3-'-diaminodiphenyl) benzo [1,2-d: 4,5-d'] bisoxazole and the like can be mentioned. Further, a part or all of the hydrogen atoms on the aromatic ring of the aromatic diamine may be substituted with a halogen atom, an alkyl group or an alkoxyl group having 1 to 3 carbon atoms, or a cyano group, and further, the carbon number 1 may be substituted. A part or all of the hydrogen atom of the alkyl group or the alkoxyl group of ~ 3 may be substituted with a halogen atom.
脂環族ジアミン類としては、例えば、1,4-ジアミノシクロヘキサン、1,4-ジアミノ-2-メチルシクロヘキサン、1,4-ジアミノ-2-エチルシクロヘキサン、1,4-ジアミノ-2-n-プロピルシクロヘキサン、1,4-ジアミノ-2-イソプロピルシクロヘキサン、1,4-ジアミノ-2-n-ブチルシクロヘキサン、1,4-ジアミノ-2-イソブチルシクロヘキサン、1,4-ジアミノ-2-sec-ブチルシクロヘキサン、1,4-ジアミノ-2-tert-ブチルシクロヘキサン、4,4’-メチレンビス(2,6-ジメチルシクロヘキシルアミン)、9,10-ビス(4-アミノフェニル)アデニン、2,4-ビス(4-アミノフェニル)シクロブタン-1,3-ジカルボン酸ジメチル、等が挙げられる。 Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, and 1,4-diamino-2-n-propyl. Cyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-Diamino-2-tert-butylcyclohexane, 4,4'-methylenebis (2,6-dimethylcyclohexylamine), 9,10-bis (4-aminophenyl) adenine, 2,4-bis (4-) Aminophenyl) cyclobutane-1,3-dimethyl dicarboxylate, and the like can be mentioned.
分子内にアミド結合を有するジアミンとしては、4-アミノ-N-(4-アミノフェニル)ベンズアミドが好ましい。アミド結合を有するジアミンは全ジアミン中の70質量%以上が好ましく、80質量%以上、さらには90質量%以上の使用が好ましい。
また、トリフルオロメチル基を有するジアミンとしては、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル、1,4-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン、2,2’-トリフルオロメチル-4,4’-ジアミノジフェニルエーテルが好ましい。これら分子内にフッ素原子を有するジアミン化合物、特にトリフルオロメチル基を分子内に有するジアミンを使用する場合に、その使用量は、全ジアミン中の70質量%以上が好ましく、80質量%以上、さらには90質量%以上の使用が好ましい。
As the diamine having an amide bond in the molecule, 4-amino-N- (4-aminophenyl) benzamide is preferable. The diamine having an amide bond is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more of the total diamine.
Examples of the diamine having a trifluoromethyl group include 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, and 2, 2'-Trifluoromethyl-4,4'-diaminodiphenyl ether is preferred. When a diamine compound having a fluorine atom in these molecules, particularly a diamine having a trifluoromethyl group in the molecule is used, the amount used is preferably 70% by mass or more, more preferably 80% by mass or more, and further, 80% by mass or more of the total diamine. Is preferably used in an amount of 90% by mass or more.
<無機フィラー>
本発明で無機フィラー(a)として用いられる酸化亜鉛は、化学式 ZnO で表される亜鉛の酸化物であり、亜鉛華、亜鉛白とも呼ばれる。酸化亜鉛は粒子状態でポリイミドフィルムに含有される。含有量は、ポリイミド樹脂の質量に対して625ppm以上、好ましくは800ppm以上、なお好ましくは1200ppm以上であり、20000ppm以下、好ましくは12000ppm以下、さらに好ましくは6000ppm以下である。ここで酸化亜鉛含有量の単位ppmは質量換算(mg/kg)の単位である。
市販されている酸化亜鉛粒子の具体例としては、ZnO-350、ZnO-510、ZnO-610、ZnO-650(住友大阪セメント社製)、MZ-300、MZY-303S、MZ-306X、MZ-500、MZY-505S、MZY-510M3S、MZ-506X、MZ-510HPSX(テイカ社製)、XZ-Fシリーズ、XZ-100P、FINEX-30、FINEX-30S-LP2、FINEX-30S-LPT、FINEX-30W-LP2、FINEX-30W-LPT、FINEX-50、FINEX-50S-LP2、FINEX-50W-LP2、FINEX-50S-LPT、FINEX-50W-LPT、ZINCA-20、微細酸化亜鉛(堺化学工業社製)、F-1、F-2(ハクスイテック社製)、FZO-50(石原産業社製)等を例示することができる。これらの酸化亜鉛は単独で用いても、二種以上を混合して用いても構わない。
<Inorganic filler>
Zinc oxide used as the inorganic filler (a) in the present invention is an oxide of zinc represented by the chemical formula ZnO, and is also called zinc white or zinc white. Zinc oxide is contained in the polyimide film in the form of particles. The content is 625 ppm or more, preferably 800 ppm or more, more preferably 1200 ppm or more, more preferably 20000 ppm or less, preferably 12000 ppm or less, still more preferably 6000 ppm or less with respect to the mass of the polyimide resin. Here, the unit ppm of the zinc oxide content is a unit in terms of mass (mg / kg).
Specific examples of commercially available zinc oxide particles include ZnO-350, ZnO-510, ZnO-610, ZnO-650 (manufactured by Sumitomo Osaka Cement Co., Ltd.), MZ-300, MZY-303S, MZ-306X, and MZ-. 500, MZY-505S, MZY-510M3S, MZ-506X, MZ-510HPSX (manufactured by Teika), XZ-F series, XZ-100P, FINEX-30, FINEX-30S-LP2, FINEX-30S-LPT, FINEX- 30W-LP2, FINEX-30W-LPT, FINEX-50, FINEX-50S-LP2, FINEX-50W-LP2, FINEX-50S-LPT, FINEX-50W-LPT, ZINCA-20, fine zinc oxide (Sakai Chemical Industry Co., Ltd.) , F-1, F-2 (manufactured by HakusuiTech Co., Ltd.), FZO-50 (manufactured by Ishihara Sangyo Co., Ltd.) and the like can be exemplified. These zinc oxides may be used alone or in combination of two or more.
本発明で無機フィラー(a)として用いられる硫化亜鉛は、化学式ZnSで表される亜鉛の硫化物である。硫化亜鉛粒子の含有量はポリイミド樹脂の質量に対して750ppm以上、好ましくは900ppm以上、なお好ましくは1200ppm以上であり、20000ppm以下、好ましくは12000ppm以下、さらに好ましくは6000ppm以下である。ここで硫化亜鉛含有量の単位ppmは質量換算(mg/kg)の単位である。
本発明では、酸化亜鉛粒子、硫化亜鉛粒子のいずれか、または両方がポリイミドフィルムに含有されることが必須である。なお酸化亜鉛粒子と硫化亜鉛粒子の両方が用いられる場合には、両者の合計が750ppm以上20000ppm以下の範囲となるように調製することが好ましい。酸化亜鉛粒子、硫化亜鉛粒子の配合量がこの範囲を超えるとフィルムの白化が無視できなくなりヘイズ値が上昇することがあり、この範囲に満たない場合には紫外線吸収効果が不十分となることがある。前記所定範囲が、後述する酸化ジルコニウムないしケイ酸ジルコニウムとの併用により十分な紫外線吸収能(紫外線遮蔽能)と、かつ可視光線の高い透過性(無色性、透明性)を両立できる範囲となる。
The zinc sulfide used as the inorganic filler (a) in the present invention is a zinc sulfide represented by the chemical formula ZnS. The content of the zinc sulfide particles is 750 ppm or more, preferably 900 ppm or more, more preferably 1200 ppm or more, more preferably 20000 ppm or less, preferably 12000 ppm or less, still more preferably 6000 ppm or less, based on the mass of the polyimide resin. Here, the unit ppm of the zinc sulfide content is a unit in terms of mass (mg / kg).
