JP2022008353A - Method for producing electronic device - Google Patents
Method for producing electronic device Download PDFInfo
- Publication number
- JP2022008353A JP2022008353A JP2021146539A JP2021146539A JP2022008353A JP 2022008353 A JP2022008353 A JP 2022008353A JP 2021146539 A JP2021146539 A JP 2021146539A JP 2021146539 A JP2021146539 A JP 2021146539A JP 2022008353 A JP2022008353 A JP 2022008353A
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- general formula
- polyimide
- structural unit
- unit represented
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920001721 polyimide Polymers 0.000 claims abstract description 114
- 239000011521 glass Substances 0.000 claims abstract description 47
- 229920005575 poly(amic acid) Polymers 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 69
- 239000002253 acid Substances 0.000 abstract description 12
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 44
- 239000010408 film Substances 0.000 description 35
- 150000004985 diamines Chemical class 0.000 description 29
- 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 27
- -1 biphenyl-3,3', 4,4'-tetrayl group Chemical group 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 26
- 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 21
- 239000002904 solvent Substances 0.000 description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 7
- 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 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010923 batch production Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- 150000001408 amides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C(C)c1c2)c1ccc2-c1ccc(C(C)(*)C2C)c2c1 Chemical compound CC(C(C)c1c2)c1ccc2-c1ccc(C(C)(*)C2C)c2c1 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
- 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
- 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
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic 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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 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
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 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
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- UIYJZBVVQDMLQX-UHFFFAOYSA-N 4-(3-carboxyphenyl)cyclohexa-3,5-diene-1,1,2-tricarboxylic acid Chemical compound C1=CC(C(O)=O)(C(O)=O)C(C(=O)O)C=C1C1=CC=CC(C(O)=O)=C1 UIYJZBVVQDMLQX-UHFFFAOYSA-N 0.000 description 1
- FNJFWOJEIGPYAS-UHFFFAOYSA-N 4-[4-(9h-fluoren-1-yl)phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)C=C1 FNJFWOJEIGPYAS-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HCHDYJCQAHZANX-UHFFFAOYSA-N C(=O)(O)C=1C=C(C=CC1C(=O)O)C1(C2=CC=CC=C2C=2C=CC=C(C12)C(=O)O)C1=CC(=C(C=C1)C(=O)O)C(=O)O Chemical compound C(=O)(O)C=1C=C(C=CC1C(=O)O)C1(C2=CC=CC=C2C=2C=CC=C(C12)C(=O)O)C1=CC(=C(C=C1)C(=O)O)C(=O)O HCHDYJCQAHZANX-UHFFFAOYSA-N 0.000 description 1
- QRPLOHKXUBXIOT-UHFFFAOYSA-N CCCC[SiH-](C)(C)O[Si+](C)(C)CCCN(C(C)=O)C(CBC(N(C)C(C)=O)=O)=O Chemical compound CCCC[SiH-](C)(C)O[Si+](C)(C)CCCN(C(C)=O)C(CBC(N(C)C(C)=O)=O)=O QRPLOHKXUBXIOT-UHFFFAOYSA-N 0.000 description 1
- ZDHQBCJOAYDOPU-UHFFFAOYSA-N CCCC[SiH-](C)(C)O[SiH-](C)(C)CCCNC(c(ccc(-c(cc1)cc(C(NCC)=O)c1C(O)=O)c1)c1C(O)=O)=O Chemical compound CCCC[SiH-](C)(C)O[SiH-](C)(C)CCCNC(c(ccc(-c(cc1)cc(C(NCC)=O)c1C(O)=O)c1)c1C(O)=O)=O ZDHQBCJOAYDOPU-UHFFFAOYSA-N 0.000 description 1
- OWBGVGGPQBZRNU-UHFFFAOYSA-N CCNc(cc(cc1)-c2ccc(C(NCCCS(C)(C)OS(C)(C)C)=O)c(C(O)=O)c2)c1C(C)=O Chemical compound CCNc(cc(cc1)-c2ccc(C(NCCCS(C)(C)OS(C)(C)C)=O)c(C(O)=O)c2)c1C(C)=O OWBGVGGPQBZRNU-UHFFFAOYSA-N 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material 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
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 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 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing 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
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 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
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition 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
Abstract
Description
本発明は、ポリアミド酸、ポリアミド酸溶液、ポリイミド、およびポリイミド基板に関する。 The present invention relates to polyamic acids, polyamic acid solutions, polyimides, and polyimide substrates.
ディスプレイ、タッチパネル、太陽電池等の電子デバイスにおいて、薄型化、軽量化、およびフレキシブル化が要求されており、ガラス基板に代えて樹脂フィルム基板の利用が検討されている。 Electronic devices such as displays, touch panels, and solar cells are required to be thinner, lighter, and more flexible, and the use of resin film substrates instead of glass substrates is being considered.
これらの電子デバイスの製造プロセスでは、基板上に、薄膜トランジスタ等の半導体等や電極等の電子素子が形成される。これらの素子の形成は高温プロセスを要するため、樹脂クフィルム基板に高い耐熱性が要求される。基板上に設けられる素子は一般に無機材料からなる。基板の線熱膨張係数と素子を構成する無機材料の線熱膨張係数とが大きく異なると、素子形成界面の応力等に起因して、基板の反りや素子の破壊が生じる場合がある。そのため、樹脂フィルム基板は、素子を構成する無機材料と同等の線熱膨張係数を有することが望まれる。液晶ディスプレイやボトムエミッション型の有機ＥＬ素子では、表示素子からの光が基板を透過して出射するため、樹脂フィルム基板には透明性が求められ、特に、可視光領域での光透過率が高いことが要求される。上記の理由により、電子デバイス用の樹脂フィルム基板材料には、高耐熱性、低熱膨張、および高透明性が求められる。 In the manufacturing process of these electronic devices, semiconductors such as thin film transistors and electronic elements such as electrodes are formed on the substrate. Since the formation of these elements requires a high temperature process, high heat resistance is required for the resin film substrate. The element provided on the substrate is generally made of an inorganic material. If the coefficient of linear thermal expansion of the substrate and the coefficient of linear thermal expansion of the inorganic material constituting the element are significantly different, the substrate may be warped or the element may be destroyed due to stress at the element forming interface or the like. Therefore, it is desired that the resin film substrate has a coefficient of linear thermal expansion equivalent to that of the inorganic material constituting the device. In liquid crystal displays and bottom emission type organic EL elements, the light from the display element is transmitted through the substrate and emitted, so transparency is required for the resin film substrate, and the light transmittance is particularly high in the visible light region. Is required. For the above reasons, resin film substrate materials for electronic devices are required to have high heat resistance, low thermal expansion, and high transparency.
電子デバイスの製造プロセスは、バッチタイプとロール・トゥ・ロールタイプに分けられる。樹脂フィルム基板は、ロール・トゥ・ロールプロセスにも適用できるが、ロール・トゥ・ロールプロセスによる電子デバイスの製造には、新たな設備が必要となることに加えて、ロール搬送に伴う新たな問題を克服しなければならない。一方、バッチプロセスでは、支持体上に樹脂溶液を塗布、乾燥してフィルム基板を形成し、その上に素子を形成すればよく、現行のガラス基板用プロセス設備を利用できるため、コスト面で優位である。 The manufacturing process of electronic devices is divided into batch type and roll-to-roll type. Resin film substrates can also be applied to roll-to-roll processes, but the manufacture of electronic devices by roll-to-roll processes requires new equipment and new problems associated with roll transfer. Must be overcome. On the other hand, in the batch process, a resin solution may be applied on the support and dried to form a film substrate, and an element may be formed on the film substrate. Since the current process equipment for glass substrates can be used, it is advantageous in terms of cost. Is.
ガラスに匹敵する高耐熱性、低熱膨張、および高透明性を実現可能な樹脂材料として、耐熱性に優れるポリイミド系材料が検討されている。剛直な構造のモノマーや脂環式モノマーを用いたポリイミドは、透明性が高く、低熱膨張性を示すことが知られている（特許文献１、特許文献２）。また、ポリイミド前駆体としてのポリアミド酸にシリコーンオイルを添加してイミド化を行うことにより、得られるポリイミドフィルムが基材への高い密着性を示すことが知られている（特許文献３）。 As a resin material capable of achieving high heat resistance, low thermal expansion, and high transparency comparable to glass, a polyimide-based material having excellent heat resistance is being studied. Polyimides using a monomer having a rigid structure or an alicyclic monomer are known to have high transparency and low thermal expansion (Patent Documents 1 and 2). Further, it is known that the obtained polyimide film exhibits high adhesion to a substrate by adding silicone oil to polyamic acid as a polyimide precursor to perform imidization (Patent Document 3).
ポリイミド基板をバッチプロセスに適用するためには、高耐熱性、低熱膨張、および高透明性に加えて、素子形成プロセスにおいて支持体として用いられるガラスとの適度の接着性を示し、かつ素子形成後にガラス支持体から容易に剥離できることが求められる。しかしながら、上記特許文献１～３に開示のポリイミド材料は、これらすべての要求特性を同時に満足することはできない。 In order to apply the polyimide substrate to the batch process, in addition to high heat resistance, low thermal expansion, and high transparency, it exhibits appropriate adhesion to glass used as a support in the element forming process, and after element forming. It is required that it can be easily peeled off from the glass support. However, the polyimide materials disclosed in Patent Documents 1 to 3 cannot satisfy all of these required characteristics at the same time.
上記に鑑みて、本発明は、高耐熱性、低熱膨張性、および高透明性を有し、かつ、支持体であるガラスと適度な密着性を示すポリイミド、およびその前駆体としてのポリアミド酸の提供を目的とする。 In view of the above, the present invention relates to polyimide having high heat resistance, low thermal expansion, and high transparency and exhibiting appropriate adhesion to glass as a support, and polyamic acid as a precursor thereof. The purpose is to provide.
本願発明者らは、ポリマー骨格中に剛直な構造および脂環構造を導入し、さらにシロキサン結合を有するモノマー成分を併用することにより、上記特性を満足するポリイミド、およびその前駆体としてのポリアミド酸が得られることを見出した。 The inventors of the present application have introduced a rigid structure and an alicyclic structure into the polymer skeleton, and by using a monomer component having a siloxane bond in combination, a polyimide satisfying the above characteristics and a polyamic acid as a precursor thereof can be obtained. I found that I could get it.
