TW202409147A - Polyamide composition, method for manufacturing polyimide, method for manufacturing laminated body, and method for manufacturing electronic device - Google Patents
Polyamide composition, method for manufacturing polyimide, method for manufacturing laminated body, and method for manufacturing electronic device Download PDFInfo
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- TW202409147A TW202409147A TW112123419A TW112123419A TW202409147A TW 202409147 A TW202409147 A TW 202409147A TW 112123419 A TW112123419 A TW 112123419A TW 112123419 A TW112123419 A TW 112123419A TW 202409147 A TW202409147 A TW 202409147A
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- polyamic acid
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- polyimide
- polyimide film
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 99
- 229920002647 polyamide Polymers 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 229920001721 polyimide Polymers 0.000 title claims description 173
- 238000000034 method Methods 0.000 title claims description 63
- 239000004642 Polyimide Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 78
- 239000003960 organic solvent Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000000962 organic group Chemical group 0.000 claims abstract description 33
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical group C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 150000004985 diamines Chemical group 0.000 claims description 43
- 229920000768 polyamine Polymers 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 125000004427 diamine group Chemical group 0.000 claims description 19
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 claims description 6
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical group NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 6
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical group COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims description 6
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 48
- 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 45
- 239000011521 glass Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 39
- 239000002904 solvent Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010410 layer Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 229920001690 polydopamine Polymers 0.000 description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 description 16
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 150000002460 imidazoles Chemical class 0.000 description 12
- -1 p-phenylenediphenyl Chemical group 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 102100031503 Barrier-to-autointegration factor-like protein Human genes 0.000 description 9
- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000013585 weight reducing agent Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102100021999 Cytosolic Fe-S cluster assembly factor NUBP2 Human genes 0.000 description 3
- 101710139686 Cytosolic Fe-S cluster assembly factor NUBP2 Proteins 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
- 101100216008 Gallus gallus ANPEP gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013557 residual solvent 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
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 2
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 2
- RLFZYIUUQBHRNV-UHFFFAOYSA-N 2,5-dihydrooxadiazole Chemical group C1ONN=C1 RLFZYIUUQBHRNV-UHFFFAOYSA-N 0.000 description 2
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-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
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 238000011282 treatment 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-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
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-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
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-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
- VIVLBCLZNBHPGE-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropan-1-amine Chemical compound COCCCN(C)C VIVLBCLZNBHPGE-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
- 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
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
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- DWJXWSIJKSXJJA-UHFFFAOYSA-N 4-n-[4-(4-aminoanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC(C=C1)=CC=C1NC1=CC=C(N)C=C1 DWJXWSIJKSXJJA-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
- 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
- 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
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- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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Abstract
本發明之聚醯胺酸組合物包含聚醯胺酸及有機溶劑。聚醯胺酸具有包含下述化學式(1)所表示之二價有機基之殘基、3,3',4,4'-聯苯四羧酸二酐殘基、及對苯二胺殘基。有機溶劑包含選自由下述通式(2)所表示之化合物及下述通式(3)所表示之化合物所組成之群中之一種以上之化合物。下述通式(2)中，R 1、R 2及R 3分別獨立地表示氫原子或碳原子數1以上之一價有機基，R 1、R 2及R 3中之至少一者表示碳原子數2以上之一價有機基。下述通式(3)中，R 4表示碳原子數2以上之一價有機基。 The polyamide composition of the present invention includes polyamide and an organic solvent. Polyamic acid has a residue containing a divalent organic group represented by the following chemical formula (1), a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue, and a p-phenylenediamine residue . The organic solvent contains one or more compounds selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3). In the following general formula (2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and at least one of R 1 , R 2 and R 3 represents a carbon A monovalent organic group with an atomic number of 2 or more. In the following general formula (3), R 4 represents a monovalent organic group having 2 or more carbon atoms.
Description
本發明係關於一種聚醯胺酸組合物、聚醯亞胺之製造方法、積層體之製造方法及電子裝置之製造方法。本發明進而關於一種使用聚醯亞胺之電子裝置材料、薄膜電晶體(TFT)基板、可撓性顯示器基板、彩色濾光片、印刷物、光學材料、圖像顯示裝置(更具體而言，液晶顯示裝置、有機EL(Electroluminescence，電致發光)、電子紙等)、3D顯示器、太陽電池、觸控面板、透明導電膜基板、及當前使用玻璃之構件之替代材料。The present invention relates to a polyamide composition, a method for producing polyimide, a method for producing a laminate, and a method for producing an electronic device. The present invention further relates to an electronic device material using polyimide, a thin film transistor (TFT) substrate, a flexible display substrate, a color filter, a printed matter, an optical material, an image display device (more specifically, a liquid crystal display device, an organic EL (Electroluminescence), an electronic paper, etc.), a 3D display, a solar cell, a touch panel, a transparent conductive film substrate, and a substitute material for components currently using glass.
隨著液晶顯示器、有機EL、電子紙等顯示器、或太陽電池、觸控面板等電子裝置之快速發展，裝置之薄型化或輕量化、撓性化不斷進展。於該等裝置中，使用聚醯亞胺代替玻璃基板作為基板材料。With the rapid development of displays such as liquid crystal displays, organic EL, electronic paper, or electronic devices such as solar cells and touch panels, the thinning, lightening, and flexibility of devices are constantly progressing. In these devices, polyimide is used as a substrate material instead of a glass substrate.
該等裝置中，在基板上形成有各種電子元件、例如薄膜電晶體或透明電極等，該等電子元件之形成需要高溫製程。聚醯亞胺具有能適應高溫製程之程度之充分之耐熱性，熱膨脹係數(CTE)亦與玻璃基板或電子元件接近，因此不易產生內部應力，適合用作可撓性顯示器等之基板材料。In these devices, various electronic components, such as thin film transistors or transparent electrodes, are formed on the substrate, and the formation of these electronic components requires a high temperature process. Polyimide has sufficient heat resistance to adapt to the high temperature process, and its coefficient of thermal expansion (CTE) is close to that of glass substrates or electronic components. Therefore, it is not easy to generate internal stress and is suitable for use as a substrate material for flexible displays.
如上所述之基板材料可藉由如下方式而製造：將溶解有聚醯胺酸之溶液(聚醯胺酸組合物)塗佈於支持體，並將聚醯胺酸進行醯亞胺化，藉此形成聚醯亞胺膜，進而於其上積層電子元件。The substrate material described above can be manufactured by applying a solution containing polyamide (polyamide composition) onto a support, imidizing the polyamide to form a polyimide film, and then stacking electronic components thereon.
作為使聚醯胺酸溶解之溶劑，通常使用N,N-二甲基甲醯胺(DMF)、N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基乙醯胺(DMAC)等碳原子數相對較小之醯胺系溶劑，就對環境或人體之影響之觀點而言，逐漸要求向安全性較高之溶劑變更。As solvents for dissolving polyamine, amide-based solvents with relatively small carbon atoms such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and N,N-dimethylacetamide (DMAC) are generally used. From the perspective of the impact on the environment or the human body, there is a gradual demand for a change to a safer solvent.
作為使用安全性較高之溶劑之聚醯胺酸組合物之製備例，已知有藉由利用聚醯胺酸鹽而使用水作為溶劑之例(專利文獻1等)。又，已知有使用烷氧基-N-取代丙醯胺作為致畸胎性之顧慮較低之溶劑而合成聚醯胺酸之例(專利文獻2及專利文獻3等)。 [先前技術文獻] [專利文獻] As an example of preparing a polyamine composition using a safer solvent, there is a known example of using water as a solvent by using a polyamine salt (Patent Document 1, etc.). In addition, there is a known example of synthesizing polyamine using alkoxy-N-substituted propionamide as a solvent with lower teratogenicity concerns (Patent Documents 2 and 3, etc.). [Prior Art Documents] [Patent Documents]
[專利文獻1]日本專利特開2012-36382號公報 [專利文獻2]日本專利特表2017-517582號公報 [專利文獻3]國際公開第2022/054850號 [Patent Document 1] Japanese Patent Application Publication No. 2012-36382 [Patent Document 2] Japanese Patent Publication No. 2017-517582 [Patent Document 3] International Publication No. 2022/054850
[發明所欲解決之問題][The problem the invention is trying to solve]
本發明人等進行了驗證，結果判明若將專利文獻1～3所記載之聚醯胺酸組合物塗佈於支持體上，並將聚醯胺酸進行醯亞胺化，則呈現出於所獲得之聚醯亞胺膜與支持體之間容易產生密接性不良，並且於聚醯亞胺膜與支持體之界面產生之內部應力變大之趨勢。以下，有時將聚醯亞胺膜與支持體之間之密接性不良簡記為「密接性不良」。又，有時將於聚醯亞胺膜與支持體之界面產生之內部應力簡記為「內部應力」。若內部應力變大，則存在難以應用於電子裝置之可能性。The inventors of the present invention have conducted verification and found that if the polyamide composition described in patent documents 1 to 3 is coated on a support and the polyamide is imidized, poor adhesion is likely to occur between the obtained polyimide film and the support, and the internal stress generated at the interface between the polyimide film and the support tends to increase. Hereinafter, the poor adhesion between the polyimide film and the support is sometimes referred to as "poor adhesion". In addition, the internal stress generated at the interface between the polyimide film and the support is sometimes referred to as "internal stress". If the internal stress increases, there is a possibility that it is difficult to apply to electronic devices.
本發明係鑒於上述實際情況而完成者，其目的在於提供一種不僅能夠使用安全性較高之溶劑並且抑制密接性不良之產生而且能夠降低內部應力之聚醯胺酸組合物、以及使用該聚醯胺酸組合物之聚醯亞胺之製造方法、積層體之製造方法及電子裝置之製造方法。 [解決問題之技術手段] The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a polyamide composition that can not only use a highly safe solvent and suppress the occurrence of poor adhesion but also reduce internal stress, and use the polyamide composition using the polyamide composition. A method for manufacturing polyimide of an amino acid composition, a method for manufacturing a laminated body, and a method for manufacturing an electronic device. [Technical means to solve problems]
＜本發明之態樣＞ 本發明包含以下態樣。 <Aspects of the present invention> The present invention includes the following aspects.
[1]一種聚醯胺酸組合物，其包含聚醯胺酸及有機溶劑，且 上述聚醯胺酸具有包含下述化學式(1)所表示之二價有機基之殘基、3,3',4,4'-聯苯四羧酸二酐殘基、及對苯二胺殘基， 上述有機溶劑包含選自由下述通式(2)所表示之化合物及下述通式(3)所表示之化合物所組成之群中之一種以上之化合物。 [1] A polyamide composition containing polyamide and an organic solvent, and The above-mentioned polyamide has a residue containing a divalent organic group represented by the following chemical formula (1), a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue, and a p-phenylenediamine residue. base, The organic solvent includes one or more compounds selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
[化1] [Chemistry 1]
上述通式(2)中，R 1、R 2及R 3分別獨立地表示氫原子或碳原子數1以上之一價有機基，R 1、R 2及R 3中之至少一者表示碳原子數2以上之一價有機基， 上述通式(3)中，R 4表示碳原子數2以上之一價有機基。 In the above general formula (2), R1 , R2 and R3 each independently represent a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and at least one of R1 , R2 and R3 represents a monovalent organic group having 2 or more carbon atoms. In the above general formula (3), R4 represents a monovalent organic group having 2 or more carbon atoms.
[2]如上述[1]所記載之聚醯胺酸組合物，其中包含上述化學式(1)所表示之二價有機基之殘基係選自由下述化學式(4)所表示之四價有機基、下述化學式(5)所表示之四價有機基、及下述化學式(6)所表示之二價有機基所組成之群中之一種以上之殘基。[2] The polyamino acid composition described in [1] above, wherein the residue of the divalent organic group represented by the chemical formula (1) is selected from one or more residues of the group consisting of a tetravalent organic group represented by the chemical formula (4), a tetravalent organic group represented by the chemical formula (5), and a divalent organic group represented by the chemical formula (6).
[化2] [Chemicalization 2]
[3]如上述[1]或[2]所記載之聚醯胺酸組合物，其中包含上述化學式(1)所表示之二價有機基之殘基之含有率相對於構成上述聚醯胺酸之全部四羧酸二酐殘基及構成上述聚醯胺酸之全部二胺殘基之合計100莫耳%，為15莫耳%以下。[3] The polyamic acid composition according to the above [1] or [2], wherein the content rate of the residues containing the divalent organic group represented by the above chemical formula (1) is relative to the ratio of the residues constituting the above-mentioned polyamic acid. The total 100 mol% of all the tetracarboxylic dianhydride residues and all the diamine residues constituting the above-mentioned polyamide acid is 15 mol% or less.
[4]如上述[1]至[3]中任一項所記載之聚醯胺酸組合物，其中上述有機溶劑為3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺或1-丁基-2-吡咯啶酮。[4] The polyamine composition as described in any one of [1] to [3] above, wherein the organic solvent is 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide or 1-butyl-2-pyrrolidone.
[5]如上述[1]至[4]中任一項所記載之聚醯胺酸組合物，其中上述聚醯胺酸進而具有1,3-雙(3-胺基丙基)四甲基二矽氧烷殘基。[5] The polyamic acid composition according to any one of the above [1] to [4], wherein the polyamic acid further has 1,3-bis(3-aminopropyl)tetramethyl Disiloxane residue.
[6]如上述[5]所記載之聚醯胺酸組合物，其中上述1,3-雙(3-胺基丙基)四甲基二矽氧烷殘基之含有率相對於構成上述聚醯胺酸之二胺殘基之總量，為0.1莫耳%以上1.0莫耳%以下。[6] The polyamide composition according to the above [5], wherein the content of the 1,3-bis(3-aminopropyl)tetramethyldisiloxane residue is The total amount of diamine residues of amide acid is 0.1 mol% or more and 1.0 mol% or less.
[7]如上述[1]至[6]中任一項所記載之聚醯胺酸組合物，其進而包含矽烷偶合劑。[7] The polyamide composition as described in any one of [1] to [6] above, further comprising a silane coupling agent.
[8]一種聚醯亞胺之製造方法，其係對如上述[1]至[7]中任一項所記載之聚醯胺酸組合物進行加熱而將上述聚醯胺酸進行醯亞胺化。[8] A method for producing polyimide, comprising heating the polyimide composition as described in any one of [1] to [7] above to imidize the polyimide.
[9]一種積層體之製造方法，上述積層體具有支持體及聚醯亞胺膜，且 上述方法係藉由將如上述[1]至[7]中任一項所記載之聚醯胺酸組合物塗佈於支持體上，而形成包含上述聚醯胺酸之塗佈膜，並對上述塗佈膜進行加熱而將上述聚醯胺酸進行醯亞胺化。 [9] A method for manufacturing a laminated body, the laminated body having a support and a polyimide film, and The above method is to form a coating film containing the above-mentioned polyamic acid by coating the polyamic acid composition as described in any one of the above-mentioned [1] to [7] on a support, and then The above-mentioned coating film is heated to imidize the above-mentioned polyamide acid.
