CN117043230A - Polyamic acid, polyamic acid solution, polyimide substrate, laminate, and method for producing same - Google Patents
Polyamic acid, polyamic acid solution, polyimide substrate, laminate, and method for producing same Download PDFInfo
- Publication number
- CN117043230A CN117043230A CN202280021912.XA CN202280021912A CN117043230A CN 117043230 A CN117043230 A CN 117043230A CN 202280021912 A CN202280021912 A CN 202280021912A CN 117043230 A CN117043230 A CN 117043230A
- Authority
- CN
- China
- Prior art keywords
- polyamic acid
- polyimide
- amount
- charged
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 143
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 139
- 239000004642 Polyimide Substances 0.000 title claims abstract description 85
- 239000000758 substrate Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 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 claims abstract description 54
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000004985 diamines Chemical class 0.000 claims abstract description 27
- -1 3, 4-dicarboxyphenyl Chemical group 0.000 claims abstract description 21
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 20
- 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 claims abstract description 19
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000012644 addition polymerization Methods 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003960 organic solvent Substances 0.000 claims description 22
- 125000003368 amide group Chemical group 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 239000002243 precursor Substances 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 56
- 239000011521 glass Substances 0.000 description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 229910052814 silicon oxide Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 229940044174 4-phenylenediamine Drugs 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 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 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 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 5
- 150000001408 amides Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010409 thin film Substances 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
- 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
- 238000000354 decomposition reaction Methods 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
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 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
- 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
- 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 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
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 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
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012546 transfer 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 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
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-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
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-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
- 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
- SDQCONAKTCBAMG-UHFFFAOYSA-N 2-pentadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCC1=NC=CN1 SDQCONAKTCBAMG-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
- HYTCSCBDAFJMIP-UHFFFAOYSA-N 3-ethyl-1,1-dimethylurea Chemical compound CCNC(=O)N(C)C HYTCSCBDAFJMIP-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
- 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
- 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
- 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
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- AMNPXXIGUOKIPP-UHFFFAOYSA-N [4-(carbamothioylamino)phenyl]thiourea Chemical compound NC(=S)NC1=CC=C(NC(N)=S)C=C1 AMNPXXIGUOKIPP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 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
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000010304 firing Methods 0.000 description 1
- 230000009477 glass transition Effects 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
- 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
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 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
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 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
- 238000002360 preparation method Methods 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000004544 sputter deposition Methods 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
- 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
- 230000009974 thixotropic effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising 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
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The purpose of the present invention is to provide: polyimide having high heat resistance and high transparency and improved adhesion to inorganic films, and polyamic acid, polyimide substrate and laminate, which are precursors thereof, and methods for producing the same. The above problems can be solved by a polyamic acid, a polyimide obtained therefrom, and a polyimide substrate, wherein the polyamic acid is an addition polymerization product of a diamine and a tetracarboxylic dianhydride, the diamine comprises 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, and the tetracarboxylic dianhydride comprises 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride.
Description
Technical Field
The present invention relates to a polyamic acid, a polyamic acid solution, a polyimide substrate, a laminate, and methods for producing the same.
Background
In electronic devices such as displays, touch panels, and solar cells, thinning, weight saving, and flexibility are demanded, and a resin film substrate is used instead of a glass substrate.
In these devices, various electronic components, such as thin film transistors and transparent electrodes, are formed on a substrate, and a high-temperature process is required for forming these electronic components. The general aromatic polyimide has sufficient heat resistance to be suitable only for high temperature processes, and the glass substrate and the electronic component have a coefficient of linear thermal expansion (CTE) close to each other, and thus are not likely to generate internal stress, and therefore, are suitable for substrate materials for flexible displays and the like.
Generally, aromatic polyimides are colored yellow brown due to intramolecular conjugation and formation of Charge Transfer (CT) complexes. In the case of a top emission type organic EL, light is extracted from the side opposite to the substrate side, and therefore transparency is not required for the substrate, and thus a general aromatic polyimide has been conventionally used. However, when light emitted from a display element is emitted through a substrate, such as a transparent display, a bottom emission type organic EL, and a liquid crystal display, and when a sensor and a camera module are disposed on the back surface of the substrate in order to form a full-area display (without a gap) such as a smart phone, high optical characteristics are required for the substrate.
In view of such a background, a material having heat resistance equivalent to that of conventional aromatic polyimide and further excellent in transparency has been demanded.
In order to reduce the coloration of polyimide, it has been reported that the formation of CT complex can be suppressed by using an aliphatic monomer (patent document 1 and patent document 2). Further, although a technique for reducing the coloration of polyimide is not known, a polyimide film obtained by adding silicone oil to polyamic acid as a polyimide precursor and imidizing the silicone oil has high adhesion to a substrate (patent document 3).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-04530
Patent document 2: japanese patent No. 5660249
Patent document 3: japanese patent application laid-open No. 2015-229691
Disclosure of Invention
Problems to be solved by the invention
However, the above-mentioned conventional techniques have room for improvement in terms of having high heat resistance and further being excellent in transparency. The polyimides described in patent documents 1 and 2 have high transparency and low CTE, but have an aliphatic structure, and therefore have a low thermal decomposition temperature, and are not suitable for high-temperature processes for forming electronic devices.
In addition, the light-emitting element of the organic EL has low moisture resistance, and causes occurrence of black spots, occurrence of leakage current, and non-lighting due to moisture penetrating from the outside. If a resin is used as the substrate, moisture cannot be completely blocked. Therefore, in order to improve the barrier property of the substrate, an inorganic film such as a silicon oxide film or a silicon nitride film is used as an intermediate layer of each polyimide layer formed with a polyimide film having two layers, or is used on a film formed with a polyimide film having two layers. However, there is a problem that adhesion between the inorganic film and the polyimide film is low, and peeling or floating occurs at the interface between the inorganic film and the polyimide film in the process.
In view of the above, an object of the present application is to provide: polyimide having high heat resistance and high transparency, and further improved adhesion to inorganic films, and polyamic acid, polyimide substrate and laminate, which are precursors thereof, and methods for producing the same.