本発明のポリアミド酸は、一般式１で表される構成単位、および一般式２で表される構成単位を含有する。 The polyamic acid of the present invention contains a structural unit represented by the general formula 1 and a structural unit represented by the general formula 2.
本発明のポリイミドは、一般式Iで表される構成単位、および一般式IIで表される構成単位を端有する。 The polyimide of the present invention has a structural unit represented by the general formula I and a structural unit represented by the general formula II.
一般式１および一般式IにおけるＡ、ならびに一般式２および一般式IIにおけるＢは、いずれも４価の芳香族基である。一般式２および一般式IIにおいて、Ｒ１およびＲ２は、それぞれ独立に２価の炭化水素基であり、ｎは１～５の整数である。 A in the general formula 1 and I, and B in the general formula 2 and the general formula II are all tetravalent aromatic groups. In the general formula 2 and the general formula II, R 1 and R 2 are independently divalent hydrocarbon groups, and n is an integer of 1 to 5.
４価の芳香族基ＡおよびＢは、いずれも芳香族テトラカルボン酸二無水物の残基であり、好ましくは、ビフェニル－３，３’，４，４’－テトライル基である。Ｒ１およびＲ２は、それぞれ独立に、メチレン基、エチレン基、またはプロピレン基であることが好ましく、中でもプロピレン基であることが特に好ましい。ｎは１～３であることがより好ましく、１であることが最も好ましい。 The tetravalent aromatic groups A and B are both residues of the aromatic tetracarboxylic acid dianhydride, preferably a biphenyl-3,3', 4,4'-tetrayl group. Each of R 1 and R 2 is preferably a methylene group, an ethylene group, or a propylene group independently, and particularly preferably a propylene group. n is more preferably 1 to 3, and most preferably 1.
すなわち、本発明のポリアミド酸は、好ましくは、下記の式１Ａで表される構成単位および下記の式２Ｃで表される構成単位を含有し、本発明のポリイミドは、好ましくは下記の式IＡで表される構成単位および下記の式IIＣで表される構成単位を含有する。 That is, the polyamic acid of the present invention preferably contains a structural unit represented by the following formula 1A and a structural unit represented by the following formula 2C, and the polyimide of the present invention preferably contains the structural unit represented by the following formula IA. It contains a structural unit represented and a structural unit represented by the following formula IIC.
本発明は、上記のポリイミドを含有するポリイミド基板に関する。例えば、上記のポリアミド酸と有機溶媒とを含有するポリアミド酸溶液を支持体上に塗布し、有機溶媒の除去およびポリアミド酸のイミド化を行うことにより、ポリイミド基板が得られる。このポリイミド基板は、支持体に密着積層されたポリイミド膜として形成される。ポリアミド酸溶液を塗布する支持体としては、例えばガラスが用いられる。 The present invention relates to a polyimide substrate containing the above-mentioned polyimide. For example, a polyimide substrate can be obtained by applying a polyamic acid solution containing the above polyamic acid and an organic solvent onto a support, removing the organic solvent, and imidizing the polyamic acid. This polyimide substrate is formed as a polyimide film closely laminated on a support. As the support to which the polyamic acid solution is applied, for example, glass is used.
本発明のポリアミド酸から得られるポリイミドは、高耐熱性、低熱膨張性、および高透明性に加えて、ガラス等の支持体への適度な密着性を有する。そのため、バッチプロセスにおいて支持体への適度な密着性が要求される電子デバイス用基板材料として好適である。 The polyimide obtained from the polyamic acid of the present invention has high heat resistance, low thermal expansion, and high transparency, as well as appropriate adhesion to a support such as glass. Therefore, it is suitable as a substrate material for electronic devices, which requires appropriate adhesion to a support in a batch process.
［ポリアミド酸およびポリイミドの構造］
本発明のポリアミド酸は、以下の一般式１で表される構成単位および一般式２で表される構成単位を含む。
[Structure of polyamic acid and polyimide]
The polyamic acid of the present invention includes a structural unit represented by the following general formula 1 and a structural unit represented by the general formula 2.
本発明のポリイミドは、以下の一般式Iで表される構成単位および一般式IIで表される構成単位を含み、例えば上記の構造１および構造２を有するポリアミド酸をイミド化することにより得られる。 The polyimide of the present invention contains a structural unit represented by the following general formula I and a structural unit represented by the general formula II, and is obtained, for example, by imidizing a polyamic acid having the above structure 1 and structure 2. ..
上記一般式１および上記一般式IにおけるＡ、ならびに上記一般式２および上記一般式IIにおけるＢは、いずれも４価の芳香族基である。芳香族基は、単一の芳香族環を有するものでもよく、複数の芳香族環が結合したものでもよく、縮合多環でもよい。上記一般式２および上記一般式IIにおいて、Ｒ１およびＲ２はそれぞれ独立に２価の炭化水素基であり、ｎは１～５の整数である。 A in the general formula 1 and the general formula I, and B in the general formula 2 and the general formula II are all tetravalent aromatic groups. The aromatic group may have a single aromatic ring, may be a combination of a plurality of aromatic rings, or may be a fused polycycle. In the general formula 2 and the general formula II, R 1 and R 2 are independently divalent hydrocarbon groups, and n is an integer of 1 to 5.
上記一般式１の構成単位および上記一般式２の構成単位を有するポリアミド酸をイミド化することにより、一般式Iの構成単位および一般式IIの構成単位を有するポリイミドが得られる。この構造を有するポリイミドは、ガラスとの密着性に優れるため、バッチプロセスでの樹脂フィルム基板の形成、およびフィルム基板上への素子の形成プロセスへの利用に適している。 By imidizing the polyamic acid having the structural unit of the general formula 1 and the structural unit of the general formula 2, a polyimide having the structural unit of the general formula I and the structural unit of the general formula II can be obtained. Since the polyimide having this structure has excellent adhesion to glass, it is suitable for use in the process of forming a resin film substrate in a batch process and the process of forming an element on a film substrate.
上記ＡおよびＢは、好ましくは芳香族テトラカルボン酸二無水物の残基である。芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、３，３’,４，４－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，２，５，６－ナフタレンテトラカルボン酸二無水物、４，４’－オキシジフタル酸無水物、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、９，９’－ビス［４－（３，４－ジカルボキシフェノキシ）フェニル］フルオレン二無水物、３，３’，４，４′－ビフェニルエーテルテトラカルボン酸二無水物、２，３，５，６－ピリジンテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、４，４’－スルホニルジフタル酸二無水物、パラテルフェニル－３，４，３’，４’－テトラカルボン酸二無水物、メタテルフェニル－３，３’，４，４’－テトラカルボン酸二無水物、３，３’，４，４’－ジフェニルエーテルテトラカルボン酸二無水物等が挙げられるが、これらに限定されるものではない。一般式１および一般式IにおけるＡと、一般式２および一般式IIにおけるＢとは、同一でもよく異なっていてもよい。 The above A and B are preferably residues of aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4-biphenyltetracarboxylic acid dianhydride, and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride. Anhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetra Carboxydic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, 9, 9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,3', 4,4 ′ -Biphenyl ether tetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 4,4'-sulfonyldi Phthalate dianhydride, paratelphenyl-3,4,3', 4'-tetracarboxylic acid dianhydride, metatelphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, 3, Examples thereof include, but are not limited to, 3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride. A in general formulas 1 and I and B in general formulas 2 and II may be the same or different.
高透明性かつ低線膨張係数のポリイミドを得られることから、Ａは、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物の残基（下記の化学式で表されるビフェニル－３，３’，４，４’－テトライル基）であることが特に好ましい。 Since a polyimide having high transparency and a low linear expansion coefficient can be obtained, A is a residue of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (biphenyl-3 represented by the following chemical formula). , 3', 4,4'-tetrayl group) is particularly preferable.
すなわち、一般式１の構成単位は、下記の式１Ａで表されるアミド酸構成単位であることが好ましく、一般式Iの構成単位は、下記の式IＡで表されるイミド構成単位であることが好ましい。これらの構成単位は、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物と１，４－シクロヘキサンジアミンとから得られる。 That is, the structural unit of the general formula 1 is preferably the amic acid structural unit represented by the following formula 1A, and the structural unit of the general formula I is the imide structural unit represented by the following formula IA. Is preferable. These building blocks are obtained from 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 1,4-cyclohexanediamine.
高透明性かつ低線膨張係数のポリイミドを得られることから、Ｂは、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物の残基であることが特に好ましい。すなわち、一般式２で表される構成単位は、下記の一般式２Ａで表されるアミド酸構成単位であることが好ましく、一般式IIで表される構成単位は、下記の一般式IIＡで表されるイミド構成単位であることが好ましい。これらの構成単位は、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物とシロキサン構造含有ジアミンとから得られる。 It is particularly preferable that B is a residue of 3,3', 4,4'-biphenyltetracarboxylic dianhydride because a polyimide having high transparency and a low linear expansion coefficient can be obtained. That is, the structural unit represented by the general formula 2 is preferably the amic acid structural unit represented by the following general formula 2A, and the structural unit represented by the general formula II is represented by the following general formula IIA. It is preferable that it is an imide constituent unit to be formed. These building blocks are obtained from 3,3', 4,4'-biphenyltetracarboxylic dianhydride and siloxane structure-containing diamines.
前述のように、ＡとＢは同一でもよい。ポリイミドフィルムの高透明性と低線膨張係数とを同時に実現する観点から、ＡおよびＢは、いずれもビフェニル－３，３’，４，４’－テトライル基であることが好ましい。 As described above, A and B may be the same. From the viewpoint of simultaneously achieving high transparency and a low linear expansion coefficient of the polyimide film, A and B are preferably biphenyl-3,3', 4,4'-tetrayl groups.
ポリアミド酸の重合時の反応性に優れ、かつポリイミドが低熱膨張性を示すことから、上記一般式２および上記一般式IIにおけるＲ１およびＲ２は、それぞれ独立に、メチレン基、エチレン基、またはプロピレン基であることが好ましく、中でもプロピレン基であることが特に好ましい。ポリアミド酸が高い溶解性を示し、かつポリイミドフィルムが高透明性を示すことから、上記一般式２および上記一般式IIにおけるｎは、１～５であることが好ましく、１～３であることがより好ましく、１であることが最も好ましい。 Since the reactivity of the polyamic acid during polymerization is excellent and the polyimide exhibits low thermal expansion, R 1 and R 2 in the general formula 2 and the general formula II are independently methylene group, ethylene group, or It is preferably a propylene group, and particularly preferably a propylene group. Since the polyamic acid exhibits high solubility and the polyimide film exhibits high transparency, n in the general formula 2 and the general formula II is preferably 1 to 5, preferably 1 to 3. More preferably, it is most preferably 1.