In the present invention, it is essential that zinc oxide particles, zinc sulfide particles, or both are contained in the polyimide film. When both zinc oxide particles and zinc sulfide particles are used, it is preferable to prepare so that the total of both particles is in the range of 750 ppm or more and 20000 ppm or less. If the blending amount of zinc oxide particles and zinc sulfide particles exceeds this range, the whitening of the film cannot be ignored and the haze value may increase. If the amount is less than this range, the ultraviolet absorption effect may be insufficient. be. The predetermined range is a range in which sufficient ultraviolet absorption ability (ultraviolet shielding ability) and high transparency of visible light (colorlessness, transparency) can be achieved at the same time when used in combination with zirconium oxide or zirconium silicate described later.
本発明で無機フィラー(b)として用いられる酸化ジルコニウムは、化学式 ZrO2で表されるジルコニウムの酸化物であり、ジルコニアとも呼ばれる。酸化ジルコニウムは粒子状態でポリイミドフィルムに含有される。含有量は、ポリイミド樹脂の質量に対して680ppm以上、好ましくは900ppm以上、なお好ましくは1200ppm以上であり、10000ppm以下、好ましくは8000ppm以下、さらに好ましくは6000ppm以下である。ここで酸化ジルコニウム含有量の単位ppmは質量換算(mg/kg)の単位である。
本発明で無機フィラー(b)として用いられるケイ酸ジルコニウムは、化学式ZrSiO4、あるいはZrO2・SiO2で表されるジルコニウムのケイ酸塩であり、ジルコンとも呼ばれる。ケイ酸ジルコニウムの含有量はポリイミド樹脂の質量に対して1000ppm以上、好ましくは1200ppm以上、なお好ましくは2000ppm以上であり、10000ppm以下、好ましくは8000ppm以下、さらに好ましくは6000ppm以下である。ここでケイ酸ジルコニウム含有量の単位ppmは質量換算(mg/kg)の単位である。
本発明では、酸化ジルコニウム粒子、ケイ酸ジルコニウム粒子のいずれか、または両方がポリイミドフィルムに含有されることが必須である。なお酸化ジルコニウム粒子とケイ酸ジルコニウム粒子の両方が用いられる場合には、両者の合計が1000ppm以上20000ppm以下の範囲となるように調製することが好ましい。酸化ジルコニウム粒子、ケイ酸ジルコニウム粒子の配合量がこの範囲を超えるとフィルムの白化が無視できなくなりヘイズ値が上昇することがあり、この範囲に満たない場合には酸化亜鉛または硫化亜鉛の紫外線吸収能を十分にサポートすることができなくなることがある。かかる所定範囲が、十分な紫外線吸収能(紫外線遮蔽能)と、かつ可視光線の高い透過性(無色性、透明性)を両立できる範囲となる。
なお、ジルコニウムには不純物として同じ第4族元素であるハフニウムが含まれることが知られている。両者は化学的性質が非常に似ているために分離しにくい。そのため、一般にジルコニウム化合物として販売されている製品にはハフニウム化合物が含まれている。本発明はジルコニウムとハフニウムの合計に対してハフニウムの含有量が5質量%以下であれば、ハフニウムを含めて総量をジルコニウムとして扱うこととする。
Zirconium oxide used as the inorganic filler (b) in the present invention is an oxide of zirconium represented by the chemical formula ZrO 2 , and is also called zirconia. Zirconium oxide is contained in the polyimide film in the form of particles. The content is 680 ppm or more, preferably 900 ppm or more, more preferably 1200 ppm or more, more preferably 10,000 ppm or less, preferably 8000 ppm or less, still more preferably 6000 ppm or less with respect to the mass of the polyimide resin. Here, the unit ppm of the zirconium oxide content is a unit in terms of mass (mg / kg).
The zirconium silicate used as the inorganic filler (b) in the present invention is a silicate of zirconium represented by the chemical formula ZrSiO 4 or ZrO 2 · SiO 2 , and is also called zircon. The content of zirconium silicate is 1000 ppm or more, preferably 1200 ppm or more, more preferably 2000 ppm or more, and 10,000 ppm or less, preferably 8000 ppm or less, still more preferably 6000 ppm or less, based on the mass of the polyimide resin. Here, the unit ppm of the zirconium silicate content is a unit in terms of mass (mg / kg).
In the present invention, it is essential that either or both of the zirconium oxide particles and the zirconium silicate particles are contained in the polyimide film. When both zirconium oxide particles and zirconium silicate particles are used, it is preferable to prepare so that the total of both particles is in the range of 1000 ppm or more and 20000 ppm or less. If the blending amount of zirconium oxide particles and zirconium silicate particles exceeds this range, the whitening of the film cannot be ignored and the haze value may increase. If this range is not reached, the ultraviolet absorption capacity of zinc oxide or zinc sulfide May not be fully supported. Such a predetermined range is a range in which sufficient ultraviolet absorption ability (ultraviolet shielding ability) and high transparency of visible light (colorlessness, transparency) can be achieved at the same time.
It is known that zirconium contains hafnium, which is the same Group 4 element, as an impurity. The two are very similar in chemical properties and are difficult to separate. Therefore, products generally sold as zirconium compounds contain hafnium compounds. In the present invention, if the hafnium content is 5% by mass or less with respect to the total of zirconium and hafnium, the total amount including hafnium is treated as zirconium.
無機フィラーの粒子径は、400nm以下であることが好ましく、より好ましくは350nm以下であり、さらに好ましくは300nm以下である。また、10nm以上であることが好ましく、より好ましくは20nm以上である。前記範囲内とすることで散乱効果を高めることができる。 The particle size of the inorganic filler is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Further, it is preferably 10 nm or more, more preferably 20 nm or more. By setting it within the above range, the scattering effect can be enhanced.
本発明のポリイミドフィルムでは、酸化亜鉛、硫化亜鉛、酸化ジルコニウム、ケイ酸ジルコニウム以外に、下記の無機フィラーを滑剤としてポリイミド中に添加含有せしめ、フィルム表面に微細な凹凸を付与しフィルムの滑り性などを改善することが好ましい。
滑剤としては、無機や有機の0.03μm~3μm程度の平均粒子径を有する微粒子が使用でき、具体例として、酸化チタン、アルミナ、シリカ、炭酸カルシウム、燐酸カルシウム、燐酸水素カルシウム、ピロ燐酸カルシウム、酸化マグネシウム、酸化カルシウム、粘土鉱物などが挙げられる。
In the polyimide film of the present invention, in addition to zinc oxide, zinc sulfide, zirconium oxide, and zirconium silicate, the following inorganic fillers are added and contained in the polyimide as a lubricant to impart fine irregularities to the film surface and to make the film slippery. It is preferable to improve.
As the lubricant, fine particles having an average particle size of about 0.03 μm to 3 μm of inorganic or organic can be used, and specific examples thereof include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, and the like. Examples include magnesium oxide, calcium oxide and clay minerals.