Solution for solving the problem
The inventors of the present application found that: by introducing a rigid structure into the polymer skeleton and further using a monomer component having a siloxane bond in combination, a polyimide satisfying the above characteristics and a polyamic acid as a precursor thereof are obtained. An embodiment of the present application is configured as follows.
A polyamic acid that is an addition polymerization reactant of a diamine comprising 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and a tetracarboxylic dianhydride comprising 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride.
ADVANTAGEOUS EFFECTS OF INVENTION
The present application can provide: polyimide having high heat resistance and high transparency and improved adhesion to inorganic films, and polyamic acid as a precursor thereof. They are suitable as substrate materials for electronic devices.
Detailed Description
The polyamic acid according to one embodiment of the present invention is the following polyamic acid: which is the polyaddition reactant of a diamine comprising 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and a tetracarboxylic dianhydride comprising 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride.
The polyimide obtained from the polyamic acid of the present embodiment has a siloxane bond in the resin, so that affinity for an inorganic film (for example, a silicon oxide film) is improved, and improvement of adhesion to the inorganic film is expected. On the other hand, if the repeating unit of the siloxane bond becomes long, there is a possibility that the glass transition temperature (Tg) of the resin is greatly lowered, or that the heat resistance is lowered or the equipment is contaminated due to the occurrence of cyclic siloxane by intramolecular condensation or the like, and therefore, the repeating unit of the siloxane bond is preferably small. Specifically, by using 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, a polyimide having high adhesion to an inorganic film and high heat resistance can be obtained. From the viewpoint of both adhesion and heat resistance, the ratio of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is preferably 0.1 to 10.0mol%, more preferably 0.15 to 1.0 mol%, and even more preferably 0.2 to 0.5mol%, based on 100mol% of the total of all diamines. By setting the range to the above range, the polyimide obtained from the polyamic acid can have sufficient adhesion to an inorganic film (for example, a silicon oxide film) and heat resistance to cope with a high-temperature process.
In order to obtain a polyimide having a low internal stress, the polyamide acid is preferably a polyamide acid having a ratio of 3, 4-biphenyltetracarboxylic dianhydride of 70 to 99mol%, more preferably 75 to 98mol%, still more preferably 75 to 97mol%, still more preferably 75 to 96mol%, still more preferably 75 to 95mol%, and still more preferably 80 to 90mol%, based on 100mol% of the total of all tetracarboxylic dianhydrides.
The 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride is effective in exhibiting the transparency of polyimide obtained from the polyamic acid because it is derived from a bulky structure and suppresses the formation of a charge transfer complex. On the other hand, the bulky structure prevents the accumulation of molecular chains, and thus the polyimide obtained from the polyamic acid tends to have an internal stress that is high. Therefore, from the viewpoint of both transparency and moderate internal stress, the polyamide acid is preferably a polyamide acid having a ratio of 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride of 1mol% to 30mol%, more preferably 5mol% to 25mol%, still more preferably 10mol% to 20mol%, where the total of all tetracarboxylic acid dianhydrides is 100 mol%. By setting the range to the above range, an increase in the internal stress of polyimide obtained from the polyamic acid is suppressed, and the internal stress generated when forming a laminate with a glass substrate or the like can be reduced. Therefore, in the production process of a laminate using a polyimide obtained from the polyamic acid or an electronic device using the laminate, a material excellent in process suitability can be obtained without warpage of the laminate.
The polyamic acid of the present embodiment may contain diamine components other than 1, 4-phenylenediamine and other than 1, 3-bis (3-aminopropyl) tetramethyldisiloxane within a range that does not impair the performance thereof. Examples of the other diamine component include 1, 4-diaminocyclohexane, 1, 3-phenylenediamine, 4 '-oxydiphenylamine, 3,4' -oxydiphenylamine, 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether, 2 '-bis (trifluoromethyl) benzidine, 4' -diaminobenzidine, and N, N '-bis (4-aminophenyl) terephthalamide, 4' -diaminodiphenyl sulfone, 4- (aminophenyl) 4-aminobenzoate, m-tolidine, o-tolidine, 4 '-bis (aminophenoxy) biphenyl, 2- (4-aminophenyl) -6-aminobenzoxazole, 3, 5-diaminobenzoic acid, 4' -diamino-3, 3 '-dihydroxybiphenyl, 4' -methylenebis (cyclohexane amine) and their analogues, which may be used alone or in combination of 2 or more. Among them, 4- (aminophenyl) 4-aminobenzoate and the like are preferable from the viewpoints of improvement of Tg and transparency.
The polyamic acid of the present embodiment may contain an acid dianhydride component other than 3, 4-biphenyltetracarboxylic dianhydride and other than 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride within a range that does not impair the performance. Examples of the other acid dianhydride component include pyromellitic dianhydride, 1, 4-phenylene bis (trimellitic acid dianhydride), 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' -oxyphthalic dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, dicyclohexyl-3, 3', 4' -tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 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 dianhydrides and their analogues, which may be used alone or in combination of 2 or more.
[ Synthesis of Polyamic acid and polyimide ]
The polyimide having the above structure is obtained by a known method. Polyimide can be synthesized by synthesis of precursors such as polyamide acid and polyimide ester, or by synthesis of precursors not. For the availability of monomers and ease of polymerization, it is preferable to synthesize polyimide by the imide of the polyamic acid as a precursor.
The polyamic acid having the above structure is obtained by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent. For example, the diamine may be dissolved in an organic solvent or dispersed in a slurry form in an organic solvent to form a diamine solution, and the tetracarboxylic dianhydride may be dissolved in an organic solvent or dispersed in a slurry form in a solution or solid of an organic solvent, and the diamine solution may be added thereto in this state. 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 inert gas atmosphere such as argon or nitrogen.
In the synthesis of the polyamic acid, the number of moles of the total diamine component and the number of moles of the total tetracarboxylic dianhydride component are preferably adjusted to be substantially equal to each other. By using a plurality of diamines and/or a plurality of tetracarboxylic dianhydrides, polyamic acid having a plurality of structural units is obtained. In addition, by blending polyamide acids having different structures, a blend of polyamide acids having a plurality of structural units having different structures can also be obtained.