すなわち、一般式２の構成単位は、下記の一般式２Ｂで表されるアミド酸構成単位であることが好ましく、一般式IIの構成単位は、下記の一般式IIBで表されるイミド構成単位であることが好ましい。これらの構成単位は、芳香族テトラカルボン酸二無水物とジアミン成分としての１，３－ビス（３－アミノプロピル）テトラメチルジシロキサンとから得られる。 That is, the structural unit of the general formula 2 is preferably the amic acid structural unit represented by the following general formula 2B, and the structural unit of the general formula II is the imide structural unit represented by the following general formula IIB. It is preferable to have. These building blocks are obtained from aromatic tetracarboxylic acid dianhydride and 1,3-bis (3-aminopropyl) tetramethyldisiloxane as a diamine component.
前述のように、一般式２および一般式IIにおける４価の芳香族基Ｂはビフェニル－３，３’，４，４’－テトライル基であることが好ましい。したがって、一般式２の構成単位は、下記の式２Ｃで表されるアミド酸構成単位であることが特に好ましく、一般式IIの構成単位は、下記の式IICで表されるイミド構成単位であることが特に好ましい。これらの構成単位は、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物と１，３－ビス（３－アミノプロピル）テトラメチルジシロキサンとから得られる。 As described above, the tetravalent aromatic group B in the general formula 2 and the general formula II is preferably a biphenyl-3,3', 4,4'-tetrayl group. Therefore, the structural unit of the general formula 2 is particularly preferably the amic acid structural unit represented by the following formula 2C, and the structural unit of the general formula II is the imide structural unit represented by the following formula IIC. Is particularly preferred. These building blocks are obtained from 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
ポリイミドフィルムに、高耐熱性、低熱膨張性、高透明性、およびガラスとの適度な密着性を持たせる観点から、ポリイミド中の一般式Iで表される構成単位と一般式IIで表される構成単位との合計は、ポリイミド全量に対して、８０モル％以上が好ましく、９０モル％以上がより好ましく、９５モル％以上が特に好ましい。一般式Iで表される構成単位と一般式IIで表される構成単位との合計を上記範囲とするためには、前駆体であるポリアミド酸中の一般式１で表される構成単位と一般式２で表される構成単位との合計が、ポリアミド酸全量に対して、８０モル％以上であることが好ましく、９０モル％以上であることがより好ましく、９５モル％以上であることが特に好ましい。 From the viewpoint of giving the polyimide film high heat resistance, low thermal expansion, high transparency, and appropriate adhesion to glass, it is represented by the structural unit represented by the general formula I and the general formula II in the polyimide. The total with the constituent units is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more with respect to the total amount of polyimide. In order to make the total of the structural unit represented by the general formula I and the structural unit represented by the general formula II within the above range, the structural unit represented by the general formula 1 and the general formula 1 in the polyamic acid as a precursor are used. The total with the structural unit represented by the formula 2 is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more with respect to the total amount of polyamic acid. preferable.
ポリイミドのモル数とは、ポリイミドを構成する全ジアミン由来の構成単位のモル数である。ポリアミド酸のモル数とは、ポリアミド酸を構成する全ジアミン由来構成単位のモル数である。ポリイミドおよびポリアミド酸は、ジアミン由来の構成単位と酸二無水物由来の構成単位を等モル有するため、ポリイミドおよびポリアミド酸では、全ジアミン由来の構成単位のモル数は、全酸二無水物由来の構成単位のモル数に等しい。 The number of moles of polyimide is the number of moles of structural units derived from all diamines constituting polyimide. The number of moles of polyamic acid is the number of moles of all diamine-derived structural units constituting the polyamic acid. Since polyimide and polyamic acid have equimolars of diamine-derived structural units and acid dianhydride-derived structural units, in polyimide and polyamic acid, the number of moles of total diamine-derived structural units is derived from total acid dianhydride. Equal to the number of moles in the building block.
高透明性および低熱膨張性に加えて、支持体との適度の密着性を有するポリイミドを得る観点から、ポリイミド中の一般式Iで表される構成単位のモル数ＭＡと一般式IIで表される構成単位のモル数ＭＢとの比ＭＡ／ＭＢは、９５．０／５．０～９９．９／０．１の範囲であることが好ましい。すなわち、本発明のポリイミドは、ジアミン成分の大半が１，４－シクロヘキサンジアミンであり、１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン等のシロキサン構造含有ジアミンを少量含むことが好ましい。ジアミン成分に少量のシロキサン構造を導入することにより、ガラス等の支持体へのポリイミドの密着性が向上する傾向がある。そのため、支持体上にポリアミド酸溶液を塗布してイミド化したとき、ポリイミドと支持体との間の剥離または浮きを抑制できる。 From the viewpoint of obtaining a polyimide having appropriate adhesion to a support in addition to high transparency and low thermal expansion, the number of moles MA of the structural unit represented by the general formula I in the polyimide and the general formula II are used. The ratio MA / MB to the number of moles MB of the constituent unit is preferably in the range of 95.0 / 5.0 to 99.9 / 0.1. That is, it is preferable that the polyimide of the present invention contains most of the diamine components of 1,4-cyclohexanediamine and contains a small amount of siloxane structure-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane. By introducing a small amount of siloxane structure into the diamine component, the adhesion of polyimide to a support such as glass tends to be improved. Therefore, when the polyamic acid solution is applied onto the support and imidized, peeling or floating between the polyimide and the support can be suppressed.
シロキサン構造の含有量の増大に伴ってガラス等との密着性が向上する傾向がある。一方、密着性が過度に高いと、支持体からポリイミド膜の剥離が困難となったり、剥離時に寸法変化や不透明化を生じる場合がある。ＭＡ／ＭＢが９５．０／５．０以上であれば、ポリイミド膜上に電子素子等を形成した後の支持体からのポリイミド膜の剥離を問題なく実施可能である。また、ＭＡ／ＭＢが９５．０／５．０以上であれば、ポリイミド膜の低熱膨張特性および高透明性を維持できる。 As the content of the siloxane structure increases, the adhesion to glass or the like tends to improve. On the other hand, if the adhesion is excessively high, it may be difficult to peel the polyimide film from the support, or dimensional change or opacity may occur at the time of peeling. When M A / MB is 95.0 / 5.0 or more, it is possible to peel off the polyimide film from the support after forming an electronic element or the like on the polyimide film without any problem. Further, when MA / MB is 95.0 / 5.0 or more, the low thermal expansion characteristics and high transparency of the polyimide film can be maintained.
ＭＡ／ＭＢは、９６．０／４．０～９９．８／０．２がより好ましく、９７．０／３．０～９９．７／０．３がさらに好ましく、９８．０／２．０～９９．６／０．４が特に好ましく、９９．０／１．０～９９．５／０．５が最も好ましい。 The MA / MB is more preferably 96.0 / 4.0 to 99.8 / 0.2, further preferably 97.0 / 3.0 to 99.7 / 0.3, and 98.0 / 2. 9.0 to 99.6 / 0.4 is particularly preferable, and 99.0 / 1.0 to 99.5 / 0.5 is most preferable.
ポリイミド中の一般式Iで表される構成単位と一般式IIで表される構成単位との比率を上記範囲とするためには、前駆体であるポリアミド酸中の一般式１で表される構成単位のモル数ｍＡと一般式２で表される構成単位のモル数ｍＢとの比ｍＡ／ｍＢが、９５．０／５．０～９９．９／０．１の範囲であることが好ましく、９６．０／４．０～９９．８／０．２がより好ましく、９７．０／３．０～９９．７／０．３がさらに好ましく、９８．０／２．０～９９．６／０．４が特に好ましく、９９．０／１．０～９９．６／０．４が最も好ましい。 In order to keep the ratio of the structural unit represented by the general formula I in the polyimide and the structural unit represented by the general formula II within the above range, the configuration represented by the general formula 1 in the precursor polyamic acid is used. The ratio mA / MB of the number of moles mA of the unit to the number of moles mA B of the constituent unit represented by the general formula 2 is in the range of 95.0 / 5.0 to 99.9 / 0.1. It is preferably 96.0 / 4.0 to 99.8 / 0.2, more preferably 97.0 / 3.0 to 99.7 / 0.3, and even more preferably 98.0 / 2.0 to 9. 99.6 / 0.4 is particularly preferable, and 99.0 / 1.0 to 99.6 / 0.4 is most preferable.
本発明のポリアミド酸およびポリイミドは、ゲルパーミレーションクロマトグラフィー（ＧＰＣ）によるポリエチレンオキシド換算の重量平均分子量が、１０，０００～５００，０００であることが好ましく、２０，０００～３００，０００あることがより好ましく、３０，０００～２００，０００であることがさらに好ましい。重量平均分子量が１０，０００以上であれば、ポリアミド酸およびポリイミドを塗膜またはフィルムとすることが可能となる。一方、重量平均分子量が５００，０００以下であると、溶媒に対して十分な溶解性を示すため、表面が平滑で膜厚が均一な塗膜またはフィルムが得られやすい。 The polyamic acid and polyimide of the present invention preferably have a polyethylene oxide equivalent weight average molecular weight of 10,000 to 500,000 by gel permeation chromatography (GPC), preferably 20,000 to 300,000. More preferably, it is more preferably 30,000 to 200,000. When the weight average molecular weight is 10,000 or more, the polyamic acid and the polyimide can be used as a coating film or a film. On the other hand, when the weight average molecular weight is 500,000 or less, sufficient solubility in a solvent is exhibited, so that a coating film or film having a smooth surface and a uniform film thickness can be easily obtained.
［ポリアミド酸およびポリイミドの合成］
上記の構造Iおよび構造IIを含むポリイミドは、公知の方法により得られる。ポリイミドは、ポリアミド酸やポリイミドエステル等の前躯体を経由する合成法、および前躯体を経由しない合成法により合成できる。モノマーの入手性および重合の簡便さから、前駆体としてのポリアミド酸のイミド化により、ポリイミドを合成することが好ましい。
[Synthesis of polyamic acid and polyimide]
The polyimide containing the above Structure I and Structure II can be obtained by a known method. Polyimide can be synthesized by a synthetic method via a precursor such as polyamic acid or a polyimide ester, or a synthetic method not via a precursor. From the viewpoint of the availability of the monomer and the ease of polymerization, it is preferable to synthesize the polyimide by imidizing the polyamic acid as a precursor.