[10]一種電子裝置之製造方法，其包括： 步驟Sa，其係對如上述[1]至[7]中任一項所記載之聚醯胺酸組合物進行加熱而將上述聚醯胺酸進行醯亞胺化；及 步驟Sb，其係於藉由上述步驟Sa而獲得之聚醯亞胺膜上配置電子元件。 [發明之效果] [10] A method for manufacturing an electronic device, comprising: Step Sa, which is to heat the polyimide composition described in any one of [1] to [7] above to imidize the polyimide; and Step Sb, which is to arrange an electronic element on the polyimide film obtained by the above step Sa. [Effect of the invention]
根據本發明，可提供一種不僅能夠使用安全性較高之溶劑並且抑制密接性不良之產生而且能降低內部應力之聚醯胺酸組合物、以及使用該聚醯胺酸組合物之聚醯亞胺之製造方法、積層體之製造方法及電子裝置之製造方法。According to the present invention, a polyamic acid composition can be provided which can not only use a safer solvent and suppress the occurrence of poor adhesion but also reduce internal stress, as well as a method for producing polyimide, a method for producing a laminate, and a method for producing an electronic device using the polyamic acid composition.
以下，對本發明之較佳實施方式詳細地進行說明，但本發明並不限定於其等。又，本說明書中記載之學術文獻及專利文獻全部以參考之形式被引入至本說明書中。The preferred embodiments of the present invention are described in detail below, but the present invention is not limited thereto. In addition, all the academic documents and patent documents described in this specification are introduced into this specification in the form of reference.
首先，對本說明書中所使用之用語進行說明。「結構單元」係指構成聚合物之重複單元。「聚醯胺酸」係包含下述通式(7)所表示之結構單元(以下，有時記載為「結構單元(7)」)之聚合物。First, the terms used in this specification are explained. "Structural unit" refers to a repeating unit constituting a polymer. "Polyamide" refers to a polymer containing a structural unit represented by the following general formula (7) (hereinafter, sometimes described as "structural unit (7)").
[化3] [Chemical 3]
通式(7)中，A 1表示四羧酸二酐殘基(源自四羧酸二酐之四價有機基)，A 2表示二胺殘基(源自二胺之二價有機基)。 In the general formula (7), A 1 represents a tetracarboxylic dianhydride residue (a tetravalent organic group derived from a tetracarboxylic dianhydride), and A 2 represents a diamine residue (a divalent organic group derived from a diamine). .
結構單元(7)相對於構成聚醯胺酸之全部結構單元之含有率例如為50莫耳%以上100莫耳%以下，較佳為60莫耳%以上100莫耳%以下，更佳為70莫耳%以上100莫耳%以下，進而較佳為80莫耳%以上100莫耳%以下，進而更佳為90莫耳%以上100莫耳%以下，亦可為100莫耳%。The content of the structural unit (7) relative to all the structural units constituting polyamide is, for example, 50 mol % to 100 mol %, preferably 60 mol % to 100 mol %, more preferably 70 mol % to 100 mol %, further preferably 80 mol % to 100 mol %, further preferably 90 mol % to 100 mol %, and may also be 100 mol %.
「1%重量減少溫度」係指以150℃之測定溫度下之聚醯亞胺之重量為基準(100重量%)，相對於上述基準之重量減少1重量%時之測定溫度。1%重量減少溫度之測定方法係與下述實施例相同之方法或參照下述實施例之方法。"1% weight loss temperature" refers to the measurement temperature at which the weight of polyimide at a measurement temperature of 150°C is reduced by 1% by weight relative to the weight of the above reference (100% by weight). The method for measuring the 1% weight loss temperature is the same as the following examples or the method referring to the following examples.
「烷基」及「烷氧基烷基」均為直鏈狀或支鏈狀且未經取代。"Alkyl" and "alkoxyalkyl" are both linear or branched and unsubstituted.
以下，有時會在化合物名之後附加「系」來總括地統稱化合物及其衍生物。又，於在化合物名之後附加「系」來表示聚合物名之情形時，若無任何規定，則意指聚合物之重複單元源自化合物或其衍生物。又，四羧酸二酐有時記載為「酸二酐」。又，本說明書中例示之成分或官能基等只要未作特別說明，則可單獨使用，亦可併用兩種以上。Hereinafter, "system" may be appended to the compound name to collectively refer to the compound and its derivatives. In addition, when "system" is appended to the compound name to represent the polymer name, unless otherwise specified, it means that the repeating units of the polymer are derived from the compound or its derivatives. Moreover, tetracarboxylic dianhydride may be described as "acid dianhydride". In addition, unless otherwise specified, the components, functional groups, etc. exemplified in this specification may be used alone or two or more types may be used in combination.
＜本發明之較佳之實施方式＞ 本實施方式之聚醯胺酸組合物包含聚醯胺酸及有機溶劑。本實施方式之聚醯胺酸組合物所包含之聚醯胺酸(以下，有時記為「特定聚醯胺酸」)具有包含下述化學式(1)所表示之二價有機基之殘基(以下，有時記為「殘基(1)」)、3,3',4,4'-聯苯四羧酸二酐殘基、及對苯二胺殘基。本實施方式之聚醯胺酸組合物所包含之有機溶劑包含選自由下述通式(2)所表示之化合物(以下，有時記為「化合物(2)」)及下述通式(3)所表示之化合物(以下，有時記為「化合物(3)」)所組成之群中之一種以上之化合物。以下，有時將選自由化合物(2)及化合物(3)所組成之群中之一種以上之化合物(有機溶劑)記為「特定有機溶劑」。又，有時將3,3',4,4'-聯苯四羧酸二酐記為「BPDA」。又，有時將對苯二胺記為「PDA」。 <Preferred embodiment of the present invention> The polyamine composition of the present embodiment comprises polyamine and an organic solvent. The polyamine contained in the polyamine composition of the present embodiment (hereinafter, sometimes referred to as "specific polyamine") has a residue containing a divalent organic group represented by the following chemical formula (1) (hereinafter, sometimes referred to as "residue (1)"), a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue, and a p-phenylenediamine residue. The organic solvent contained in the polyamine composition of the present embodiment comprises one or more compounds selected from the group consisting of a compound represented by the following general formula (2) (hereinafter, sometimes referred to as "compound (2)") and a compound represented by the following general formula (3) (hereinafter, sometimes referred to as "compound (3)"). Hereinafter, one or more compounds (organic solvents) selected from the group consisting of compound (2) and compound (3) may be referred to as "specific organic solvent". Also, 3,3',4,4'-biphenyltetracarboxylic dianhydride may be referred to as "BPDA". Also, p-phenylenediamine may be referred to as "PDA".
[化4] [Chemistry 4]
通式(2)中，R 1、R 2及R 3分別獨立地表示氫原子或碳原子數1以上之一價有機基，R 1、R 2及R 3中之至少一者表示碳原子數2以上之一價有機基。又，通式(3)中，R 4表示碳原子數2以上之一價有機基。 In the general formula (2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group with a carbon number of 1 or more, and at least one of R 1 , R 2 and R 3 represents a carbon atom. 2 or more monovalent organic bases. Moreover, in the general formula (3), R 4 represents a monovalent organic group having 2 or more carbon atoms.
一般而言，聚醯胺酸組合物中，就溶解性或特性提高等觀點而言，使用N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺等碳原子數相對較小之醯胺系溶劑，但人們逐漸認識到該等溶劑有害健康之問題。相對於此，特定有機溶劑對環境或人體之影響較小，安全性較高。Generally speaking, in polyamide compositions, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N,N- Dimethylacetamide and other amide solvents with relatively small carbon atoms are gradually recognized as harmful to health. In contrast, specific organic solvents have less impact on the environment or human body and are safer.
為了提高安全性，作為通式(2)中之R 1、R 2及R 3，分別獨立地較佳為碳原子數1以上之一價有機基，更佳為碳原子數1以上6以下之一價有機基。為了進一步提高安全性，作為通式(2)中之R 1及R 2，分別獨立地較佳為碳原子數1以上之烷基，更佳為碳原子數1以上6以下之烷基。為了進一步提高安全性，作為通式(2)中之R 3，較佳為碳原子數2以上之烷氧基烷基，更佳為碳原子數2以上6以下之烷氧基烷基。 In order to improve safety, R 1 , R 2 and R 3 in the general formula (2) are each independently preferably a monovalent organic group having 1 or more carbon atoms, more preferably a monovalent organic group having 1 or more carbon atoms and less than 6 carbon atoms. In order to further improve safety, R 1 and R 2 in the general formula (2) are each independently preferably an alkyl group having 1 or more carbon atoms, more preferably an alkyl group having 1 or more carbon atoms and less than 6 carbon atoms. In order to further improve safety, R 3 in the general formula (2) is each independently preferably an alkoxyalkyl group having 2 or more carbon atoms, more preferably an alkoxyalkyl group having 2 or more carbon atoms and less than 6 carbon atoms.
為了提高安全性，作為通式(3)中之R 4，較佳為碳原子數2以上6以下之一價有機基。為了進一步提高安全性，作為通式(3)中之R 4，較佳為碳原子數2以上6以下之烷基。 In order to improve safety, R 4 in the general formula (3) is preferably a monovalent organic group having 2 to 6 carbon atoms. In order to further improve safety, R 4 in the general formula (3) is preferably an alkyl group having 2 to 6 carbon atoms.
作為化合物(2)，例如可例舉：3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N,N-二乙基乙醯胺、N,N-二甲基丙醯胺等。該等之中，就安全性之觀點而言，較佳為3-甲氧基-N,N-二甲基丙醯胺或3-丁氧基-N,N-二甲基丙醯胺。Examples of compound (2) include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-diethylacetamide, and N,N-dimethylpropionamide. Among these, 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide are preferred from the viewpoint of safety.
作為化合物(3)，例如可例舉：1-乙基-2-吡咯啶酮、1-丁基-2-吡咯啶酮等。該等之中，就安全性之觀點而言，較佳為1-丁基-2-吡咯啶酮。Examples of the compound (3) include 1-ethyl-2-pyrrolidone and 1-butyl-2-pyrrolidone. Among these, 1-butyl-2-pyrrolidone is preferred from the viewpoint of safety.
本實施方式之聚醯胺酸組合物可僅包含化合物(2)作為特定有機溶劑，亦可僅包含化合物(3)作為特定有機溶劑，亦可包含化合物(2)及化合物(3)之兩者作為特定有機溶劑。為了提高安全性，作為特定有機溶劑，較佳為3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺或1-丁基-2-吡咯啶酮，更佳為3-甲氧基-N,N-二甲基丙醯胺或1-丁基-2-吡咯啶酮。The polyamide composition of this embodiment may include only compound (2) as a specific organic solvent, may include only compound (3) as a specific organic solvent, or may include both compound (2) and compound (3) As a specific organic solvent. In order to improve safety, as the specific organic solvent, 3-methoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide or 1-butylamine is preferred. base-2-pyrrolidone, more preferably 3-methoxy-N,N-dimethylpropylamine or 1-butyl-2-pyrrolidone.
特定聚醯胺酸包含BPDA殘基及PDA殘基，因此具有剛性結構。因此，特定聚醯胺酸能夠降低內部應力。The specific polyamide contains BPDA residues and PDA residues and therefore has a rigid structure. Therefore, certain polyamides are able to reduce internal stress.
另一方面，根據本發明人等之研究，已判明若使用包含具有剛性結構之聚醯胺酸及特定有機溶劑之聚醯胺酸組合物製造聚醯亞胺膜，則於聚醯亞胺膜與支持體之界面變得容易產生***。若於聚醯亞胺膜與支持體之界面存在***，則有引起於形成電子元件時聚醯亞胺膜剝離、或者於形成電子元件後將聚醯亞胺膜自支持體剝離時良率下降之虞。再者，所謂「***」，係指因於醯亞胺化時所產生之副成分或殘存溶劑而於聚醯亞胺膜與其他材料層(更具體而言，玻璃基板、犧牲層等)之間產生密接性不良之狀態。作為具體之「***」，可例舉：聚醯亞胺膜自支持體***之狀態、聚醯亞胺膜之一部分被破壞而於聚醯亞胺膜與其他材料層之間產生層間剝離之狀態等。On the other hand, according to the research of the inventors, it has been found that if a polyimide film is produced using a polyimide composition comprising a polyimide having a rigid structure and a specific organic solvent, ridges are easily generated at the interface between the polyimide film and the support. If ridges exist at the interface between the polyimide film and the support, there is a risk of causing the polyimide film to be peeled off when forming an electronic component, or a decrease in yield when the polyimide film is peeled off from the support after the electronic component is formed. Furthermore, the so-called "ridge" refers to a state in which poor adhesion occurs between the polyimide film and other material layers (more specifically, a glass substrate, a sacrificial layer, etc.) due to by-products or residual solvents generated during imidization. Specific examples of "protrusion" include a state where the polyimide film protrudes from the support, a state where a portion of the polyimide film is damaged and interlayer peeling occurs between the polyimide film and other material layers, and the like.
一般而言，由具有BPDA殘基及PDA殘基之聚醯胺酸獲得之聚醯亞胺膜之分子鏈緊密堆積，因此若使用如特定有機溶劑之碳原子數相對較大之溶劑，則呈現出排氣性變差之趨勢。因此，推測在將包含剛性結構之聚醯胺酸之聚醯胺酸組合物塗佈於支持體上，並進行醯亞胺化之過程中，殘存溶劑或因醯亞胺化而產生之脫離分子被封入，從而容易於聚醯亞胺膜與支持體之界面產生***。對此，本發明人等進行了銳意研究，結果判明，若使用具有BPDA殘基及PDA殘基與殘基(1)之聚醯胺酸(特定聚醯胺酸)，則能夠藉由殘基(1)之蓬鬆之結構而實現良好之排氣性，並且能夠降低內部應力。即，根據本實施方式之聚醯胺酸組合物，由於包含特定聚醯胺酸及特定有機溶劑，故能夠使用安全性較高之溶劑並且藉由良好之排氣性而抑制密接性不良之產生，而且能夠降低內部應力。Generally speaking, the molecular chains of polyimide films obtained from polyamide having BPDA residues and PDA residues are closely packed, so if a solvent with a relatively large number of carbon atoms, such as a specific organic solvent, is used, it will appear The tendency of exhaust performance to deteriorate. Therefore, it is speculated that in the process of coating a polyamic acid composition containing a polyamic acid with a rigid structure on a support and performing imidization, residual solvent or detached molecules generated due to the imidization Being sealed, it is easy to cause bulges at the interface between the polyimide film and the support. In this regard, the inventors of the present invention conducted intensive studies, and as a result, it was found that if a polyamide (specific polyamide) having a BPDA residue, a PDA residue, and the residue (1) is used, it is possible to use the residues (1) The fluffy structure achieves good exhaust and can reduce internal stress. That is, according to the polyamic acid composition of this embodiment, since it contains a specific polyamic acid and a specific organic solvent, it is possible to use a relatively safe solvent and suppress the occurrence of poor adhesion due to good outgassing properties. , and can reduce internal stress.