<ポリイミドフィルムおよび積層体の製造方法>
一般に、ポリイミドフィルムは、溶媒中でテトラカルボン酸無水物とジアミンを反応させてポリイミド前駆体であるポリアミド酸の溶液を得て、該ポリアミド酸溶液を仮支持体に塗布、乾燥、さらにアミド酸結合からイミド結合への化学的転化反応を行い、ポリイミドフィルムを得る。また、溶液中でポリアミド酸からポリイミドへと転化させてポリイミド溶液とした後に仮支持体に塗布、乾燥させてポリイミドフィルムとする場合もある。さらにポリアミド酸溶液またはポリイミド溶液から再沈操作などによりポリマーを分離して、別の溶剤に再溶解させて得られた溶液を用いてフィルム化する場合もある。
<Manufacturing method of polyimide film and laminate>
In general, a polyimide film is obtained by reacting a tetracarboxylic acid anhydride with a diamine in a solvent to obtain a solution of polyamic acid as a polyimide precursor, and the polyamic acid solution is applied to a temporary support, dried, and further amidic acid bonded. Is chemically converted to an imide bond to obtain a polyimide film. In some cases, polyamic acid is converted to polyimide in a solution to form a polyimide solution, which is then applied to a temporary support and dried to form a polyimide film. Further, the polymer may be separated from the polyamic acid solution or the polyimide solution by a reprecipitation operation or the like and redissolved in another solvent to form a film using the obtained solution.
無機フィラーの添加は、溶媒中でのテトラカルボン酸無水物とジアミンを反応の前に、あらかじめ無機フィラーを溶媒に分散させた状態で添加する方法、あるいは重合後のポリイミドないしポリアミド酸溶液に添加する方法を用いることができる。無機粒子の前駆体(加熱により分解するなどの経緯を経て所定の無機粒子を生成する化合物)をあらかじめ溶液中に添加し、乾燥ないしアミド酸結合からイミド結合への化学反応の過程で無機粒子をフィルム内に生成させて含有させる方法も例示できる。 The inorganic filler is added by adding the tetracarboxylic acid anhydride and the diamine in the solvent in a state where the inorganic filler is dispersed in the solvent in advance before the reaction, or adding the inorganic filler to the polyimide or polyamic acid solution after the polymerization. The method can be used. A precursor of an inorganic particle (a compound that produces a predetermined inorganic particle through a process such as decomposition by heating) is added to the solution in advance, and the inorganic particle is formed in the process of drying or a chemical reaction from an amic acid bond to an imide bond. A method of producing and containing it in a film can also be exemplified.
本発明で用いられる仮支持体上としては、ガラス、金属板、金属ベルト、金属ドラム、高分子フィルム、金属箔などを用いることができる。本発明では長尺でフレキシブルな仮支持体を用いることが好ましく、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイミドなどのフィルムを仮支持体として用いることができる。仮支持体表面に離型処理を施すことは好ましい態様のひとつである。 As the temporary support used in the present invention, glass, a metal plate, a metal belt, a metal drum, a polymer film, a metal foil, or the like can be used. In the present invention, it is preferable to use a long and flexible temporary support, and a film such as polyethylene terephthalate, polyethylene naphthalate, or polyimide can be used as the temporary support. It is one of the preferable embodiments to perform a mold release treatment on the surface of the temporary support.
ポリイミド溶液ないしポリイミド前駆体溶液を仮支持体に塗布し、塗膜の残溶剤量が5~40質量%となるまで乾燥させ、半乾燥状態とすると、半乾燥塗膜は自己支持性のあるフィルムとなり、仮支持体から剥がすことが可能となる。この場合、仮支持体から自己支持性のあるフィルムを剥離し、さらに前記自己支持性のあるフィルムの両端をクリップで挟む、あるいはピンに突き刺して把持し、加熱環境内を搬送して、さらに乾燥および加熱による化学反応を行い、ポリイミドフィルムを得ることができる。 When a polyimide solution or a polyimide precursor solution is applied to a temporary support, dried until the residual solvent amount of the coating film reaches 5 to 40% by mass, and the semi-dried state is obtained, the semi-dried coating film is a self-supporting film. It becomes possible to peel it off from the temporary support. In this case, the self-supporting film is peeled off from the temporary support, and both ends of the self-supporting film are clipped or pierced into a pin to grip the film, and the film is conveyed in a heating environment for further drying. A polyimide film can be obtained by performing a chemical reaction by heating.
本発明では、前記自己支持性フィルムを、延伸してもよい。延伸はフィルム長手方向(MD方向)フィルムの幅方向(TD)のいずれでも良く、両方でも良い。フィルム長手方向の延伸は搬送ロールの速度差あるいは搬送ロールと、両端を把持した後の速度の差を使って行うことができる。フィルム幅方向の延伸は把持したクリプないしピン間を広げることにより行うことができる。延伸と加熱は同時に行っても良い。延伸倍率は1.00倍~2.5倍の間で任意に選ぶことができる。 In the present invention, the self-supporting film may be stretched. The stretching may be in either the longitudinal direction of the film (MD direction) or the width direction (TD) of the film, or both. Stretching in the longitudinal direction of the film can be performed by using the speed difference of the transport roll or the difference in speed between the transport roll and the speed after gripping both ends. Stretching in the film width direction can be performed by widening the gripped clip or pin. Stretching and heating may be performed at the same time. The draw ratio can be arbitrarily selected from 1.00 times to 2.5 times.
前述の仮支持体を無機基板として用い、無機基板にポリイミド溶液ないしポリアミド酸溶液を塗布し、無機基板から剥離することなく、乾燥と必要に応じて化学反応を行うことにより、本発明のポリイミドフィルムと無機基板との積層体を得ることができる。この方法では、ポリイミドフィルムと無機基板は直接的に接する形態となる。 Using the above-mentioned temporary support as an inorganic substrate, a polyimide solution or a polyamic acid solution is applied to the inorganic substrate, and the polyimide film of the present invention is dried and, if necessary, chemically reacted without peeling from the inorganic substrate. And an inorganic substrate can be obtained. In this method, the polyimide film and the inorganic substrate are in direct contact with each other.
本発明ではポリイミドフィルムを無機基板に貼り合わせることにより、本発明の積層体を得ることができる。貼り合わせには公知の接着剤、粘着剤を利用することができる。またポリイミドフィルムおよび/または無機基板の表面処理により両者を接合して積層体とすることができる。表面処理としてはシランカップリング剤処理、真空ないし大気圧プラズマ処理をあげることができる。表面処理にシランカップリング剤を用いた場合にはポリイミドフィルムと無機基板とは、シランアップリング材の縮合物を介して接着された形態となる。 In the present invention, the laminate of the present invention can be obtained by laminating a polyimide film on an inorganic substrate. A known adhesive or adhesive can be used for bonding. Further, the polyimide film and / or the inorganic substrate can be surface-treated to join the two to form a laminated body. Examples of the surface treatment include silane coupling agent treatment and vacuum or atmospheric pressure plasma treatment. When a silane coupling agent is used for the surface treatment, the polyimide film and the inorganic substrate are in a form of being bonded via a condensate of a silane upling material.
本発明におけるシランカップリング剤は、特に限定されるものではないが、アミノ基或はエポキシ基を持ったものが、好ましい。シランカップリング剤の具体例としては、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3―トリエトキシシリルーN-(1,3-ジメチルーブチリデン)プロピルアミン、2-(3,4-エポキシシクロへキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシランビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-(ビニルベンジル)-2-アミノエチル-3-アミノプロピルトリメトキシシラン塩酸塩、3-ウレイドプロピルトリエトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリエトキシシラン、トリス-(3- トリメトキシシリルプロピル)イソシアヌレート、クロロメチルフェネチルトリメトキシシラン、クロロメチルトリメトキシシランなどが挙げられる。このうち好ましいものとしては、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3―トリエトキシシリルーN-(1,3-ジメチルーブチリデン)プロピルアミン、2-(3,4-エポキシシクロへキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、アミノフェニルトリメトキシシラン、アミノフェネチルトリメトキシシラン、アミノフェニルアミノメチルフェネチルトリメトキシシランなどが挙げられる。プロセスで耐熱性を要求する場合、Siとアミノ基などの間を芳香族でつないだものが望ましい。 The silane coupling agent in the present invention is not particularly limited, but one having an amino group or an epoxy group is preferable. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (amino). Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-Epoxycyclohexyl) Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilanevinyl trichlorsilane, vinyl Trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-Chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isoxapropyltriethoxysilane, tris- (3-trimethoxysilyl) Propyl) isocyanurate, chloromethylphenetyltrimethoxysilane, chloromethyltrimethoxysilane and the like. Of these, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)-are preferred. 3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, amino Examples thereof include phenetyltrimethoxysilane and aminophenylaminomethylphenetyltrimethoxysilane. When heat resistance is required in the process, it is desirable to connect Si and an amino group with an aromatic.