上記の構造１および構造２を含むポリアミド酸は、有機溶媒中でジアミンとテトラカルボン酸二無水物とを反応させることにより得られる。例えば、ジアミンを、有機溶媒中に溶解またはスラリー状に分散させて、ジアミン溶液とし、テトラカルボン酸二無水物を、有機溶媒に溶解もしくはスラリー状に分散させた溶液または固体の状態で、上記ジアミン溶液中に添加すればよい。テトラカルボン酸二無水物溶液中に、ジアミンを添加してもよい。ジアミンおよびテトラカルボン酸二無水物の溶解および反応は、アルゴン、窒素等の不活性ガス雰囲気中で実施することが好ましい。 The polyamic acid containing the above structures 1 and 2 is obtained by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent. For example, the diamine is dissolved in an organic solvent or dispersed in a slurry to form a diamine solution, and the tetracarboxylic acid dianhydride is dissolved in an organic solvent or dispersed in a slurry in a solution or solid state. It may be added to the solution. Diamine may be added to the tetracarboxylic dianhydride solution. The dissolution and reaction of the diamine and the tetracarboxylic dianhydride are preferably carried out in an atmosphere of an inert gas such as argon or nitrogen.
ポリアミド酸の合成においては、ジアミン成分全量のモル数と、テトラカルボン酸二無水物成分全量のモル数とを、実質上等モルに調整することが好ましい。複数種のジアミンおよび／または複数種のテトラカルボン酸二無水物を用いることにより、複数の構造を有するポリアミド酸が得られる。また、構造の異なるポリアミド酸をブレンドすることにより、構造の異なる複数種の構成単位を有するポリアミド酸を得ることもできる。 In the synthesis of polyamic acid, it is preferable to adjust the number of moles of the total amount of the diamine component and the number of moles of the total amount of the tetracarboxylic acid dianhydride component to substantially the same molar number. By using a plurality of diamines and / or a plurality of tetracarboxylic acid dianhydrides, a polyamic acid having a plurality of structures can be obtained. Further, by blending polyamic acids having different structures, it is also possible to obtain polyamic acids having a plurality of types of structural units having different structures.
テトラカルボン酸二無水物として芳香族テトラカルボン酸二無水物を用い、ジアミンとして１，４－シクロヘキサンジアミンおよびシロキサン構造含有ジアミンを用いることにより、一般式１で表される構成単位および一般式２で表される構成単位を含有するポリアミド酸が得られる。芳香族ジアミンとして３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用い、シロキサン構造含有ジアミンとして１，３－ビス（３－アミノプロピル）テトラメチルジシロキサンを用いることにより、式１Ａで表されるアミド酸構成単位および式１Ｃで表されるアミド酸構成単位を有するポリアミド酸が得られる。１，４－シクロヘキサンジアミンのモル数とシロキサン構造含有ジアミンのモル数の比を、９５．０／５．０～９９．９／０．１の範囲とすることにより、ｍＡ／ｍＢが９５．０／５．０～９９．９／０．１の範囲のポリアミド酸が得られる。 By using an aromatic tetracarboxylic acid dianhydride as the tetracarboxylic acid dianhydride and using 1,4-cyclohexanediamine and a siloxane structure-containing diamine as the diamine, the structural unit represented by the general formula 1 and the general formula 2 can be used. A polyamic acid containing the represented building blocks is obtained. By using 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride as the aromatic diamine and 1,3-bis (3-aminopropyl) tetramethyldisiloxane as the siloxane structure-containing diamine, the formula A polyamic acid having an amidoic acid constituent unit represented by 1A and an amidoic acid constituent unit represented by the formula 1C can be obtained. By setting the ratio of the number of moles of 1,4 - cyclohexanediamine to the number of moles of siloxane structure - containing diamine in the range of 95.0 / 5.0 to 99.9 / 0.1, mA / MB is 95. Polyamic acids in the range of 0.0 / 5.0 to 99.9 / 0.1 can be obtained.
ポリアミド酸の合成反応に使用する有機溶媒は特に限定されない。有機溶媒は、使用するテトラカルボン酸二無水物およびジアミン類を溶解可能であり、かつ重合により生成するポリアミド酸を溶解可能であるものが好ましい。有機溶媒の具体例としては、テトラメチル尿素、Ｎ，Ｎ－ジメチルエチルウレア等のウレア系溶媒；ジメチルスルホキシド、ジフェニルスルホン、テトラメチルスルフォン等のスルホキシドまたはスルホン系溶媒；Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡＣ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ’－ジエチルアセトアミド、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、γ―ブチロラクトン等のエステル系溶媒；ヘキサメチルリン酸トリアミド等のアミド系溶媒；クロロホルム、塩化メチレン等のハロゲン化アルキル系溶媒；ベンゼン、トルエン等の芳香族炭化水素系溶媒；フェノール、クレゾール等のフェノール系溶媒；シクロペンタノン等のケトン系溶媒；テトラヒドロフラン、１，３－ジオキソラン、１，４－ジオキサン、ジメチルエーテル、ジエチルエーテル、ｐ－クレゾールメチルエーテル等のエーテル系溶媒が挙げられる。必要に応じて２種以上の有機溶媒を組合せて用いてもよい。ポリアミド酸の溶解性および反応性を高めるために、ポリアミド酸の合成に使用する有機溶媒は、アミド系溶媒、ケトン系溶媒、エステル系溶媒およびエーテル系溶媒より選択されることが好ましく、特にＤＭＦ、ＤＭＡＣ、ＮＭＰ等のアミド系溶媒が好ましい。 The organic solvent used for the synthetic reaction of polyamic acid is not particularly limited. The organic solvent is preferably one that can dissolve the tetracarboxylic dianhydride and diamines to be used, and can dissolve the polyamic acid produced by the polymerization. Specific examples of the organic solvent include urea-based solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide or sulfone-based solvents such as dimethylsulfoxide, diphenylsulfone and tetramethylsulphon; N, N-dimethylacetamide (DMAC). ), N, N-dimethylformamide (DMF), N, N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone and other ester solvents; amide-based solvents such as hexamethylphosphate triamide. Alkyl halide solvents such as chloroform and methylene chloride; Aromatic hydrocarbon solvents such as benzene and toluene; Phenolic solvents such as phenol and cresol; Ketone solvents such as cyclopentanone; tetrahydrofuran, 1,3-dioxolane , 1,4-Dioxane, dimethyl ether, diethyl ether, p-cresol methyl ether and other ether solvents. If necessary, two or more kinds of organic solvents may be used in combination. In order to enhance the solubility and reactivity of the polyamic acid, the organic solvent used for the synthesis of the polyamic acid is preferably selected from an amide-based solvent, a ketone-based solvent, an ester-based solvent and an ether-based solvent, and in particular, DMF, Amide solvents such as DMAC and NMP are preferred.
ポリアミド酸の合成反応の温度条件は、特に限定されない。ジアミンとテトラカルボン酸二無水物との反応が進行するにつれてポリアミド酸が生成し、反応液の粘度が上昇する。１，４－シクロヘキサンジアミン等の脂環式ジアミンを用いると、塩形成が起こる場合があるため、合成反応の温度を、必要に応じて５０℃～１５０℃の範囲としてもよい。塩が溶解し、重合反応が進行しはじめた後は、ポリアミド酸の解重合による分子量低下を抑制するために、温度を８０℃以下とすることが好ましく、０℃～５０℃とすることがより好ましい。反応時間は１０分～３０時間の範囲で任意に設定すればよい。 The temperature conditions for the synthetic reaction of polyamic acid are not particularly limited. As the reaction between the diamine and the tetracarboxylic dianhydride proceeds, polyamic acid is produced and the viscosity of the reaction solution increases. When an alicyclic diamine such as 1,4-cyclohexanediamine is used, salt formation may occur. Therefore, the temperature of the synthesis reaction may be in the range of 50 ° C to 150 ° C, if necessary. After the salt has dissolved and the polymerization reaction has begun to proceed, the temperature is preferably 80 ° C. or lower, more preferably 0 ° C. to 50 ° C., in order to suppress the decrease in molecular weight due to depolymerization of the polyamic acid. preferable. The reaction time may be arbitrarily set in the range of 10 minutes to 30 hours.
有機溶媒中でジアミンとテトラカルボン酸二無水物とを重合することにより、ポリアミド酸と有機溶媒とを含むポリアミド酸溶液が得られる。この重合溶液は、そのままポリアミド酸溶液として使用できる。また、重合溶液から溶媒の一部を除去したり、溶媒を添加することにより、ポリアミド酸の濃度および溶液の粘度を調整してもよい。添加する溶媒は、ポリアミド酸の重合に用いた溶媒と異なっていてもよい。また、重合溶液から溶媒を除去して得られた固体のポリアミド酸樹脂を溶媒に溶解してポリアミド酸溶液を調製してもよい。ポリアミド酸溶液の有機溶媒としては、ポリアミド酸の溶解性が高いものが好ましく、ポリアミド酸の合成に使用する有機溶媒として先に例示の有機溶媒を使用できる。中でも、ＤＭＦ、ＤＭＡＣ、ＮＭＰ等のアミド系溶媒が好ましい。 By polymerizing diamine and tetracarboxylic acid dianhydride in an organic solvent, a polyamic acid solution containing the polyamic acid and the organic solvent can be obtained. This polymerization solution can be used as it is as a polyamic acid solution. Further, the concentration of the polyamic acid and the viscosity of the solution may be adjusted by removing a part of the solvent from the polymerization solution or adding the solvent. The solvent to be added may be different from the solvent used for the polymerization of the polyamic acid. Alternatively, a solid polyamic acid resin obtained by removing the solvent from the polymerization solution may be dissolved in the solvent to prepare a polyamic acid solution. As the organic solvent of the polyamic acid solution, one having high solubility of the polyamic acid is preferable, and the organic solvent exemplified above can be used as the organic solvent used for the synthesis of the polyamic acid. Of these, amide-based solvents such as DMF, DMAC, and NMP are preferable.