殘基(1)係聚醯胺酸所包含之殘基，因此係選自由四羧酸二酐殘基及二胺殘基所組成之群中之一種以上之殘基。特定聚醯胺酸可僅具有四羧酸二酐殘基作為殘基(1)，亦可僅具有二胺殘基作為殘基(1)，亦可具有四羧酸二酐殘基及二胺殘基之兩者作為殘基(1)。The residue (1) is a residue contained in the polyamic acid, and is one or more residues selected from the group consisting of tetracarboxylic dianhydride residues and diamine residues. The specific polyamic acid may have only tetracarboxylic dianhydride residues as the residue (1), may have only diamine residues as the residue (1), or may have both tetracarboxylic dianhydride residues and diamine residues as the residue (1).
作為用以形成殘基(1)之四羧酸二酐，例如可例舉：螺[11H-二呋喃并[3,4-b:3',4'-i]𠮿-11,9'-[9H]茀]-1,3,7,9-四酮(以下，有時記為「SFDA」)、9,9-雙(3,4-二羧基苯基)茀二酐(以下，有時記為「BPAF」)、9,9-雙[4-(3,4-二羧基苯氧基)苯基]茀二酐、5,5'-[9H-茀-9-亞基雙(2-甲基-4,1-伸苯基)]雙(1,3-二氫-1,3-二側氧基-5-異苯并呋喃羧酸酯)、N,N'-(9H-茀-9-亞基二-4,1-伸苯基)雙[1,3-二氫-1,3-二側氧基-5-異苯并呋喃甲醯胺基]、5,5'-螺[9H-茀-9,9'-[9H]𠮿]-3',6'-二基雙(1,3-二氫-1,3-二側氧基-5-異苯并呋喃羧酸酯)等。為了進一步抑制密接性不良之產生，作為用以形成殘基(1)之四羧酸二酐，較佳為SFDA或BPAF。Examples of the tetracarboxylic dianhydride used to form the residue (1) include: spiro[11H-difuro[3,4-b:3',4'-i]𠮿 -11,9'-[9H]fluorine]-1,3,7,9-tetraketone (hereinafter sometimes referred to as "SFDA"), 9,9-bis(3,4-dicarboxyphenyl)fluorine Dianhydride (hereinafter, sometimes referred to as "BPAF"), 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluoride dianhydride, 5,5'-[9H-fluoride- N ,N'-(9H-fluorine-9-ylidene-4,1-phenylene)bis[1,3-dihydro-1,3-dioxy-5-isobenzofuranmethamide base], 5,5'-spiro[9H-茀-9,9'-[9H]𠮿 ]-3',6'-diylbis(1,3-dihydro-1,3-bisoxy-5-isobenzofurancarboxylate), etc. In order to further suppress the occurrence of poor adhesion, SFDA or BPAF is preferred as the tetracarboxylic dianhydride used to form the residue (1).
作為用以形成殘基(1)之二胺，例如可例舉：9,9-雙(4-胺基苯基)茀(以下，有時記為「BAFL」)、3,3'-(9H-茀-9,9-二基)二苯胺、4,4'-(9H-茀-9-亞基)雙[2-氟苯胺]等。為了進一步抑制密接性不良之產生，作為用以形成殘基(1)之二胺，較佳為BAFL。Examples of the diamine used to form the residue (1) include 9,9-bis(4-aminophenyl)fluorene (hereinafter, sometimes referred to as "BAFL"), 3,3'-(9H-fluorene-9,9-diyl)diphenylamine, and 4,4'-(9H-fluorene-9-ylidene)bis[2-fluoroaniline]. In order to further suppress the occurrence of poor adhesion, BAFL is preferably used as the diamine used to form the residue (1).
為了進一步抑制密接性不良之產生，作為殘基(1)，較佳為選自由SFDA殘基、BPAF殘基及BAFL殘基所組成之群中之一種以上之殘基。SFDA殘基係下述化學式(4)所表示之四價有機基。BPAF殘基係下述化學式(5)所表示之四價有機基。BAFL殘基係下述化學式(6)所表示之二價有機基。In order to further suppress the occurrence of poor adhesion, the residue (1) is preferably one or more residues selected from the group consisting of SFDA residues, BPAF residues and BAFL residues. The SFDA residue is a tetravalent organic group represented by the following chemical formula (4). The BPAF residue is a tetravalent organic group represented by the following chemical formula (5). The BAFL residue is a bivalent organic group represented by the following chemical formula (6).
[化5] [Chemistry 5]
其中，SFDA殘基具有源自𠮿結構之剛性結構，因此為了進一步降低內部應力並且進一步抑制密接性不良之產生，作為殘基(1)，特佳為SFDA殘基。Among them, the SFDA residue has origin from 𠮿 The structure has a rigid structure, so in order to further reduce internal stress and further suppress the occurrence of poor adhesion, the SFDA residue is particularly preferred as the residue (1).
為了抑制熱膨脹係數之增大，殘基(1)之含有率(於包含複數種殘基(1)之情形時為其等之合計含有率)相對於構成特定聚醯胺酸之全部四羧酸二酐殘基與構成特定聚醯胺酸之全部二胺殘基之合計100莫耳%，較佳為15莫耳%以下，更佳為10莫耳%以下，亦可為5莫耳%以下。又，為了進一步抑制密接性不良之產生，殘基(1)之含有率(於包含複數種殘基(1)之情形時為其等之合計含有率)相對於構成特定聚醯胺酸之全部四羧酸二酐殘基與構成特定聚醯胺酸之全部二胺殘基之合計100莫耳%，較佳為0.1莫耳%以上，更佳為0.5莫耳%以上，進而較佳為1莫耳%以上。In order to suppress an increase in the thermal expansion coefficient, the content rate of the residue (1) (the equal total content rate when multiple types of residues (1) are included) is determined relative to all the tetracarboxylic acids constituting the specific polyamic acid. The total of dianhydride residues and all diamine residues constituting the specific polyamide acid is 100 mol%, preferably 15 mol% or less, more preferably 10 mol% or less, and may also be 5 mol% or less. . In addition, in order to further suppress the occurrence of poor adhesion, the content rate of the residue (1) (when a plurality of types of residues (1) is included, the total content rate of the same) is determined relative to all the components constituting the specific polyamide. The total of tetracarboxylic dianhydride residues and all diamine residues constituting the specific polyamide acid is 100 mol%, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 More than mol%.
於合成特定聚醯胺酸時，亦可在不損害其性能之範圍內，使用除BPDA及用以形成殘基(1)之酸二酐以外之酸二酐作為單體。作為除BPDA及用以形成殘基(1)之酸二酐以外之酸二酐，例如可例舉：均苯四甲酸二酐、對伸苯基雙苯偏三甲酸酯二酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、4,4'-氧二鄰苯二甲酸酐、二環己基-3,3',4,4'-四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、2'-側氧基二螺[雙環[2.2.1]庚烷-2,1'-環戊烷-3',2''-雙環[2.2.1]庚烷]-5,6:5'',6''-四羧酸二酐及該等之衍生物，可將其等單獨使用，或使用兩種以上。When synthesizing the specific polyamide, an acid dianhydride other than BPDA and the acid dianhydride used to form the residue (1) may be used as a monomer within a range that does not impair its performance. Examples of the acid dianhydride other than BPDA and the acid dianhydride used to form the residue (1) include pyromellitic acid dianhydride, p-phenylenediphenyl trimellitic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, dicyclohexyl -3,3',4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2'-oxodispiro[bicyclo[2.2.1]heptane-2,1'-cyclopentane-3',2''-bicyclo[2.2.1]heptane]-5,6:5'',6''-tetracarboxylic dianhydride and derivatives thereof may be used alone or in combination of two or more.
為了進一步降低內部應力，BPDA殘基之含有率相對於構成特定聚醯胺酸之四羧酸二酐殘基之總量(100莫耳%)，較佳為70莫耳%以上，更佳為80莫耳%以上，進而較佳為90莫耳%以上，亦可為100莫耳%。In order to further reduce internal stress, the content rate of BPDA residues is preferably 70 mol% or more relative to the total amount of tetracarboxylic dianhydride residues constituting the specific polyamide (100 mol%), and more preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% may also be used.
於殘基(1)為源自酸二酐之殘基(SFDA殘基、BPAF殘基等)之情形時，為了進一步抑制密接性不良之產生，殘基(1)之含有率相對於構成特定聚醯胺酸之四羧酸二酐殘基之總量(100莫耳%)，較佳為0.1莫耳%以上，更佳為0.5莫耳%以上。又，於殘基(1)為源自酸二酐之殘基(SFDA殘基、BPAF殘基等)之情形時，為了進一步降低內部應力，殘基(1)之含有率相對於構成特定聚醯胺酸之四羧酸二酐殘基之總量(100莫耳%)，較佳為10莫耳%以下，更佳為8莫耳%以下。In the case where the residue (1) is a residue derived from an acid dianhydride (SFDA residue, BPAF residue, etc.), in order to further suppress the occurrence of poor adhesion, the content of the residue (1) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, relative to the total amount (100 mol%) of tetracarboxylic dianhydride residues constituting the specific polyamide. In addition, in the case where the residue (1) is a residue derived from an acid dianhydride (SFDA residue, BPAF residue, etc.), in order to further reduce the internal stress, the content of the residue (1) is preferably 10 mol% or less, more preferably 8 mol% or less, relative to the total amount (100 mol%) of tetracarboxylic dianhydride residues constituting the specific polyamide.
為了進一步抑制密接性不良之產生並且進一步降低內部應力，源自酸二酐之殘基(1)及BPDA殘基之合計含有率相對於構成特定聚醯胺酸之四羧酸二酐殘基之總量(100莫耳%)，較佳為60莫耳%以上，更佳為70莫耳%以上，進而較佳為80莫耳%以上，特佳為90莫耳%以上，亦可為100莫耳%。In order to further suppress the occurrence of poor adhesion and further reduce internal stress, the total content rate of the residue (1) derived from the acid dianhydride and the BPDA residue is determined relative to the tetracarboxylic dianhydride residue constituting the specific polyamide. The total amount (100 mol%) is preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, and may be 100 Mol%.
於合成特定聚醯胺酸時，亦可在不損害其性能之範圍內，使用除PDA及用以形成殘基(1)之二胺以外之二胺作為單體。作為除PDA及用以形成殘基(1)之二胺以外之二胺，例如可例舉：4-胺基苯甲酸4-胺基苯酯、2,2'-雙(三氟甲基)-4,4'-二胺基二苯醚、1,4-環己烷二胺、4,4'-二胺基苯甲醯苯胺、間苯二胺、4,4'-氧二苯胺、3,4'-氧二苯胺、N,N'-雙(4-胺基苯基)對苯二甲醯胺、4,4'-二胺基二苯基碸、間聯甲苯胺、鄰聯甲苯胺、4,4'-雙(4-胺基苯氧基)聯苯、2-(4-胺基苯基)-6-胺基苯并㗁唑、3,5-二胺基苯甲酸、4,4'-二胺基-3,3'-二羥基聯苯、4,4'-亞甲基雙(環己胺)、1,3-雙(3-胺基丙基)四甲基二矽氧烷(以下，有時記為「PAM-E」)及該等之衍生物，可將其等單獨使用，或使用兩種以上。In the synthesis of the specific polyamide, diamines other than PDA and the diamine used to form the residue (1) may be used as monomers within the range that the performance is not impaired. Examples of diamines other than PDA and the diamine used to form the residue (1) include: 4-aminophenyl 4-aminobenzoate, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 1,4-cyclohexanediamine, 4,4'-diaminobenzanilide, m-phenylenediamine, 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, N,N'-bis(4-aminophenyl)-p-phenylenediamine, 4,4'-diaminodiphenylsulfone, intermolecularly linked diamine, Toluidine, o-tolidine, 4,4'-bis(4-aminophenoxy)biphenyl, 2-(4-aminophenyl)-6-aminobenzoxazole, 3,5-diaminobenzoic acid, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, sometimes referred to as "PAM-E"), and derivatives thereof may be used alone or in combination of two or more.
為了提高聚醯亞胺膜與支持體之密接性，作為除PDA及用以形成殘基(1)之二胺以外之二胺，較佳為PAM-E。即，為了提高聚醯亞胺膜與支持體之密接性，特定聚醯胺酸較佳為具有PAM-E殘基。In order to improve the adhesion between the polyimide film and the support, PAM-E is preferred as the diamine other than PDA and the diamine used to form the residue (1). That is, in order to improve the adhesion between the polyimide film and the support, the specific polyamide preferably has a PAM-E residue.
為了進一步提高聚醯亞胺膜與支持體之密接性，PAM-E殘基之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為0.05莫耳%以上，更佳為0.1莫耳%以上，亦可為0.2莫耳%以上。又，為了抑制於形成電子元件後將聚醯亞胺膜自支持體剝離時之良率下降，PAM-E殘基之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為1.0莫耳%以下，更佳為0.9莫耳%以下，進而較佳為0.8莫耳%以下，進而更佳為0.7莫耳%以下，亦可為0.6莫耳%以下。In order to further improve the adhesion between the polyimide film and the support, the content of the PAM-E residue is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and can also be 0.2 mol% or more relative to the total amount (100 mol%) of the diamine residues constituting the specific polyamide. In addition, in order to suppress the decrease in yield when the polyimide film is peeled off from the support after forming the electronic element, the content of the PAM-E residue is preferably 1.0 mol% or less, more preferably 0.9 mol% or less, further preferably 0.8 mol% or less, further preferably 0.7 mol% or less, and can also be 0.6 mol% or less relative to the total amount (100 mol%) of the diamine residues constituting the specific polyamide.
為了進一步降低內部應力，PDA殘基之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為70莫耳%以上，更佳為80莫耳%以上，進而較佳為90莫耳%以上，亦可為100莫耳%。In order to further reduce the internal stress, the content of PDA residues relative to the total amount of diamine residues constituting the specific polyamide (100 mol %) is preferably 70 mol % or more, more preferably 80 mol % or more, further preferably 90 mol % or more, and can also be 100 mol %.
於殘基(1)為源自二胺之殘基(BAFL殘基等)之情形時，為了進一步抑制密接性不良之產生，殘基(1)之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為0.1莫耳%以上，更佳為0.5莫耳%以上。又，於殘基(1)為源自二胺之殘基(BAFL殘基等)之情形時，為了進一步降低內部應力，殘基(1)之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為10莫耳%以下，更佳為8莫耳%以下，進而較佳為5莫耳%以下。When the residue (1) is a residue derived from a diamine (BAFL residue, etc.), in order to further suppress the occurrence of poor adhesion, the content rate of the residue (1) is determined relative to the content of the residue constituting the specific polyamide. The total amount of diamine residues (100 mol%) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. In addition, when the residue (1) is a residue derived from a diamine (BAFL residue, etc.), in order to further reduce the internal stress, the content rate of the residue (1) is determined relative to the second component of the specific polyamide. The total amount of amine residues (100 mol%) is preferably 10 mol% or less, more preferably 8 mol% or less, and still more preferably 5 mol% or less.