The organic solvent used in the synthesis reaction of the polyamic acid is not particularly limited. The organic solvent is preferably one which can dissolve the tetracarboxylic dianhydride and diamine to be used and can dissolve the polyamic acid produced by polymerization. Specific examples of the organic solvent include urea solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide or sulfone solvents such as dimethyl sulfoxide, diphenyl sulfone, and tetramethylsulfone; amide solvents such as N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), N' -diethylacetamide, N-methyl-2-pyrrolidone (NMP); ester solvents such as gamma-butyrolactone; amide solvents such as hexamethylphosphoric triamide; 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, and p-cresol methyl ether. If necessary, 2 or more organic solvents may be used in combination. In order to improve the solubility and reactivity of the polyamic acid, the organic solvent used for the synthesis of the polyamic acid is preferably selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ester-based solvent, and an ether-based solvent, and particularly preferably an amide-based solvent such as DMF, DMAC, NMP.
The temperature conditions for the synthesis reaction of the polyamic acid are not particularly limited. The reaction temperature is preferably 80℃or lower from the viewpoint of suppressing the decrease in molecular weight of the polyamide acid by depolymerization. The reaction temperature is more preferably 0 to 50℃from the viewpoint of properly conducting the polymerization reaction. The reaction time may be arbitrarily set within a range of 10 minutes to 30 hours.
The diamine and the tetracarboxylic dianhydride are polymerized in the organic solvent to obtain a polyamic acid solution containing a polyamic acid and an organic solvent. The polymerization solution can be used as it is as a polyamic acid solution. In addition, the concentration of the polyamide acid and the viscosity of the solution can also be adjusted by removing a part of the solvent from the polymerization solution or adding the solvent. The added solvent may be different from the solvent used in the polymerization of the polyamic acid. In addition, a polyamic acid solution may be prepared by dissolving a solid polyamic acid resin obtained by removing a solvent from a polymerization solution in a solvent. As the organic solvent of the polyamic acid solution, those having high solubility of polyamic acid are preferable, and those exemplified above as the organic solvent used in the synthesis of polyamic acid can be used. Among them, an amide solvent such as DMF, DMAC, NMP is preferable.
Imidization is performed by dehydrating and ring-closing the polyamic acid. The dehydration ring closure is performed by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method. In the case of imidization in the form of a solution, chemical imidization is preferably performed by adding an imidizing agent and/or a dehydration catalyst to the polyamic acid solution. The imidizing agent is not particularly limited, and tertiary amines are preferably used, and among them, heterocyclic tertiary amines are more 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, and gamma valerolactone.
In the case of imidization by removing the solvent from the polyamic acid solution, thermal imidization by dehydration ring closure by heating is preferable. The method for heating the polyamic acid is not particularly limited, and for example, the polyamic acid solution may be applied to a support such as a glass plate, a metal plate, or PET (polyethylene terephthalate), and then heat-treated at 80 to 500 ℃. The heating time varies depending on the throughput and heating temperature of the polyamic acid solution to be dehydrated and closed, but it is generally preferable to heat the solution for 1 minute to 5 hours after the treatment temperature reaches the highest temperature. Imidizing agent and/or dehydration catalyst may be added to the polyamic acid solution, and the imidization may be performed by heating in the above-described manner.
When the polyamic acid is thermally imidized, the imidization reaction and the decomposition of the polyamic acid are simultaneously performed, whereby the decomposition of the polyamic acid is suppressed, and thus the formation of terminal groups can be reduced, or a polyimide film excellent in transparency can be obtained. Examples of the method for suppressing the decomposition of the polyamic acid include esterification, silyl esterification, and acceleration of the reaction of the polyamic acid, but any method can be used. Specifically, by adding a small amount of tertiary amine such as imidazole, the imidization rate at the time of thermal imidization can be accelerated, and a polyimide film excellent in transparency can be obtained. Examples of the imidazoles include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Among them, 1, 2-dimethylimidazole is preferable.
The imidazole content in the polyamic acid solution is preferably 0.005mol to 0.100mol, more preferably 0.010mol to 0.080mol, and still more preferably 0.015mol to 0.050mol, based on 1.000mol of the amide group of the polyamic acid. "the amide group of the polyamic acid" means an amide group formed by the addition polymerization reaction of a diamine and a tetracarboxylic dianhydride. If the amount of the imidazole to be added is within the above range, improvement in transparency and low internal stress of the polyimide film can be expected.
In the case of adding the imidazole, it is preferable to add the imidazole after the polymerization of the polyamic acid. The imidazole may be added directly to the polyamic acid solution, or may be added as an imidazole solution to the polyamic acid solution.
Imidization of the polyamic acid to polyimide may be performed at an arbitrary ratio of 1% to 100% imidization, or a part of imidized polyamic acid may be synthesized. Imidization from polyamic acid to polyimide tends to change solubility in an organic solvent and viscosity of a solution. In addition, stopping imidization at a specific imidization rate is not generally easy. When a thin film is formed by coating and drying a solution, the viscosity and thixotropic properties of the solution affect the uniformity of the film thickness. Therefore, if the stability of the process is considered, it is preferable that the polyamic acid solution is applied to the support in a state where the imidization rate is 0% without adding an imidizing agent or a dehydration catalyst to the polyamic acid, and the solvent is removed and imidized by heating the support.
[ use of Polyamic acid and polyimide ]
The polyamic acid and polyimide according to one embodiment of the present invention can be directly used for the production of products and members. Alternatively, a thermosetting component, a photocurable component, a non-polymerizable binder resin, a dye, a surfactant, a leveling agent, a plasticizer, a silane coupling agent, microparticles, a sensitizer, and the like may be added to the polyamic acid and the polyimide to form a composition. The blending ratio of these optional components is preferably in the range of 0.1 to 95% by weight based on the entire solid content of the polyimide. The solid component of the composition means all components except the organic solvent, and the liquid monomer component is also contained in the solid component.