ポリアミド酸を脱水閉環することにより、イミド化が行われる。脱水閉環は、共沸溶媒を用いた共沸法、熱的手法または化学的手法により行われる。溶液の状態でイミド化を行う場合は、イミド化剤および／または脱水触媒をポリアミド酸溶液に添加して、化学的イミド化を行うことが好ましい。イミド化剤は特に限定されないが、３級アミンを用いることが好ましく、中でも複素環式の３級アミンが好ましい。複素環式の３級アミンとしては、ピリジン、ピコリン、キノリン、イソキノリン、イミダゾール類等が挙げられる。脱水触媒としては、無水酢酸、プロピオン酸無水物、ｎ－酪酸無水物、安息香酸無水物、トリフルオロ酢酸無水物、γ―バレロラクトン等が挙げられる。 Imidization is performed by dehydrating and ring-closing the polyamic acid. Dehydration ring closure is performed by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method. When imidization is performed in the state of a solution, it is preferable to add an imidizing agent and / or a dehydration catalyst to the polyamic acid solution to perform chemical imidization. The imidizing agent is not particularly limited, but it is preferable to use a tertiary amine, and a heterocyclic tertiary amine is particularly preferable. Examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline, and imidazoles. Examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, γ-valerolactone and the like.
ポリアミド酸溶液から溶媒を除去してイミド化を行う場合は、加熱により脱水閉環を行う熱イミド化が好ましい。ポリアミド酸を加熱する方法は特に制限されないが、例えば、ガラス板、金属板、ＰＥＴ（ポリエチレンテレフタレート）等の支持体に、ポリアミド酸溶液を塗布した後、８０℃～５００℃の範囲内で熱処理を行えばよい。加熱時間は、脱水閉環を行うポリアミド酸溶液の処理量や加熱温度により異なるが、一般的には、処理温度が最高温度に達してから１分～５時間加熱を行うことが好ましい。ポリアミド酸溶液にイミド化剤および／または脱水触媒を加えて、上記のような方法で加熱してイミド化を行ってもよい。 When imidization is performed by removing the solvent from the polyamic acid solution, thermal imidization in which dehydration ring closure is performed by heating is preferable. The method for heating the polyamic acid is not particularly limited, but for example, after applying the polyamic acid solution to a support such as a glass plate, a metal plate, or PET (polyethylene terephthalate), heat treatment is performed in the range of 80 ° C to 500 ° C. Just do it. The heating time varies depending on the treatment amount of the polyamic acid solution for dehydration ring closure and the heating temperature, but in general, it is preferable to heat for 1 minute to 5 hours after the treatment temperature reaches the maximum temperature. An imidizing agent and / or a dehydration catalyst may be added to the polyamic acid solution and heated by the method as described above for imidization.
ポリアミド酸からポリイミドへのイミド化は、１～１００％の任意の割合で行うことができ、一部がイミド化されたポリアミド酸を合成してもよい。ポリアミド酸からポリイミドへのイミド化が進行すると、有機溶媒への溶解性や溶液の粘度が変化する傾向がある。また、特定のイミド化率でイミド化を停止することは一般に容易ではない。溶液の塗布および乾燥によりフィルムを形成する場合は、溶液の粘度やチクソトロピーが膜厚の均一性に影響を及ぼす。そのため、プロセスの安定性を考慮すると、ポリアミド酸にはイミド化剤および脱水触媒を添加せずに、イミド化率が略ゼロの状態で支持体上への塗布を行い、支持体上での加熱により溶媒の除去およびイミド化を行うことが好ましい。 The imidization of the polyamic acid to the polyimide can be performed at an arbitrary ratio of 1 to 100%, and a partially imidized polyamic acid may be synthesized. As the imidization of polyamic acid to polyimide progresses, the solubility in organic solvents and the viscosity of the solution tend to change. Also, it is generally not easy to stop imidization at a particular imidization rate. When a film is formed by applying and drying the solution, the viscosity and thixotropy of the solution affect the uniformity of the film thickness. Therefore, considering the stability of the process, the polyamic acid is applied onto the support with an imidization ratio of almost zero without adding an imidizing agent and a dehydration catalyst, and heated on the support. It is preferable to remove and imidize the solvent.
［ポリアミド酸およびポリイミドの用途］
ポリアミド酸およびポリイミドは、そのまま製品や部材の作製に用いてもよい。ポリアミド酸およびポリイミドに、熱硬化性成分、光硬化性成分、非重合性バインダー樹脂、染料、界面活性剤、レベリング剤、可塑剤、シランカップリング剤、微粒子、増感剤等を添加して組成物としてもよい。これらの任意成分の配合割合は、ポリイミドの固形分全体に対し、０．１重量％～９５重量％の範囲であることが好ましい。なお、組成物の固形分とは有機溶媒以外の全成分であり、液状のモノマー成分も固形分に含まれる。
[Use of polyamic acid and polyimide]
Polyamic acid and polyimide may be used as they are in the production of products and members. Composition by adding thermosetting component, photocurable component, non-polymerizable binder resin, dye, surfactant, leveling agent, plasticizer, silane coupling agent, fine particles, sensitizer, etc. to polyamic acid and polyimide. It may be a thing. The blending ratio of these optional components is preferably in the range of 0.1% by weight to 95% by weight with respect to the total solid content of the polyimide. The solid content of the composition is all components other than the organic solvent, and the liquid monomer component is also included in the solid content.
本発明のポリイミドは、透明性および耐熱性に優れるため、ガラス代替用途等の透明基板として使用可能であり、例えば、ＴＦＴ基板、電極基板等の電子デバイス用基板への適用が期待できる。電子デバイスの中でも、液晶表示装置、有機ＥＬ素子、電子ペーパー、タッチパネル等の光透過性を必要とするデバイス用の基板としての使用が好ましい。本発明のポリイミドは、カラーフィルター、反射防止膜、ホログラム等の光学部材または建築材料や構造物の材料としても利用できる。本発明のポリイミドの表面に、金属酸化物や透明電極等の各種無機薄膜を形成していてもよい。無機薄膜は、例えば、スパッタリング法、真空蒸着法およびイオンプレーティング法等のＰＶＤ法、ならびにＣＶＤ法等のドライプロセスにより形成される。 Since the polyimide of the present invention is excellent in transparency and heat resistance, it can be used as a transparent substrate for glass substitute applications, and can be expected to be applied to, for example, a substrate for electronic devices such as a TFT substrate and an electrode substrate. Among electronic devices, it is preferable to use it as a substrate for devices that require light transmission such as liquid crystal displays, organic EL elements, electronic papers, and touch panels. The polyimide of the present invention can also be used as an optical member such as a color filter, an antireflection film, a hologram, or a material for a building material or a structure. Various inorganic thin films such as metal oxides and transparent electrodes may be formed on the surface of the polyimide of the present invention. The inorganic thin film is formed by, for example, a PVD method such as a sputtering method, a vacuum vapor deposition method and an ion plating method, and a dry process such as a CVD method.
［ポリイミド基板および電子デバイスの作製］
本発明のポリイミドは、耐熱性、低熱膨張性、および透明性に加えて、支持体との密着性が良いことから、バッチプロセスで製造される電子デバイスの基板として好ましく用いられる。バッチプロセスでは、支持体上にポリイミド膜（基板）を形成し、その上に素子を形成した後、素子が形成されたポリイミド基板を支持体から剥離することにより電子デバイスが得られる。
[Manufacturing of polyimide substrate and electronic device]
The polyimide of the present invention is preferably used as a substrate for an electronic device manufactured by a batch process because it has good adhesion to a support in addition to heat resistance, low thermal expansion, and transparency. In the batch process, an electronic device is obtained by forming a polyimide film (substrate) on a support, forming an element on the polyimide film, and then peeling off the polyimide substrate on which the element is formed from the support.
支持体上にポリアミド酸溶液を塗布し、加熱による乾燥およびイミド化を行うことにより、支持体上に密着積層されたポリイミド膜（ポリイミド基板）が得られる。ポリイミド基板の厚みは、１～２００μｍ程度であり、５～１００μｍ程度が好ましい。 By applying a polyamic acid solution on the support, drying and imidizing by heating, a polyimide film (polyimide substrate) closely laminated on the support can be obtained. The thickness of the polyimide substrate is about 1 to 200 μm, preferably about 5 to 100 μm.
ポリアミド酸溶液を塗布する支持体としては、ガラス基板；ＳＵＳ等の金属基板または金属ベルト；ポリエチレンテレフタレート、ポリカーボネート、ポリアクリレート、ポリエチレンナフタレート、トリアセチルセルロース等の樹脂フィルム等が挙げられる。現行のバッチタイプのデバイス製造プロセスに適応させるためには、支持体としてガラス基板を用いることが好ましい。 Examples of the support to which the polyamic acid solution is applied include a glass substrate; a metal substrate such as SUS or a metal belt; a resin film such as polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate, and triacetyl cellulose. In order to adapt to the current batch type device manufacturing process, it is preferable to use a glass substrate as a support.
ガラス等の支持体にポリアミド酸溶液を塗布し、加熱すると、溶媒の蒸発とともにポリアミド酸のイミド化が始まり、有機溶媒およびイミド化（ポリアミド酸の脱水）により生成した水がポリアミド酸溶液から揮発する。このとき、一部の水および／または有機溶媒が揮発せずに、支持体とイミド化中の樹脂膜との間に滞留し、支持体と樹脂膜との界面での剥離の原因となる。支持体と樹脂膜との界面に滞留した水および／または有機溶媒は、その後、高温で加熱する工程において、ポリイミド膜を透過して排出され、剥離または浮きが生じた部分に気泡が残存する。このような気泡が生じると、ポリイミド基板上に素子を形成する際に不具合を生じる。特に、薄型化または小型化されたデバイスでは、細かい剥離または浮きでも、素子等の形成または実装に大きな影響を与える。 When a polyamic acid solution is applied to a support such as glass and heated, imidization of the polyamic acid begins with the evaporation of the solvent, and the organic solvent and the water produced by imidization (dehydration of the polyamic acid) volatilize from the polyamic acid solution. .. At this time, a part of the water and / or the organic solvent does not volatilize and stays between the support and the resin film being imidized, which causes peeling at the interface between the support and the resin film. The water and / or the organic solvent retained at the interface between the support and the resin film is subsequently discharged through the polyimide film in the step of heating at a high temperature, and bubbles remain in the portion where peeling or floating occurs. When such bubbles are generated, a problem occurs when the element is formed on the polyimide substrate. In particular, in a device that has been made thinner or smaller, even fine peeling or floating has a great influence on the formation or mounting of an element or the like.