為了進一步抑制密接性不良之產生並且進一步降低內部應力，源自二胺之殘基(1)及PDA殘基之合計含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為60莫耳%以上，更佳為70莫耳%以上，進而較佳為80莫耳%以上，特佳為90莫耳%以上，亦可為100莫耳%。In order to further suppress the occurrence of poor adhesion and further reduce internal stress, the total content rate of the diamine-derived residue (1) and the PDA residue is determined relative to the total amount of diamine residues constituting the specific polyamide (100 Mol%), preferably 60 Mol% or more, more preferably 70 Mol% or more, further preferably 80 Mol% or more, particularly preferably 90 Mol% or more, and may be 100 Mol%.
於特定聚醯胺酸具有PAM-E殘基之情形時，為了獲得能夠進一步抑制密接性不良之產生並且進一步降低內部應力，而且能夠進一步提高聚醯亞胺膜與支持體之密接性之聚醯胺酸組合物，PAM-E殘基、源自二胺之殘基(1)及PDA殘基之合計含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，較佳為60莫耳%以上，更佳為70莫耳%以上，進而較佳為80莫耳%以上，特佳為90莫耳%以上，亦可為100莫耳%。When the specific polyamide has PAM-E residues, in order to obtain a polyamide composition that can further suppress the occurrence of poor adhesion and further reduce internal stress, and can further improve the adhesion between the polyimide film and the support, the total content of PAM-E residues, diamine-derived residues (1) and PDA residues is preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, and can also be 100 mol% relative to the total amount of diamine residues constituting the specific polyamide (100 mol%).
為了進一步降低內部應力並且進一步抑制密接性不良之產生，特定聚醯胺酸較佳為滿足下述條件1，更佳為滿足下述條件2，進而較佳為滿足下述條件3，特佳為滿足下述條件4。 條件1：殘基(1)、BPDA殘基及PDA殘基之合計含有率相對於構成特定聚醯胺酸之全部四羧酸二酐殘基與構成特定聚醯胺酸之全部二胺殘基之合計100莫耳%，為90莫耳%以上。 條件2：滿足上述條件1，且進而具有PAM-E殘基。 條件3：滿足上述條件2，且PAM-E殘基之含有率相對於構成特定聚醯胺酸之二胺殘基之總量(100莫耳%)，為0.1莫耳%以上1.0莫耳%以下。 條件4：滿足上述條件3，且殘基(1)、BPDA殘基、PDA殘基及PAM-E殘基之合計含有率相對於構成特定聚醯胺酸之全部四羧酸二酐殘基與構成特定聚醯胺酸之全部二胺殘基之合計100莫耳%，為95莫耳%以上100莫耳%以下。 In order to further reduce the internal stress and further suppress the occurrence of poor adhesion, the specific polyamide preferably satisfies the following condition 1, more preferably satisfies the following condition 2, further preferably satisfies the following condition 3, and particularly preferably satisfies the following condition 4. Condition 1: The total content of the residue (1), BPDA residue and PDA residue is 90 mol% or more relative to the total of 100 mol% of all tetracarboxylic dianhydride residues constituting the specific polyamide and all diamine residues constituting the specific polyamide. Condition 2: Satisfy the above condition 1 and further have a PAM-E residue. Condition 3: The above condition 2 is satisfied, and the content of PAM-E residues is 0.1 mol% or more and 1.0 mol% or less relative to the total amount of diamine residues constituting the specific polyamide (100 mol%). Condition 4: The above condition 3 is satisfied, and the total content of residues (1), BPDA residues, PDA residues and PAM-E residues is 95 mol% or more and 100 mol% or less relative to the total of all tetracarboxylic dianhydride residues constituting the specific polyamide and all diamine residues constituting the specific polyamide (100 mol%).
特定聚醯胺酸可藉由公知之一般方法進行合成，例如可藉由使二胺與四羧酸二酐於有機溶劑中進行反應而獲得。對特定聚醯胺酸之具體之合成方法之一例進行說明。首先，於氬氣、氮氣等惰性氣體氛圍中，使二胺溶解或呈漿料狀分散於有機溶劑中，而製備二胺溶液。然後，將四羧酸二酐於設為溶解或呈漿料狀分散於有機溶劑中之狀態後、或者以固體之狀態，添加至上述二胺溶液中。The specific polyamide can be synthesized by a known general method, for example, by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent. An example of a specific synthesis method of the specific polyamide is described. First, in an atmosphere of an inert gas such as argon or nitrogen, a diamine is dissolved or dispersed in an organic solvent in a slurry form to prepare a diamine solution. Then, the tetracarboxylic dianhydride is added to the above diamine solution after being dissolved or dispersed in an organic solvent in a slurry form, or in a solid state.
於使用二胺與四羧酸二酐合成特定聚醯胺酸之情形時，藉由調整二胺之物質量(於使用複數種二胺之情形時，為各二胺之物質量)及四羧酸二酐之物質量(於使用複數種四羧酸二酐之情形時，為各四羧酸二酐之物質量)，能夠獲得所期望之特定聚醯胺酸(二胺與四羧酸二酐之聚合物)。特定聚醯胺酸中之各殘基之莫耳分率例如與聚醯胺酸之合成所使用之各單體(二胺及四羧酸二酐)之莫耳分率一致。又，藉由摻和兩種聚醯胺酸，亦能夠獲得含有複數種四羧酸二酐殘基及複數種二胺殘基之特定聚醯胺酸。二胺與四羧酸二酐之反應、即特定聚醯胺酸之合成反應之溫度條件並無特別限定，例如為20℃以上150℃以下之範圍。特定聚醯胺酸之合成反應之反應時間例如為10分鐘以上30小時以下之範圍。When using diamine and tetracarboxylic dianhydride to synthesize a specific polyamide, by adjusting the amount of diamine (when using multiple diamines, the amount of each diamine) and the amount of tetracarboxylic acid The amount of acid dianhydride (when using a plurality of tetracarboxylic dianhydrides, the amount of each tetracarboxylic dianhydride) can obtain the desired specific polyamide (diamine and tetracarboxylic dianhydride). anhydride polymer). The molar fraction of each residue in a specific polyamic acid is, for example, consistent with the molar fraction of each monomer (diamine and tetracarboxylic dianhydride) used in the synthesis of the polyamic acid. Furthermore, by blending two types of polyamic acids, a specific polyamic acid containing a plurality of tetracarboxylic dianhydride residues and a plurality of diamine residues can be obtained. The temperature conditions of the reaction between diamine and tetracarboxylic dianhydride, that is, the synthesis reaction of the specific polyamide, are not particularly limited, but are, for example, in the range of 20°C or more and 150°C or less. The reaction time for the synthesis reaction of a specific polyamide is, for example, in the range of from 10 minutes to 30 hours.
特定聚醯胺酸之合成所使用之有機溶劑較佳為能溶解所使用之四羧酸二酐及二胺之溶劑，更佳為能溶解要生成之特定聚醯胺酸之溶劑。作為特定聚醯胺酸之合成所使用之有機溶劑，就安全性之觀點而言，較佳為上述特定有機溶劑。又，於特定聚醯胺酸之合成中，亦可使用特定有機溶劑以外之有機溶劑。作為特定有機溶劑以外之有機溶劑，例如可例舉：四甲基脲、N,N-二甲基乙基脲等脲系溶劑；二甲基亞碸等亞碸系溶劑；二苯碸、四甲基碸等碸系溶劑；N,N-二甲基乙醯胺(DMAC)、N,N-二甲基甲醯胺(DMF)、N-甲基-2-吡咯啶酮(NMP)、六甲基磷醯三胺等除特定有機溶劑以外之醯胺系溶劑；γ-丁內酯等酯系溶劑；氯仿、二氯甲烷等鹵化烷基系溶劑；苯、甲苯等芳香族烴系溶劑；苯酚、甲酚等酚系溶劑；環戊酮等酮系溶劑；四氫呋喃、1,3-二氧戊環、1,4-二㗁烷、二甲醚、二***、二乙二醇二***、二乙二醇二甲醚、對甲酚甲醚等醚系溶劑。通常單獨使用該等溶劑，但亦可視需要適當組合兩種以上來使用。又，特定聚醯胺酸之合成反應較佳為於氬氣或氮氣等惰性氣體氛圍下進行。The organic solvent used in the synthesis of the specific polyamic acid is preferably a solvent that can dissolve the tetracarboxylic dianhydride and diamine used, and more preferably a solvent that can dissolve the specific polyamic acid to be produced. As an organic solvent used for the synthesis of specific polyamide, from the viewpoint of safety, the above-mentioned specific organic solvent is preferred. In addition, in the synthesis of the specific polyamide, organic solvents other than the specific organic solvent may also be used. Examples of organic solvents other than the specific organic solvent include urea-based solvents such as tetramethylurea and N,N-dimethylethylurea; teresine-based solvents such as dimethyl teresine; Methyl alcohol and other methyl solvents; N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), Amide solvents other than specific organic solvents such as hexamethylphosphotriamine; ester solvents such as γ-butyrolactone; halogenated alkyl solvents such as chloroform and dichloromethane; 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, diethylene glycol diethyl ether , diethylene glycol dimethyl ether, p-cresol methyl ether and other ether solvents. These solvents are usually used alone, but two or more of them may be used in appropriate combination as necessary. In addition, the synthesis reaction of the specific polyamide is preferably carried out under an inert gas atmosphere such as argon or nitrogen.
本實施方式之聚醯胺酸組合物含有特定聚醯胺酸及特定有機溶劑。於藉由上述方法而獲得特定聚醯胺酸之情形時，亦可將反應溶液(反應後之溶液)本身作為本實施方式之聚醯胺酸組合物。於將反應溶液本身作為本實施方式之聚醯胺酸組合物之情形時，作為用於合成特定聚醯胺酸之有機溶劑，較佳為上述特定有機溶劑。又，亦可將自反應溶液去除溶劑而獲得之固體之特定聚醯胺酸溶解於特定有機溶劑，而製備本實施方式之聚醯胺酸組合物。The polyamine composition of the present embodiment contains a specific polyamine and a specific organic solvent. When the specific polyamine is obtained by the above method, the reaction solution (solution after the reaction) itself can also be used as the polyamine composition of the present embodiment. When the reaction solution itself is used as the polyamine composition of the present embodiment, the organic solvent used to synthesize the specific polyamine is preferably the above-mentioned specific organic solvent. In addition, the solid specific polyamine obtained by removing the solvent from the reaction solution can be dissolved in a specific organic solvent to prepare the polyamine composition of the present embodiment.
本實施方式之聚醯胺酸組合物中亦可包含特定有機溶劑以外之有機溶劑。其中，就安全性之觀點而言，本實施方式之聚醯胺酸組合物中之特定有機溶劑之含有率相對於聚醯胺酸組合物中之有機溶劑之總量，較佳為70重量%以上，更佳為80重量%以上，進而較佳為90重量%以上，特佳為100重量%。再者，本實施方式之聚醯胺酸組合物中之特定聚醯胺酸之含有率並無特別限制，例如相對於聚醯胺酸組合物總量，為1重量%以上80重量%以下。The polyamine composition of the present embodiment may also contain an organic solvent other than the specific organic solvent. Among them, from the perspective of safety, the content of the specific organic solvent in the polyamine composition of the present embodiment is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 100% by weight relative to the total amount of the organic solvent in the polyamine composition. Furthermore, the content of the specific polyamine in the polyamine composition of the present embodiment is not particularly limited, for example, it is 1% by weight or more and 80% by weight or less relative to the total amount of the polyamine composition.
特定聚醯胺酸之重量平均分子量較佳為10,000以上1,000,000以下之範圍、更佳為20,000以上500,000以下之範圍、進而較佳為30,000以上200,000以下之範圍，但亦取決於其用途。若重量平均分子量為10,000以上，則容易將特定聚醯胺酸、或使用特定聚醯胺酸獲得之聚醯亞胺製成塗佈膜或聚醯亞胺膜(膜)。另一方面，若重量平均分子量為1,000,000以下，則對溶劑表現出充分之溶解性，因此使用下述聚醯胺酸組合物可獲得表面平滑且厚度均勻之塗佈膜或聚醯亞胺膜。此處所使用之重量平均分子量係指使用凝膠滲透層析法(GPC)所測得之聚環氧乙烷換算值。The weight average molecular weight of the specific polyamine is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000, and further preferably in the range of 30,000 to 200,000, but it also depends on its use. If the weight average molecular weight is 10,000 or more, it is easy to make a coating film or a polyimide film (film) from the specific polyamine or the polyimide obtained using the specific polyamine. On the other hand, if the weight average molecular weight is 1,000,000 or less, it shows sufficient solubility in the solvent, so the following polyamine composition can be used to obtain a coating film or a polyimide film with a smooth surface and uniform thickness. The weight average molecular weight used here refers to the polyethylene oxide equivalent value measured by gel permeation chromatography (GPC).
又，作為控制特定聚醯胺酸之分子量之方法，可例舉使酸二酐與二胺之任一者過量之方法、或者藉由與鄰苯二甲酸酐或苯胺之類的單官能性酸酐或胺進行反應而使反應淬滅之方法。於使酸二酐與二胺之任一者過量來進行聚合之情形時，若其等之饋入莫耳比為0.95至1.05之間，則能夠獲得具有充分之強度之聚醯亞胺膜。再者，上述饋入莫耳比係特定聚醯胺酸之合成所使用之二胺之合計物質量相對於特定聚醯胺酸之合成所使用之酸二酐之合計物質量的比(二胺之合計物質量/酸二酐之合計物質量)。又，藉由利用鄰苯二甲酸酐、順丁烯二酸酐、苯胺等進行末端封端，亦能夠進一步減少使用特定聚醯胺酸所獲得之聚醯亞胺之著色。In addition, as a method of controlling the molecular weight of a specific polyamic acid, there can be exemplified a method of making an excess of either an acid dianhydride or a diamine, or a method of controlling the molecular weight of a specific polyamic acid with a monofunctional acid anhydride such as phthalic anhydride or aniline. Or a method of quenching the reaction by reacting with an amine. When polymerizing an acid dianhydride or a diamine in an excess amount, a polyimide film with sufficient strength can be obtained if the molar ratio of the two is between 0.95 and 1.05. Furthermore, the above-mentioned feed molar ratio is the ratio of the total amount of diamines used in the synthesis of the specific polyamic acid to the total amount of the acid dianhydride used in the synthesis of the specific polyamic acid (diamine The total material quantity/the total material quantity of acid dianhydride). Furthermore, by terminal capping with phthalic anhydride, maleic anhydride, aniline, etc., the coloring of the polyimide obtained using a specific polyamide can be further reduced.
又，本實施方式之聚醯胺酸組合物為了縮短加熱時間或表現特性，亦可包含醯亞胺化促進劑及/或脫水觸媒。Furthermore, the polyamide composition of the present embodiment may also contain an imidization accelerator and/or a dehydration catalyst in order to shorten the heating time or improve the performance.