The polyimide according to one embodiment of the present invention is excellent in transparency and heat resistance, and therefore can be used as a transparent substrate for glass substitution applications or the like, and for example, can be expected to be applied to substrates for electronic devices such as TFT substrates and electrode substrates. Among the above-mentioned electronic devices, the use of the substrate as a substrate for a device requiring light transmittance such as a liquid crystal display device, an organic EL element, electronic paper, or a touch panel is preferable. The polyimide according to one embodiment of the present invention can be used as a material for optical members such as color filters, antireflection films, holograms, and the like, building materials, and structures. Various inorganic thin films such as metal oxides and transparent electrodes can be formed on the surface of the polyimide according to one embodiment of the present invention. The inorganic thin film is formed by a dry process such as a PVD method such as a sputtering method, a vacuum deposition method, an ion plating method, or the like, or a CVD method, for example.
[ production of polyimide substrate and electronic device ]
The polyimide according to one embodiment 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 and transparency. In the batch process, a polyimide film (substrate) is formed on a support, and after electrodes and/or electronic components are formed thereon, the polyimide substrate on which the electrodes and/or electronic components are formed is peeled off from the support, thereby obtaining an electronic device.
Accordingly, an embodiment of the present invention further comprises: a polyimide substrate comprising the polyimide, a laminate of the polyimide substrate and a support, and an electronic device comprising the polyimide substrate and an electrode and/or an electronic component. In addition, an embodiment of the present invention also includes a method for producing a laminate of a polyimide substrate and a support, wherein the polyamic acid solution is cast on the support and imidized, thereby forming a polyimide substrate on the support.
The thickness of the polyimide substrate is about 1 to 200. Mu.m, preferably about 5 to 100. Mu.m.
In one embodiment of the present invention, in order to improve the barrier property of the polyimide substrate, an inorganic film such as a silicon oxide film or a silicon nitride film may be used as an intermediate layer of each polyimide layer in which a two-layer polyimide film is formed, or may be used as a film in which a two-layer polyimide film is formed.
As a specific example, for example, the polyamic acid solution is applied to a support, dried by heating and imidized, and then the polyimide film formed on the support is subjected to CVD deposition of an inorganic film. Next, the polyamic acid solution was applied again to the inorganic film, and dried and imidized by heating, thereby obtaining a polyimide film (polyimide substrate) which was laminated on the support in an adhesion manner. This example is an example of a polyimide substrate in which an inorganic film is used as an intermediate layer of each polyimide layer in which a two-layer polyimide film is formed.
As a support to which the polyamic acid solution is applied, a glass substrate (glass plate) may be mentioned; metal substrates such as SUS or metal strips; polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate, triacetyl cellulose, and the like. In order to be suitable for the conventional batch-type device manufacturing process, a glass substrate (glass plate) is more preferably used as a support.
When the polyamic acid solution is applied to the support such as glass and heated, imidization of the polyamic acid is started together with evaporation of the solvent, and the organic solvent and water generated by imidization (dehydration of the polyamic acid) are volatilized from the polyamic acid solution. At this time, a part of the water and/or the organic solvent does not volatilize and remains between the support and the resin film during imidization, which causes peeling at the interface between the support and the resin film. In the step of heating the resin film at a high temperature after water and/or an organic solvent which have remained at the interface between the support and the resin film, the polyimide film is permeated and the bubbles remain in the portion where peeling or floating has occurred. If such bubbles are generated, defects occur when an element is formed on the polyimide substrate. In particular, in a thinned or miniaturized device, even if the device is peeled off or lifted up finely, formation or mounting of elements or the like is greatly affected.
Since the polyamic acid and polyimide according to an embodiment of the present invention having a siloxane structure have high adhesion to glass and also high adhesion to an inorganic film used as an intermediate layer or the like, floating and peeling due to retention of an organic solvent or water at the interface between the glass support and the resin film are less likely to occur during drying or imidization of the solvent on the support. Therefore, the formation and mounting of the element pair on the polyimide substrate closely laminated on the support can be accurately performed.
The polyimide film produced using the polyamic acid solution according to an embodiment of the present invention can have improved adhesion to an inorganic film in addition to high heat resistance and high transparency.
For the polyimide film (polyimide substrate) which is closely laminated on the support, the 90 ° peel strength from the support is preferably 0.08N/cm to 5.00N/cm, more preferably 0.09N/cm to 4.00N/cm, still more preferably 0.10N/cm to 3.50N/cm. When the polyimide film (polyimide substrate) laminated on the support in an adhesion manner has the adhesion, peeling from the support is less likely to occur in the element forming and mounting process, and peeling from the support after element forming and mounting is easier. The 90 ° peel strength can be measured by the method described in examples described below.
For applications such as displays, the transparency of the polyimide or the polyimide film is required to be high in transmittance in the entire wavelength region of visible light. The Yellowness (YI) of the polyimide or the polyimide film is preferably 20 or less, more preferably 18 or less. YI can be measured according to JIS K7373-2006. Polyimide films having such high transparency can be used as transparent substrates for glass substitution applications and the like.
The internal stress generated between the polyimide substrate and the support is preferably 30MPa or less, more preferably 25MPa or less, and still more preferably 20MPa or less. The internal stress generated between the polyimide substrate and the support can be measured by the method described in examples described later. If the internal stress is 30MPa or less, the laminate is not warped in the manufacturing process of the electronic device, and therefore, the polyimide substrate has an advantage of excellent process suitability.
An embodiment of the present invention may have the following configuration.
1) A polyamic acid which is an addition polymerization reactant of a diamine comprising 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and a tetracarboxylic dianhydride comprising 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride.
2) The polyamic acid according to 1), wherein the ratio of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is 0.1 to 10.0mol% based on the total amount of the diamine.
3) The polyamic acid according to 1) or 2), wherein the ratio of 3, 4-biphenyltetracarboxylic dianhydride to the total amount of tetracarboxylic dianhydride is 70 to 99mol%.
4) A polyamic acid solution comprising: 1) The polyamic acid according to any one of 3) and an organic solvent.