シロキサン構造を有する本発明のポリアミド酸およびポリイミドは、ガラスとの密着性が高いため、支持体上での溶媒の乾燥およびイミド化の際に、ガラス支持体と樹脂膜との界面への有機溶媒や水の滞留に起因する浮きや剥離が生じ難い。そのため、支持体上に密着積層されたポリイミド基板上への素子の形成や実装を正確に実施できる。また、ポリイミド中の脂環式構造（一般式I）とシロキサン構造（一般式II）との比率を調整することにより、素子を形成後のポリイミド基板の支持体からの剥離を容易に実施できる。 Since the polyamic acid and polyimide of the present invention having a siloxane structure have high adhesion to glass, an organic solvent to the interface between the glass support and the resin film during drying and imidization of the solvent on the support It is unlikely that floating or peeling will occur due to the retention of water or water. Therefore, it is possible to accurately form and mount the element on the polyimide substrate closely laminated on the support. Further, by adjusting the ratio of the alicyclic structure (general formula I) and the siloxane structure (general formula II) in the polyimide, the polyimide substrate can be easily peeled off from the support after the element is formed.
支持体上に密着積層されたポリイミド膜（ポリイミド基板）は、支持体からの９０°ピール強度が、０．０８～５．００Ｎ／ｃｍがあることが好ましく、０．０９～４．００Ｎ／ｃｍであることがより好ましく、０．１０～３．５Ｎ／ｃｍであることがさらに好ましい。上記の密着性を有する場合、素子の形成および実装プロセスにおいて剥離が生じ難く、かつ素子の形成および実装後の支持体からの剥離が容易である。９０°ピール強度は、後述の実施例に記載の方法により測定できる。 The polyimide film (polyimide substrate) closely laminated on the support preferably has a 90 ° peel strength from the support of 0.08 to 5.00 N / cm, preferably 0.09 to 4.00 N / cm. Is more preferable, and 0.10 to 3.5 N / cm is further preferable. When the device has the above-mentioned adhesion, peeling is unlikely to occur in the process of forming and mounting the device, and peeling from the support after forming and mounting the device is easy. The 90 ° peel strength can be measured by the method described in Examples described later.
ポリイミド膜の透明性は、例えば、全光線透過率およびヘイズにより評価できる。ポリイミド膜の全光線透過率は、８０％以上であることが好ましく、８５％以上であることがより好ましい。ヘイズは、２．０％以下であることが好ましく、１．０％以下であることがより好ましい。ポリイミドは短波長側の光を吸収しやすい傾向があり、膜自体が黄色に着色することが多い。着色の少ない膜とするためには、ポリイミド膜の波長４５０ｎｍでの光透過率は７０％以上が好ましく、７５％以上がより好ましい。本発明のポリイミドは、膜厚１０μｍの膜を形成した際の全光線透過率、ヘイズ、および波長４５０ｎｍにおける光透過率が上記範囲であることが好ましい。 The transparency of the polyimide film can be evaluated by, for example, the total light transmittance and the haze. The total light transmittance of the polyimide film is preferably 80% or more, more preferably 85% or more. The haze is preferably 2.0% or less, more preferably 1.0% or less. Polyimide tends to absorb light on the short wavelength side, and the film itself is often colored yellow. In order to obtain a film having less coloring, the light transmittance of the polyimide film at a wavelength of 450 nm is preferably 70% or more, more preferably 75% or more. The polyimide of the present invention preferably has a total light transmittance, haze, and light transmittance at a wavelength of 450 nm when a film having a film thickness of 10 μm is formed in the above range.
本発明のポリイミドを含むポリイミド基板は、線熱膨張が小さく、加熱前後の寸法安定性に優れる。ポリイミド膜の線熱膨張係数は、３０ｐｐｍ／Ｋ以下が好ましく、２０ｐｐｍ／Ｋ以下がより好ましい。線熱膨張係数は、後述の実施例に記載の方法により測定できる。本発明のポリイミドは、膜厚１０μｍの膜を形成した際の線熱膨張係数が上記範囲であることが好ましい。 The polyimide substrate containing the polyimide of the present invention has a small linear thermal expansion and is excellent in dimensional stability before and after heating. The coefficient of linear thermal expansion of the polyimide film is preferably 30 ppm / K or less, more preferably 20 ppm / K or less. The coefficient of linear thermal expansion can be measured by the method described in Examples described later. The polyimide of the present invention preferably has a linear thermal expansion coefficient in the above range when a film having a film thickness of 10 μm is formed.
［ポリアミド酸溶液の調製］
＜実施例１＞
ステンレス製撹拌翼を備える撹拌機および窒素導入管を取り付けた５００ｍＬのガラス製セパラブルフラスコに、トランス－１，４－シクロヘキサンジアミン（ＣＨＤＡ）８．３８ｇ、およびＮ－メチル－２－ピロリドン（ＮＭＰ）１７０．０ｇを仕込み、室温（２３℃）で攪拌して溶解させた。ＣＨＤＡの溶解を目視で確認した後、１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン（ＰＡＭ－Ｅ）を０．０２ｇ添加し、さらに撹拌した。この溶液に、３，３’，４，４’－ビフェニルテトラカルボン酸無水物（ＢＰＤＡ）２１．６１ｇを加え、８０℃で１時間加熱した後、室温で５時間攪拌して、ポリアミド酸溶液を得た。この反応溶液におけるジアミンおよびテトラカルボン酸二無水物の仕込み濃度は、反応溶液全量に対して１５重量％であった。
[Preparation of polyamic acid solution]
<Example 1>
8.38 g of trans-1,4-cyclohexanediamine (CHDA) and N-methyl-2-pyrrolidone (NMP) in a 500 mL glass separable flask equipped with a stirrer equipped with a stainless stirrer and a nitrogen inlet tube. 170.0 g was charged and stirred at room temperature (23 ° C.) to dissolve. After visually confirming the dissolution of CHDA, 0.02 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (PAM-E) was added, and the mixture was further stirred. To this solution, 21.61 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added, heated at 80 ° C. for 1 hour, and then stirred at room temperature for 5 hours to prepare a polyamic acid solution. Obtained. The concentration of diamine and tetracarboxylic dianhydride in this reaction solution was 15% by weight based on the total amount of the reaction solution.
＜実施例２＞
ＣＨＤＡの仕込み量を８．３７ｇ、ＰＡＭ－Ｅの仕込み量を０．０４ｇ、ＢＰＤＡの仕込み量を２１．６０ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 2>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was 8.37 g, the amount of PAM-E charged was 0.04 g, and the amount of BPDA charged was 21.60 g.
＜実施例３＞
ＣＨＤＡの仕込み量を８．３６ｇ、ＰＡＭ－Ｅの仕込み量を０．０６ｇ、ＢＰＤＡの仕込み量を２１．５９ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 3>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was 8.36 g, the amount of PAM-E charged was 0.06 g, and the amount of BPDA charged was 21.59 g.
＜実施例４＞
ＣＨＤＡの仕込み量を８．３３ｇ、ＰＡＭ－Ｅの仕込み量を０．０９ｇ、ＢＰＤＡの仕込み量を２１．５８ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 4>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was 8.33 g, the amount of PAM-E charged was 0.09 g, and the amount of BPDA charged was 21.58 g.
＜実施例５＞
ＣＨＤＡの仕込み量を８．３０ｇ、ＰＡＭ－Ｅの仕込み量を０．１３ｇ、ＢＰＤＡの仕込み量を２１．５６ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 5>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the charging amount of CHDA was changed to 8.30 g, the charging amount of PAM-E was changed to 0.13 g, and the charging amount of BPDA was changed to 21.56 g.
＜実施例６＞
ＣＨＤＡの仕込み量を８．２８ｇ、ＰＡＭ－Ｅの仕込み量を０．１８ｇ、ＢＰＤＡの仕込み量を２１．５４ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 6>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the charging amount of CHDA was changed to 8.28 g, the charging amount of PAM-E was changed to 0.18 g, and the charging amount of BPDA was changed to 21.54 g.
＜実施例７＞
ＣＨＤＡの仕込み量を８．０６ｇ、ＰＡＭ－Ｅの仕込み量を０．５４ｇ、ＢＰＤＡの仕込み量を２１．４０ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 7>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was 8.06 g, the amount of PAM-E charged was 0.54 g, and the amount of BPDA charged was 21.40 g.
＜実施例８＞
ＣＨＤＡの仕込み量を７．８４ｇ、ＰＡＭ－Ｅの仕込み量を０．９０ｇ、ＢＰＤＡの仕込み量を２１．２６ｇに変更したこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Example 8>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was 7.84 g, the amount of PAM-E charged was 0.90 g, and the amount of BPDA charged was 21.26 g.
＜比較例１＞
ＣＨＤＡの仕込み量を８．３９ｇに変更し、ＰＡＭ－Ｅを添加せずにＢＰＤＡ２１．６１ｇを加えたこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Comparative Example 1>
A polyamic acid solution was obtained in the same manner as in Example 1 except that the amount of CHDA charged was changed to 8.39 g and 21.61 g of BPDA was added without adding PAM-E.
＜比較例２＞
比較例１で合成したポリアミド酸溶液に、ポリアミド酸に対して０．１重量％のシランカップリング剤：γ―アミノプロピルトリエトキシシランを添加し、２４時間撹拌して、アルコキシシラン変性ポリアミド酸溶液を調製した。
<Comparative Example 2>
To the polyamic acid solution synthesized in Comparative Example 1, 0.1% by weight of a silane coupling agent: γ-aminopropyltriethoxysilane with respect to the polyamic acid was added, and the mixture was stirred for 24 hours to obtain an alkoxysilane-modified polyamic acid solution. Was prepared.
＜比較例３＞
ＣＨＤＡの仕込み量を８．３６ｇに変更し、ＰＡＭ－Ｅを添加せずに、ＢＰＤＡ２１．３１ｇと、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン酸二無水物（以下、ＢＰＡＦ）０．３３５ｇとを同時に加えたこと以外は、実施例１と同様にしてポリアミド酸溶液を得た。
<Comparative Example 3>
The amount of CHDA charged was changed to 8.36 g, and without adding PAM-E, 21.31 g of BPDA and 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid dianhydride (hereinafter, BPAF). A polyamic acid solution was obtained in the same manner as in Example 1 except that 0.335 g was added at the same time.