作為上述醯亞胺化促進劑，並無特別限定，可使用三級胺。作為三級胺，較佳為雜環式三級胺。作為雜環式三級胺之較佳之具體例，可例舉：吡啶、甲基吡啶、喹啉、異喹啉、咪唑類等。作為上述脫水觸媒，可例舉乙酸酐、丙酸酐、正丁酸酐、苯甲酸酐、三氟乙酸酐等作為較佳之具體例。The above-mentioned imidization accelerator is not particularly limited, and a tertiary amine can be used. As the tertiary amine, a heterocyclic tertiary amine is preferred. Preferred specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline, and imidazoles. Preferred specific examples of the above-mentioned dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
就縮短加熱時間之觀點及表現特性之觀點而言，醯亞胺化促進劑之量相對於100重量份之特定聚醯胺酸，較佳為0.1重量份以上20重量份以下，更佳為0.5重量份以上20重量份以下。又，就縮短加熱時間之觀點及表現特性之觀點而言，脫水觸媒之量相對於100重量份之特定聚醯胺酸，較佳為0.1重量份以上10重量份以下，更佳為0.5重量份以上5重量份以下。From the viewpoint of shortening the heating time and the viewpoint of showing the characteristics, the amount of the imidization accelerator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the specific polyamide. Also, from the viewpoint of shortening the heating time and the viewpoint of showing the characteristics, the amount of the dehydration catalyst is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific polyamide.
作為醯亞胺化促進劑，較佳為咪唑類。再者，本說明書中，咪唑類係指具有1,3-二唑環(1,3-二唑環結構)之化合物。作為能夠向本實施方式之聚醯胺酸組合物中添加之咪唑類，並無特別限定，例如可例舉：1H-咪唑、2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑等。該等之中，較佳為1,2-二甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑，更佳為1,2-二甲基咪唑、1-苄基-2-甲基咪唑。As the imidization accelerator, imidazoles are preferred. In addition, in this specification, imidazoles refer to the compound which has a 1,3-oxadiazole ring (1,3-oxadiazole ring structure). The imidazoles that can be added to the polyamic acid composition of this embodiment are not particularly limited, and examples thereof include: 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-decane Heptalkyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl 1-Benzyl imidazole, 1-benzyl-2-phenylimidazole, etc. Among these, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole are preferred, and 1,2-dimethylimidazole is more preferred. , 1-benzyl-2-methylimidazole.
咪唑類之含量相對於特定聚醯胺酸之醯胺基1莫耳，較佳為0.005莫耳以上0.1莫耳以下，更佳為0.01莫耳以上0.08莫耳以下，進而較佳為0.015莫耳以上0.050莫耳以下。藉由含有0.005莫耳以上之咪唑類，能夠提高聚醯亞胺之膜強度及透明性，藉由使咪唑類之含量為0.1莫耳以下，能夠維持特定聚醯胺酸之保存穩定性，並且提高耐熱性。再者，本說明書中，「特定聚醯胺酸之醯胺基」係指藉由二胺與四羧酸二酐之聚合反應而生成之醯胺基。The content of imidazoles is preferably 0.005 mol or more and 0.1 mol or less, more preferably 0.01 mol or more and 0.08 mol or less, and further preferably 0.015 mol or more and 0.050 mol or less, relative to 1 mol of the amide group of the specific polyamide. By containing 0.005 mol or more of imidazoles, the film strength and transparency of the polyimide can be improved, and by making the content of imidazoles 0.1 mol or less, the storage stability of the specific polyamide can be maintained and the heat resistance can be improved. Furthermore, in this specification, "amide groups of specific polyamides" refer to amide groups generated by the polymerization reaction of diamines and tetracarboxylic dianhydride.
特定聚醯胺酸與咪唑類之混合方法並無特別限制。就控制特定聚醯胺酸之分子量之容易性之觀點而言，較佳為向聚合後之特定聚醯胺酸中添加咪唑類。此時，可將咪唑類直接添加至特定聚醯胺酸，亦可預先將咪唑類溶解於溶劑中，並將該溶液添加至特定聚醯胺酸中，添加方法並無特別限制。亦可向聚合後之包含特定聚醯胺酸之溶液(反應後之溶液)中添加咪唑類，而製備本實施方式之聚醯胺酸組合物。The mixing method of the specific polyamide and imidazoles is not particularly limited. From the viewpoint of ease of controlling the molecular weight of the specific polyamic acid, it is preferable to add imidazoles to the specific polyamic acid after polymerization. At this time, imidazoles can be added directly to the specific polyamic acid, or imidazoles can be dissolved in a solvent in advance and the solution can be added to the specific polyamic acid. The adding method is not particularly limited. The polyamic acid composition of this embodiment can also be prepared by adding imidazoles to a solution containing a specific polyamic acid after polymerization (solution after reaction).
本實施方式之聚醯胺酸組合物中，亦可調配各種有機或無機之低分子化合物、或高分子化合物作為添加劑。作為添加劑，例如可使用塑化劑、抗氧化劑、染料、界面活性劑、調平劑、矽酮、微粒子、增感劑等。微粒子包括包含聚苯乙烯、聚四氟乙烯等之有機微粒子、或包含膠體氧化矽、碳、層狀矽酸鹽等之無機微粒子等，其等亦可為多孔質結構或中空結構。又，微粒子之功能及形態並無特別限定，例如可為顏料，亦可為填料，亦可為纖維狀粒子。In the polyamide composition of the present embodiment, various organic or inorganic low molecular weight compounds or high molecular weight compounds may also be formulated as additives. As additives, for example, plasticizers, antioxidants, dyes, surfactants, leveling agents, silicones, microparticles, sensitizers, etc. may be used. Microparticles include organic microparticles containing polystyrene, polytetrafluoroethylene, etc., or inorganic microparticles containing colloidal silicon oxide, carbon, layered silicate, etc., which may also be porous structures or hollow structures. In addition, the function and morphology of the microparticles are not particularly limited, for example, they may be pigments, fillers, or fiber-like particles.
又，為了表現出與支持體之適當之密接性，可使本實施方式之聚醯胺酸組合物含有矽烷偶合劑。矽烷偶合劑可無特別限制地使用公知之矽烷偶合劑。為了表現出與支持體之良好之密接性，作為可使用之矽烷偶合劑，較佳為含有胺基之化合物，更佳為選自由3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-(乙氧基二甲基矽烷基)丙胺、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷及N-苯基-3-胺基丙基三甲氧基矽烷所組成之群中之一種以上之化合物，進而較佳為選自由3-胺基丙基三乙氧基矽烷及3-胺基丙基二乙氧基甲基矽烷所組成之群中之一種以上之化合物，特佳為3-胺基丙基三乙氧基矽烷。In order to express appropriate adhesion with the support, the polyamic acid composition of the present embodiment may contain a silane coupling agent. As the silane coupling agent, a known silane coupling agent can be used without particular limitation. In order to exhibit good adhesion with the support, the silane coupling agent that can be used is preferably a compound containing an amine group, and more preferably a compound selected from the group consisting of 3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane. Triethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-(ethoxydimethylsilyl)propylamine, N-2-(aminoethyl)-3-amino Composed of propyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane One or more compounds in the group, and more preferably one or more compounds selected from the group consisting of 3-aminopropyltriethoxysilane and 3-aminopropyldiethoxymethylsilane, Particularly preferred is 3-aminopropyltriethoxysilane.
矽烷偶合劑相對於100重量份之特定聚醯胺酸之調配比率較佳為0.01重量份以上0.50重量份以下，更佳為0.01重量份以上0.30重量份以下，進而較佳為0.01重量份以上0.20重量份以下。藉由使矽烷偶合劑之調配比率為0.01重量份以上，能夠充分地發揮對支持體之剝離抑制效果，藉由使矽烷偶合劑之調配比率為0.50重量份以下，能夠抑制特定聚醯胺酸之分子量下降，因此能夠抑制聚醯亞胺膜之脆化。The mixing ratio of the silane coupling agent to 100 parts by weight of the specific polyamide is preferably 0.01 parts by weight to 0.50 parts by weight, more preferably 0.01 parts by weight to 0.30 parts by weight, and further preferably 0.01 parts by weight to 0.20 parts by weight. By making the mixing ratio of the silane coupling agent 0.01 parts by weight or more, the peeling-inhibiting effect on the support can be fully exerted, and by making the mixing ratio of the silane coupling agent 0.50 parts by weight or less, the molecular weight reduction of the specific polyamide can be suppressed, thereby suppressing the embrittlement of the polyimide film.
於3-甲氧基-N,N-二甲基丙醯胺等pH值較高之有機溶劑中，存在矽烷偶合劑之反應速度變高之情形，由於難以控制所生成之矽烷醇基之縮合反應，因此較佳為視需要減少烷氧基之數量、或使用具有反應性較低之烷氧基之矽烷偶合劑。具體而言，藉由使用3-胺基丙基三乙氧基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-(乙氧基二甲基矽烷基)丙胺等，能夠控制矽烷醇基之縮合反應並且實現與支持體之良好之密接性及剝離性。In organic solvents with a high pH value such as 3-methoxy-N,N-dimethylpropionamide, the reaction rate of the silane coupling agent may increase. Since it is difficult to control the condensation reaction of the generated silanol group, it is better to reduce the number of alkoxy groups as needed or use a silane coupling agent with a less reactive alkoxy group. Specifically, by using 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-(ethoxydimethylsilyl)propylamine, etc., the condensation reaction of the silanol group can be controlled and good adhesion and releasability with the support can be achieved.
本實施方式之聚醯亞胺之製造方法具備對本實施方式之聚醯胺酸組合物進行加熱而將特定聚醯胺酸進行醯亞胺化之步驟。作為將特定聚醯胺酸進行醯亞胺化之方法，並無特別限制，可採用公知之方法。以下，對將特定聚醯胺酸進行醯亞胺化之方法之一例進行說明。醯亞胺化係藉由使特定聚醯胺酸進行脫水閉環而進行。該脫水閉環能夠藉由使用共沸溶劑之共沸法、熱方法或化學方法來進行。或者，亦能夠藉由直接將聚醯胺酸組合物放入利用氟系樹脂實施了塗佈等離型處理之容器中，並於減壓下對該聚醯胺酸組合物進行加熱、乾燥，而進行特定聚醯胺酸之脫水閉環。藉由利用該等方法所進行之特定聚醯胺酸之脫水閉環，能夠獲得聚醯亞胺。再者，上述各處理之加熱時間根據進行脫水閉環之聚醯胺酸組合物之處理量或加熱溫度而不同，但一般而言，較佳為設為在處理溫度達到最高溫度後之1分鐘以上300分鐘以下之範圍。The method for producing polyimide of the present embodiment comprises the step of heating the polyamic acid composition of the present embodiment to imidize the specific polyamic acid. There is no particular limitation on the method for imidizing the specific polyamic acid, and a known method can be used. Hereinafter, an example of a method for imidizing the specific polyamic acid is described. The imidization is carried out by dehydrating and ring-closing the specific polyamic acid. The dehydration and ring-closing can be carried out by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method. Alternatively, the polyamine composition can be directly placed in a container that has been subjected to plasma treatment with a fluorine resin, and the polyamine composition can be heated and dried under reduced pressure to perform dehydration and ring-closing of a specific polyamine. By performing dehydration and ring-closing of a specific polyamine using these methods, polyimide can be obtained. Furthermore, the heating time of each of the above treatments varies depending on the amount of the polyamine composition to be dehydrated and ring-closed or the heating temperature, but in general, it is preferably set to a range of more than 1 minute and less than 300 minutes after the treatment temperature reaches the highest temperature.
又，自特定聚醯胺酸向聚醯亞胺之醯亞胺化可設為1%以上100%以下之任意之比率。即，亦可合成一部分被醯亞胺化之特定聚醯胺酸。特別是於藉由加熱升溫而進行醯亞胺化之情形時，存在自特定聚醯胺酸向聚醯亞胺之閉環反應與特定聚醯胺酸之水解同時進行，使得製成聚醯亞胺時之分子量低於特定聚醯胺酸之分子量之可能性，因此於形成下述聚醯亞胺膜之前，預先將聚醯胺酸組合物中之特定聚醯胺酸之一部分進行醯亞胺化就提高機械特性之觀點而言較佳。本說明書中，一部分被醯亞胺化之聚醯胺酸有時亦記為「聚醯胺酸」。Moreover, the imidization from a specific polyamic acid to a polyimide can be set to any ratio of 1% or more and 100% or less. That is, it is also possible to synthesize a specific polyamide partially imidized. Especially when imidization is performed by raising the temperature by heating, the ring-closing reaction from a specific polyamic acid to a polyimide proceeds simultaneously with the hydrolysis of the specific polyamic acid, so that a polyimide can be produced. It is possible that the molecular weight is lower than the molecular weight of the specific polyamic acid. Therefore, before forming the following polyimide film, a part of the specific polyamic acid in the polyamic acid composition is imidized in advance. It is preferable from the viewpoint of improving mechanical properties. In this specification, a partially imidized polyamide may also be referred to as "polyamic acid".
本實施方式之積層體之製造方法係具有支持體及聚醯亞胺膜(詳細而言，包含特定聚醯胺酸之醯亞胺化物之聚醯亞胺膜)之積層體之製造方法。本實施方式之積層體之製造方法中，藉由對特定聚醯胺酸進行加熱，而使特定聚醯胺酸脫水閉環，從而醯亞胺化。對特定聚醯胺酸進行加熱之方法並無特別限制，例如可例舉如下方法：藉由在支持體上塗佈上述本實施方式之聚醯胺酸組合物，而形成包含特定聚醯胺酸之塗佈膜，將所獲得之塗佈膜於例如溫度40℃以上500℃以下之範圍內進行熱處理。作為支持體，可例舉：玻璃基板、金屬板、PET膜(聚對苯二甲酸乙二酯膜)、或於玻璃基板上積層有非晶矽層(a-Si層)之附犧牲層之玻璃基板等。根據該方法，可獲得具有支持體、及配置於該支持體上之聚醯亞胺膜(詳細而言，包含特定聚醯胺酸之醯亞胺化物之聚醯亞胺膜)之積層體。The manufacturing method of the laminated body of this embodiment is a manufacturing method of the laminated body which has a support and a polyimide film (specifically, a polyimide film containing the imide compound of a specific polyamide). In the manufacturing method of the laminated body of this embodiment, by heating a specific polyamic acid, the specific polyamic acid is dehydrated and ring-closed, and is imidized. The method of heating the specific polyamic acid is not particularly limited. For example, the following method can be used: by coating the polyamic acid composition of the present embodiment on a support to form a mixture containing the specific polyamic acid. The coating film obtained is subjected to heat treatment at a temperature ranging from 40°C to 500°C, for example. Examples of the support include a glass substrate, a metal plate, a PET film (polyethylene terephthalate film), or a glass substrate with an amorphous silicon layer (a-Si layer) and a sacrificial layer. Glass substrate, etc. According to this method, a laminated body having a support and a polyimide film (specifically, a polyimide film containing an imide compound of a specific polyamide acid) disposed on the support can be obtained.