5) The polyamic acid solution according to 4), which further contains imidazoles.
6) The polyamic acid solution according to 5), wherein the imidazole content is 0.10mol or less based on 1mol of the amide group of the polyamic acid.
7) A polyimide which is an imidized product of the polyamic acid solution according to any one of 4) to 6).
8) The polyimide according to 7), which has a Yellowness (YI) of 20 or less at a film thickness of 10. Mu.m.
9) A method for producing a laminate of a polyimide substrate and a support, wherein the polyamic acid solution according to any one of 4) to 6) is cast onto a support and imidized, thereby forming a polyimide substrate on the support.
10 A laminate of a polyimide substrate and a support, which is formed of the polyimide described in 7) or 8).
11 The laminate according to 10), wherein an internal stress generated between the polyimide substrate and the support is 30MPa or less.
12 An electronic device comprising an electrode and/or an electronic component on the polyimide substrate according to 10) or 11).
The present invention is not limited to the above embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the scope of the present invention.
Examples
(evaluation method)
The material property values and the like described in the present specification are obtained by the following methods.
(1) Peel strength of
For a laminate of a glass plate (alkali-free glass) and a polyimide film, and a laminate of a glass plate formed with a silicon oxide film (inorganic film) and a polyimide film, 90 ° peel strength was measured from the glass plate and the glass plate formed with a silicon oxide film (inorganic film) according to ASTM D1876-01, respectively. A10 mm wide slit was introduced into a polyimide film by a cutter, and a 90℃peel test was performed at a tensile speed of 50 mm/min and a peel length of 50mm using an eastern precision machine tensile tester (Stroggraph VES 1D) at 23℃and 55% RH, and the average value of peel strengths was used as peel strength.
Here, the laminate of the glass plate (alkali-free glass) and the polyimide film was produced in the same manner as in the case of [ production of polyimide film ] described later. The laminate of the glass plate having the silicon oxide film (inorganic film) and the polyimide film was produced in the same manner as in the case of [ production of polyimide film ] described later, except that the glass plate having the silicon oxide film (inorganic film) formed thereon was used as the glass plate. The glass plate having the silicon oxide film (inorganic film) formed thereon is produced by CVD deposition of the silicon oxide film on the glass plate.
(2) Determination of internal stress
The polyamic acid solutions prepared in examples and comparative examples were applied to Corning Incorporated alkali-free glass (thickness: 0.7mm, 100 mm. Times.100 mm) having a warp amount measured in advance by a spin coater, and the glass plate coated with the polyamic acid solution was baked at 120℃for 30 minutes in air and at 430℃for 30 minutes in a nitrogen atmosphere, to obtain a laminate of a glass substrate and a polyimide film having a film thickness of 10. Mu.m. The warpage amount of the laminate of the glass substrate and the polyimide film was measured by a film stress measuring device FLX-2320-S manufactured by Tencor, and the internal stress generated between the glass substrate and the polyimide film under a nitrogen atmosphere at 25℃was evaluated. In order to avoid water absorption of the polyimide film, the laminate of the glass substrate and the polyimide film was measured immediately after firing or after drying at 120 ℃ for 10 minutes.
(3) 1% weight loss temperature (TD 1)
A polyimide film was laminated on N using TG/DTA/7200 made by Hitachi High-Tech Corporation 2 The temperature was increased from 25℃to 650℃at 20℃per minute under an atmosphere. Taking the weight of the polyimide film at 150 ℃ as a reference, taking the influence of moisture into consideration, the temperature at which the weight is reduced by 1% as TD1 of the polyimide film.
(4) Yellowness of polyimide film (YI)
The transmittance at 200 to 800nm of the polyimide film was measured by an ultraviolet-visible near infrared spectrophotometer (V-650) manufactured by Japanese Specification Co., ltd. And the Yellow Index (YI) as an index indicating the degree of yellowness was calculated from the formula described in JIS K7373.
(5) Appearance after heating test (stability of high temperature film forming process)
The polyamic acid solutions prepared in examples and comparative examples were applied to Corning Incorporated alkali-free glass (thickness: 0.7mm, 100 mm. Times.100 mm) by a spin coater, and the glass substrate coated with the polyamic acid solution was baked at 120℃for 30 minutes in air and at 430℃for 30 minutes in a nitrogen atmosphere, to obtain a laminate of a glass substrate and a polyimide film having a film thickness of 10. Mu.m. SiOx was laminated on a polyimide film of the laminate by PE-CVD method to 1 μm, the laminate was heated from room temperature to 470℃at 5℃per minute under a nitrogen atmosphere, and the laminate was left to stand for 10 minutes after reaching 470℃to burn, and then whether or not there was any floating between SiOx or a glass substrate and the polyimide film was visually confirmed. The case where there was no floating was designated as "delta" (normal), the case where there was not floating was 1 or more and less than 5 was designated as "delta" (normal), the case where there was 5 or more was designated as "X" (poor), and the case where the film was damaged by thermal decomposition was designated as "X" (very poor).
[ preparation of polyamic acid solution ]
Example 1 >
Into a 300mL glass-made removable flask equipped with a stirrer equipped with a stainless steel stirring blade and a nitrogen inlet tube, 8.68g of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA), 2.55g of 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride (BPAF), and 85.0g of N-methyl-2-pyrrolidone (NMP) were charged, stirred and dissolved at room temperature (23 ℃). After 30 minutes, 0.009g of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (PAM-E) was added to the obtained solution, followed by further stirring. To this solution, 3.76g of 1, 4-Phenylenediamine (PDA) was added and stirred at room temperature for 5 hours to obtain a polyamic acid solution. The concentration of diamine and tetracarboxylic dianhydride added to the reaction solution was 15% by weight based on the total amount of the reaction solution. Further, 1, 2-Dimethylimidazole (DMI) was added to the solution so as to be 1 wt% with respect to the polyamic acid (resin component).
Example 2 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.68g, the amount of BPAF charged was changed to 2.55g, the amount of PAM-E charged was changed to 0.013g, and the amount of PDA charged was changed to 3.76 g.