また両者の折衷的な手法として、高分子溶液ないし高分子前駆体溶液を自己支持性のある半乾燥フィルムの状態、すなわち溶剤と高分子、あるいは溶剤と高分子前駆体を含むフィルムを無機基板に接着して、その後に乾燥あるいは乾燥と化学反応を生じさせて高分子フィルムと無機基板の積層体とする方法を用いることもできる。この方法によれば、ポリイミドフィルムと無機基板は直接的に接する形態となる。 As an eclectic method of both, a polymer solution or a polymer precursor solution is used as a self-supporting semi-dry film, that is, a solvent and a polymer, or a film containing a solvent and a polymer precursor is used as an inorganic substrate. It is also possible to use a method of adhering and then drying or causing a chemical reaction with drying to form a laminate of a polymer film and an inorganic substrate. According to this method, the polyimide film and the inorganic substrate are in direct contact with each other.
以下、本発明に関し実施例を用いて詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、製造例、実施例中の各物性値などは以下の方法で測定した。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The physical property values in the production examples and the examples were measured by the following methods.
<フィラーの粒子径>
島津製作所製のーザ回折式粒子径分布測定装置SALD-2300から得られる中心径D50を各フィラーの粒子径とした。
<Filler particle size>
The center diameter D50 obtained from the SALD-2300 diffractive particle size distribution measuring device manufactured by Shimadzu Corporation was used as the particle size of each filler.
<フィルムの厚さ測定>
マイクロメーター(ファインリューフ社製、ミリトロン1245D)を用いて測定した。
<Measurement of film thickness>
The measurement was performed using a micrometer (Millitron 1245D manufactured by Fine Wolf Co., Ltd.).
<引張弾性率、引張強度(破断強度)、および、破断伸度>
フィルムを、塗布時の流れ方向(MD方向)および幅方向(TD方向)にそれぞれ100mm×10mmの短冊状に切り出したものを試験片とした。引張試験機(島津製作所製、オートグラフ(R) 機種名AG-5000A)を用い、引張速度50mm/分、チャック間距離40mmの条件で、MD方向、TD方向それぞれについて、引張弾性率、引張強度及び破断伸度を求め、MD方向とTD方向の測定値の平均値を求めた。
<Tension modulus, tensile strength (breaking strength), and breaking elongation>
The film was cut into strips of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction) at the time of coating, and used as test pieces. Using a tensile tester (manufactured by Shimadzu, Autograph (R) model name AG-5000A), the tensile elastic modulus and tensile strength in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a chuck distance of 40 mm. And the elongation at break were obtained, and the average value of the measured values in the MD direction and the TD direction was obtained.
<線膨張係数(CTE)>
フィルムを、塗布時の流れ方向(MD方向)および幅方向(TD方向)において、各々の寸法について、下記条件にて伸縮率を測定し、30℃~45℃、45℃~60℃のように15℃の間隔での伸縮率/温度を測定し、この測定を300℃まで行い、全測定値の平均値をCTEとして算出し、さらにMD方向とTD方向の測定値の平均値を求めた。
機器名 ; MACサイエンス社製TMA4000S
試料長さ ; 20mm
試料幅 ; 2mm
昇温開始温度 ; 25℃
昇温終了温度 ; 300℃
昇温速度 ; 5℃/min
雰囲気 ; アルゴン
<Line expansion coefficient (CTE)>
The stretch ratio of the film was measured under the following conditions for each dimension in the flow direction (MD direction) and width direction (TD direction) at the time of coating, and the temperature was 30 ° C. to 45 ° C. and 45 ° C. to 60 ° C. The expansion / contraction rate / temperature was measured at intervals of 15 ° C., this measurement was performed up to 300 ° C., the average value of all the measured values was calculated as CTE, and the average value of the measured values in the MD direction and the TD direction was obtained.
Device name; TMA4000S manufactured by MAC Science
Sample length; 20 mm
Sample width; 2 mm
Temperature rise start temperature; 25 ° C
Temperature rise end temperature; 300 ° C
Temperature rise rate; 5 ° C / min
Atmosphere; Argon
<ヘイズ>
HAZEMETER(NDH5000、日本電色社製)を用いてフィルムのヘイズを測定した。光源としてはD65ランプを使用した。尚、同様の測定を3回行い、その算術平均値を採用した。
<Haze>
The haze of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. The same measurement was performed three times, and the arithmetic mean value was adopted.
<全光線透過率>
HAZEMETER(NDH5000、日本電色社製)を用いてフィルムの全光線透過率(TT)を測定し
<Total light transmittance>
The total light transmittance (TT) of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Co., Ltd.).
<紫外線透過率>
分光光度系により波長350nmの透過率をもって紫外線透過率とした。
<Ultraviolet transmittance>
The transmittance at a wavelength of 350 nm was defined as the ultraviolet transmittance by the spectrophotometric system.
<イエローインデックス>
カラーメーター(ZE6000、日本電色社製)およびC2光源を使用して、ASTM D1925に準じてフィルムの三刺激値XYZ値を測定し、下記式により黄色度指数(YI)を算出した。尚、同様の測定を3回行い、その算術平均値を採用した。
YI=100×(1.28X-1.06Z)/Y
<Yellow index>
Using a color meter (ZE6000, manufactured by Nippon Denshoku Co., Ltd.) and a C2 light source, the tristimulatory value XYZ value of the film was measured according to ASTM D1925, and the yellowness index (YI) was calculated by the following formula. The same measurement was performed three times, and the arithmetic mean value was adopted.
YI = 100 × (1.28X-1.06Z) / Y
<フィルムの反り>
100mm×100mmのサイズの正方形に裁断したフィルムを試験片とし、室温で平面上に試験片を凹状となるように静置し、四隅の平面からの距離(h1rt、h2rt、h3rt、h4rt:単位mm)を測定し、その平均値を反り量(mm)とした。
<Film warp>
A film cut into a square having a size of 100 mm × 100 mm is used as a test piece, and the test piece is placed on a flat surface at room temperature so as to have a concave shape, and the distances from the flat surface at the four corners (h1rt, h2rt, h3rt, h4rt: unit mm). ) Was measured, and the average value was taken as the amount of warpage (mm).
〔製造例1 ポリアミド酸溶液A(PAA溶液A)の製造〕
窒素導入管、還流管、攪拌棒を備えた反応容器内を窒素置換した後、22.73質量部の4,4’-ジアミノベンズアニリド(DABAN)を、201.1質量部のN,N-ジメチルアセトアミド(DMAc)に加えて溶解させ、次いで、19.32質量部の1,2,3,4-シクロブタンテトラカルボン酸無二水物(CBDA)を固体のまま分割添加した後、室温で24時間攪拌した。その後、173.1質量部のDMAcを加え希釈し、NV10%、還元粘度3.10dl/gのポリアミド酸溶液Aを得た。
[Production Example 1 Production of Polyamic Acid Solution A (PAA Solution A)]
After nitrogen substitution in the reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod, 22.73 parts by mass of 4,4'-diaminobenzanilide (DABAN) was added to 21.1 parts by mass of N, N-. It is dissolved by adding it to dimethylacetamide (DMAc), and then 19.32 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic acid anilides (CBDA) is added separately as a solid, and then 24 at room temperature. Stir for hours. Then, 173.1 parts by mass of DMAc was added and diluted to obtain a polyamic acid solution A having an NV of 10% and a reduction viscosity of 3.10 dl / g.
〔製造例2 ポリアミド酸溶液B(PAA溶液B)の製造〕
窒素導入管、還流管、攪拌棒を備えた反応容器内を窒素置換した後、32.02質量部の2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル(TFMB)を、279.9質量部のN,N-ジメチルアセトアミド(DMAc)に溶解させ、次いで、9.81質量部の1,2,3,4-シクロブタンテトラカルボン酸無二水物(CBDA)及び15.51質量部の(ODPA)をそれぞれ固体のまま分割添加した後、室温で24時間攪拌した。その後、固形分17質量%、還元粘度3.60dl/gのポリアミド酸溶液Bを得た。
[Production Example 2 Production of Polyamic Acid Solution B (PAA Solution B)]
After nitrogen substitution in the reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod, 32.02 parts by mass of 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl (TFMB) was added to 279. Dissolved in 9 parts by mass of N, N-dimethylacetamide (DMAc), then 9.81 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic acid unihydrate (CBDA) and 15.51 parts by mass. (ODPA) was added separately in solid form, and then stirred at room temperature for 24 hours. Then, a polyamic acid solution B having a solid content of 17% by mass and a reducing viscosity of 3.60 dl / g was obtained.
〔製造例3 ポリイミド溶液C(PI溶液C)の製造〕
窒素導入管、ディーン・スターク管及び還流管、温度計、攪拌棒を備えた反応容器に、窒素ガスを導入しながら、32.02質量部の2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル(TFMB)、230質量部のN,N-ジメチルアセトアミド(DMAc)を加えて完全に溶解させ、次いで、44.42質量部の4,4’-(2,2-ヘキサフルオロイソプロピリデン)ジフタル酸二無水物(6FDA)を固体のまま分割添加した後、室温で24時間攪拌した。その後、固形分25質量%、還元エンド1.10dl/gのポリアミド酸溶液Caaを得た。
次に、得られたポリアミド酸溶液にDMAc204質量部を加えてポリアミド酸の濃度が15質量%になるように希釈した後、イミド化促進剤としてイソキノリン1.3質量部を加えた。次いで、ポリアミド酸溶液を攪拌しながら、イミド化剤として無水酢酸12.25質量部をゆっくりと滴下した。その後、24時間攪拌を続けて化学イミド化反応を行って、ポリイミド溶液Cpiを得た。
次に、得られたポリイミド溶液100質量部を攪拌装置と攪拌機を備えた反応容器に移し替え、攪拌しながらメタノール150質量部をゆっくりと滴下させたところ、粉体状の固体の析出が確認された。
その後、反応容器の内容物である粉末を脱水濾過し、さらにメタノールを用いて洗浄した後に50℃で24時間真空乾燥した後、260℃で更に5時間加熱し、ポリイミド粉体Cpdを得た。得られたポリイミド粉体20質量部を80質量部のDMAcに溶解させてポリイミド溶液Cを得た。
[Production Example 3 Production of Polyimide Solution C (PI Solution C)]
32.02 parts by mass of 2,2'-ditrifluoromethyl-4,4'while introducing nitrogen gas into a reaction vessel equipped with a nitrogen introduction tube, a Dean Stark tube and a recirculation tube, a thermometer, and a stirring rod. -Diaminobiphenyl (TFMB), 230 parts by weight N, N-dimethylacetamide (DMAc) was added and completely dissolved, followed by 44.42 parts by weight of 4,4'-(2,2-hexafluoroisopropylidene). ) Diphthalic acid dianhydride (6FDA) was added in portions as a solid, and then stirred at room temperature for 24 hours. Then, a polyamic acid solution Caa having a solid content of 25% by mass and a reduction end of 1.10 dl / g was obtained.
Next, 204 parts by mass of DMAc was added to the obtained polyamic acid solution to dilute the polyamic acid concentration to 15% by mass, and then 1.3 parts by mass of isoquinoline was added as an imidization accelerator. Then, while stirring the polyamic acid solution, 12.25 parts by mass of acetic anhydride was slowly added dropwise as an imidizing agent. Then, stirring was continued for 24 hours and a chemical imidization reaction was carried out to obtain a polyimide solution Cpi.
Next, 100 parts by mass of the obtained polyimide solution was transferred to a reaction vessel equipped with a stirrer and a stirrer, and 150 parts by mass of methanol was slowly dropped while stirring. As a result, precipitation of a powdery solid was confirmed. rice field.
Then, the powder contained in the reaction vessel was dehydrated and filtered, washed with methanol, vacuum dried at 50 ° C. for 24 hours, and then heated at 260 ° C. for another 5 hours to obtain a polyimide powder Cpd. 20 parts by mass of the obtained polyimide powder was dissolved in 80 parts by mass of DMAc to obtain a polyimide solution C.
〔製造例4 ポリイミド溶液D(PI溶液D)の製造〕
窒素導入管、ディーン・スターク管及び還流管、温度計、攪拌棒を備えた反応容器に、窒素ガスを導入しながら、120.5質量部の4,4’-ジアミノジフェニルスルホン(4,4’-DDS)、51.6質量部の3,3’-ジアミノジフェニルスルホン(3,3’-DDS)、500質量部のガンマブチロラクトン(GBL)を加えた。続いて217.1質量部の4,4’-オキシジフタル酸無二水物(ODPA)、223質量部のGBL、260質量部のトルエンを室温で加えた後、内温160℃まで昇温し、160℃で1時間加熱還流を行い、イミド化を行った。イミド化完了後、180℃まで昇温し、トルエンを抜き出しながら反応を続けた。12時間反応後、オイルバスを外して室温に戻し、固形分が20質量%濃度となるようにGBLを加え、ポリイミド溶液Dを得た。
[Production Example 4 Production of Polyimide Solution D (PI Solution D)]
While introducing nitrogen gas into a reaction vessel equipped with a nitrogen introduction tube, a Dean Stark tube and a recirculation tube, a thermometer, and a stirring rod, 120.5 parts by mass of 4,4'-diaminodiphenyl sulfone (4,4') was introduced. -DDS), 51.6 parts by mass of 3,3'-diaminodiphenyl sulfone (3,3'-DDS) and 500 parts by mass of gamma butyrolactone (GBL) were added. Subsequently, 217.1 parts by mass of 4,4'-oxydiphthalic acid unihydrate (ODPA), 223 parts by mass of GBL, and 260 parts by mass of toluene were added at room temperature, and then the temperature was raised to 160 ° C. The mixture was heated under reflux at 160 ° C. for 1 hour for imidization. After the imidization was completed, the temperature was raised to 180 ° C., and the reaction was continued while extracting toluene. After the reaction for 12 hours, the oil bath was removed and the temperature was returned to room temperature, GBL was added so that the solid content had a concentration of 20% by mass, and a polyimide solution D was obtained.
〔製造例5 ポリアミド酸溶液E(PAA溶液E)の製造〕
窒素導入管、還流管、攪拌棒を備えた反応容器に窒素雰囲気下、2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル(TFMB)161質量部とN-メチルー2-ピロリドン1090質量部を混合攪拌して溶解させた後、1,2,4,5-シクロヘキサンテトラカルボン酸ニ無水物(CHDA)112質量部を室温にて固体のまま分割添加し、室温下12時間攪拌した。次に共沸溶媒としてキシレン400質量部を添加して180℃に昇温して3時間反応を行い、共沸してくる生成水を分離した。水の流出が終わったことを確認し、1hかけて190℃に昇温しながらキシレンを除去することでポリアミド酸溶液Eを得た。
[Production Example 5 Production of Polyamic Acid Solution E (PAA Solution E)]
161 parts by mass of 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl (TFMB) and 1090 parts by mass of N-methyl-2-pyrrolidone in a reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod under a nitrogen atmosphere. After mixing and stirring the parts to dissolve, 112 parts by mass of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (CHDA) was added separately at room temperature as a solid, and the mixture was stirred at room temperature for 12 hours. Next, 400 parts by mass of xylene was added as an azeotropic solvent, the temperature was raised to 180 ° C., and the reaction was carried out for 3 hours to separate the azeotropic generated water. After confirming that the outflow of water was completed, xylene was removed while raising the temperature to 190 ° C. over 1 hour to obtain a polyamic acid solution E.
〔製造例6 ポリアミド酸溶液F(PAA溶液F)の製造)〕
窒素導入管、還流管、攪拌棒を備えた反応容器内を窒素置換した後、11.36質量部の4,4’-ジアミノベンズアニリド(DABAN)、および16.01質量部の2,2’-ジトリフルオロメチル-4,4’-ジアミノビフェニル(TFMB)を、201.1質量部のN,N-ジメチルアセトアミド(DMAc)を加え完全に溶解させた。次いで、19.32質量部の1,2,3,4-シクロブタンテトラカルボン酸無二水物(CBDA)を固体のまま分割添加した後、室温で24時間攪拌した。その後、173.1質量部のDMAcを加え希釈し、NV10%、還元粘度3.10dl/gのポリアミド酸溶液Fを得た。
[Production Example 6 Production of Polyamic Acid Solution F (PAA Solution F)]]
After nitrogen substitution in the reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod, 11.36 parts by mass of 4,4'-diaminobenzanilide (DABAN) and 16.01 parts by mass of 2,2'. -Ditrifluoromethyl-4,4'-diaminobiphenyl (TFMB) was completely dissolved by adding 21.1 parts by mass of N, N-dimethylacetamide (DMAc). Then, 19.32 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was added separately as a solid, and then stirred at room temperature for 24 hours. Then, 173.1 parts by mass of DMAc was added and diluted to obtain a polyamic acid solution F having an NV of 10% and a reduction viscosity of 3.10 dl / g.
製造例にて得られたポリイミド溶液、ポリアミド酸溶液(ポリイミド前駆体溶液)を以下の方法でフィルム化し、光学特性、機械特性を測定した。結果を表1に示す。
(単独で物性測定のためのフィルムを得る方法)
ポリイミド溶液またはポリアミド酸溶液を、一辺30cmのガラス板の中央部、おおむね20cm四方のエリアにバーコーターを用いて、最終厚さが25±2μmとなるように塗布し、ドライ窒素を静かに流したイナートオーブンにて100℃で30分間加熱し、塗膜の残溶剤量が40質量%以下であることを確認した後に、ドライ窒素で置換したマッフル炉にて300℃にて20分間加熱した。次いでマッフル炉から取り出し、乾燥塗膜(フィルム)の端をカッターナイフで起こし、慎重にガラスから剥離してフィルムを得る。
The polyimide solution and the polyamic acid solution (polyimide precursor solution) obtained in the production example were formed into a film by the following method, and the optical properties and mechanical properties were measured. The results are shown in Table 1.
(How to obtain a film for measuring physical properties by itself)
A polyimide solution or a polyamic acid solution was applied to the center of a glass plate having a side of 30 cm, approximately 20 cm square, using a bar coater so that the final thickness was 25 ± 2 μm, and dry nitrogen was gently poured. After heating in an inert oven at 100 ° C. for 30 minutes and confirming that the amount of residual solution in the coating film was 40% by mass or less, the mixture was heated in a muffle furnace substituted with dry nitrogen at 300 ° C. for 20 minutes. Then, it is taken out from the muffle furnace, the end of the dry coating film (film) is raised with a utility knife, and it is carefully peeled from the glass to obtain a film.
〔無機フィラー〕
表2に示す無機フィラーを準備し、実施例、比較例に用いた。参考に記載した屈折率は化学便覧、各種物性表などに掲載されている代表的な数値である。
[Inorganic filler]
The inorganic fillers shown in Table 2 were prepared and used in Examples and Comparative Examples. The refractive index described in the reference is a typical numerical value published in the chemical handbook, various physical property tables, etc.
(実施例1)
製造例にて得られたポアミド酸溶液Fに、無機フィラーとしてZnO-65を樹脂成分に対して質量比で2000ppm、ZrO2-10を樹脂成分に対して質量比で700ppm、さらに滑剤としてSiO2-80を樹脂成分に対して質量比で3000ppm加え、均一に分散させた。
25℃45%RHに空調された大気中にて、ロールトゥロール式のコンマコーターと連続式乾燥炉と熱処理炉を備えた装置を用い、まず、前記無機フィラーを分散したポリアミド酸溶液を、仮支持体であるポリエチレンテレフタレート製フィルムA4100(東洋紡株式会社製、以下PETフィルムと略記する)の無滑材面上に最終膜厚が25μmとなるよう塗布し、次いで連続式乾燥炉にて110℃にて15分間乾燥し、残溶剤量23質量%の自己支持性フィルムを得た。該自己支持性フィルムを支持体としてきたA4100フィルムから剥離し、ピンを配置したピンシートを有するピンテンターに通し、フィルム端部をピンに差し込むことにより把持し、フィルムが破断しないように、かつ不必要なたるみが生じないようにピンシート間隔を調整して搬送し、200℃で5分、250℃で5分、300℃で10分の条件で加熱し、溶媒除去とイミド化反応を進行させた。その後、3分間で室温にまで冷却し、フィルムの両端の平面性が悪い部分をスリッターにて切り落とし、ロール状に巻き上げ、幅580mm、長さ200mのフィルム(実1)のロールを得た。
得られたフィルム(実1)の評価結果を表3に示す。
(Example 1)
In the poamidic acid solution F obtained in the production example, ZnO-65 as an inorganic filler was added to the resin component at a mass ratio of 2000 ppm, ZrO2-10 was added to the resin component at a mass ratio of 700 ppm, and the lubricant was SiO2-80. Was added at a mass ratio of 3000 ppm to the resin component and uniformly dispersed.
Using a device equipped with a roll-to-roll type comma coater, a continuous drying furnace, and a heat treatment furnace in the air air-conditioned at 25 ° C. and 45% RH, first, a polyamic acid solution in which the inorganic filler is dispersed is tentatively prepared. A polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film), which is a support, is coated on a non-slip material surface so that the final film thickness is 25 μm, and then heated to 110 ° C. in a continuous drying oven. And dried for 15 minutes to obtain a self-supporting film having a residual solvent amount of 23% by mass. The self-supporting film is peeled off from the A4100 film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting the pin into the pin so that the film does not break and is unnecessary. The pin sheet spacing was adjusted so that sagging did not occur, and the film was transported under the conditions of 200 ° C. for 5 minutes, 250 ° C. for 5 minutes, and 300 ° C. for 10 minutes to proceed with solvent removal and imidization reaction. .. Then, the film was cooled to room temperature in 3 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain a roll of a film (actual 1) having a width of 580 mm and a length of 200 m.
Table 3 shows the evaluation results of the obtained film (actual 1).
(実施例2~17)(比較例1~7)
以下同様に、表3、表4、表5、表6に示すポリアミド酸溶液または、ポリイミド溶液と、無機フィラーを組み合わせて実施例1と同様にフィルムを製造し評価した。結果を表3、表4、表5、表6に示す。紫外線透過率が50%以下であれば、UVレーザーでの加工性が良好となる。
(Examples 2 to 17) (Comparative Examples 1 to 7)
Similarly, a film was produced and evaluated in the same manner as in Example 1 by combining the polyamic acid solution or the polyimide solution shown in Table 3, Table 4, Table 5, and Table 6 with the inorganic filler. The results are shown in Table 3, Table 4, Table 5, and Table 6. When the ultraviolet transmittance is 50% or less, the processability with a UV laser is good.
比較例1は、滑剤以外の無機フィラーを添加していない系であり、紫外線透過率は高く遮蔽効果は乏しい。比較例2、比較例3は 酸化亜鉛粒子、ケイ酸ジルコニウム粒子を単独添加した系である。実施例1~12のフィラー添加量より多めに添加しているが、紫外線透過率は50%を超えている。一方、実施例13は比較例2に酸化ジルコニウムを、実施例14は比較例3に酸化亜鉛を添加することにより無機フィラー(a)と(b)を共存させている系である。両者の相乗効果により紫外線透過率は低く抑えられていることがわかる。
比較例5は無機フィラーを一切添加していない系である。フィルムの滑り性が著しく低下して、シワなく巻き取るのが困難であった。実施例15と、比較例6と比較例7は、相乗効果が得られる最小量を求めるための実験であり、フィラー添加の下限値をここから得ることができる。
Comparative Example 1 is a system to which an inorganic filler other than a lubricant is not added, and has a high ultraviolet transmittance and a poor shielding effect. Comparative Example 2 and Comparative Example 3 are systems in which zinc oxide particles and zirconium silicate particles are added alone. Although it is added in a larger amount than the amount of the filler added in Examples 1 to 12, the ultraviolet transmittance exceeds 50%. On the other hand, Example 13 is a system in which zirconium oxide is added to Comparative Example 2 and zinc oxide is added to Comparative Example 3 so that the inorganic fillers (a) and (b) coexist. It can be seen that the ultraviolet transmittance is kept low due to the synergistic effect of the two.
Comparative Example 5 is a system to which no inorganic filler is added. The slipperiness of the film was significantly reduced, and it was difficult to wind the film without wrinkles. Example 15, Comparative Example 6 and Comparative Example 7 are experiments for obtaining the minimum amount at which a synergistic effect can be obtained, and the lower limit of the filler addition can be obtained from here.
(実施例18~21、比較例8、9)
製造例にて得られたポアミド酸溶液Dに、無機フィラーとしてZnO-300とZrSO4-700を、表4に従って均一に分散させた。次いで、ディスプレイ用ガラス(370mm×470mm、厚さ0.7mmのガラス基板:日本電気硝子社製OA10G)にフィラーを分散させたポリアミド酸溶液をバーコーターで最終膜厚が16μmとなるように塗布し、ドライ窒素を静かに流したイナートオーブンにて100℃で20分間加熱し、塗膜の残溶剤量が40質量%以下であることを確認した後に、ドライ窒素で置換したマッフル炉にて300℃にて15分間加熱し、乾燥とポリアミド酸からポリイミドへの転化反応を行い、ポリイミドフィルムとガラス基板からなる積層体を得た。
得られた積層体からポリイミドフィルムを剥離して、光学特性を測定した。結果を表4に示す。
比較例8、9ではヘイズ値が高くなり透明性が低下している。
(Examples 18 to 21, Comparative Examples 8 and 9)
ZnO-300 and ZrSO4-700 as inorganic fillers were uniformly dispersed in the poamidic acid solution D obtained in the production example according to Table 4. Next, a polyamic acid solution in which a filler was dispersed on a display glass (370 mm × 470 mm, 0.7 mm thick glass substrate: OA10G manufactured by Nippon Electric Glass Co., Ltd.) was applied with a bar coater so that the final film thickness was 16 μm. , Heat in an inert oven gently flowing dry nitrogen at 100 ° C. for 20 minutes, confirm that the residual solvent amount of the coating film is 40% by mass or less, and then in a muffle oven replaced with dry nitrogen at 300 ° C. After heating for 15 minutes in the oven, drying and a conversion reaction from polyamic acid to polyimide were carried out to obtain a laminate composed of a polyimide film and a glass substrate.
The polyimide film was peeled off from the obtained laminate, and the optical characteristics were measured. The results are shown in Table 4.
In Comparative Examples 8 and 9, the haze value is high and the transparency is low.
(応用実施例1)
まず、実施例1で得たポリイミドフィルム(実1)を360mm×460mmの長方形に切り出した。 次に、フィルム表面処理として UV/O3照射器(LANテクニカル製SKR1102N-03)を用い、(a)層側にUV/O3の照射を3分間行った。この時UV/O3ランプとフィルムとの距離は30mmとした。
ディスプレイ用ガラス(370mm×470mm、厚さ0.7mmのガラス基板:日本電気硝子社製OA10G)にシランカップリング剤として3-アミノプロピルトリメトキシシラン(信越化学工業社製、KBM-903)をスプレーコーターにて塗布した。なおガラス基板は、純水洗浄、乾燥後にUV/O3照射器(LANテクニカル製SKR1102N-03)で1分間照射してドライ洗浄したものを用いた。
次いで、シランカップリング剤を塗布したガラス基板を、シリコーンゴムローラーを装備したロールラミネータにセットし、まずシランカップリング剤塗布面にスポイトで500mlの純水を基板全体に広がるように滴下し、基板を濡らした。
前記表面処理を行った多層ポリイミドフィルムの表面処理面を、ガラス基板のシランカップリング剤塗布面、すなわち純水で濡らした面に対向するように重ね、ガラス基板の一方の一辺から順次回転ロールでポリイミドフィルムとガラス基板間の純水を押し出しながら加圧してガラス基板とポリイミドフィルムをラミネートして仮積層体を得た。使用したラミネータは、MCK社製の有効ロール幅650mmのラミネータであり、貼合条件は、エアー元圧力:0.5MPa、ラミネート速度:50mm/秒、ロール温度:22℃、環境温度22度、湿度55%RHであった。
得られた仮積層体を、クリーンオーブンにて200℃10分間加熱処理し、多層ポリイミドフィルムとガラス基板からなる積層体LB-E01を得た。
(Application Example 1)
First, the polyimide film (actual 1) obtained in Example 1 was cut into a rectangle having a size of 360 mm × 460 mm. Next, a UV / O3 irradiator (SKR1102N-03 manufactured by LAN Technical) was used as the film surface treatment, and the layer ( a) was irradiated with UV / O3 for 3 minutes. At this time, the distance between the UV / O3 lamp and the film was set to 30 mm.
Spray 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent on display glass (glass substrate of 370 mm x 470 mm, thickness 0.7 mm: OA10G manufactured by Nippon Electric Glass Co., Ltd.). It was applied with a coater. The glass substrate used was washed with pure water, dried, and then irradiated with a UV / O3 irradiator (SKR1102N- 03 manufactured by LAN Technical) for 1 minute to dry wash.
Next, the glass substrate coated with the silane coupling agent is set on a roll laminator equipped with a silicone rubber roller, and first, 500 ml of pure water is dropped on the surface coated with the silane coupling agent with a dropper so as to spread over the entire substrate. Wet.
The surface-treated surface of the multilayer polyimide film subjected to the surface treatment is laminated so as to face the silane coupling agent-coated surface of the glass substrate, that is, the surface wetted with pure water, and sequentially from one side of the glass substrate with a rotating roll. A temporary laminate was obtained by laminating the glass substrate and the polyimide film under pressure while extruding pure water between the polyimide film and the glass substrate. The laminator used was a laminator with an effective roll width of 650 mm manufactured by MCK, and the bonding conditions were air source pressure: 0.5 MPa, laminating speed: 50 mm / sec, roll temperature: 22 ° C, environmental temperature 22 ° C, humidity. It was 55% RH.
The obtained temporary laminate was heat-treated in a clean oven at 200 ° C. for 10 minutes to obtain a laminate LB-E01 composed of a multilayer polyimide film and a glass substrate.
得られた積層体LB-E01のポリイミドフィルム面に、以下の工程によりタングステン膜(膜厚75nm)を形成し、さらに大気にふれることなく、絶縁膜として酸化シリコン膜(膜厚150nm)を積層形成した。次いで、プラズマCVD法で下地絶縁膜となる酸化窒化シリコン膜(膜厚100nm)を形成し、さらに大気にふれることなく、アモルファスシリコン膜(膜厚54nm)を積層形成した。 A tungsten film (thickness 75 nm) is formed on the polyimide film surface of the obtained laminate LB-E01 by the following steps, and a silicon oxide film (thickness 150 nm) is laminated as an insulating film without being exposed to the atmosphere. did. Next, a silicon oxide nitride film (thickness 100 nm) to be a base insulating film was formed by a plasma CVD method, and an amorphous silicon film (thickness 54 nm) was laminated and formed without being exposed to the atmosphere.
得られたアモルファスシリコン膜を用いてTFT素子を作製した。まず、アモルファスシリコン薄膜をパターニングを行って所定の形状のシリコン領域を形成し、適宜、ゲート絶縁膜の形成、ゲート電極の形成、活性領域へのドーピングによるソース領域またはドレイン領域の形成、層間絶縁膜の形成、ソース電極およびドレイン電極の形成、活性化処理を行い、PチャンネルTFTのアレイを作製した。
TFTアレイ外周の0.5mm程度内側に沿ってUV-YAGレーザーにてポリイミドフィルム部を焼き切り、さらにガラス基板面から85mJ/平方cmのエネルギー量で308nmのラインビームによるエキシマレーザーの照射を行った。なお、ラインビームのオーバーラップ率は50%とした。次いで、切れ目の端部から薄いカミソリ状の刃を用いてすくい上げるように剥離を行い、フレキシブルなA3サイズのTFTアレイを得た。剥離は極微力で可能であり、TFTにダメージを与えること無く剥離することが可能であった。UV-YAGレーザーによる切断面は乱れなく、スミアなどの飛び散りも見られなかった。得られたフレキシブルTFTアレイは5mmφの丸棒に巻き付けても性能劣化は見られず、良好な特性を維持した。
A TFT element was manufactured using the obtained amorphous silicon film. First, the amorphous silicon thin film is patterned to form a silicon region having a predetermined shape, and a gate insulating film is formed, a gate electrode is formed, a source region or a drain region is formed by doping the active region, and an interlayer insulating film is formed. , The source electrode and the drain electrode were formed, and the activation treatment was performed to prepare an array of P-channel TFTs.
The polyimide film portion was burnt off with a UV-YAG laser along the inside of the outer circumference of the TFT array by about 0.5 mm, and further, the excimer laser was irradiated with a line beam of 308 nm from the glass substrate surface with an energy amount of 85 mJ / square cm. The overlap rate of the line beams was set to 50%. Then, peeling was performed from the end of the cut so as to scoop up with a thin razor-shaped blade to obtain a flexible A3 size TFT array. The peeling was possible with a very small force, and it was possible to peel without damaging the TFT. The cut surface by the UV-YAG laser was not disturbed, and no splattering such as smear was observed. The obtained flexible TFT array did not show any deterioration in performance even when wound around a round bar having a diameter of 5 mm, and maintained good characteristics.
(応用実施例2)
実施例21にて得られた積層体LB-E21を用い、応用実施例1と同様にポリイミド面にアモルファスシリコンTFTを形成し、同様に周囲をUV-YAGレーザーでトリミングし、さらに応用実施例1と同じ条件にてガラス基板面側からエキシマレーザーの照射を行い、以下同様にガラス基板から剥離し、フレキシブルTFTアレイを得た。得られたフレキシブルTFTアレイは5mmφの丸棒に巻き付けても性能劣化は見られず、良好な特性を維持した。
(Application Example 2)
Using the laminated body LB-E21 obtained in Example 21, an amorphous silicon TFT is formed on the polyimide surface in the same manner as in Application Example 1, and the periphery is similarly trimmed with a UV-YAG laser, and further, Application Example 1 is performed. The excimer laser was irradiated from the surface side of the glass substrate under the same conditions as above, and the mixture was peeled off from the glass substrate in the same manner to obtain a flexible TFT array. The obtained flexible TFT array did not show any deterioration in performance even when wound around a round bar having a diameter of 5 mm, and maintained good characteristics.
(応用比較例1)
比較例3で得られたポリイミドフィルム比3を用い、応用実施例1と同様の操作にてガラス基板にラミネートして積層体LB-C03を得た。得られた積層体LB-C03を用いて同様にTFT形成を行い、さらに同様に周囲をUV-YAGレーザーにてトリミングした後にガラス基板から剥離し、フレキシブルTFTアレイを得た。UV-YAGレーザーによる切断面にギザが見られ、さらにTFTの約20%程度が動作不良であった。動作不良個所を詳細に分析した結果、素子内の絶縁層のガラス面側の一部に微細な剥離個所が見出された。これは、ポリイミドフィルムを透過したエキシマレーザー光の影響と推察される。
(Application Comparative Example 1)
Using the polyimide film ratio 3 obtained in Comparative Example 3, the laminate was laminated on a glass substrate by the same operation as in Application Example 1 to obtain a laminated body LB-C03. The obtained laminated body LB-C03 was used to form a TFT in the same manner, and the periphery was similarly trimmed with a UV-YAG laser and then peeled off from the glass substrate to obtain a flexible TFT array. Jaggedness was seen on the cut surface by the UV-YAG laser, and about 20% of the TFTs were malfunctioning. As a result of detailed analysis of the malfunctioning part, a fine peeling part was found in a part of the insulating layer on the glass surface side in the element. This is presumed to be due to the effect of excimer laser light transmitted through the polyimide film.
以上述べてきたように、本発明のポリイミドフィルムは、適度なUV遮蔽性能を有し、高い透明性、無色性を維持しつつ、さらに必要最低限度の無機フィラー量でフィルム化が可能であるためフィルム機械物性に優れた特性を有する。
本発明のポリイミドフィルムはガラス基板などの無機基板との積層体を経由して、フレキシブルでかつ軽量な表示装置の部材として、あるいは透明性が必要なタッチパネルなどのスイッチ素子、ポインティングデバイスなどに広く利用することができる。
As described above, the polyimide film of the present invention has an appropriate UV shielding performance, maintains high transparency and colorlessness, and can be formed into a film with the minimum necessary amount of inorganic filler. The film has excellent physical properties.
The polyimide film of the present invention is widely used as a member of a flexible and lightweight display device, a switch element such as a touch panel, a pointing device, etc., which requires transparency, via a laminate with an inorganic substrate such as a glass substrate. can do.
Claims (5)
(a)625ppm以上20000ppm以下の酸化亜鉛粒子、および/または、750ppm以上20000ppm以下の硫化亜鉛粒子
(b)680ppm以上10000ppm以下の酸化ジルコニウム粒子、および/または、1000ppm以上10000ppm以下のケイ酸ジルコニウム粒子 The yellow index is 10 or less, the total light transmittance is 85% or more, the tensile elastic modulus is 3 GPa or more, the CTE is -5 ppm / ° C. to + 55 ppm / ° C., and the following (a) and (b) are included as inorganic fillers. A characteristic polyimide film.
(A) Zinc oxide particles of 625 ppm or more and 20000 ppm or less, and / or zinc sulfide particles of 750 ppm or more and 20000 ppm or less (b) Zinc oxide particles of 680 ppm or more and 10000 ppm or less, and / or zirconium silicate particles of 1000 ppm or more and 10000 ppm or less.
A flexible electronic device using the polyimide film according to claim 1 or 2 as a member.
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