藉由本實施方式之積層體之製造方法而形成之聚醯亞胺膜(詳細而言，包含特定聚醯胺酸之醯亞胺化物之聚醯亞胺膜)因無色透明且黃度較低，具有能耐受TFT製作步驟之玻璃轉移溫度(耐熱性)，故適於可撓性顯示器之透明基板材料。關於上述聚醯亞胺膜中之聚醯亞胺(詳細而言，特定聚醯胺酸之醯亞胺化物)之含有率，相對於聚醯亞胺膜總量，例如為70重量%以上，較佳為80重量%以上，更佳為90重量%以上，亦可為100重量%。作為聚醯亞胺膜中之除聚醯亞胺以外之成分，例如可例舉上述添加劑(更具體而言，微粒子等)。The polyimide film (specifically, the polyimide film containing the imide compound of a specific polyamic acid) formed by the manufacturing method of the laminate of the present embodiment is colorless, transparent, and has a low yellowness, and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing step, so it is suitable for a transparent substrate material for a flexible display. The content of the polyimide (specifically, the imide compound of a specific polyamic acid) in the polyimide film is, for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and may be 100% by weight, relative to the total amount of the polyimide film. As components other than polyimide in the polyimide film, for example, the above-mentioned additives (more specifically, fine particles etc.) can be mentioned.
本實施方式之電子裝置(更具體而言，可撓性裝置等)之製造方法包括：步驟Sa，其係對本實施方式之聚醯胺酸組合物進行加熱而將特定聚醯胺酸進行醯亞胺化；及步驟Sb，其係於藉由步驟Sa而獲得之聚醯亞胺膜上配置電子元件。步驟Sa例如與上述本實施方式之積層體之製造方法相同。步驟Sb中，例如於藉由步驟Sa而獲得之聚醯亞胺膜上直接或間接地配置電子元件(TFT等)。The manufacturing method of an electronic device (more specifically, a flexible device, etc.) of this embodiment includes step Sa, which is to heat the polyamic acid composition of this embodiment to melt a specific polyamic acid. Amination; and step Sb, which is to configure electronic components on the polyimide film obtained by step Sa. Step Sa is, for example, the same as the manufacturing method of the laminated body of this embodiment mentioned above. In step Sb, for example, an electronic component (TFT, etc.) is directly or indirectly disposed on the polyimide film obtained in step Sa.
於製造電子裝置用於可撓性顯示器之情形時，首先，將玻璃等無機基材作為支持體，於其上形成聚醯亞胺膜。然後，藉由在聚醯亞胺膜上配置(形成)TFT等電子元件，而於支持體上形成電子裝置。形成TFT之步驟通常於150℃以上650℃以下之較廣之溫度區域內實施，但為了實質上達成所期望之性能，會以300℃以上形成氧化物半導體層或a-Si(非晶矽)層，視情形有時會進一步利用雷射等使a-Si等結晶化。When manufacturing electronic devices for use in flexible displays, first, an inorganic substrate such as glass is used as a support, and a polyimide film is formed on it. Then, electronic components such as TFTs are arranged (formed) on the polyimide film to form an electronic device on the support. The step of forming a TFT is usually carried out in a wide temperature range of 150°C to 650°C. However, in order to substantially achieve the desired performance, the oxide semiconductor layer or a-Si (amorphous silicon) is formed at 300°C or higher. layer, depending on the situation, a-Si, etc. may be further crystallized using laser or the like.
此時，於聚醯亞胺膜之熱分解溫度較低之情形時，有可能會在形成電子元件之過程中產生釋氣，該釋氣以昇華物之形式附著於烘箱內而造成爐內污染，或者形成於聚醯亞胺膜上之無機膜(下述障壁膜等)或電子元件剝離，因此聚醯亞胺之1%重量減少溫度較佳為500℃以上。聚醯亞胺之1%重量減少溫度之上限越高越好，例如為600℃。1%重量減少溫度例如能夠藉由變更具有剛性結構之殘基(更具體而言，BPDA殘基、PDA殘基等)之含有率來調整。進一步詳細地進行說明，於形成TFT之前，在聚醯亞胺膜上形成氧化矽膜(SiOx膜)或氮化矽膜(SiNx膜)等無機膜作為障壁膜。此時，於聚醯亞胺之耐熱性較低之情形或醯亞胺化未完全進行之情形時，或者殘存溶劑較多之情形時，有在積層無機膜之後的高溫製程中因聚醯亞胺之分解氣體等揮發成分而使聚醯亞胺與無機膜剝離之情形。因此，理想的是除了聚醯亞胺之1%重量減少溫度為500℃以上以外，在400℃以上450℃以下之範圍內之溫度下等溫保持聚醯亞胺時之重量減少率亦未達1%。At this time, when the thermal decomposition temperature of the polyimide film is low, outgassing may be generated during the process of forming electronic components. This outgassing will adhere to the oven in the form of sublimates and cause contamination in the oven. , or the inorganic film (barrier film described below, etc.) or electronic components formed on the polyimide film is peeled off, so the 1% weight loss temperature of polyimide is preferably 500°C or above. The higher the upper limit of the 1% weight reduction temperature of polyimide, the better, for example, 600°C. The 1% weight loss temperature can be adjusted, for example, by changing the content rate of residues having a rigid structure (more specifically, BPDA residues, PDA residues, etc.). To explain in further detail, before forming the TFT, an inorganic film such as a silicon oxide film (SiOx film) or a silicon nitride film (SiNx film) is formed as a barrier film on the polyimide film. At this time, when the heat resistance of the polyimide is low, imidization is not completely progressed, or when there is a large amount of residual solvent, the polyimide may be lost during the high-temperature process after laminating the inorganic film. The decomposition gas of amine and other volatile components cause the polyimide to peel off the inorganic film. Therefore, it is ideal that in addition to the 1% weight reduction temperature of the polyimide being 500°C or higher, the weight reduction rate when the polyimide is isothermally maintained at a temperature in the range of 400°C to 450°C should not reach 1%.
又，於聚醯亞胺之玻璃轉移溫度(Tg)顯著低於製程溫度之情形時，形成電子元件之過程中有可能會產生位置偏移等，因此聚醯亞胺之Tg較佳為300℃以上，更佳為350℃以上，進而較佳為400℃以上，進而更佳為420℃以上。聚醯亞胺之Tg之上限越高則越佳，例如為470℃。又，一般而言，玻璃基板之熱膨脹係數小於樹脂，因此玻璃基板與聚醯亞胺膜之間會產生內部應力。若用作支持體之玻璃基板或電子元件與聚醯亞胺膜之積層體之內部應力較高，則包含聚醯亞胺膜之積層體在高溫之TFT形成步驟中會膨脹，然後在冷卻至常溫時會收縮，而產生玻璃基板之翹曲或破損、以及聚醯亞胺膜自玻璃基板剝離等問題。因此，具有支持體及聚醯亞胺膜之積層體中，聚醯亞胺膜與支持體之間之內部應力較佳為40 MPa以下，更佳為30 MPa以下，進而較佳為20 MPa，特佳為10 MPa以下。內部應力之下限越低則越佳，亦可為0 MPa。內部應力之測定方法係與下述實施例相同之方法或依據其之方法。In addition, when the glass transition temperature (Tg) of polyimide is significantly lower than the process temperature, positional deviation may occur during the process of forming electronic components, so the Tg of polyimide is preferably 300°C or higher, more preferably 350°C or higher, further preferably 400°C or higher, further preferably 420°C or higher. The higher the upper limit of the Tg of polyimide, the better, for example, 470°C. In addition, generally speaking, the thermal expansion coefficient of the glass substrate is smaller than that of the resin, so internal stress is generated between the glass substrate and the polyimide film. If the internal stress of the laminate of the glass substrate or electronic components and the polyimide film used as a support is high, the laminate including the polyimide film will expand during the high-temperature TFT formation step, and then shrink when cooled to room temperature, resulting in problems such as warping or damage of the glass substrate and peeling of the polyimide film from the glass substrate. Therefore, in the laminate having a support and a polyimide film, the internal stress between the polyimide film and the support is preferably 40 MPa or less, more preferably 30 MPa or less, further preferably 20 MPa, and particularly preferably 10 MPa or less. The lower the lower limit of the internal stress, the better, and it may be 0 MPa. The internal stress is determined by the same method as in the following embodiment or a method based thereon.
藉由本實施方式之製造方法而獲得之聚醯亞胺可良好地用作TFT基板或觸控面板基板等顯示器基板之材料。於將聚醯亞胺用於上述用途時，大多情況下會採用如上所述般於支持體上形成電子裝置(詳細而言，於聚醯亞胺膜上形成電子元件所得之電子裝置)之後，將聚醯亞胺膜自支持體剝離之方法。又，作為支持體之材料，適宜使用無鹼玻璃。以下，對聚醯亞胺膜與支持體之積層體之製造方法之一例詳細地進行敍述。The polyimide obtained by the manufacturing method of this embodiment can be favorably used as a material for display substrates such as TFT substrates and touch panel substrates. When polyimide is used for the above-mentioned purposes, in most cases, an electronic device is formed on a support as described above (specifically, an electronic device in which electronic components are formed on a polyimide film) is then formed. Method for peeling polyimide film from support. In addition, as the material of the support, alkali-free glass is suitably used. Hereinafter, an example of a method for producing a laminate of a polyimide film and a support will be described in detail.
首先，於支持體上塗佈(流延)本實施方式之聚醯胺酸組合物，形成包含含有特定聚醯胺酸之塗佈膜、及支持體的含塗佈膜之積層體。其次，對含塗佈膜之積層體於例如溫度40℃以上200℃以下之條件下進行加熱。此時之加熱時間例如為3分鐘以上120分鐘以下。再者，亦可設置多階段之加熱步驟，比如將含塗佈膜之積層體於50℃之溫度下加熱30分鐘後，於100℃之溫度下加熱30分鐘等。其次，為了促進塗佈膜中之特定聚醯胺酸之醯亞胺化，將含塗佈膜之積層體於例如最高溫度200℃以上500℃以下之條件下進行加熱。此時之加熱時間(最高溫度下之加熱時間)例如為1分鐘以上300分鐘以下。此時，較佳為自低溫逐漸升溫至最高溫度。升溫速度較佳為2℃/分鐘以上10℃/分鐘以下，更佳為4℃/分鐘以上10℃/分鐘以下。又，最高溫度較佳為250℃以上480℃以下之範圍。若最高溫度為250℃以上，則醯亞胺化充分進行，若最高溫度為480℃以下，則能夠抑制聚醯亞胺之熱劣化或著色。又，亦可於達到最高溫度之前以任意溫度保持任意時間。醯亞胺化反應能夠於空氣下、減壓下、或氮氣等惰性氣體中進行，為了表現出更高之透明性，較佳為於減壓下、或氮氣等惰性氣體中進行。又，作為加熱裝置，可使用熱風烘箱、紅外烘箱、真空烘箱、無氧化烘箱、加熱板等公知之裝置。經過該等步驟，塗佈膜中之特定聚醯胺酸被醯亞胺化，能夠獲得支持體與聚醯亞胺膜(包含特定聚醯胺酸之醯亞胺化物之膜)之積層體。First, the polyamic acid composition of this embodiment is coated (cast) on a support to form a laminate including a coating film containing a specific polyamide and a coating film on the support. Next, the laminated body containing the coating film is heated under conditions such as a temperature of not less than 40°C and not more than 200°C. The heating time at this time is, for example, 3 minutes or more and 120 minutes or less. Furthermore, a multi-stage heating step can also be provided, for example, the laminate containing the coating film is heated at a temperature of 50°C for 30 minutes, and then heated at a temperature of 100°C for 30 minutes. Next, in order to promote the imidization of the specific polyamic acid in the coating film, the laminate containing the coating film is heated under conditions such as a maximum temperature of 200°C or more and 500°C or less. The heating time at this time (heating time at the highest temperature) is, for example, from 1 minute to 300 minutes. At this time, it is preferable to gradually increase the temperature from low temperature to the highest temperature. The temperature rising rate is preferably 2°C/min or more and 10°C/min or less, more preferably 4°C/min or more and 10°C/min or less. Moreover, the maximum temperature is preferably in the range of 250°C or more and 480°C or less. If the maximum temperature is 250° C. or higher, the imidization proceeds sufficiently, and if the maximum temperature is 480° C. or lower, thermal deterioration or coloring of the polyimide can be suppressed. In addition, it can also be maintained at any temperature for any time before reaching the maximum temperature. The imidization reaction can be carried out under air, under reduced pressure, or in an inert gas such as nitrogen. In order to exhibit higher transparency, it is preferably carried out under reduced pressure or in an inert gas such as nitrogen. In addition, as the heating device, known devices such as hot air oven, infrared oven, vacuum oven, non-oxidation oven, and heating plate can be used. Through these steps, the specific polyamic acid in the coating film is imidized, and a laminate of a support and a polyimide film (a film containing an imide compound of the specific polyamic acid) can be obtained.
將聚醯亞胺膜自所獲得之支持體與聚醯亞胺膜之積層體剝離之方法可使用公知之方法。例如，可用手剝離，亦可使用驅動輥、機器人等機械裝置來剝離。進而，亦可採用在支持體與聚醯亞胺膜之間設置剝離層之方法；或者藉由在具有多個溝槽之基板上形成氧化矽膜，以氧化矽膜作為基底層形成聚醯亞胺膜，使氧化矽之蝕刻液浸潤至基板與氧化矽膜之間，而將聚醯亞胺膜剝離的方法。又，亦可採用藉由照射雷射光而使聚醯亞胺膜分離之方法。The method of peeling the polyimide film from the obtained support and the laminate of the polyimide film can use a known method. For example, it can be peeled off by hand, or it can be peeled off using a mechanical device such as a drive roller or a robot. Furthermore, a method of providing a peeling layer between the support and the polyimide film can also be adopted; or a method of peeling the polyimide film by forming a silicon oxide film on a substrate having a plurality of grooves, forming a polyimide film with the silicon oxide film as a base layer, and allowing an etching solution of silicon oxide to penetrate between the substrate and the silicon oxide film. In addition, a method of separating the polyimide film by irradiating laser light can also be adopted.
聚醯亞胺膜之透明性能夠利用按照JIS K7361-1：1997之全光線透過率(TT)、及按照JIS K7136-2000之霧度來評價。於將聚醯亞胺膜用於要求高透明性之用途之情形時，聚醯亞胺膜之全光線透過率較佳為75%以上，更佳為80%以上。又，於將聚醯亞胺膜用於要求高透明性之用途之情形時，聚醯亞胺膜之霧度較佳為1.5%以下，更佳為1.2%以下，進而較佳為1.0%以下，亦可為0%。於要求高透明性之用途中，聚醯亞胺膜被要求於全波長區域內之透過率較高，但聚醯亞胺膜有容易吸收短波長側之光之傾向，膜本身著色成黃色之情況較多。為了將聚醯亞胺膜用於要求高透明性之用途，較佳為減少聚醯亞胺膜之著色。具體而言，為了將聚醯亞胺膜用於要求高透明性之用途，聚醯亞胺膜之黃度(YI)較佳為25以下，更佳為20以下，亦可為0。YI能夠按照JIS K7373-2006進行測定。YI例如可藉由變更特定聚醯胺酸中之殘基(1)之含有率而進行調整。如此，著色減少而被賦予透明性之聚醯亞胺膜適於替代玻璃之用途等之透明基板、或在背面設置感測器或相機模組之基板。The transparency of the polyimide film can be evaluated by the total light transmittance (TT) according to JIS K7361-1:1997 and the haze according to JIS K7136-2000. When the polyimide film is used for applications requiring high transparency, the total light transmittance of the polyimide film is preferably 75% or more, more preferably 80% or more. Furthermore, when the polyimide film is used for applications requiring high transparency, the haze of the polyimide film is preferably 1.5% or less, more preferably 1.2% or less, further preferably 1.0% or less, and may be 0%. In applications requiring high transparency, polyimide films are required to have a higher transmittance in the entire wavelength range, but polyimide films tend to easily absorb light on the short wavelength side, and the film itself is often colored yellow. In order to use polyimide films for applications requiring high transparency, it is better to reduce the coloring of the polyimide film. Specifically, in order to use polyimide films for applications requiring high transparency, the yellowness (YI) of the polyimide film is preferably 25 or less, more preferably 20 or less, and can also be 0. YI can be measured in accordance with JIS K7373-2006. YI can be adjusted, for example, by changing the content of the residue (1) in the specific polyamide acid. Thus, the polyimide film with reduced coloration and given transparency is suitable for transparent substrates for use as glass substitutes, or substrates with sensors or camera modules provided on the back.
又，於可撓性顯示器之光提取方式中，有自TFT之正面側提取光之頂部發光方式與自TFT之背面側提取光之底部發光方式這兩種。頂部發光方式中，具有因光未被TFT遮擋而易於提高開口率，能獲得高精細之畫質之特徵，底部發光方式具有容易將TFT與像素電極進行位置對準而易於製造等特徵。若TFT透明，則於底部發光方式中，亦能提高開口率，因此大型顯示器有採用容易製造之底部發光方式之傾向。藉由本實施方式之製造方法而獲得之聚醯亞胺膜之YI較低，耐熱性亦優異，因此能夠應用於上述任一種光提取方式。Furthermore, among the light extraction methods of the flexible display, there are two types: a top emission method that extracts light from the front side of the TFT and a bottom emission method that extracts light from the back side of the TFT. The top emission method has the characteristics of being easy to increase the aperture ratio because the light is not blocked by the TFT, and being able to obtain high-precision image quality. The bottom emission method has the characteristics of being easy to align the position of the TFT and the pixel electrode and being easy to manufacture. If the TFT is transparent, the aperture ratio can also be increased in the bottom emission method, so large displays tend to adopt the bottom emission method that is easy to manufacture. The polyimide film obtained by the manufacturing method of this embodiment has a lower YI and excellent heat resistance, so it can be applied to any of the above-mentioned light extraction methods.
又，於在玻璃基板等支持體上塗佈聚醯胺酸組合物，並進行加熱而進行醯亞胺化，從而形成電子元件等之後，將聚醯亞胺膜剝離這種批次式裝置製作程序中，較佳為使支持體與聚醯亞胺膜之間的密接性優異。此處所謂之密接性意指密接強度。於在支持體上之聚醯亞胺膜上形成電子元件等之後，將形成有電子元件等之聚醯亞胺膜自支持體剝離之製作程序中，若聚醯亞胺膜與支持體之密接性優異，則能更準確地形成或安裝電子元件等。於在支持體上介隔聚醯亞胺膜而配置電子元件等之製造程序中，就提高生產性之觀點而言，支持體與聚醯亞胺膜之間之剝離強度較佳為0.05 N/cm以上，更佳為0.1 N/cm以上。上述剝離強度之測定方法係與下述實施例相同之方法或依據其之方法。In a batch device manufacturing process in which a polyimide composition is coated on a support such as a glass substrate and heated to be imidized to form electronic components, the polyimide film is peeled off, and it is preferred that the adhesion between the support and the polyimide film is excellent. The adhesion here refers to the adhesion strength. In a manufacturing process in which electronic components are formed on the polyimide film on the support, the polyimide film formed with the electronic components is peeled off from the support, if the adhesion between the polyimide film and the support is excellent, the electronic components can be formed or mounted more accurately. In the manufacturing process of arranging electronic components on a support with a polyimide film interposed therebetween, from the viewpoint of improving productivity, the peel strength between the support and the polyimide film is preferably 0.05 N/cm or more, more preferably 0.1 N/cm or more. The method for measuring the peel strength is the same as the method in the following embodiment or a method based thereon.
於如上所述之製造程序中，將聚醯亞胺膜自支持體與聚醯亞胺膜之積層體剝離時，大多情況下會藉由雷射照射來將聚醯亞胺膜自支持體剝離。於此情形時，必須使聚醯亞胺膜吸收雷射光，因此要求聚醯亞胺膜之截止波長較剝離所使用之雷射光之波長更長。雷射剝離多使用波長308 nm之XeCl準分子雷射，因此聚醯亞胺膜之截止波長較佳為312 nm以上，更佳為330 nm以上。另一方面，若截止波長為長波長，則聚醯亞胺膜將有著色成黃色之趨勢，因此聚醯亞胺膜之截止波長較佳為390 nm以下。就兼顧透明性(低黃色程度)與雷射剝離之加工性之觀點而言，聚醯亞胺膜之截止波長較佳為320 nm以上390 nm以下，更佳為330 nm以上380 nm以下。再者，本說明書中之截止波長意指利用紫外-可見分光光度計所測得之透過率變成0.1%以下之波長。In the manufacturing process described above, when the polyimide film is peeled off from the support and the laminate of the polyimide film, in most cases, the polyimide film is peeled off from the support by laser irradiation. In this case, the polyimide film must absorb the laser light, so the cutoff wavelength of the polyimide film is required to be longer than the wavelength of the laser light used for peeling. Laser stripping often uses a XeCl excimer laser with a wavelength of 308 nm, so the cutoff wavelength of the polyimide film is preferably above 312 nm, and more preferably above 330 nm. On the other hand, if the cutoff wavelength is a long wavelength, the polyimide film will tend to be colored yellow, so the cutoff wavelength of the polyimide film is preferably below 390 nm. From the perspective of both transparency (low yellowness) and laser stripping processability, the cutoff wavelength of the polyimide film is preferably 320 nm to 390 nm, more preferably 330 nm to 380 nm. In addition, the cutoff wavelength in this specification refers to the wavelength at which the transmittance measured by an ultraviolet-visible spectrophotometer becomes 0.1% or less.
本實施方式之聚醯胺酸組合物、及藉由本實施方式之製造方法所獲得之聚醯亞胺可直接用於供製作製品或構件之塗佈或成形製程中，但亦可用作供對成形為膜狀之成形物進一步進行塗佈等處理之材料。為了用於塗佈或成形製程，亦可將聚醯胺酸組合物或聚醯亞胺視需要溶解或分散於有機溶劑中，進而，視需要調配光硬化性成分、熱硬化性成分、非聚合性黏合劑樹脂及其他成分，來製備包含特定聚醯胺酸或聚醯亞胺之組合物。The polyamide composition of this embodiment and the polyimide obtained by the manufacturing method of this embodiment can be directly used in the coating or forming process for making products or components, but they can also be used for manufacturing products or components. A material that is formed into a film and further processed by coating. In order to be used in the coating or forming process, the polyamic acid composition or polyimide can also be dissolved or dispersed in an organic solvent as needed, and further, photo-curable components, thermosetting components, and non-polymerizable components can be prepared as necessary. Adhesive resins and other ingredients are used to prepare compositions containing specific polyamides or polyimides.
亦可於藉由本實施方式之製造方法而獲得之聚醯亞胺膜之表面形成金屬氧化物薄膜或透明電極等各種無機薄膜。作為該等無機薄膜之製膜方法，並無特別限定，例如可例舉：濺鍍法、真空蒸鍍法、離子鍍覆法等PVD(Physical Vapor Deposition，物理氣相沈積)法、或CVD(Chemical Vapor Deposition，化學氣相沈積)法。Various inorganic thin films such as a metal oxide film or a transparent electrode can also be formed on the surface of the polyimide film obtained by the manufacturing method of this embodiment. The method of forming the inorganic thin film is not particularly limited, and examples thereof include PVD (Physical Vapor Deposition) methods such as sputtering, vacuum evaporation, and ion plating, or CVD (Physical Vapor Deposition). Chemical Vapor Deposition, chemical vapor deposition) method.
藉由本實施方式之製造方法而獲得之聚醯亞胺膜除了具有耐熱性、低熱膨脹性、透明性以外，與玻璃基板形成積層體時所產生之內部應力亦較小，且於高溫製程中能確保與無機材料之密接性，因此較佳為用於可發揮該等特性之領域及製品。例如，藉由本實施方式之製造方法而獲得之聚醯亞胺膜較佳為用於液晶顯示裝置、有機EL、電子紙等圖像顯示裝置、印刷物、彩色濾光片、可撓性顯示器、光學膜、3D顯示器、觸控面板、透明導電膜基板、太陽電池等，進而，更佳為用作當前使用玻璃之部分之替代材料。該等用途中，聚醯亞胺膜之厚度例如為1 μm以上200 μm以下，較佳為5 μm以上100 μm以下。聚醯亞胺膜之厚度可使用雷射全息計(laser holo gauge)來測定。The polyimide film obtained by the manufacturing method of the present embodiment has heat resistance, low thermal expansion, and transparency. When forming a laminate with a glass substrate, the internal stress generated is also small, and the close contact with inorganic materials can be ensured during the high-temperature process. Therefore, it is preferably used in fields and products where these characteristics can be brought into play. For example, the polyimide film obtained by the manufacturing method of the present embodiment is preferably used in liquid crystal display devices, organic EL, electronic paper and other image display devices, printed materials, color filters, flexible displays, optical films, 3D displays, touch panels, transparent conductive film substrates, solar cells, etc., and further, it is more preferably used as a substitute material for parts currently using glass. In such applications, the thickness of the polyimide film is, for example, 1 μm to 200 μm, preferably 5 μm to 100 μm. The thickness of the polyimide film can be measured using a laser holo gauge.
又，本實施方式之聚醯胺酸組合物可良好地用於如下聚醯亞胺膜之製造方法：於支持體上塗佈聚醯胺酸組合物，進行加熱而進行醯亞胺化後，將聚醯亞胺膜自支持體剝離。又，本實施方式之聚醯胺酸組合物可良好地用於如下批次式裝置製作程序：於支持體上塗佈聚醯胺酸組合物，進行加熱而進行醯亞胺化，於所形成之聚醯亞胺膜上形成電子元件等之後，將形成有電子元件等之聚醯亞胺膜自支持體剝離。因此，本實施方式之電子裝置之製造方法亦可包括將形成有電子元件等之聚醯亞胺膜自支持體剝離之步驟。 [實施例] Furthermore, the polyamide composition of the present embodiment can be well used in the following method for producing a polyimide film: the polyamide composition is coated on a support, heated to be imidized, and then the polyimide film is peeled off from the support. Furthermore, the polyamide composition of the present embodiment can be well used in the following batch device manufacturing process: the polyamide composition is coated on a support, heated to be imidized, and then electronic components, etc. are formed on the formed polyimide film, and then the polyimide film formed with the electronic components, etc. is peeled off from the support. Therefore, the method for producing an electronic device of the present embodiment can also include the step of peeling the polyimide film formed with the electronic components, etc. from the support. [Example]
以下，對本發明之實施例進行說明，但本發明之範圍並不限定於下述實施例。Hereinafter, embodiments of the present invention will be described, but the scope of the present invention is not limited to the following embodiments.
＜物性之測定方法及評價方法＞ 首先，對聚醯亞胺(聚醯亞胺膜)之物性之測定方法及評價方法進行說明。 <Methods for measuring and evaluating physical properties> First, the methods for measuring and evaluating physical properties of polyimide (polyimide film) are explained.
[內部應力] 於預先測量了翹曲量之康寧公司製造之玻璃基板(商品名：Eagle XG，材質：無鹼玻璃，厚度：0.7 mm，尺寸：100 mm×100 mm)上，利用旋轉塗佈機塗佈下述實施例及比較例中所製備之各聚醯胺酸組合物，於空氣中在120℃下加熱30分鐘後，於氮氣氛圍下在460℃下加熱45分鐘，而獲得於玻璃基板上具備厚度10 μm之聚醯亞胺膜之積層體。為了排除聚醯亞胺膜吸水之影響，將積層體於120℃下乾燥10分鐘，然後使用薄膜應力測定裝置(KLA-Tencor公司製造之「FLX-2320-S」)測定溫度25℃之氮氣氛圍下之積層體之翹曲量。然後，根據聚醯亞胺膜形成前之玻璃基板之翹曲量及積層體之翹曲量，利用Stoney公式算出玻璃基板與聚醯亞胺膜之間產生之內部應力。於內部應力為30 MPa以下之情形時，評價為「能降低內部應力」。另一方面，於內部應力超過30 MPa之情形時，評價為「無法降低內部應力」。 [Internal stress] On a glass substrate manufactured by Corning Incorporated (trade name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm×100 mm) whose warp was measured in advance, each polyamide composition prepared in the following embodiments and comparative examples was coated using a rotary coater, and then heated at 120°C for 30 minutes in air and then heated at 460°C for 45 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film with a thickness of 10 μm on the glass substrate. In order to eliminate the influence of water absorption of the polyimide film, the laminate was dried at 120°C for 10 minutes, and then the warp of the laminate was measured in a nitrogen atmosphere at a temperature of 25°C using a thin film stress measuring device ("FLX-2320-S" manufactured by KLA-Tencor). Then, based on the warp of the glass substrate before the polyimide film was formed and the warp of the laminate, the internal stress generated between the glass substrate and the polyimide film was calculated using the Stoney formula. When the internal stress is below 30 MPa, it is evaluated as "the internal stress can be reduced". On the other hand, when the internal stress exceeds 30 MPa, it is evaluated as "the internal stress cannot be reduced".
[1%重量減少溫度(TD1)] 將自下述之實施例及比較例中所獲得之各積層體取樣之聚醯亞胺膜(詳細而言，以重量成為10 mg之方式取樣之聚醯亞胺膜)作為測定用試樣，使用示差熱-熱重量同步測定裝置(Hitachi High-Tech Science公司製造之「TG/DTA7200」)，於氮氣氛圍下，以20℃/分鐘之條件自25℃升溫至650℃，以150℃之測定溫度下之試樣重量為基準，將相對於該基準之重量減少1重量%時之測定溫度作為1%重量減少溫度(TD1)。 [1% weight loss temperature (TD1)] The polyimide film sampled from each laminate obtained in the following Examples and Comparative Examples (specifically, the polyimide film sampled so that the weight became 10 mg) was used as a measurement sample, Using a differential thermogravimetric simultaneous measurement device ("TG/DTA7200" manufactured by Hitachi High-Tech Science Co., Ltd.), in a nitrogen atmosphere, the temperature was increased from 25°C to 650°C at a rate of 20°C/min, and the measurement was performed at 150°C. The weight of the sample at the temperature is used as the basis, and the measurement temperature when the weight is reduced by 1% by weight relative to the basis is regarded as the 1% weight reduction temperature (TD1).
[製膜性] (玻璃基板上之製膜性) 利用旋轉塗佈機將下述實施例及比較例中所製備之各聚醯胺酸組合物塗佈於康寧公司製造之玻璃基板(商品名：Eagle XG，材質：無鹼玻璃，厚度：0.7 mm，尺寸：100 mm×100 mm)上，於空氣中在120℃下加熱30分鐘後，於氮氣氛圍下在460℃下加熱45分鐘，而獲得於玻璃基板上具備厚度10 μm之聚醯亞胺膜之積層體。對所獲得之積層體以目視確認玻璃基板與聚醯亞胺膜之間有無***。 [Film-forming property] (Film-forming property on glass substrate) Each polyamide composition prepared in the following examples and comparative examples was coated on a glass substrate (trade name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm×100 mm) manufactured by Corning Incorporated using a rotary coater, and then heated at 120°C for 30 minutes in air and then at 460°C for 45 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film with a thickness of 10 μm on the glass substrate. The obtained laminate was visually checked for the presence or absence of ridges between the glass substrate and the polyimide film.
(a-Si層上之製膜性) 於康寧公司製造之玻璃基板(商品名：Eagle XG，材質：無鹼玻璃，厚度：0.7 mm，尺寸：100 mm×100 mm)上積層a-Si層(厚度：100 nm)後，利用旋轉塗佈機將下述實施例及比較例中所製備之各聚醯胺酸組合物塗佈於a-Si層上。繼而，將塗佈有聚醯胺酸組合物之基板於空氣中在120℃下加熱30分鐘後，於氮氣氛圍下在460℃下加熱45分鐘，而獲得於玻璃基板上依序具備a-Si層及厚度10 μm之聚醯亞胺膜之積層體。對所獲得之積層體以目視確認a-Si層與聚醯亞胺膜之間有無***。 (Film-forming properties on a-Si layer) After depositing an a-Si layer (thickness: 100 nm) on a glass substrate (trade name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm×100 mm) manufactured by Corning, each polyamide composition prepared in the following embodiments and comparative examples was coated on the a-Si layer using a spin coater. Subsequently, the substrate coated with the polyamide composition was heated at 120°C in air for 30 minutes, and then heated at 460°C in a nitrogen atmosphere for 45 minutes, to obtain a laminate having an a-Si layer and a polyimide film with a thickness of 10 μm on the glass substrate in sequence. The obtained laminate was visually checked to see if there was any bulge between the a-Si layer and the polyimide film.
(製膜性之評價基準) 於玻璃基板與聚醯亞胺膜之間、及a-Si層與聚醯亞胺膜之間均無***之情形時，評價為「密接性不良之產生被抑制，製膜性較佳」。另一方面，於玻璃基板與聚醯亞胺膜之間、及a-Si層與聚醯亞胺膜之間之至少一者有***之情形時，評價為「密接性不良之產生未被抑制，製膜性欠佳」。 (Evaluation criteria for film forming properties) When there is no bulging between the glass substrate and the polyimide film and between the a-Si layer and the polyimide film, it is evaluated that "the occurrence of poor adhesion is suppressed and the film forming properties are better." On the other hand, when at least one of the bulges exists between the glass substrate and the polyimide film and between the a-Si layer and the polyimide film, it is evaluated that "the occurrence of poor adhesion is not suppressed." , poor film-forming properties."
[剝離強度] 於下述實施例及比較例中所獲得之各積層體之聚醯亞胺膜，按照ASTM D1876-01標準，利用截切刀切出寬度10 mm之切縫，使用拉力試驗機(東洋精機公司製造之「Strograph VES1D」)，於溫度23℃且濕度55%RH之環境下，以拉伸速度50 mm/分鐘且剝離角度90°之條件，將聚醯亞胺膜自玻璃基板剝離50 mm，將此時之剝離強度之平均值作為剝離強度。 [Peel Strength] The polyimide films of each laminate obtained in the following examples and comparative examples were cut with a slit of 10 mm width using a guillotine according to ASTM D1876-01 standard. The polyimide films were peeled off 50 mm from the glass substrate using a tensile tester ("Strograph VES1D" manufactured by Toyo Seiki Co., Ltd.) at a temperature of 23°C and a humidity of 55%RH, at a tensile speed of 50 mm/min and a peeling angle of 90°. The average peel strength at this time was taken as the peel strength.
＜聚醯亞胺膜之製作＞ 以下，對實施例及比較例之聚醯亞胺膜(積層體)之製作方法進行說明。再者，以下，用下述簡稱記載化合物及試劑類。又，製作聚醯亞胺膜時所使用之聚醯胺酸組合物之製備均於氮氣氛圍下進行。 MPA：3-甲氧基-N,N-二甲基丙醯胺 NBP：1-丁基-2-吡咯啶酮 BPDA：3,3',4,4'-聯苯四羧酸二酐 BPAF：9,9-雙(3,4-二羧基苯基)茀二酐 SFDA：螺[11H-二呋喃并[3,4-b:3',4'-i]𠮿-11,9'-[9H]茀]-1,3,7,9-四酮 PDA：對苯二胺 BAFL：9,9-雙(4-胺基苯基)茀 PAM-E：1,3-雙(3-胺基丙基)四甲基二矽氧烷 ODA：4,4'-氧二苯胺 APS：3-胺基丙基三乙氧基矽烷 APDE：3-胺基丙基二乙氧基甲基矽烷 <Preparation of polyimide film> Hereinafter, the method of producing the polyimide film (laminated body) of Examples and Comparative Examples will be described. In addition, below, the compounds and reagents are described using the following abbreviations. In addition, the preparation of the polyamide acid composition used in making the polyimide film was carried out under a nitrogen atmosphere. MPA: 3-methoxy-N,N-dimethylpropionamide NBP: 1-butyl-2-pyrrolidinone BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BPAF : 9,9-Bis(3,4-dicarboxyphenyl)dianhydride SFDA: Spiro[11H-Difuro[3,4-b:3',4'-i]𠮿 -11,9'-[9H]fluorine]-1,3,7,9-tetraketonePDA: p-phenylenediamine BAFL: 9,9-bis(4-aminophenyl)fluorinePAM-E: 1, 3-Bis(3-aminopropyl)tetramethyldisiloxane ODA: 4,4'-oxydiphenylamine APS: 3-aminopropyltriethoxysilane APDE: 3-aminopropyldi Ethoxymethylsilane
[實施例1] 向安裝有具備不鏽鋼製攪拌棒之攪拌機及氮氣導入管之300 mL之玻璃製可分離式燒瓶中，加入85.0 g之MPA作為聚合用有機溶劑。繼而，一面攪拌燒瓶內容物，一面將4.037 g之PDA加入燒瓶中進行溶解。繼而，向燒瓶內容物中加入0.171 g之BPAF及10.792 g之BPDA後，於溫度25℃之環境下，將燒瓶內容物攪拌6小時。繼而，向燒瓶內容物中添加0.005 g之APS後，於溫度25℃之環境下，將燒瓶內容物進一步攪拌6小時，而獲得聚醯胺酸組合物。使用旋轉塗佈機將所獲得之聚醯胺酸組合物塗佈於康寧公司製造之玻璃基板(商品名：Eagle XG，材質：無鹼玻璃，厚度：0.7 mm，尺寸：100 mm×100 mm)上，於空氣中在120℃下加熱30分鐘後，於氮氣氛圍下在460℃下加熱45分鐘，而獲得於玻璃基板上具備厚度10 μm之聚醯亞胺膜之積層體(實施例1之積層體)。 [Example 1] To a 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stirring rod and a nitrogen introduction tube, 85.0 g of MPA was added as the organic solvent for polymerization. Then, while stirring the contents of the flask, 4.037 g of PDA was added to the flask and dissolved. Then, after adding 0.171 g of BPAF and 10.792 g of BPDA to the contents of the flask, the contents of the flask were stirred for 6 hours in an environment with a temperature of 25°C. Then, after adding 0.005 g of APS to the contents of the flask, the contents of the flask were further stirred for 6 hours in an environment with a temperature of 25°C, to obtain a polyamic acid composition. The obtained polyamic acid composition was coated on a glass substrate manufactured by Corning Corporation using a spin coater (trade name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm × 100 mm) above, after heating at 120°C for 30 minutes in the air, and then heating at 460°C for 45 minutes in a nitrogen atmosphere, a laminate having a polyimide film with a thickness of 10 μm on a glass substrate was obtained (Example 1) laminated body).
[實施例2～21及比較例1～7] 除了使所使用之酸二酐及其饋入比率、所使用之二胺及其饋入比率、所使用之矽烷偶合劑及其添加量、以及溶劑之種類如表1及表2所示以外，藉由與實施例1相同之方法，分別獲得實施例2～21及比較例1～7之積層體。再者，於未使用矽烷偶合劑之實施例2～4、9～14、17、19及21、以及比較例1、3及5～7中，將所有酸二酐加入燒瓶後，於溫度25℃之環境下，將燒瓶內容物攪拌6小時，獲得聚醯胺酸組合物。又，關於實施例2～21及比較例1～7之任一者，製備聚醯胺酸組合物時之酸二酐之合計物質量均與實施例1相同。又，關於實施例2～21及比較例1～7之任一者，製備聚醯胺酸組合物時之二胺之合計物質量均與實施例1相同。 [Examples 2 to 21 and Comparative Examples 1 to 7] Except that the acid dianhydride used and its feeding ratio, the diamine used and its feeding ratio, the silane coupling agent used and its addition amount, and the type of solvent are as shown in Tables 1 and 2, the laminates of Examples 2 to 21 and Comparative Examples 1 to 7 are obtained by the same method as Example 1. Furthermore, in Examples 2 to 4, 9 to 14, 17, 19 and 21, and Comparative Examples 1, 3 and 5 to 7, in which no silane coupling agent is used, after all the acid dianhydride is added to the flask, the contents of the flask are stirred for 6 hours at a temperature of 25°C to obtain a polyamide composition. In addition, regarding any one of Examples 2 to 21 and Comparative Examples 1 to 7, the total mass of the acid dianhydride when preparing the polyamide composition is the same as that of Example 1. In addition, regarding any one of Examples 2 to 21 and Comparative Examples 1 to 7, the total mass of the diamine when preparing the polyamide composition is the same as that of Example 1.
關於實施例1～21及比較例1～7，將所使用之酸二酐、二胺、矽烷偶合劑及溶劑、以及內部應力、TD1、製膜性及剝離強度示於表1及表2。再者，表1及表2中，酸二酐、二胺及矽烷偶合劑之欄之「-」係指未使用該成分。又，表1及表2中，剝離強度之欄之「-」係指未測定剝離強度。Regarding Examples 1 to 21 and Comparative Examples 1 to 7, the acid dianhydride, diamine, silane coupling agent and solvent used, as well as the internal stress, TD1, film forming properties and peel strength are shown in Table 1 and Table 2. In addition, in Table 1 and Table 2, "-" in the columns of acid dianhydride, diamine and silane coupling agent means that these components are not used. In addition, in Table 1 and Table 2, "-" in the column of peel strength means that the peel strength was not measured.
又，表1及表2中，「酸二酐」之欄之數值係各酸二酐相對於所使用之二胺之總量(100莫耳%)之含有率(單位：莫耳%)。又，表1及表2中，「二胺」之欄之數值係各二胺相對於所使用之二胺之總量(100莫耳%)之含有率(單位：莫耳%)。又，表1及表2中，「矽烷偶合劑」之欄之數值係矽烷偶合劑相對於聚醯胺酸100重量份之添加量(單位：重量份)。又，關於實施例1～21及比較例1～7之任一者，所製備之聚醯胺酸組合物中之聚醯胺酸之各殘基的莫耳分率均與聚醯胺酸之合成所使用之各單體(二胺及四羧酸二酐)的莫耳分率一致。In addition, in Tables 1 and 2, the numerical value in the column "Acid dianhydride" is the content rate (unit: mole %) of each acid dianhydride relative to the total amount of diamine used (100 mole %). In addition, in Table 1 and Table 2, the numerical value in the "diamine" column is the content rate (unit: mole %) of each diamine relative to the total amount of the diamine used (100 mole %). In addition, in Table 1 and Table 2, the numerical value in the "silane coupling agent" column is the amount of the silane coupling agent added relative to 100 parts by weight of polyamide (unit: parts by weight). Furthermore, regarding any one of Examples 1 to 21 and Comparative Examples 1 to 7, the molar fraction of each residue of the polyamic acid in the prepared polyamic acid composition is equal to that of the polyamic acid. The molar fractions of each monomer (diamine and tetracarboxylic dianhydride) used in the synthesis are consistent.
[表1]
[表2]
實施例1～21中所使用之聚醯胺酸組合物中之聚醯胺酸具有殘基(1)、BPDA殘基及PDA殘基。實施例1～21中所使用之聚醯胺酸組合物包含特定有機溶劑。The polyamic acid in the polyamic acid composition used in Examples 1 to 21 has residue (1), a BPDA residue and a PDA residue. The polyamide composition used in Examples 1 to 21 contains a specific organic solvent.
如表1及表2所示，於實施例1～21中，內部應力為30 MPa以下。因此，實施例1～21中，能夠降低內部應力。實施例1～21中，玻璃基板與聚醯亞胺膜之間、及a-Si層與聚醯亞胺膜之間之任一者均無***。因此，實施例1～21中，密接性不良之產生被抑制，製膜性較佳。As shown in Tables 1 and 2, in Examples 1 to 21, the internal stress is 30 MPa or less. Therefore, in Examples 1 to 21, the internal stress can be reduced. In Examples 1 to 21, there is no bulge between the glass substrate and the polyimide film, and between the a-Si layer and the polyimide film. Therefore, in Examples 1 to 21, the occurrence of poor adhesion is suppressed, and the film forming property is good.
比較例1～7中所使用之聚醯胺酸組合物中之聚醯胺酸具有BPDA殘基及PDA殘基，但不具有殘基(1)。比較例1～7中所使用之聚醯胺酸組合物包含特定有機溶劑。The polyamic acid in the polyamic acid composition used in Comparative Examples 1 to 7 has a BPDA residue and a PDA residue, but does not have the residue (1). The polyamide composition used in Comparative Examples 1 to 7 contains a specific organic solvent.
如表2所示，比較例1～6中，玻璃基板與聚醯亞胺膜之間、及a-Si層與聚醯亞胺膜之間之任一者均具有***。因此，比較例1～6中，密接性不良之產生未被抑制，製膜性欠佳。比較例7中，內部應力超過30 MPa。因此，比較例7中，無法降低內部應力。As shown in Table 2, in Comparative Examples 1 to 6, there were ridges both between the glass substrate and the polyimide film and between the a-Si layer and the polyimide film. Therefore, in Comparative Examples 1 to 6, the occurrence of poor adhesion was not suppressed, and the film forming properties were poor. In Comparative Example 7, the internal stress exceeded 30 MPa. Therefore, in Comparative Example 7, the internal stress cannot be reduced.
以上結果顯示，根據本發明，能夠使用安全性較高之溶劑並且抑制密接性不良之產生，而且能夠降低內部應力。The above results show that according to the present invention, a safer solvent can be used and the occurrence of poor adhesion can be suppressed, and internal stress can be reduced.
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