Example 3 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.68g, the amount of BPAF charged was changed to 2.55g, the amount of PAM-E charged was changed to 0.017g, and the amount of PDA charged was changed to 3.76.
Example 4 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.69g, the amount of BPAF charged was changed to 2.55g, the amount of PAM-E charged was changed to 0.026g, and the amount of PDA charged was changed to 3.74 g.
Example 5 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.68g, the amount of BPAF charged was changed to 2.55g, the amount of PAM-E charged was changed to 0.043g, and the amount of PDA charged was changed to 3.73 g.
Example 6 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.67g, the amount of BPAF charged was changed to 2.54g, the amount of PAM-E charged was changed to 0.086g, and the amount of PDA charged was changed to 3.70 g.
Example 7 >
A polyamic acid solution was obtained in the same manner as in example 1 except that the amount of BPDA charged was changed to 10.085g, the amount of BPAF charged was changed to 0.993g, the amount of PAM-E charged was changed to 0.018g, the amount of PDA charged was changed to 3.904g, and 1, 2-dimethylimidazole was not added.
Example 8 >
A polyamic acid solution was obtained in the same manner as in example 7, except that the amount of BPDA charged was changed to 9.370g, the amount of BPAF charged was changed to 1.784g, the amount of PAM-E charged was changed to 0.018g, and the amount of PDA charged was changed to 3.829 g.
Example 9 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 9.366g, the amount of BPAF charged was changed to 1.784g, the amount of PAM-E charged was changed to 0.026g, and the amount of PDA charged was changed to 3.823 g.
Example 10 >
A polyamic acid solution was obtained in the same manner as in example 7, except that the amount of BPDA charged was changed to 8.681g, the amount of BPAF charged was changed to 2.546g, the amount of PAM-E charged was changed to 0.017g, and the amount of PDA charged was changed to 3.756 g.
Example 11 >
A polyamic acid solution was obtained in the same manner as in example 7, except that the amount of BPDA charged was changed to 8.629g, the amount of BPAF charged was changed to 2.551g, the amount of PAM-E charged was changed to 0.043g, and the amount of PDA charged was changed to 3.766 g.
Example 12 >
A polyamic acid solution was obtained in the same manner as in example 7, except that the amount of BPDA charged was changed to 8.018g, the amount of BPAF charged was changed to 3.279g, the amount of PAM-E charged was changed to 0.017g, and the amount of PDA charged was changed to 3.686 g.
Example 13 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.015g, the amount of BPAF charged was changed to 3.278g, the amount of PAM-E charged was changed to 0.025g, and the amount of PDA charged was changed to 3.681 g.
Example 14 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 7.543g, the amount of BPAF charged was changed to 3.871g, the amount of PAM-E charged was changed to 0.025g, and the amount of PDA charged was changed to 3.651 g.
Example 15 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 8.587g, the amount of BPAF charged was changed to 2.549g, the amount of PAM-E charged was changed to 0.173g, and the amount of PDA charged was changed to 3.692 g.
Example 16 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 4.548g, the amount of BPAF charged was changed to 7.087g, the amount of PDA charged was changed to 3.342g, and PAM-E charged was changed to 0.023 g.
Comparative example 1 >
Into a 300mL glass-made detachable flask equipped with a stirrer equipped with a stainless steel stirring blade and a nitrogen inlet tube, BPDA8.70g, BPAF2.55g, and NMP85.0g were charged, and stirred and dissolved at room temperature (23 ℃). After 30 minutes, to the solution was added PDA3.75g, and the mixture was stirred at room temperature for 5 hours to obtain a polyamic acid solution. Further, 1, 2-dimethylimidazole was added to the solution so as to be 1 wt% relative to the polyamic acid (resin component).
Comparative example 2 >
A polyamic acid solution was obtained in the same manner as in comparative example 1, except that the amount of BPDA charged was changed to 9.478g, the amount of BPAF charged was changed to 1.641g, the amount of PDA charged was changed to 3.881g, and 1, 2-dimethylimidazole was not added.
Comparative example 3 >
A polyamic acid solution was obtained in the same manner as in comparative example 1, except that the amount of BPDA charged was changed to 8.107g, the amount of BPAF charged was changed to 3.158g, the amount of PDA charged was changed to 3.734g, and 1, 2-dimethylimidazole was not added.
Comparative example 4 >
A polyamic acid solution was obtained in the same manner as in example 1, except that the amount of BPDA charged was changed to 10.950g, the amount of BPAF charged was changed to 0g, the amount of PDA charged was changed to 4.023g, and PAM-E charged was changed to 0.028 g.
Comparative example 5 >
A polyamic acid solution was obtained in the same manner as in comparative example 2, except that 3-aminopropyl triethoxysilane (APS) was added so that the amount of BPDA added was 8.643g, the amount of BPAF added was 2.565g, the amount of PDA added was 3.792g, and the amount of PAM-E added was 0g, and the amount was 0.05% by weight.
Comparative example 6 >
A polyamic acid solution was obtained in the same manner as in comparative example 5, except that APS was added so as to be 0.2 wt%.
Comparative example 7 >
A polyamic acid solution was obtained in the same manner as in comparative example 5, except that APS was added so as to be 0.3 wt%.
Comparative example 8 >
Into a 300mL glass-made detachable flask equipped with a stirrer equipped with a stainless steel stirring blade and a nitrogen inlet tube, 4.166g of trans-1, 4-Cyclohexanediamine (CHDA), 0.046g of PAM-E and 85g of NMP were charged, and stirred and dissolved at room temperature (23 ℃). After 30 minutes, 10.788g of BPDAS was added, and after heating at 80℃for 30 minutes, the mixture was cooled to room temperature and stirred for 5 hours to obtain a polyamic acid solution. Further, 1, 2-dimethylimidazole was added to the solution so as to be 1 wt% relative to the polyamic acid (resin component).
