CN116348296A - Polyamic acid, polyamic acid solution, polyimide film, laminate, electronic device, and method for producing polyimide film - Google Patents
Polyamic acid, polyamic acid solution, polyimide film, laminate, electronic device, and method for producing polyimide film Download PDFInfo
- Publication number
- CN116348296A CN116348296A CN202180072116.4A CN202180072116A CN116348296A CN 116348296 A CN116348296 A CN 116348296A CN 202180072116 A CN202180072116 A CN 202180072116A CN 116348296 A CN116348296 A CN 116348296A
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- CN
- China
- Prior art keywords
- polyamic acid
- polyimide film
- group
- polyimide
- residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 192
- 229920001721 polyimide Polymers 0.000 title claims description 211
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 125000004427 diamine group Chemical group 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 125000000962 organic group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000003368 amide group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- VFXMQOBHRJEVDM-UHFFFAOYSA-N (4-amino-2-phenylphenyl) 4-aminobenzoate Chemical group C1=CC=CC=C1C1=C(OC(=O)C2=CC=C(N)C=C2)C=CC(=C1)N VFXMQOBHRJEVDM-UHFFFAOYSA-N 0.000 claims abstract description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 239000004642 Polyimide Substances 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 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 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 6
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical group C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 claims description 3
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical group C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 description 56
- 239000000758 substrate Substances 0.000 description 47
- 239000010408 film Substances 0.000 description 38
- 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 29
- 150000004985 diamines Chemical class 0.000 description 29
- 239000011521 glass Substances 0.000 description 29
- 239000002253 acid Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- -1 n-octyl Chemical group 0.000 description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 238000004040 coloring Methods 0.000 description 14
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 14
- 125000006159 dianhydride group Chemical group 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 13
- 102100031503 Barrier-to-autointegration factor-like protein Human genes 0.000 description 12
- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002460 imidazoles Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 2
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FMACFWAQBPYRFO-UHFFFAOYSA-N 5-[9-(1,3-dioxo-2-benzofuran-5-yl)fluoren-9-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 FMACFWAQBPYRFO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RPOHXHHHVSGUMN-UHFFFAOYSA-N 1-n,4-n-bis(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(C(=O)NC=2C=CC(N)=CC=2)C=C1 RPOHXHHHVSGUMN-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- IBKFNGCWUPNUHY-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2O1 IBKFNGCWUPNUHY-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XWQDPPJDXCZWQE-UHFFFAOYSA-N 2-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1N XWQDPPJDXCZWQE-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- HYTCSCBDAFJMIP-UHFFFAOYSA-N 3-ethyl-1,1-dimethylurea Chemical compound CCNC(=O)N(C)C HYTCSCBDAFJMIP-UHFFFAOYSA-N 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- OYFJQPXVCSSHAI-QFPUQLAESA-N enalapril maleate Chemical compound OC(=O)\C=C/C(O)=O.C([C@@H](C(=O)OCC)N[C@@H](C)C(=O)N1[C@@H](CCC1)C(O)=O)CC1=CC=CC=C1 OYFJQPXVCSSHAI-QFPUQLAESA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The polyamic acid has a 4-valent organic group represented by the following general formula (1) as a tetracarboxylic dianhydride residue, and has one or more selected from the group consisting of a p-phenylenediamine residue and a (2-phenyl-4-aminophenyl) -4-aminobenzoate residue as a diamine residue. The content of the 4-valent organic group represented by the following general formula (1) is 90 mol% or more and 100 mol% or less with respect to the total tetracarboxylic dianhydride residues. In the following general formula (1), R 1 R is R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a hydroxyl groupA group, nitrile group, nitro group, carboxyl group, or amide group.
Description
Technical Field
The present invention relates to a polyamic acid, a polyamic acid solution, a polyimide film, a laminate, an electronic device, and a method for producing a polyimide film. The present invention also relates to an electronic device material using polyimide, a Thin Film Transistor (TFT) substrate, a flexible display substrate, a color filter, a printed matter, an optical material, an image display device (more specifically, a liquid crystal display device, an organic EL, electronic paper, or the like), a 3D display, a solar cell, a touch panel, a transparent conductive film substrate, and a substitute material for a member currently using glass.
Background
With rapid progress in liquid crystal displays, organic EL, electronic paper and other displays, solar cells, touch panels and other electronic devices, thinning, weight saving and flexibility of the devices are advancing. In these devices, polyimide is used as a substrate material instead of a glass substrate.
In these devices, various electronic components, such as thin film transistors, transparent electrodes, etc., are formed on a substrate, and the formation of these electronic components requires a high-temperature process. Polyimide has heat resistance enough to accommodate high temperature processes, and also has a coefficient of linear expansion close to that of glass substrates and electronic components, and therefore is less likely to generate internal stress, and is suitable for substrate materials for flexible displays and the like.
Generally, an aromatic polyimide is colored to a yellowish brown color by intramolecular conjugation or formation of a Charge Transfer (CT) complex, but in a top emission type organic EL or the like, light is extracted from the opposite side of a substrate, and therefore transparency is not required for the substrate, and a previously aromatic polyimide is used. However, when light emitted from a display element such as a transparent display, a bottom emission type organic EL, or a liquid crystal display is emitted through a substrate, or when a sensor or a camera module is disposed on the back surface of a substrate in order to make a smart phone or the like a full-screen display (without a gap), high optical characteristics (more specifically, low coloring) are required for the substrate.
In addition, when the polyimide substrate is used for an image display device, if the retardation (Rth) in the thickness direction of the polyimide substrate is high, the display performance of the image display device tends to be lowered.
Against such a background, a material having a linear expansion coefficient equivalent to that of a conventional aromatic polyimide, reduced in coloring, and capable of realizing low Rth has been demanded.
As a plastic material having a small linear expansion coefficient (low thermal expansion) and high transparency, polyimide using a monomer having a rigid structure is known (for example, refer to patent document 1). Patent document 2 describes that a polyimide film having excellent transparency and heat resistance can be obtained by using a diamine having a fluorene structure.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-046054
Patent document 2: japanese patent laid-open publication 2016-179969
Disclosure of Invention
Problems to be solved by the invention
However, it is difficult to obtain a polyimide having low coloration and low thermal expansion, while reducing Rth, by the techniques described in patent document 1 and patent document 2.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyimide which can reduce Rth and has low colorability and low thermal expansion, and a polyamic acid which is a precursor thereof. Further, it is an object to provide a product or member which is produced using the polyimide and the polyamic acid and is required to have low Rth, low colorability, and low thermal expansion.
Solution for solving the problem
The polyamic acid of the present invention has a 4-valent organic group represented by the following general formula (1) as a tetracarboxylic dianhydride residue, and has one or more selected from the group consisting of a p-phenylenediamine residue and a (2-phenyl-4-aminophenyl) -4-aminobenzoate residue as a diamine residue. The content of the 4-valent organic group represented by the following general formula (1) is 90 mol% or more and 100 mol% or less with respect to the total tetracarboxylic dianhydride residues.
In the general formula (1), R 1 R is R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.
In one embodiment of the polyamic acid of the present invention, R in the general formula (1) 1 R is R 2 All represent a hydrogen atom.
In one embodiment of the present invention, the polyamic acid further has, as a diamine residue, at least one selected from the group consisting of a 4,4 '-diaminobenzanilide residue, a 2,2' -bis (trifluoromethyl) benzidine residue, and a 9, 9-bis (4-aminophenyl) fluorene residue.
The polyamic acid solution of the present invention contains the polyamic acid of the present invention and an organic solvent.
The polyimide of the present invention is an imide of the polyamic acid of the present invention.
The glass transition temperature of the polyimide of the present invention is preferably 350℃or higher.
The polyimide film of the present invention comprises the polyimide of the present invention.
The laminate of the present invention comprises a support and the polyimide film of the present invention.
The electronic device of the present invention comprises: the polyimide film of the present invention and an electronic component disposed on the polyimide film.