＜比較例４＞
ステンレス製撹拌翼を備える撹拌機および窒素導入管を取り付けた５００ｍＬのガラス製セパラブルフラスコに、パラフェニレンジアミン（ＰＤＡ）７．９８ｇおよびＮＭＰ１７０．０ｇを仕込み、室温で攪拌して溶解させた。ＰＤＡの溶解を目視で確認した後、ＰＡＭ－Ｅを０．１９ｇ添加し、さらに撹拌した。その後、ＢＰＤＡ２１．８３ｇを加え、溶解するまで５０℃で攪拌した後、溶液の温度を約９０℃に調整して攪拌を続けて溶液の粘度を下げ、２３℃における粘度が２８，８００ｍＰａ・ｓであるポリアミド酸溶液を得た。
<Comparative Example 4>
7.98 g of paraphenylenediamine (PDA) and 170.0 g of NMP were placed in a 500 mL glass separable flask equipped with a stirrer equipped with a stainless steel stirring blade and a nitrogen introduction tube, and stirred at room temperature to dissolve them. After visually confirming the dissolution of the PDA, 0.19 g of PAM-E was added, and the mixture was further stirred. Then, 21.83 g of BPDA was added and stirred at 50 ° C. until the solution was dissolved. Then, the temperature of the solution was adjusted to about 90 ° C. and stirring was continued to lower the viscosity of the solution, and the viscosity at 23 ° C. was 28,800 mPa · s. A polyamic acid solution was obtained.
＜比較例５＞
ステンレス製撹拌翼を備える撹拌機および窒素導入管を取り付けた５００ｍＬのガラス製セパラブルフラスコに、ＣＨＤＡ８．３４ｇおよびＮＭＰ１７０．０ｇを仕込み、室温で攪拌して溶解させた。ＣＨＤＡの溶解を目視で確認した後、信越シリコーン製の反応性シリコーンオイル：ＫＦ－８０１０（アミン当量：４３０ｇ／ｍｏｌ）を０．１３ｇ添加し、さらに撹拌した。この溶液に、ＢＰＤＡ２１．５３ｇを加え、８０℃で１時間加熱し、その後冷却し、室温（２３℃）で５時間攪拌して、ポリアミド酸溶液を得た。
<Comparative Example 5>
8.34 g of CHDA and 170.0 g of NMP were placed in a 500 mL glass separable flask equipped with a stirrer equipped with a stainless stirrer blade and a nitrogen introduction tube, and the mixture was stirred and dissolved at room temperature. After visually confirming the dissolution of CHDA, 0.13 g of a reactive silicone oil made by Shinetsu Silicone: KF-8010 (amine equivalent: 430 g / mol) was added, and the mixture was further stirred. To this solution, 21.53 g of BPDA was added, heated at 80 ° C. for 1 hour, then cooled, and stirred at room temperature (23 ° C.) for 5 hours to obtain a polyamic acid solution.
＜比較例６＞
ＣＨＤＡの仕込み量を８．３６ｇ、ＢＰＤＡの仕込み量を２１．５０ｇに変更し、反応性シリコーンオイルとして、ＫＦ－８０１０に代えて信越シリコーン製の反応性シリコーンオイル：Ｘ－２２－１６８ＡＳ（酸無水物当量：５００ｇ／ｍｏｌ）０．１５ｇを添加した。これらの変更点以外は、比較例５と同様にしてポリアミド酸溶液を得た。
<Comparative Example 6>
The amount of CHDA charged was changed to 8.36 g, and the amount of BPDA charged was changed to 21.50 g. As the reactive silicone oil, Shinetsu Silicone's reactive silicone oil: X-22-168AS (acid anhydride) was used instead of KF-8010. Equivalent amount: 500 g / mol) 0.15 g was added. Except for these changes, a polyamic acid solution was obtained in the same manner as in Comparative Example 5.
［ポリアミド酸の評価］
＜分子量＞
表１の条件にて重量平均分子量（Ｍｗ）を求めた。
[Evaluation of polyamic acid]
<Molecular weight>
The weight average molecular weight (Mw) was determined under the conditions shown in Table 1.
［ポリイミド膜の作製］
上記の実施例および比較例で得られたポリアミド酸溶液を、固形分濃度が１０％になるようにＮＭＰで希釈した。希釈した溶液を、バーコーターを用いて、１５０ｍｍ×１５０ｍｍの無アルカリガラス板（コーニング社製 イーグルＸＧ、厚さ０．７ｍｍ）上に、乾燥後の厚みが１０μｍになるように流延し、熱風オーブン内で８０℃にて３０分乾燥して、ガラス板上にポリアミド酸の塗膜を形成した。ガラス板とポリアミド酸塗膜との積層体を、窒素雰囲気下で、２０℃から３５０℃まで５℃／分で昇温した後、３５０℃で１時間加熱して、塗膜のイミド化を行い、ポリイミド膜とガラスとの積層体を得た。比較例４のみ、乾燥後の厚みが２０μｍとなるようにポリアミド酸溶液の流延を行い、熱風オーブンでの乾燥温度を１２０℃とし、窒素雰囲気下で昇温速度７℃／分で４５０℃まで昇温を行った後、４５０℃で１０分間加熱してイミド化を実施した。
[Preparation of polyimide film]
The polyamic acid solutions obtained in the above Examples and Comparative Examples were diluted with NMP so that the solid content concentration was 10%. Using a bar coater, the diluted solution is poured onto a 150 mm × 150 mm non-alkali glass plate (Eagle XG manufactured by Corning Inc., thickness 0.7 mm) so that the thickness after drying becomes 10 μm, and hot air is blown. It was dried in an oven at 80 ° C. for 30 minutes to form a coating of polyamic acid on a glass plate. The laminate of the glass plate and the polyamic acid coating film was heated from 20 ° C. to 350 ° C. at 5 ° C./min under a nitrogen atmosphere, and then heated at 350 ° C. for 1 hour to imidize the coating film. , A laminate of a polyimide film and glass was obtained. Only in Comparative Example 4, the polyamic acid solution was cast so that the thickness after drying was 20 μm, the drying temperature in a hot air oven was set to 120 ° C, and the temperature was raised to 450 ° C at a heating rate of 7 ° C / min under a nitrogen atmosphere. After raising the temperature, imidization was carried out by heating at 450 ° C. for 10 minutes.
比較例１では、ガラスとポリイミド膜との間に多数の気泡が確認された。比較例１以外では、ポリイミド膜の剥離による気泡は確認されなかった。一方、実施例８では、ガラスとポリイミド膜との密着性が高く、ガラスから剥離することができなかったため、下記の物性評価は実施しなかった。 In Comparative Example 1, a large number of bubbles were confirmed between the glass and the polyimide film. Except for Comparative Example 1, no bubbles due to peeling of the polyimide film were confirmed. On the other hand, in Example 8, since the adhesion between the glass and the polyimide film was high and the glass could not be peeled off, the following physical property evaluation was not performed.
［ポリイミド膜の評価］
＜ピール強度＞
ガラス板とポリイミド膜との積層体を、２３℃５５％ＲＨの環境下で２４時間静置して調湿した後、ＡＳＴＭ Ｄ１８７６－０１規格に従い、９０°ピール強度を測定した。ポリイミド膜にカッターナイフにて１０ｍｍ幅の切り込みを入れ、東洋精機製引張試験機（ストログラフＶＥＳ１Ｄ）を用いて、２３℃５５％ＲＨ条件下、引張速度５０ｍｍ／分、剥離長さ５０ｍｍにて９０°ピール試験を実施し、剥離強度の平均値をピール強度とした。実施例６および実施例７では、ピール強度がロードセルの最大荷重（５．０Ｎ）を上回っていた。
[Evaluation of polyimide film]
<Peel strength>
The laminate of the glass plate and the polyimide film was allowed to stand for 24 hours in an environment of 23 ° C. and 55% RH to control the humidity, and then the 90 ° peel strength was measured according to the ASTM D1876-01 standard. Make a 10 mm wide notch in the polyimide film with a cutter knife, and use a tensile tester (Strograph VES1D) manufactured by Toyo Seiki Co., Ltd. under 23 ° C. 55% RH conditions, a tensile speed of 50 mm / min, and a peeling length of 50 mm. ° A peel test was carried out, and the average peel strength was taken as the peel strength. In Examples 6 and 7, the peel strength exceeded the maximum load (5.0 N) of the load cell.
＜線熱膨張係数（ＣＴＥ）＞
線熱膨張係数の測定は、日立ハイテクサイエンス社製ＴＭＡ／ＳＳ７１００を用いて（サンプルサイズ：幅３ｍｍ×長さ１０ｍｍ；膜厚を測定し、フィルムの断面積を算出）、荷重２９．４ｍＮとし、１０℃／分で１０℃から３５０℃まで一旦昇温させた後、４０℃／分で降温させ、降温時の１００～３００℃における単位温度あたりの試料の歪の変化量から線膨張係数を求めた。
<Coefficient of linear thermal expansion (CTE)>
The linear thermal expansion coefficient was measured using TMA / SS7100 manufactured by Hitachi High-Tech Science Co., Ltd. (sample size: width 3 mm x length 10 mm; measuring the film thickness and calculating the cross-sectional area of the film) with a load of 29.4 mN. After raising the temperature from 10 ° C to 350 ° C at 10 ° C / min and then lowering the temperature at 40 ° C / min, the linear expansion coefficient is obtained from the amount of change in the strain of the sample per unit temperature at 100 to 300 ° C when the temperature is lowered. rice field.
＜光透過率＞
日本分光社製紫外可視近赤外分光光度計（Ｖ－６５０）を用いて、２００～８００ｎｍにおける光透過率を測定し、４５０ｎｍの波長における光透過率をポリイミド膜の透過率とした。
<Light transmittance>
The light transmittance at 200 to 800 nm was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650) manufactured by JASCO Corporation, and the light transmittance at a wavelength of 450 nm was taken as the transmittance of the polyimide film.
＜ポリイミド膜の全光線透過率（ＴＴ）およびヘイズ＞
日本電色工業製の積分球式ヘイズメーター３００Ａにより、ＪＩＳ Ｋ７１０５－１９８１記載の方法により測定した。
<Total light transmittance (TT) and haze of polyimide film>
It was measured by the method described in JIS K7105-1981 with an integrating sphere type haze meter 300A manufactured by Nippon Denshoku Kogyo.
実施例および比較例のポリアミド酸重合時のモノマー仕込み量（酸二無水物およびジアミンのそれぞれのモル比）、ポリアミド酸の重量平均分子量および変性の有無、ポリイミド膜の膜厚、イミド化時のガラス板からの剥離の有無、ポリイミド膜のガラス板からのピール強度、ならびにポリイミド膜の特性の評価結果を、表２に示す。 Amount of monomer charged during polyamic acid polymerization in Examples and Comparative Examples (molar ratio of acid dianhydride and diamine), weight average molecular weight of polyamic acid and presence / absence of modification, polyimide film film thickness, glass during imidization Table 2 shows the presence or absence of peeling from the plate, the peel strength of the polyimide film from the glass plate, and the evaluation results of the characteristics of the polyimide film.
酸二無水物としてのＢＰＤＡとジアミンとしてのＣＨＤＡから得られた比較例１のポリアミド酸溶液は、ガラス板上への塗布後の熱イミド化の際にガラス板とポリイミド膜との間に多数の気泡が発生し、塗布面積の２５％以上がガラス板から剥離していた。比較例１のポリアミド酸をシランカップリング剤により変性した比較例２では、比較例１に比べるとガラス板との密着性が向上していたが、ピール強度が小さく、密着性は十分といえるものではなかった。酸二無水物として、ＢＰＤＡに１モル％のＢＰＡＦを添加した比較例３においても同様であった。 The polyamic acid solution of Comparative Example 1 obtained from BPDA as an acid dianhydride and CHDA as a diamine had a large number between the glass plate and the polyimide film during thermal imidization after coating on the glass plate. Bubbles were generated, and 25% or more of the coated area was peeled off from the glass plate. In Comparative Example 2 in which the polyamic acid of Comparative Example 1 was modified with a silane coupling agent, the adhesion to the glass plate was improved as compared with Comparative Example 1, but the peel strength was small and the adhesion could be said to be sufficient. It wasn't. The same was true in Comparative Example 3 in which 1 mol% BPAF was added to BPDA as the acid dianhydride.
モノマー成分に反応性シリコーンオイルを添加した比較例５および比較例６では、比較例１に比べるとガラス板との密着性が向上していたが、ピール強度が小さく、密着性は十分ではなかった。また、比較例５および比較例６では、得られたポリイミド膜の線熱膨張係数（ＣＴＥ）が高く寸法安定性が劣っており、透明性が低下していた。 In Comparative Example 5 and Comparative Example 6 in which the reactive silicone oil was added to the monomer component, the adhesion to the glass plate was improved as compared with Comparative Example 1, but the peel strength was small and the adhesion was not sufficient. .. Further, in Comparative Example 5 and Comparative Example 6, the linear thermal expansion coefficient (CTE) of the obtained polyimide film was high, the dimensional stability was inferior, and the transparency was lowered.
ジアミン成分として、ＣＨＤＡに加えてシロキサン構造を有するＰＡＭ－Ｅを用いた実施例１～８は、いずれもガラスに対して良好な密着性を示していた。ＣＨＤＡ／ＰＡＭ－Ｅのモル数の比ｍＡ／ｍＢが９７／３～９９．０／０．１である実施例１～７は、いずれも比較例１と同等の低ＣＴＥおよび高透明性を維持していた。ＣＨＤＡ／ＰＡＭ－Ｅのモル数の比ｍＡ／ｍＢが９５／５である実施例８では、ポリイミド膜の特性評価を行っていないが、ガラス板上に形成されたポリイミド膜の目視では、実施例１～７と同様の透明性を有していた。また、実施例８は実施例７とポリアミド酸およびポリイミドの組成が類似であるため、実施例７と同様の低ＣＴＥおよび高透明性を維持していると推測される。ＣＨＤＡに代えてＰＤＡを用いた比較例４では、実施例１，２等と同等のピール強度を示したが、透明性（特に可視光短波長側）が大幅に低下しており、着色がみられた。 In Examples 1 to 8 in which PAM-E having a siloxane structure was used as the diamine component in addition to CHDA, all showed good adhesion to glass. Examples 1 to 7 in which the ratio mA / MB of the number of moles of CHDA / PAM- E is 97/3 to 99.0 / 0.1 are all the same as those of Comparative Example 1 in low CTE and high transparency. Was maintained. In Example 8 in which the ratio mA / MB of the number of moles of CHDA / PAM - E is 95/5, the characteristics of the polyimide film are not evaluated, but the polyimide film formed on the glass plate is visually observed. It had the same transparency as in Examples 1-7. Further, since the composition of polyamic acid and polyimide is similar to that of Example 7, it is presumed that the same low CTE and high transparency as in Example 7 are maintained. In Comparative Example 4 in which PDA was used instead of CHDA, the peel strength was equivalent to that in Examples 1 and 2, but the transparency (particularly on the short wavelength side of visible light) was significantly reduced, and the coloration was observed. Was done.
実施例１～８では、ＰＡＭ－Ｅの仕込み量の増加に伴ってピール強度が増加し、ガラスとの密着性が向上する傾向がみられた。ガラス板上にポリイミド膜を形成し、必要に応じてポリイミド膜上への素子の形成や実装を行った後に、ガラス板からポリイミド膜を剥離する際の剥離の容易性を考慮すると、シロキサン構造含有ジアミンの使用量は、ジアミン全量に対して５モル％以下が好ましく、１モル％以下が特に好ましいといえる。 In Examples 1 to 8, the peel strength increased as the amount of PAM-E charged increased, and the adhesion to the glass tended to improve. After forming the polyimide film on the glass plate and forming and mounting the element on the polyimide film as necessary, considering the ease of peeling when the polyimide film is peeled from the glass plate, the siloxane structure is contained. It can be said that the amount of diamine used is preferably 5 mol% or less, and particularly preferably 1 mol% or less, based on the total amount of diamine.
上記の実施例と比較例との対比から理解できるように、本発明のポリアミド酸は、ガラス支持体上への膜形成および加熱イミド化の際の加工性が良好であり、ガラス支持体との密着性に優れている。本発明のポリアミド酸のイミド化により得られるポリイミド膜は、１００～３００℃の高温領域においても低熱膨張性を有しており、かつ高透明性を有することから、ガラス代替の透明基板材料としての応用が期待できる。 As can be understood from the comparison between the above Examples and Comparative Examples, the polyamic acid of the present invention has good processability at the time of film formation on the glass support and heat imidization, and has good processability with the glass support. Has excellent adhesion. The polyimide film obtained by imidization of the polyamic acid of the present invention has low thermal expansion even in a high temperature region of 100 to 300 ° C. and has high transparency, so that it can be used as a transparent substrate material as a substitute for glass. Expected to be applied.
Claims (6)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016054094 | 2016-03-17 | ||
| JP2016054094 | 2016-03-17 | ||
| PCT/JP2017/009485 WO2017159538A1 (en) | 2016-03-17 | 2017-03-09 | Polyamide acid, polyamide acid solution, polyimide, polyimide substrate and method for producing polyimide substrate |
| JP2018505879A JPWO2017159538A1 (en) | 2016-03-17 | 2017-03-09 | Polyamic acid, polyamic acid solution, polyimide, polyimide substrate, and production method thereof |
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| JP7027867B2 (en) * | 2016-12-22 | 2022-03-02 | 大日本印刷株式会社 | Surface material for flexible displays |
| WO2018117145A1 (en) * | 2016-12-22 | 2018-06-28 | 大日本印刷株式会社 | Polyimide film, polyimide, polyimide precursor, laminate and surface material for displays |
| JP7281887B2 (en) | 2017-10-19 | 2023-05-26 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide precursor and polyimide |
| US10982048B2 (en) * | 2018-04-17 | 2021-04-20 | Jiaxing Super Lighting Electric Appliance Co., Ltd | Organosilicon-modified polyimide resin composition and use thereof |
| JP7139715B2 (en) * | 2018-06-26 | 2022-09-21 | 大日本印刷株式会社 | Polyimide film, laminate, display surface material, touch panel member, liquid crystal display device, and organic electroluminescence display device |
| CN111732910B (en) * | 2020-06-30 | 2022-05-27 | 晶科绿能(上海)管理有限公司 | Composite encapsulating material and photovoltaic module encapsulated therewith |
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| JPH10170713A (en) * | 1996-12-13 | 1998-06-26 | Toray Ind Inc | Color paste, color filter, and production thereof |
| JPH1138620A (en) * | 1997-07-23 | 1999-02-12 | Toray Ind Inc | Semiconductor device and its manufacture |
| JP2008107766A (en) * | 2006-07-21 | 2008-05-08 | Toray Ind Inc | Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid crystal display device having retardation thin film |
| WO2014162734A1 (en) * | 2013-04-03 | 2014-10-09 | 三井化学株式会社 | Polyamic acid, varnish comprising same and polyimide film |
| WO2015046019A1 (en) * | 2013-09-27 | 2015-04-02 | 東レ株式会社 | Polyimide precursor, polyimide resin film produced from said polyimide precursor, display element, optical element, light-receiving element, touch panel and circuit board each equipped with said polyimide resin film, organic el display, and methods respectively for producing organic el element and color filter |
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| CN101490607B (en) * | 2006-07-21 | 2011-06-01 | 东丽株式会社 | Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid cry |
| JP6420064B2 (en) * | 2014-06-03 | 2018-11-07 | 旭化成株式会社 | Polyimide precursor composition and polyimide film |
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| JPH10170713A (en) * | 1996-12-13 | 1998-06-26 | Toray Ind Inc | Color paste, color filter, and production thereof |
| JPH1138620A (en) * | 1997-07-23 | 1999-02-12 | Toray Ind Inc | Semiconductor device and its manufacture |
| JP2008107766A (en) * | 2006-07-21 | 2008-05-08 | Toray Ind Inc | Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid crystal display device having retardation thin film |
| WO2014162734A1 (en) * | 2013-04-03 | 2014-10-09 | 三井化学株式会社 | Polyamic acid, varnish comprising same and polyimide film |
| WO2015046019A1 (en) * | 2013-09-27 | 2015-04-02 | 東レ株式会社 | Polyimide precursor, polyimide resin film produced from said polyimide precursor, display element, optical element, light-receiving element, touch panel and circuit board each equipped with said polyimide resin film, organic el display, and methods respectively for producing organic el element and color filter |
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| WO2017159538A1 (en) | 2017-09-21 |
| TW201800445A (en) | 2018-01-01 |
| JP7157859B2 (en) | 2022-10-20 |
| TWI735550B (en) | 2021-08-11 |
| JPWO2017159538A1 (en) | 2019-01-24 |
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