[ production of polyimide film ]
NMP was added to each of the polyamic acid solutions obtained in the examples and comparative examples, and the solutions were diluted so that the polyamic acid concentration became 10.0 wt%. The polyamic acid solution diluted so that the thickness thereof after drying became 10 μm was cast on a10 mm X10 mm square alkali-free glass plate (EAGLE XG, manufactured by Corning, thickness 0.7 mm) by a spin coater. The glass plate on which the diluted polyamic acid solution was cast was dried in a hot air oven at 120℃for 30 minutes, and then heated at 430℃for 30 minutes under a nitrogen atmosphere, so as to carry out imidization, thereby obtaining a laminate of a polyimide film having a thickness of 10 μm and the glass plate. The polyimide film was peeled from the glass substrate of the obtained laminate, and the characteristics were evaluated.
Table 1 shows the compositions of the polyamic acid solutions and the evaluation results of the polyimide films of the examples and comparative examples. The composition in Table 1 is expressed as 100mol% in terms of the total of each of the tetracarboxylic dianhydride and the diamine (unit: mol%). The amount of 1, 2-Dimethylimidazole (DMI) added was 100 parts by weight (unit: parts by weight) based on the polyamide acid (resin component). In the table, "Stress" indicates an internal Stress generated between the polyimide film and the support. In the table, "-" indicates that measurement was not performed.
TABLE 1
As shown in table 1, in examples 1 to 16 using polyamic acid, which is an addition polymerization reactant of diamine including 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and tetracarboxylic dianhydride including 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride, the polyimide films obtained had the characteristics shown below.
Adhesion to glass of 0.10N/cm or more
With SiO 2 The adhesion of the adhesive to the surface of the substrate is 0.05N/cm or more
YI is 20 or less
Further, the polyimide film obtained by introducing 1, 3-bis (3-aminopropyl) tetramethyldisiloxane into a polyamic acid having a 3,3', 4' -biphenyltetracarboxylic dianhydride ratio of 70 to 99mol% and a 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride ratio of 1 to 30mol% based on 100mol% of the total tetracarboxylic dianhydride further uses 1, 4-phenylenediamine as a diamine.
Adhesion to glass of 0.10N/cm or more
With SiO 2 The adhesion of (a) is0.05N/cm or more
Internal stress of 30MPa or less
YI is 20 or less
And (3) judging: the polyimide film of example 16, in which the ratio of 3,3', 4' -biphenyltetracarboxylic dianhydride was 50mol% and the ratio of 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride was 50mol% based on the total of 100mol% of the total tetracarboxylic dianhydrides, was excellent in adhesion to glass and a silicon oxide film, and had a low YI value, but the internal stress was higher than that of other examples.
The polyimide films of comparative examples 1 to 3, which did not use 1, 3-bis (3-aminopropyl) tetramethyldisiloxane as a monomer, were also low in internal stress and high in transparency, but were small in adhesion to glass and a silicon oxide film, and a large amount of floating was generated between SiOx or a glass substrate and a polyimide film after the heat test.
The polyimide film of comparative example 4, which did not use 9, 9-bis (3, 4-dicarboxyphenyl) fluorenyl dianhydride as a monomer, was excellent in adhesion to glass and a silicon oxide film, did not cause SiOx or floating between a glass substrate and a polyimide film after a heating test, and was small in internal stress, but had a large YI value and low transparency.
The polyimide film of comparative example 5 containing 0.05phr of 3-aminopropyl triethoxysilane (APS) without using 1, 3-bis (3-aminopropyl) tetramethyldisiloxane as a monomer was also low in internal stress and high in transparency, but was less in adhesion to glass and a silicon oxide film, and a lot of floating was generated between SiOx or a glass substrate and a polyimide film after a heat test.
The polyimide films of comparative examples 6 to 7 containing 0.2phr to 0.3phr of 3-aminopropyl triethoxysilane (APS) without using 1, 3-bis (3-aminopropyl) tetramethyldisiloxane as a monomer were also low in internal stress and high in transparency, but were less adhesive to the silicon oxide film, and floating was generated between SiOx or the glass substrate and the polyimide film after the heat test.
The polyimide film of comparative example 8, which did not use 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride as a monomer and used CHDA instead of PDA, damaged the film due to thermal decomposition after the heat test.
From these results, it was confirmed that a polyimide according to an embodiment of the present invention, in which 1, 3-bis (3-aminopropyl) tetramethyldisiloxane was introduced into a polyamic acid formed from 3,3', 4' -biphenyltetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic dianhydride and 1, 4-phenylenediamine, was excellent in heat resistance, and had high adhesion to glass and a silicon oxide film and high transparency.
Further, it was confirmed that polyimide obtained by introducing 1, 3-bis (3-aminopropyl) tetramethyldisiloxane into polyamide acid further using 1, 4-phenylenediamine as diamine was excellent in heat resistance, high in adhesion to glass and a silicon oxide film, low in internal stress to an inorganic substrate, and high in transparency, in which the ratio of 9, 9-bis (3, 4-dicarboxyphenyl) fluorenic acid dianhydride was 70 to 99mol% and the ratio of 1 to 30mol% relative to the total of all tetracarboxylic dianhydrides was 100 mol%.
The present invention is not limited to the above embodiments, and various modifications are possible within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the scope of the present invention. Further, by combining the technical means disclosed in the respective embodiments, new technical features can be formed.
Claims (12)
1. A polyamic acid that is the addition polymerization reactant of a diamine comprising 1, 4-phenylenediamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and a tetracarboxylic dianhydride comprising 3, 4-biphenyltetracarboxylic dianhydride and 9, 9-bis (3, 4-dicarboxyphenyl) fluorenoic dianhydride.
2. The polyamic acid according to claim 1, wherein the ratio of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is 0.1 to 10.0mol% with respect to the total amount of diamine.
3. The polyamic acid according to claim 1 or 2, wherein the ratio of 3, 4-biphenyltetracarboxylic dianhydride to the total tetracarboxylic dianhydride is 70 to 99mol%.