In the method for producing a polyimide film of the present invention, the polyamic acid solution of the present invention is applied to a support to form a coating film containing the polyamic acid, and the coating film is heated to imidize the polyamic acid.
In one embodiment of the method for producing a polyimide film of the present invention, the maximum temperature at which the coating film is heated is 380 ℃ to 500 ℃.
In one embodiment of the method for producing a polyimide film of the present invention, the heating time at the highest temperature is 5 minutes to 60 minutes.
In one embodiment of the method for producing a polyimide film of the present invention, the polyimide film obtained by heating the coating film is peeled from the support.
In one embodiment of the method for producing a polyimide film of the present invention, the polyimide film is peeled off from the support by laser irradiation.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide produced using the polyamic acid of the present invention can reduce Rth and is excellent in low coloring property and low thermal expansion property. Therefore, the polyimide produced using the polyamic acid of the present invention is suitable as a material for electronic devices requiring low Rth, low colorability, and low thermal expansion.
Detailed Description
Hereinafter, the preferred embodiments of the present invention will be described in detail, but the present invention is not limited to these.
First, terms used in the present specification will be described. "structural unit" refers to the repeating units that make up the polymer. "polyamic acid" is a polymer comprising a structural unit represented by the following general formula (2) (hereinafter, sometimes referred to as "structural unit (2)").
In the general formula (2), A 1 Represents a tetracarboxylic dianhydride residue (a 4-valent organic group derived from tetracarboxylic dianhydride), A 2 Represents a diamine residue (a 2-valent organic group derived from diamine).
The content of the structural unit (2) relative to the total structural units constituting the polyamic acid is, for example, 50 mol% or more and 100 mol% or less, preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, still more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and may be 100 mol% or less.
The "1% weight loss temperature" is a measured temperature at which the weight of polyimide at a measured temperature of 150℃is reduced by 1% by weight relative to the weight of polyimide at a reference (100% by weight).
The "linear expansion coefficient" is a linear expansion coefficient when the temperature is lowered from 350 ℃ to 100 ℃ unless specified otherwise (linear expansion coefficient when the temperature is lowered).
"alkyl group having 1 to 12 carbon atoms" is linear or branched and unsubstituted. Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
"alkenyl group having 2 to 12 carbon atoms" is straight-chain or branched and is unsubstituted. Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, a 4-decenyl group, a 3-undecenyl group, and a 4-dodecenyl group.
"an alkoxy group having 1 to 12 carbon atoms" is linear or branched and is unsubstituted. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decyloxy, n-undecyloxy and n-dodecoxy.
"aryl group having 6 to 14 carbon atoms" is unsubstituted. Examples of the aryl group having 6 to 14 carbon atoms include an unsubstituted aromatic monocyclic hydrocarbon group having 6 to 14 carbon atoms, an unsubstituted aromatic condensed bicyclic hydrocarbon group having 6 to 14 carbon atoms, and an unsubstituted aromatic condensed tricyclic hydrocarbon group having 6 to 14 carbon atoms. More specific examples of the aryl group having 6 to 14 carbon atoms include phenyl, naphthyl, anthryl, and phenanthryl.
Hereinafter, the compound and its derivative may be generally referred to collectively by the term "system" after the name of the compound. In the case where the compound name is followed by a "system" to denote the polymer name, it is meant that the repeating units of the polymer originate from the compound or derivative thereof. In addition, the tetracarboxylic dianhydride is sometimes referred to as "acid dianhydride".
The polyamic acid of the present embodiment has a 4-valent organic group represented by the following general formula (1) as a tetracarboxylic dianhydride residue, and has one or more selected from the group consisting of a p-phenylenediamine residue and a (2-phenyl-4-aminophenyl) -4-aminobenzoate residue as a diamine residue. The content of the 4-valent organic group represented by the following general formula (1) is preferably 90 mol% or more and 100 mol% or less with respect to the total tetracarboxylic dianhydride residues constituting the polyamic acid according to the present embodiment.
In the general formula (1), R 1 R is R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group. For easy imidization, R is 1 R is R 2 Each independently is preferably a hydrogen atom, methyl or ethyl, particularly preferably R 1 R is R 2 All represent a hydrogen atom. Thus (2)The 4-valent organic group represented by the general formula (1) is particularly preferably a BPAF residue derived from a partial structure of 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (hereinafter, sometimes referred to as "BPAF"). That is, the polyamic acid of the present embodiment particularly preferably has a BPAF residue as A in the general formula (2) 1 . Hereinafter, R in the general formula (1) is as follows unless otherwise specified 1 R is R 2 The case where each represents a hydrogen atom is described.
BPAF has a bulky fluorene structure, and thus can suppress the formation of charge-mobile (CT) complexes. Therefore, BPAF is suitable as a raw material (monomer) of polyimide with reduced coloration (low coloration). In addition, in polyimide using BPAF as a raw material (monomer), a fluorene ring derived from BPAF is twisted with respect to a main chain, and birefringence is less likely to occur. Therefore, BPAF is suitable as a raw material (monomer) of polyimide capable of reducing Rth.
In the case of synthesizing the polyamic acid according to the embodiment, an acid dianhydride other than BPAF may be used as the monomer within a range that does not impair the performance. Examples of the acid dianhydride other than BPAF include pyromellitic dianhydride (hereinafter, sometimes referred to as "PMDA"), 3', 4' -biphenyltetracarboxylic dianhydride (hereinafter, sometimes referred to as "BPDA"), p-phenylenebis (trimellitic anhydride), 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2', 3' -biphenyltetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' -oxydicarboxylic anhydride, 4' - (hexafluoroisopropylidene) dicarboxylic anhydride, dicyclohexyl-3, 3', 4' -tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2' -oxydispiro [ bicyclo [2.2.1] heptane-2, 1' -cyclopentane-3 ',2 "-bicyclo [2.2.1] heptane ] -5,6:5",6" -tetracarboxylic dianhydride and derivatives thereof, which may be used singly or in an amount of 2 or more.
In order to obtain a polyimide with further reduced coloration and Rth, the content of BPAF residues is preferably 92 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and particularly preferably 100 mol% (only BPAF residues are used as acid dianhydride residues) with respect to all tetracarboxylic dianhydride residues constituting the polyamic acid.
When an acid dianhydride other than BPAF is used as a monomer, it is preferable that the acid dianhydride other than BPAF is one or more selected from the group consisting of PMDA and BPDA, and PMDA is more preferable from the viewpoints of improving heat resistance and mechanical strength. That is, when the polyamic acid of the present embodiment has an acid dianhydride residue other than a BPAF residue as the acid dianhydride residue, the acid dianhydride residue other than the BPAF residue is preferably one or more selected from the group consisting of a PMDA residue and a BPDA residue, and more preferably a PMDA residue.
In the case where the polyamic acid according to the present embodiment has at least one selected from the group consisting of PMDA residues and BPDA residues, the total content of PMDA residues and BPDA residues is preferably 1 mol% or more and 10 mol% or less, more preferably 3 mol% or more and 7 mol% or less, with respect to the total acid dianhydride residues constituting the polyamic acid, from the viewpoints of reducing coloration and improving heat resistance and mechanical strength.
In the case where the polyamic acid according to the present embodiment has one or more selected from the group consisting of PMDA residues and BPDA residues, the total content of BPAF residues, PMDA residues and BPDA residues is preferably 91 mol% or more, more preferably 93 mol% or more, still more preferably 95 mol% or more, still more preferably 97 mol% or more, or may be 100 mol% based on the total acid dianhydride residues constituting the polyamic acid, from the viewpoints of reducing coloration and Rth and improving heat resistance and mechanical strength.
The polyamic acid of the present embodiment has, as a diamine residue, at least one selected from the group consisting of a p-phenylenediamine-derived PDA residue (hereinafter, sometimes referred to as "PDA") and a (2-phenyl-4-aminophenyl) -4-aminobenzoate-derived PHBAAB residue (hereinafter, sometimes referred to as "PHBAAB") as a partial structure. That is, the polyamic acid of the present embodiment has at least one selected from the group consisting of PDA residues and PHBAAB residues as A in the general formula (2) 2 . PDA and PHBAAB have rigid structures, and are therefore suitable as raw materials (monomers) for polyimide having low thermal expansion.
The PDA residue is a 2-valent organic group represented by the following chemical formula (3). The PHBAAB residue is a 2-valent organic group represented by the following chemical formula (4).
In the case of synthesizing the polyamic acid according to the present embodiment, a diamine other than PDA and PHBAAB may be used as a monomer within a range that does not impair the performance. Examples of diamines other than PDA and PHBAAB include 4,4 '-diaminobenzanilide (hereinafter sometimes referred to as "DABA"), 2' -bis (trifluoromethyl) benzidine (hereinafter sometimes referred to as "TFMB"), 9-bis (4-aminophenyl) fluorene (hereinafter sometimes referred to as "BAFL"), 4-aminophenyl-4-aminobenzoate, 1, 4-diaminocyclohexane, metaphenylene diamine, 4 '-oxydiphenylamine, 3,4' -oxydiphenylamine, 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether, N, N '-bis (4-aminophenyl) terephthalamide, 4' -diaminodiphenyl sulfone, m-tolidine, o-tolidine, 4 '-bis (4-aminophenoxy) biphenyl, 2- (4-aminophenyl) -6-aminobenzoxazole, 3, 5-diaminobenzoic acid, 4' -diamino-3, 3 '-dihydroxybiphenyl, 4' -methylenebis (cyclohexane amine), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and derivatives thereof may be used singly or in combination of 2 or more.
In order to reduce the linear expansion coefficient, the total content of PDA residues and PHBAAB residues is preferably 0.1 mol% or more, may be 1.0 mol% or more, 10.0 mol% or more, 30.0 mol% or more, 50.0 mol% or more, 70.0 mol% or more, 90.0 mol% or more, 99.0 mol% or more, or 99.9 mol% or more, or may be 100.0 mol% or more, with respect to all diamine residues constituting the polyamic acid. In the polyamic acid of the present embodiment, the diamine residue may have only PDA residues, only PHBAAB residues, only PDA residues and PHBAAB residues, or at least one of PDA residues and PHBAAB residues, and diamine residues other than PDA residues and PHBAAB residues.
When diamines other than PDA and PHBAAB are used as monomers, one or more diamines other than PDA, TFMB, and BAFL are preferable as diamines other than PDA and PHBAAB in order to further reduce coloring and Rth and further reduce the linear expansion coefficient. That is, in the case where the polyamic acid of the present embodiment has a diamine residue other than PDA residues and PHBAAB residues as the diamine residue, it is preferable that the diamine residue other than PDA residues and PHBAAB residues is one or more selected from the group consisting of DABA residues, TFMB residues and BAFL residues.
In order to further reduce the linear expansion coefficient, the polyamic acid of the present embodiment preferably has a DABA residue as a diamine residue. In the case where the polyamic acid according to the present embodiment has a DABA residue, the content of the DABA residue is preferably 0.1 mol% or more, may be 1.0 mol% or more, 10.0 mol% or more, 30.0 mol% or more, 50.0 mol% or more, 70.0 mol% or more, 90.0 mol% or more, or 99.0 mol% or more, or may be 99.0 mol% or more and 99.9 mol% or less, with respect to the total diamine residues constituting the polyamic acid, in order to further reduce the linear expansion coefficient.
In order to further reduce coloring, the polyamic acid of the present embodiment preferably has a TFMB residue as a diamine residue. In the case where the polyamic acid according to the present embodiment has a TFMB residue, the content of the TFMB residue is preferably 0.1 mol% or more, may be 1.0 mol% or more, 10.0 mol% or more, 30.0 mol% or more, 50.0 mol% or more, 70.0 mol% or more, 90.0 mol% or more, or 99.0 mol% or more, or may be 99.0 mol% or more and 99.9 mol% or less, with respect to the total diamine residues constituting the polyamic acid, in order to further reduce coloring.
In order to further reduce Rth, the polyamic acid of the present embodiment preferably has a BAFL residue as a diamine residue. In the case where the polyamic acid of the present embodiment has a BAFL residue, the content of the BAFL residue is preferably 0.1 mol% or more, may be 1.0 mol% or more, 10.0 mol% or more, or 30.0 mol% or more, or may be 30.0 mol% or more and 50.0 mol% or less, based on the total diamine residues constituting the polyamic acid, in order to further reduce Rth.
In the case where the polyamic acid according to the present embodiment has at least one selected from the group consisting of a DABA residue, a TFMB residue and a BAFL residue, the total content of PDA residues, a PHBAAB residue, a DABA residue, a TFMB residue and a BAFL residue is preferably 90.0 mol% or more, more preferably 93.0 mol% or more, still more preferably 95.0 mol% or more, still more preferably 97.0 mol% or more, and may be 100.0 mol% with respect to all diamine residues constituting the polyamic acid, in order to further reduce the coloring and Rth and further reduce the linear expansion coefficient.
In order to obtain a polyimide that can further reduce coloring and Rth and further reduce the linear expansion coefficient, the polyamic acid of the present embodiment preferably satisfies the following condition 1, more preferably satisfies the following conditions 1 and 2, and still more preferably satisfies the following conditions 1, 2 and 3. In particular, in order to reduce the linear expansion coefficient, the following conditions 1 and 4 are preferably satisfied. In particular, in order to reduce coloring, the following conditions 1 and 5 are preferably satisfied. In particular, in order to reduce Rth, the following conditions 1 and 6 are preferably satisfied.
Condition 1: the polyamic acid has only BPAF residues as acid dianhydride residues.
Condition 2: the polyamic acid further has one or more diamine residues selected from the group consisting of DABA residues, TFMB residues and BAFL residues.
Condition 3: the total content of PDA residues, PHBAAB residues, DABA residues, TFMB residues and BAFL residues relative to the total diamine residues constituting the polyamic acid was 100.0 mol%.
Condition 4: the polyamic acid has only PDA residues and DABA residues as diamine residues.
Condition 5: the polyamic acid has only PDA residues and TFMB residues, or only PHBAAB residues and TFMB residues as diamine residues.
Condition 6: the polyamic acid has only PDA residues and BAFL residues, or only PDA residues and PHBAAB residues as diamine residues.
From the viewpoint of suppressing the decrease in transparency caused by the residual unreacted monomer at the time of polyimide formation, the ratio (molar ratio) of the amount of the total substances of the tetracarboxylic dianhydride residues divided by the amount of the total substances of the diamine residues is preferably 0.900 or more and less than 1.100, more preferably 0.950 or more and 1.080 or less. By adjusting the amount ratio of the substances to be within the above range, a polyimide excellent in transparency can be obtained.
The polyamic acid of the present invention can be synthesized by a known general method, and can be obtained, for example, by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent. The monomer component used for the synthesis of the polyamic acid may contain a monomer other than diamine and tetracarboxylic dianhydride. For example, monofunctional amines and monofunctional anhydrides may be used for the purpose of adjusting the molecular weight. An example of a specific synthesis method of the polyamic acid will be described. First, a diamine solution is prepared by dissolving or dispersing a diamine in a slurry form in an organic solvent in an inert gas atmosphere such as argon or nitrogen. Then, the tetracarboxylic dianhydride is dissolved in an organic solvent or dispersed in a slurry form, or is added to the diamine solution in a solid state.
When the polyamide acid is synthesized using diamine and tetracarboxylic dianhydride, the desired polyamide acid (polymer of diamine and tetracarboxylic dianhydride) can be obtained by adjusting the amount of diamine (amount of diamine in the case of using a plurality of diamines) and the amount of tetracarboxylic dianhydride (amount of tetracarboxylic dianhydride in the case of using a plurality of tetracarboxylic dianhydrides). The mole fraction of each residue in the polyamic acid corresponds to, for example, the mole fraction of each monomer (diamine and tetracarboxylic dianhydride) used in the synthesis of the polyamic acid. In addition, by mixing 2 kinds of polyamic acids, polyamic acids containing a plurality of tetracarboxylic dianhydride residues and a plurality of diamine residues can be obtained. The temperature conditions for the reaction of the diamine and the tetracarboxylic dianhydride, that is, the synthesis reaction of the polyamic acid are not particularly limited, and are, for example, in the range of 20℃to 150 ℃. The reaction time of the synthesis reaction of the polyamic acid is, for example, in the range of 10 minutes to 30 hours.
The organic solvent used for the synthesis of the polyamic acid is preferably a solvent capable of dissolving the tetracarboxylic dianhydride and the diamine used, and more preferably a solvent capable of dissolving the polyamic acid produced. Examples of the organic solvent used for the synthesis of the polyamic acid include urea solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide solvents such as dimethyl sulfoxide; sulfone solvents such as diphenyl sulfone and tetramethylsulfone; amide solvents such as N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), and hexamethylphosphoric triamide; ester solvents such as gamma-butyrolactone; halogenated alkyl solvents such as chloroform and methylene chloride; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; ketone solvents such as cyclopentanone; ether solvents such as tetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane, dimethyl ether, diethyl ether, diethylene glycol dimethyl ether, and p-cresol methyl ether. These solvents may be used generally alone, or 2 or more kinds may be used in combination as needed. In order to improve the solubility and reactivity of the polyamic acid, the organic solvent used in the synthesis reaction of the polyamic acid is preferably one or more solvents selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ester-based solvent, and an ether-based solvent, and more preferably an amide-based solvent (more specifically, DMF, DMAC, NMP, etc.). The synthesis reaction of the polyamic acid is preferably performed under an inert gas atmosphere such as argon or nitrogen.
The weight average molecular weight of the polyamic acid according to the present embodiment also varies depending on the application, and is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000, and still more preferably in the range of 30,000 to 200,000. When the weight average molecular weight is 10,000 or more, it is easy to prepare a coating film or polyimide film (film) from polyamic acid or polyimide obtained by using polyamic acid. On the other hand, when the weight average molecular weight is 1,000,000 or less, the solvent is sufficiently soluble, and therefore a coating film or polyimide film having a smooth surface and a uniform thickness can be obtained by using a polyamic acid solution described later. The weight average molecular weight as used herein refers to a polyethylene oxide equivalent measured using Gel Permeation Chromatography (GPC).
The polyamic acid solution of the present embodiment contains the polyamic acid of the present embodiment described above and an organic solvent. The organic solvent contained in the polyamic acid solution includes the organic solvent described above as an organic solvent usable in the synthesis reaction of the polyamic acid, and is preferably one or more solvents selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ester-based solvent, and an ether-based solvent, and more preferably an amide-based solvent (more specifically, DMF, DMAC, NMP, etc.). When the polyamic acid is obtained by the above-described method, the reaction solution (the solution after the reaction) itself can be used as the polyamic acid solution of the present embodiment. The polyamic acid solution of the present embodiment can be prepared by dissolving solid polyamic acid obtained by removing the solvent from the reaction solution in an organic solvent. The content of the polyamic acid in the polyamic acid solution according to the present embodiment is not particularly limited, and is, for example, 1% by weight or more and 80% by weight or less with respect to the total amount of the polyamic acid solution.
The polyimide of the present embodiment is the imide of the polyamic acid of the present embodiment described above. The polyimide according to the present embodiment can be obtained by a known method, and the production method thereof is not particularly limited. An example of a method for imidizing the polyamic acid to obtain the polyimide according to the present embodiment will be described below. Imidization is performed by dehydrating and ring-closing the polyamic acid. The dehydration ring closure may be performed by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method. The imidization of the polyamide acid to the polyimide may be performed at an arbitrary ratio of 1% to 100%. That is, a polyamic acid partially imidized can be synthesized. In particular, when imidization is performed by heating, the ring-closure reaction from the polyamic acid to the polyimide is performed simultaneously with the hydrolysis of the polyamic acid, and there is a possibility that the molecular weight at the time of forming the polyimide is lower than that of the polyamic acid, and therefore, imidizing a part of the polyamic acid in the polyamic acid solution in advance before forming a polyimide film described later is preferable from the viewpoint of improving mechanical properties. In the present specification, a part of the imidized polyamic acid is also sometimes referred to as "polyamic acid".
The dehydration ring closure of the polyamic acid may be performed by heating the polyamic acid. The method for heating the polyamic acid is not particularly limited, and for example, the polyamic acid according to the present embodiment may be applied to a support such as a glass substrate, a metal plate, or a PET film (polyethylene terephthalate film), and then heat-treated at a temperature of 40 ℃ to 500 ℃. According to this method, a laminate of the present embodiment including a support and a polyimide film (specifically, a polyimide film including an imide compound of the polyamic acid of the present embodiment) disposed on the support can be obtained. Alternatively, the polyamic acid solution may be directly placed in a container subjected to a mold release treatment such as coating with a fluorine-based resin, and the polyamic acid solution may be heated and dried under reduced pressure, whereby the polyamic acid may be dehydrated and closed. Polyimide can be obtained by dehydration ring closure of polyamic acid based on these methods. The heating time for each treatment varies depending on the amount of the polyamic acid solution to be treated and the heating temperature, and is preferably in the range of 1 to 300 minutes, or in the range of 5 to 60 minutes after the treatment temperature reaches the maximum temperature. In order to shorten the heating time and to exhibit the characteristics, an imidizing agent and/or a dehydration catalyst may be added to the polyamic acid solution, and the polyamic acid solution to which the imidizing agent and/or the dehydration catalyst is added may be heated by the above-described method to effect imidization.
The imidizing agent is not particularly limited, and tertiary amines may be used. As the tertiary amine, a heterocyclic tertiary amine is preferable. Preferred specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline, and 1, 2-dimethylimidazole. The dehydration catalyst may be exemplified by acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and the like.
The amount of the imidizing agent to be added is preferably 0.5 to 5.0 molar equivalents, more preferably 0.7 to 2.5 molar equivalents, still more preferably 0.8 to 2.0 molar equivalents, based on the amide groups of the polyamic acid. The amount of the dehydration catalyst to be added is preferably 0.5 to 10.0 times by mole, more preferably 0.7 to 5.0 times by mole, still more preferably 0.8 to 3.0 times by mole, based on the amide group of the polyamic acid. In the present specification, the term "amide group of polyamic acid" refers to an amide group formed by a polymerization reaction of diamine and tetracarboxylic dianhydride. When the imidizing agent and/or the dehydration catalyst are added to the polyamic acid solution, the imidizing agent and/or the dehydration catalyst may be added as they are without being dissolved in an organic solvent, or may be added as they are after being dissolved in an organic solvent. In the method of directly adding the imidizing agent insoluble in an organic solvent, the imidizing agent and/or the dehydration catalyst may react rapidly before diffusing to form a gel. Therefore, it is preferable to add a solution obtained by dissolving an imidizing agent and/or a dehydration catalyst in an organic solvent to the polyamic acid solution.
The polyimide film of the present embodiment (specifically, the polyimide film containing the imide compound of the polyamic acid of the present embodiment) is colorless and transparent, has a low yellow index, and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing process, and thus is suitable for a transparent substrate material of a flexible display. The content of polyimide (more specifically, the imide compound of the polyamic acid of the present embodiment) in the polyimide film of the present embodiment is, for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and may be 100% by weight based on the total amount of the polyimide film. Examples of the component other than polyimide in the polyimide film include additives (more specifically, nano silica particles and the like) described later.
The electronic device of the present embodiment includes: the polyimide film of the present embodiment, and an electronic component directly or indirectly disposed on the polyimide film. In the case of manufacturing the electronic device according to the present embodiment as a flexible display, first, an inorganic substrate such as glass is used as a support, and a polyimide film is formed thereon. Then, an electronic element such as a TFT is arranged (formed) on the polyimide film, whereby an electronic device is formed on the support. The process of forming a TFT is usually performed in a wide temperature range of 150 ℃ to 650 ℃, but in practice, in order to achieve desired performance, an oxide semiconductor layer and an a-Si layer are formed at 300 ℃ or higher, and in some cases, a-Si and the like are crystallized by laser light and the like.
In this case, when the thermal decomposition temperature of the polyimide film is low, outgas (out gas) may be generated during formation of the electronic component, and the outgas may adhere to the inside of the oven as a sublimate, which may cause contamination in the oven, or peeling of an inorganic film (a barrier film or the like described later) formed on the polyimide film and the electronic component may occur, and therefore, the polyimide preferably has a 1% weight loss temperature of 500 ℃. More specifically, an inorganic film such as a silicon oxide film (SiOx film) or a silicon nitride film (SiNx film) is formed as a barrier film on the polyimide film before the TFT is formed. If the polyimide has low heat resistance, the polyimide may be peeled from the inorganic film due to volatile components such as decomposed gas of the polyimide in a high-temperature process after lamination of the inorganic film. Therefore, it is desirable that the polyimide has a weight loss ratio of less than 1% when the polyimide is isothermally held at a temperature in the range of 400 ℃ to 450 ℃ in addition to a weight loss temperature of 500 ℃ to 500 ℃.
In addition, when the glass transition temperature (Tg) of the polyimide is significantly lower than the process temperature, positional shift or the like may occur during formation of the electronic component, and therefore, the Tg of the polyimide is preferably 300 ℃ or higher, more preferably 350 ℃ or higher, and further preferably 400 ℃ or higher. The higher the upper limit of Tg of the polyimide, the better, for example, 450 ℃. The Tg of the polyimide can be adjusted by changing the content of residues having a rigid structure (more specifically, PDA residues, PHBAAB residues, etc.), for example. In addition, since the glass substrate has a linear expansion coefficient smaller than that of the resin, an internal stress is generated between the glass substrate and the polyimide film. When the internal stress of a laminate of a glass substrate serving as a support and a polyimide film is high, the laminate including the polyimide film expands in a TFT forming process at a high temperature and then contracts when cooled to room temperature, and problems such as warpage and breakage of the glass substrate, peeling of the polyimide film from the glass substrate, and the like occur. Therefore, the internal stress generated in the laminate of the polyimide film and the glass substrate is preferably 50MPa or less.
In order to suppress the occurrence of the internal stress, the linear expansion coefficient of the polyimide film is preferably 100ppm/K or less, more preferably 90ppm/K or less, and still more preferably 80ppm/K or less. The linear expansion coefficient of the polyimide film may be-10 ppm/K or more and 80ppm/K or less, 0ppm/K or more and 80ppm/K or less, 10ppm/K or more and 80ppm/K or less, 20ppm/K or more and 80ppm/K or less, 30ppm/K or more and 80ppm/K or less, 40ppm/K or more and 80ppm/K or less, or 50ppm/K or more and 80ppm/K or less.
In order to suppress a decrease in display performance when applied to an image display device, the thickness direction retardation (Rth) of the polyimide film with respect to light having a wavelength of 550nm is preferably 200nm or less, more preferably 100nm or less, further preferably 90nm or less, further more preferably 80nm or less, and particularly preferably 70nm or less, in terms of a value converted to a polyimide film having a thickness of 10 μm.
The transparency of the polyimide film can be obtained by the method according to JIS K7361-1:1997, total light transmittance (TT), transmittance of light having a wavelength of 450nm (hereinafter, may be abbreviated as "light transmittance"), and haze according to JIS K7136-2000. When a polyimide film is used for applications requiring high transparency, the total light transmittance of the polyimide film is preferably 75% or more, more preferably 80% or more. In the case of using a polyimide film for applications requiring high transparency, the transmittance of the polyimide film is preferably 75% or more, more preferably 78% or more. In the case of using a polyimide film for applications requiring high transparency, the haze of the polyimide film is preferably 1.5% or less, more preferably 1.2% or less, and still more preferably less than 1.0%. In applications requiring high transparency, polyimide films are required to have high transmittance in all wavelength ranges, but polyimide films tend to absorb light on the short wavelength side easily, and the films themselves are often colored yellow. In order to use the polyimide film in applications requiring high transparency, the Yellowness Index (YI) of the polyimide film is preferably 25 or less, more preferably 20 or less, further preferably 14 or less, particularly preferably 12 or less. YI can be measured according to JIS K7373-2006. The polyimide film having the transparency is suitable for a transparent substrate for glass substitution use or the like, and a substrate having a sensor or a camera module provided on the back surface thereof.
In addition, the light extraction method of the flexible display includes both a top emission method of extracting light from the front surface side of the TFT and a bottom emission method of extracting light from the back surface side of the TFT. Since light is not blocked by the TFT in the top emission method, the aperture ratio is easily improved and a high definition image quality is obtained, and the bottom emission method has a feature that the TFT and the pixel electrode are easily aligned and easily manufactured. If the TFT is transparent, the aperture ratio can be increased even in the bottom emission method, and thus there is a tendency to adopt the bottom emission method which is easy to manufacture in a large-sized display. The polyimide film of the present embodiment has low YI and excellent heat resistance, and thus can be applied to any of the above light extraction systems.
In a process for manufacturing an electronic device, an electronic element such as a thin film transistor or a transparent electrode is provided on a substrate. The process of forming electronic components on polyimide substrates is classified into a batch process and a roll-to-roll process. In the roll-to-roll process, electronic components are sequentially mounted on a polyimide substrate (polyimide film) while conveying the polyimide substrate in a long form. In the batch process, for example, a polyimide substrate (polyimide film) is provided on a glass support to form a laminate, and after an electronic component is provided on the polyimide film of the laminate, the support is peeled off from the polyimide film. The polyimide of the present embodiment can be applied to any process. The batch process is preferable in terms of cost because it can use the existing equipment for a glass support.
The polyimide of the present embodiment can be suitably used as a material for a display substrate such as a TFT substrate or a touch panel substrate. When polyimide is used for the above-mentioned applications, the following methods are often employed: after an electronic device (specifically, an electronic device having an electronic element formed on a polyimide film) is formed on a support as described above, the polyimide film is peeled off from the support. In addition, alkali-free glass is suitably used as a material of the support. Hereinafter, an example of the method for producing a polyimide film according to the present embodiment and an example of the method for producing a laminate (laminate of a polyimide film and a support) according to the present embodiment will be described in detail.
First, the polyamic acid solution according to the present embodiment is coated on a support to form a laminate including a coating film including polyamic acid and a coating film of the support. Subsequently, the laminate containing the coating film is heated at a temperature of, for example, 40 ℃ to 200 ℃. The heating time at this time is, for example, 3 minutes to 120 minutes. The multi-stage heating step may be provided, for example, by heating the laminate containing the coating film at 50 ℃ for 30 minutes and then at 100 ℃ for 30 minutes. Next, in order to imidize the polyamic acid in the coating film, the laminate containing the coating film (laminate containing the polyamic acid film) is heated at a temperature of, for example, 250 ℃ to 500 ℃. The heating time (heating time at the highest temperature) at this time is, for example, 1 to 300 minutes, preferably 5 to 60 minutes. In this case, the temperature is preferably gradually raised from a low temperature to a maximum temperature. The temperature rise rate is preferably 2 to 10 ℃ per minute, more preferably 4 to 10 ℃ per minute. The maximum temperature is preferably 380 ℃ to 500 ℃. Imidization is sufficiently performed at a maximum temperature of 380 ℃ or higher, and thermal degradation of polyimide can be suppressed at a maximum temperature of 500 ℃ or lower. In addition, the temperature may be maintained at an arbitrary temperature for an arbitrary time before the highest temperature is reached. The imidization reaction may be performed under air, under reduced pressure, or in an inert gas such as nitrogen, and is preferably performed under reduced pressure, or in an inert gas such as nitrogen, in order to exhibit higher transparency. As the heating device, a known device such as a hot air oven, an infrared oven, a vacuum oven, an inert (insert) oven, or a hot plate can be used. Through these steps, the polyamic acid in the coating film is imidized, and a laminate (laminate of the present embodiment) of the support and the polyimide film (polyimide film containing the imidized product of the polyamic acid of the present embodiment) can be obtained. Further, for example, the polyimide film formed on the support is peeled off from the support by a method described later, whereby the polyimide film of the present embodiment (polyimide film containing the imide compound of the polyamic acid of the present embodiment) can be obtained. An electronic component may be provided on the polyimide film peeled off from the support. In order to shorten the heating time and to exhibit the characteristics, an imidizing agent and a dehydration catalyst may be added to the polyamic acid solution, and the solution may be heated by the above method to effect imidization.
The polyimide film may be peeled off from the laminate of the support and the polyimide film obtained by a known method. For example, the peeling may be performed by hand, or may be performed by using a mechanical device such as a driving roller or a robot. Furthermore, the following method may be employed: a method of disposing a release layer between a support and a polyimide film; a method of forming a silicon oxide film on a substrate having a plurality of grooves, forming a polyimide film using the silicon oxide film as a base layer, and peeling the polyimide film by immersing an etching liquid of silicon oxide between the substrate and the silicon oxide film. In addition, a method of peeling the polyimide film from the support by irradiation with laser light may be employed.
In addition, in the batch-type device manufacturing process, the adhesion between the support and the polyimide film is preferably excellent, and the batch-type device manufacturing process is: the polyamic acid solution is applied to a support such as a glass substrate, heated to imidize the solution, and then the polyimide film is peeled off after forming an electronic device or the like. The adhesion referred to herein means adhesion strength. In a manufacturing process in which the polyimide film on the support is peeled off from the support after the electronic component or the like is formed, if the adhesion between the polyimide film and the support is excellent, the electronic component or the like can be formed or mounted more accurately. In a manufacturing process in which an electronic component or the like is disposed on a support with a polyimide film interposed therebetween, the higher the peel strength between the support and the polyimide film is, the better from the viewpoint of improvement in productivity. Specifically, the peel strength is preferably 0.05N/cm or more, more preferably 0.1N/cm or more.
In the above-described production process, when the polyimide film is peeled from the laminate of the support and the polyimide film, the polyimide film is often peeled from the support by laser irradiation. In this case, since the polyimide film needs to absorb laser light, the cut-off wavelength of the polyimide film needs to be longer than the wavelength of the laser light used for the peeling. Since a XeCl excimer laser having a wavelength of 308nm is often used for laser lift-off, the cut-off wavelength of the polyimide film is preferably 312nm or more, more preferably 330nm or more. On the other hand, if the cutoff wavelength is long, the polyimide film tends to be colored yellow, and therefore the cutoff wavelength of the polyimide film is preferably 390nm or less. From the viewpoint of both transparency (low yellow index) and processability in laser lift-off, the cutoff wavelength of the polyimide film is preferably 320nm to 390nm, more preferably 330nm to 380 nm. The cutoff wavelength in the present specification means a wavelength at which the transmittance measured by an ultraviolet-visible spectrophotometer is 0.1% or less.
The polyamic acid and polyimide according to the present embodiment can be used directly in a coating and molding process for producing products and members, or can be used as a material for coating and other treatments on a molded article molded into a film shape. For use in the coating or molding process, the polyamic acid or polyimide may be dissolved or dispersed in an organic solvent as needed, and further, a photocurable component, a thermosetting component, a non-polymerizable binder resin, and other components may be blended as needed to prepare a polyamic acid composition or polyimide resin composition.
In order to impart processing characteristics and various functionalities to the polyamic acid and polyimide according to the present embodiment, various organic or inorganic low-molecular compounds or high-molecular compounds may be blended as additives in the polyamic acid solution. As the additive, for example, a dye, a surfactant, a leveling agent, a plasticizer, silicone, microparticles, a sensitizer, or the like can be used. The microparticles comprise: organic microparticles formed of polystyrene, polytetrafluoroethylene, or the like; inorganic fine particles made of colloidal silica, carbon, layered silicate, or the like may have a porous structure or a hollow structure. The function and morphology of the fine particles are not particularly limited, and may be, for example, pigment, filler, or fibrous particles.
In order to maintain the transparency of the polyimide film and to improve the heat resistance, nano silica particles may be used as the additive, and polyamic acid and nano silica particles may be compounded. The average primary particle diameter of the nano silica particles is preferably 200nm or less, more preferably 100nm or less, further preferably 50nm or less, and may be 30nm or less from the viewpoint of maintaining the transparency of the polyimide film. On the other hand, the average primary particle diameter of the nano silica particles is preferably 5nm or more, more preferably 10nm or more from the viewpoint of ensuring dispersibility into the polyamic acid. As a method for compounding the polyamic acid and the nano-silica particles, a known method can be used, and for example, a method using an organic silica sol in which the nano-silica particles are dispersed in an organic solvent can be used. As a method of compositing the polyamic acid and the nano-silica particles using the organic silica sol, after the polyamic acid is synthesized, the synthesized polyamic acid and the organic silica sol are mixed, and in order to disperse the nano-silica particles in the polyamic acid more highly, it is preferable to synthesize the polyamic acid in the organic silica sol.
In addition, the nano silica particles may be surface-treated with a surface treatment agent in order to enhance the interaction with the polyamic acid. As the surface treatment agent, a known surface treatment agent such as a silane coupling agent can be used. As the silane coupling agent, alkoxysilane compounds having an amino group, a glycidyl group, or the like as a functional group, and the like are widely known, and can be appropriately selected. In order to further enhance the interaction with the polyamic acid, an amino group-containing alkoxysilane is preferable as the silane coupling agent. Examples of the amino group-containing alkoxysilane include 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane, and 3-aminopropyl triethoxysilane is preferably used from the viewpoint of stability of the raw materials. As a surface treatment method of the nano silica particles, there is a method of stirring a mixture in which a silane coupling agent is added to a dispersion (an organic silica sol) at an atmospheric temperature of 20 ℃ or more and 80 ℃ or less. The stirring time at this time is, for example, 1 hour or more and 10 hours or less. In this case, a catalyst or the like for promoting the reaction may be added.
The polyamic acid composition containing the nano-silica particles, which is obtained by compositing the polyamic acid and the nano-silica particles, preferably contains the nano-silica particles in a range of 1 to 30 parts by weight, more preferably contains the nano-silica particles in a range of 1 to 20 parts by weight, relative to 100 parts by weight of the polyamic acid. When the content of the nano silica particles is 1 part by weight or more, the heat resistance of the polyimide containing the nano silica particles can be improved, the internal stress can be sufficiently reduced, and when the content of the nano silica particles is 30 parts by weight or less, adverse effects on the mechanical properties and transparency of the polyimide containing the nano silica particles can be suppressed.
Imidazoles may be added to the polyamic acid according to the present embodiment as the above-described additive for imparting functionality. In the present specification, imidazoles refer to compounds having a 1, 3-diazole ring (1, 3-diazole ring structure). The imidazoles to be added to the polyamic acid according to the present embodiment are not particularly limited, and examples thereof include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Among these, 1, 2-dimethylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole are preferable, and 1, 2-dimethylimidazole and 1-benzyl-2-methylimidazole are more preferable.
The content of imidazoles is preferably 0.005 mol or more and 0.1 mol or less, more preferably 0.01 mol or more and 0.08 mol or less, and still more preferably 0.015 mol or more and 0.050 mol or less, based on 1 mol of amide groups of the polyamic acid. The film strength and transparency of polyimide can be improved by containing 0.005 mol or more of imidazole, and the storage stability of polyamic acid can be maintained and Tg and heat resistance can be improved by making the content of imidazole 0.1 mol or less.
The method of mixing the polyamic acid and the imidazole is not particularly limited. From the viewpoint of easiness of molecular weight control of the polyamic acid, it is preferable to add imidazoles to the polyamic acid after polymerization. In this case, the imidazole may be directly added to the polyamic acid, or the imidazole may be dissolved in a solvent in advance, and the solution may be added to the polyamic acid, and the method of addition is not particularly limited. The polyamic acid solution (solution containing polyamic acid and imidazoles) of the present embodiment can be prepared by adding imidazoles to a solution containing polymerized polyamic acid (solution after reaction).
In addition, the polyamic acid solution according to the present embodiment may contain a silane coupling agent in order to exhibit appropriate adhesion to a support. The silane coupling agent may be added to the monomer solution before the polymerization reaction, to the solution during the polymerization reaction, or to the polyamic acid solution after the polymerization reaction. The type of the silane coupling agent is not particularly limited, and known ones may be used, but from the viewpoint of reactivity with the polyamic acid, an amino group-containing compound is particularly preferable.
The blending ratio of the silane coupling agent to 100 parts by weight of the polyamic acid is preferably 0.01 part by weight or more and 0.50 part by weight or less, more preferably 0.01 part by weight or more and 0.10 part by weight or less, and still more preferably 0.01 part by weight or more and 0.05 part by weight or less. The peeling-inhibiting effect on the support can be fully exerted by setting the compounding ratio of the silane coupling agent to 0.01 parts by weight or more, and the embrittlement of the polyimide film can be inhibited by setting the compounding ratio of the silane coupling agent to 0.50 parts by weight or less because the decrease in the molecular weight of the polyamic acid is inhibited.
Various inorganic thin films such as a metal oxide thin film and a transparent electrode can be formed on the surface of the polyimide film according to the present embodiment. The method for forming the inorganic thin film is not particularly limited, and examples thereof include PVD methods such as CVD, sputtering, vacuum evaporation, ion plating, and the like.
The polyimide film of the present embodiment is preferably used in fields and products in which these characteristics are considered to be effective because it has heat resistance, low thermal expansion and transparency and also has small internal stress generated when it is formed into a laminate with a glass substrate. For example, the polyimide film of the present embodiment is preferably used for a liquid crystal display device, an image display device such as an organic EL or electronic paper, a printed matter, a color filter, a flexible display, an optical thin film, a 3D display, a touch panel, a transparent conductive film substrate, a solar cell, or the like, and is more preferably used as a substitute material for a portion where glass is currently used. In these applications, the thickness of the polyimide film is, for example, 1 μm or more and 200 μm or less, preferably 5 μm or more and 100 μm or less. The thickness of the polyimide film can be measured using a Laser holographic micrometer (Laser Hologage).
The polyamic acid solution according to the present embodiment can be suitably used in a batch-type device manufacturing process, which is: the polyimide film is peeled off after an electronic component or the like is formed by applying a polyamic acid solution to a support and heating to imidize the polyamic acid solution. Therefore, the present embodiment also includes a method for manufacturing an electronic device, which includes the steps of applying a polyamic acid solution to a support, heating the applied polyamic acid solution to imidize the applied polyamic acid solution, and forming an electronic element on a polyimide film formed on the support. The method for manufacturing an electronic device may further include a step of peeling the polyimide film on which the electronic element or the like is formed from the support.
Examples
Hereinafter, examples of the present invention will be described, but the scope of the present invention is not limited to the following examples.
< method for measuring physical Properties >
First, a method for measuring physical properties of polyimide (polyimide film) will be described.
[ light transmittance ]
The transmittance of light having a wavelength of 450nm was measured for each of the polyimide films obtained in examples and comparative examples described below using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Japanese Specification Co., ltd. "V-650").
[ Yellow Index (YI) ]
For each of the polyimide films obtained in examples and comparative examples described below, transmittance of light having a wavelength of 200nm to 800nm was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Japanese Specification Co., ltd. "V-650"), and the Yellowness Index (YI) of the polyimide film was calculated according to the formula described in JIS K7373-2006. When YI is 14 or less, the evaluation is "excellent in low coloring property". On the other hand, when YI exceeds 14, it is evaluated as "low coloring property is not excellent".
[ haze ]
The haze of each polyimide film obtained in examples and comparative examples described below was measured by a method described in JIS K7136-2000 using an integrating sphere type haze meter (COH 300A, manufactured by Nippon Denshoku Co., ltd.).
[ internal stress ]
A polyimide film was formed on a glass substrate (material: alkali-free glass, thickness: 0.7mm, size: 100 mm. Times.100 mm) manufactured by Corning, in which the amount of warpage was measured in advance, by the same method as in examples and comparative examples described later, to obtain a laminate having a polyimide film with a thickness of 10. Mu.m on the glass substrate. In order to eliminate the influence of water absorption of the polyimide film, the laminate was dried at 120℃for 10 minutes, and then the warpage amount of the laminate was measured in a nitrogen atmosphere at 25℃using a film stress measuring apparatus (FLX-2320-S, manufactured by KLA-Tencor). Then, the internal stress generated between the glass substrate and the polyimide film was calculated by Stoney formula from the warpage amount of the glass substrate before the polyimide film was formed and the warpage amount of the laminate.
Delay (delay)
The thickness retardation (Rth) of each polyimide film obtained in examples and comparative examples described below was measured with a retardation meter (manufactured by SINTEC corporation, OPTIPRO). Then, from the thickness D (unit: μm) of the measurement sample (polyimide film), a value (Rth) of the polyimide film converted to a thickness of 10 μm was calculated based on the following formula 10 )。Rth 10 When the wavelength is 80nm or less, it is evaluated as "delay can be reduced". On the other hand, rth 10 If the wavelength exceeds 80nm, it is evaluated as "delay cannot be reduced".
Rth 10 ＝Rth×10/D
[ coefficient of Linear expansion (CTE) ]
The polyimide films obtained in examples and comparative examples described below were sampled to a width of 3mm and a length of 10mm, and used as samples for CTE measurement. Using a thermal analysis device (TMA/SS 7100 manufactured by Hitachi High-Tech Science Corporation), the sample was heated from 10℃to 400℃at a heating rate of 10℃per minute under a load of 29.4mN, and then cooled at a cooling rate of 40℃per minute. Then, CTE was determined from the amount of strain at 350℃to 100℃at the time of cooling. When the CTE was 80ppm/K or less, the test was evaluated as "excellent in low thermal expansion". On the other hand, when the CTE exceeds 80ppm/K, it is evaluated as "not excellent in low thermal expansion".
[ glass transition temperature (Tg) ]
The polyimide films obtained in examples and comparative examples described below were sampled to a width of 3mm and a length of 10mm, and used as samples for Tg measurement. A TMA curve was obtained by applying a load of 98.0mN to a sample using a thermal analysis apparatus (Hitachi High-Tech Science Corporation, "TMA/SS 7100"), heating the sample from 10℃to 450℃at 10℃per minute, and plotting the temperature and the strain (elongation). The temperature at the inflection point of the obtained TMA curve (the temperature corresponding to the peak in the differential curve of the TMA curve) was taken as the glass transition temperature (Tg).
[1% weight loss temperature (TD 1) ]
The polyimide films obtained in examples and comparative examples (more specifically, polyimide films obtained by sampling the weight of the polyimide film at 10 mg) were used as measurement samples, and a differential thermal weight simultaneous measurement apparatus (TG/DTA 7200 manufactured by Hitachi High-Tech Science Corporation) was used as a 1% weight loss temperature (TD 1) when the temperature was raised from 25 ℃ to 650 ℃ under a nitrogen atmosphere at 20 ℃/min, and the weight of the samples at 150 ℃ was used as a reference, and the weight of the samples was reduced by 1% by weight.
< preparation of polyimide film >
Hereinafter, a method for producing polyimide films of examples and comparative examples will be described. In the following, the compounds and reagents will be described in short. In addition, for both examples and comparative examples, the preparation of the polyamic acid solution was performed under a nitrogen atmosphere.
NMP: n-methyl-2-pyrrolidone
BPAF:9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride
BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride
PMDA: pyromellitic dianhydride
PDA: para-phenylenediamine
PHBAAB: (2-phenyl-4-aminophenyl) -4-aminobenzoate
TFMB:2,2' -bis (trifluoromethyl) benzidine
DABA:4,4' -diaminobenzanilides
BAFL:9, 9-bis (4-aminophenyl) fluorene
Example 1
First, a polyamic acid solution was prepared as follows. 400.0g of NMP was placed in a 1L glass separable flask equipped with a stirrer equipped with a stainless steel stirrer and a nitrogen inlet tube as an organic solvent for polymerization. Subsequently, 19.1g of PDA was placed in the flask while stirring the flask content, and dissolved. Then, 80.9g of BPAF was added to the flask while stirring the flask content, and then the flask content was stirred under an atmosphere at a temperature of 25℃for 24 hours. Then, NMP was added to the flask content so that the concentration of polyamide acid in the flask content after stirring became 10.0 wt%, to obtain a polyamide acid solution.
Next, the obtained polyamic acid solution was applied onto a glass substrate (EAGLE XG, material: alkali-free glass, thickness: 0.7mm, size: 150mm×150 mm) using a spin coater, and heated in air at 80 ℃ for 30 minutes to obtain a laminate (laminate containing a polyamic acid film) having a film containing a polyamic acid formed on the glass substrate. Next, the laminate containing the polyamic acid film was heated under the following heating conditions in a nitrogen atmosphere, and imidization of the polyamic acid was performed to obtain a laminate having a polyimide film with a thickness of 10 μm on a glass substrate. For the heating conditions at the time of imidization, first, the atmosphere temperature was raised from 20℃to 350℃at a heating rate of 5℃per minute and maintained at 350℃for 30 minutes. Then, the temperature of the atmosphere was raised to 420℃at a heating rate of 5℃per minute, and then the mixture was kept at 420℃for 30 minutes. The polyimide film was peeled off from the glass substrate of the obtained laminate to obtain a polyimide film of example 1.
Examples 2 to 35 and comparative examples 1 to 7
Polyimide films of examples 2 to 35 and comparative examples 1 to 7 were obtained in the same manner as in example 1 except that the types and ratios (feed ratios) of the acid dianhydrides and the types and ratios (feed ratios) of the diamines were as shown in tables 1 and 2, respectively. In examples 2 to 35 and comparative examples 1 to 7, the total amount of the acid dianhydride and the total amount of the diamine were the same as in example 1.
Examples 1 to 35 and comparative examples 1 to 7 show the types and ratios of acid dianhydrides, and the types and ratios of diamines in tables 1 and 2. The mole fractions of the respective residues of the polyamic acid in the polyamic acid solutions prepared in examples 1 to 35 and comparative examples 1 to 7 were identical to the mole fractions of the respective monomers (diamine and tetracarboxylic dianhydride) used in the synthesis of the polyamic acid. In examples 2 to 14 and 16 to 33, 2 kinds of diamines (component 1 and component 2) were used. In example 34, example 35 and comparative examples 4 to 7, 2 kinds of acid dianhydrides (component 1 and component 2) were used. For each of examples 2 to 14, examples 16 to 35 and comparative examples 4 to 7, component 1 and component 2 were placed in a flask at the same time. In tables 1 and 2, the values of the ratio of the acid dianhydride are the content (unit: mol%) of each acid dianhydride with respect to the total amount of the acid dianhydride used. In tables 1 and 2, the numerical values of the diamine ratios are the contents (unit: mol%) of the respective diamines with respect to the total amount of the diamines used.
TABLE 1
TABLE 2
< measurement results >
The measurement results of the physical properties of examples 1 to 35 and comparative examples 1 to 7 are shown in tables 3 and 4. In tables 3 and 4, "-" indicates that the measurement was not performed. In tables 3 and 4, the "transmittance" is the transmittance of light having a wavelength of 450 nm.
TABLE 3
TABLE 4
The polyamic acids synthesized in examples 1 to 35 have BPAF residues as acid dianhydride residues. The polyamic acid synthesized in examples 1 to 35 has one or more selected from the group consisting of PDA residues and PHBAAB residues as diamine residues. The content of BPAF residues in the polyamic acid synthesized in examples 1 to 35 was 90 mol% or more and 100 mol% or less based on the total acid dianhydride residues.
Example 1In 35, YI is 14 or less. Therefore, the polyimide films of examples 1 to 35 were excellent in low coloring property. In examples 1 to 35, rth 10 Is 80nm or less. Therefore, the polyimide films of examples 1 to 35 can reduce retardation. In examples 1 to 35, the CTE was 80ppm/K or less. Therefore, the polyimide films of examples 1 to 35 were excellent in low thermal expansion.
The polyamic acid synthesized in comparative examples 1 to 3 does not have one or more diamine residues selected from the group consisting of PDA residues and PHBAAB residues. The polyamic acid synthesized in comparative examples 2 and 3 had no BPAF residue as the acid dianhydride residue. In the polyamic acid synthesized in comparative examples 4 to 7, the content of the BPAF residues was less than 90 mol% based on the total acid dianhydride residues.
In comparative example 1, the CTE exceeded 80ppm/K. Therefore, the polyimide film of comparative example 1 is not excellent in low thermal expansion. In comparative example 2, rth 10 Exceeding 80nm. Therefore, the polyimide film of comparative example 2 cannot reduce retardation. In comparative examples 2 to 7, YI exceeded 14. Therefore, the polyimide films of comparative examples 2 to 7 were not excellent in low coloring property.
From the above results, it is shown that the polyimide obtained from the polyamic acid of the present invention can reduce Rth, and is excellent in low coloring property and low thermal expansion property.
Claims (14)
1. A polyamic acid having a 4-valent organic group represented by the following general formula (1) as a tetracarboxylic dianhydride residue and having one or more selected from the group consisting of a p-phenylenediamine residue and a (2-phenyl-4-aminophenyl) -4-aminobenzoate residue as a diamine residue,
the content of the 4-valent organic groups represented by the following general formula (1) is 90 to 100 mol% based on the total tetracarboxylic dianhydride residues,
in the general formula (1), R 1 R is R 2 Each independently of the otherRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.
2. The polyamic acid according to claim 1, wherein in the general formula (1), R 1 R is R 2 All represent a hydrogen atom.
3. The polyamic acid according to claim 1 or 2, further comprising at least one diamine residue selected from the group consisting of a 4,4 '-diaminobenzanilide residue, a 2,2' -bis (trifluoromethyl) benzidine residue, and a 9, 9-bis (4-aminophenyl) fluorene residue.
4. A polyamic acid solution comprising the polyamic acid according to any one of claims 1 to 3 and an organic solvent.
5. A polyimide which is the imide of the polyamic acid according to any one of claims 1 to 3.
6. The polyimide according to claim 5, which has a glass transition temperature of 350℃or higher.
7. A polyimide film comprising the polyimide of claim 5 or 6.
8. A laminate comprising a support and the polyimide film according to claim 7.
9. An electronic device, having: the polyimide film according to claim 7, and an electronic component disposed on the polyimide film.
10. A method for producing a polyimide film, wherein the polyamic acid solution according to claim 4 is applied to a support to form a coating film containing the polyamic acid, and the coating film is heated to imidize the polyamic acid.
11. The method for producing a polyimide film according to claim 10, wherein the maximum temperature at which the coating film is heated is 380 ℃ to 500 ℃.
12. The method for producing a polyimide film according to claim 11, wherein the heating time at the highest temperature is 5 minutes to 60 minutes.
13. The method for producing a polyimide film according to any one of claims 10 to 12, wherein the polyimide film obtained by heating the coating film is peeled from the support.
14. The method for producing a polyimide film according to claim 13, wherein the polyimide film is peeled from the support by laser irradiation.
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| JP2020177535 | 2020-10-22 | ||
| PCT/JP2021/038394 WO2022085620A1 (en) | 2020-10-22 | 2021-10-18 | Poly(amic acid), poly(amic acid) solution, polyimide, polyimide film, layered product, electronic device, and method for producing polyimide film |
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- 2021-10-18 JP JP2022557513A patent/JPWO2022085620A1/ja active Pending
- 2021-10-18 KR KR1020237014949A patent/KR20230092934A/en unknown
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