4. A polyamic acid solution comprising: the polyamic acid and organic solvent according to any one of claims 1 to 3.
5. The polyamic acid solution according to claim 4, further comprising imidazoles.
6. The polyamic acid solution according to claim 5, wherein the imidazole is contained in an amount of 0.10mol or less based on 1mol of the amide group of the polyamic acid.
7. A polyimide which is an imide of the polyamic acid solution according to any one of claims 4 to 6.
8. The polyimide according to claim 7, which has a Yellowness (YI) of 20 or less at a film thickness of 10. Mu.m.
9. A method for producing a laminate of a polyimide substrate and a support, wherein,
casting the polyamic acid solution according to any one of claims 4 to 6 on a support and imidizing, thereby forming a polyimide substrate on the support.
10. A laminate of a polyimide substrate formed of the polyimide according to claim 7 or 8 and a support.
11. The laminate according to claim 10, wherein an internal stress generated between the polyimide substrate and the support is 30MPa or less.
12. An electronic device comprising an electrode and/or an electronic element on the polyimide substrate according to claim 10 or 11.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021048939 | 2021-03-23 | ||
JP2021-048939 | 2021-03-23 | ||
PCT/JP2022/013023 WO2022202769A1 (en) | 2021-03-23 | 2022-03-22 | Poly(amic acid), poly(amic acid) solution, polyimide, polyimide substrate and layered product, and methods for producing these |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117043230A true CN117043230A (en) | 2023-11-10 |
Family
ID=83397435
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202280021912.XA Pending CN117043230A (en) | 2021-03-23 | 2022-03-22 | Polyamic acid, polyamic acid solution, polyimide substrate, laminate, and method for producing same |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2022202769A1 (en) |
KR (1) | KR20230160288A (en) |
CN (1) | CN117043230A (en) |
WO (1) | WO2022202769A1 (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3332278B2 (en) * | 1993-12-24 | 2002-10-07 | 日東電工株式会社 | Polyimide precursor and negative photosensitive material, photosensitive substrate and negative pattern forming method |
JP5903789B2 (en) | 2010-07-22 | 2016-04-13 | 宇部興産株式会社 | Copolymer polyimide precursor and copolymer polyimide |
JP5727885B2 (en) * | 2010-09-07 | 2015-06-03 | Jfeケミカル株式会社 | Polyimide and polyimide film |
KR102119426B1 (en) | 2013-06-26 | 2020-06-08 | 도레이 카부시키가이샤 | Polyimide precursor, polyimide, flexible substrate prepared therewith, color filter and production method thereof, and flexible display device |
JP6420064B2 (en) | 2014-06-03 | 2018-11-07 | 旭化成株式会社 | Polyimide precursor composition and polyimide film |
JP7003794B2 (en) * | 2017-03-29 | 2022-01-21 | 荒川化学工業株式会社 | Polyimide, adhesive, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, and multilayer wiring board and their manufacturing method. |
KR20200135955A (en) * | 2018-03-28 | 2020-12-04 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resin, polyimide varnish and polyimide film |
CN111971327B (en) * | 2018-03-30 | 2023-03-21 | 株式会社钟化 | Polyamic acid, polyamic acid solution, polyimide film, laminate, flexible device, and method for producing same |
-
2022
- 2022-03-22 CN CN202280021912.XA patent/CN117043230A/en active Pending
- 2022-03-22 KR KR1020237034036A patent/KR20230160288A/en unknown
- 2022-03-22 WO PCT/JP2022/013023 patent/WO2022202769A1/en active Application Filing
- 2022-03-22 JP JP2023509175A patent/JPWO2022202769A1/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
JPWO2022202769A1 (en) | 2022-09-29 |
WO2022202769A1 (en) | 2022-09-29 |
KR20230160288A (en) | 2023-11-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107428962B (en) | Polyamide-imide precursor, polyamide-imide film, and display device comprising same | |
CN110621721B (en) | Polyamic acid, polyimide film, laminate, flexible device, and method for producing polyimide film | |
CN111971327B (en) | Polyamic acid, polyamic acid solution, polyimide film, laminate, flexible device, and method for producing same | |
CN113227206B (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
JP2018522105A (en) | Polyamide-imide precursor, polyamide-imide film, and display element including the same | |
CN110317339B (en) | Polyimide precursor, polyimide film, and display device including the same | |
JP2008297360A (en) | Solvent-soluble polyimide resin | |
KR102302417B1 (en) | Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate and flexible device, and method for producing polyimide film | |
KR20150007335A (en) | Thermally stable, flexible substrates for electronic devices | |
JP6257302B2 (en) | POLYIMIDE PRECURSOR, RESIN COMPOSITION CONTAINING THE SAME, POLYIMIDE FILM AND ITS MANUFACTURING METHOD, AND LAMINATE AND ITS MANUFACTURING METHOD | |
KR20150031434A (en) | Polyamide acid, polyimide, polyamide acid solution, and use of polyimide | |
JP2022008353A (en) | Method for producing electronic device | |
JP2014070139A (en) | Polyimide precursor and resin composition including the same, polyimide film and method for manufacturing the same, and laminate and method for manufacturing the same | |
JP6687442B2 (en) | Utilization of polyamic acid, polyimide, polyamic acid solution, and polyimide | |
US20130292873A1 (en) | Method for preparing polyimide film | |
KR102390851B1 (en) | Polyimide copolymer and molded article using same | |
KR20140049382A (en) | Polyimide film and method for preparing same | |
CN117120514A (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
CN117043230A (en) | Polyamic acid, polyamic acid solution, polyimide substrate, laminate, and method for producing same | |
TW202239889A (en) | Polyimide precursor varnish and method for producing same, polyimide and method for producing same, flexible device, and laminate for wiring board | |
KR20230007328A (en) | Imide-amic acid copolymer and its preparation method, varnish, and polyimide film | |
CN111471176A (en) | Polyimide precursor, polyimide, film and display device | |
CN115803365B (en) | Polyamic acid, polyamic acid solution, polyimide film, laminate, method for producing laminate, and electronic device | |
CN114920931A (en) | Polyimide precursor composition, polyimide film, and method for producing same | |
TW202319452A (en) | Polyamideimide precursor and applications thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |