JP7635775B2 - Polyimide precursor composition and method for producing insulating coating layer using same - Google Patents
Polyimide precursor composition and method for producing insulating coating layer using same Download PDFInfo
- Publication number
- JP7635775B2 JP7635775B2 JP2022212592A JP2022212592A JP7635775B2 JP 7635775 B2 JP7635775 B2 JP 7635775B2 JP 2022212592 A JP2022212592 A JP 2022212592A JP 2022212592 A JP2022212592 A JP 2022212592A JP 7635775 B2 JP7635775 B2 JP 7635775B2
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- JP
- Japan
- Prior art keywords
- mol
- precursor composition
- polyimide precursor
- coating layer
- insulating coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims description 142
- 239000004642 Polyimide Substances 0.000 title claims description 119
- 239000000203 mixture Substances 0.000 title claims description 101
- 239000002243 precursor Substances 0.000 title claims description 93
- 239000011247 coating layer Substances 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 69
- 150000004985 diamines Chemical class 0.000 claims description 41
- 229920005575 poly(amic acid) Polymers 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 36
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 33
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 26
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 22
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 21
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 14
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000035699 permeability Effects 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000001294 propane Substances 0.000 claims description 11
- -1 amine compounds Chemical class 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 22
- 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 19
- 239000000523 sample Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000009719 polyimide resin Substances 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 7
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 6
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 2
- VQXBKCWOCJSIRT-UHFFFAOYSA-N octadecane-1,12-diamine Chemical compound CCCCCCC(N)CCCCCCCCCCCN VQXBKCWOCJSIRT-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- QRUWUSOUUMPANJ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-carboxyphenyl)methyl]benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1CC1=CC=C(N)C(C(O)=O)=C1 QRUWUSOUUMPANJ-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-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
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-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
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-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
- QQPYIXJPRJQUDC-UHFFFAOYSA-N 5-(3-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1C(O)=O QQPYIXJPRJQUDC-UHFFFAOYSA-N 0.000 description 1
- JJJDAERKXDTMPH-UHFFFAOYSA-N 5-(4-phenylphenyl)benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=C1C(O)=O JJJDAERKXDTMPH-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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Description
本発明は、優れた耐熱性、機械的特性を有するポリイミド絶縁被覆層を効率よく製造することができるポリイミド前駆体組成物、およびそれを用いた絶縁被覆層の製造方法に関する。 The present invention relates to a polyimide precursor composition that can efficiently produce a polyimide insulating coating layer that has excellent heat resistance and mechanical properties, and a method for producing an insulating coating layer using the same.
ポリイミド樹脂は、非常に耐熱性に優れた樹脂として知られており、様々な分野で広く利用されている。例えば、高い耐熱性に加えて、低誘電率で機械特性にも優れるため、要求特性の高い電線の絶縁層として用いられている。特許文献１には、芯線上に、ビフェニルテトラカルボン酸二無水物と４、４’－ジアミノジフェニルエーテルとの反応により得られるポリアミック酸をイミド化した絶縁層が設けられていることを特徴とする絶縁被覆電線が記載されており、このポリイミド絶縁被覆電線は、熱劣化に対する優れた抵抗性を有していることが記載されている。 Polyimide resin is known as a resin with excellent heat resistance and is widely used in various fields. For example, in addition to high heat resistance, it has a low dielectric constant and excellent mechanical properties, so it is used as an insulating layer for electric wires with high requirements. Patent Document 1 describes an insulated electric wire characterized in that an insulating layer made of imidized polyamic acid obtained by reacting biphenyltetracarboxylic dianhydride with 4,4'-diaminodiphenyl ether is provided on a core wire, and it is described that this polyimide insulated electric wire has excellent resistance to thermal degradation.
ポリイミドは、テトラカルボン酸成分とジアミン成分の組み合わせによって結晶性となることがあり、その結果、ポリイミド前駆体であるポリアミック酸をイミド化する際の条件に制限が生じることがある。例えば、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いると、結晶性のポリイミド樹脂が得られ易く、イミド化の条件によっては、特に、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易い。そのため、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド層を形成する場合、昇温速度を上げて生産性を高めることができない場合があった。 Polyimide can become crystalline depending on the combination of the tetracarboxylic acid component and the diamine component, and as a result, there are restrictions on the conditions for imidizing the polyamic acid, which is the polyimide precursor. For example, when 3,3',4,4'-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component, a crystalline polyimide resin is easily obtained, but depending on the imidization conditions, partial crystallization is likely to occur, especially when imidization is performed by a short heat treatment with rapid heating. Therefore, when a polyimide layer is formed by imidizing a polyamic acid using 3,3',4,4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component, it may not be possible to increase the heating rate and increase productivity.
このようなテトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド絶縁被覆層を形成する方法であって、急速な昇温を行っても、結晶化を起こすことなく、ポリイミド絶縁被覆層を形成できる方法が特許文献２に記載されている。具体的には、基材にポリイミド前駆体組成物を塗布、焼付けする工程を有するポリイミド絶縁被覆層の製造方法であって、ポリイミド前駆体組成物が、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸と、イミダゾール類及びアミン化合物からなる群より選択される塩基性化合物とを含み、かつ、焼付け工程において、ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、最高加熱温度が３００～５００℃であることを特徴とする絶縁被覆層の製造方法が特許文献２に記載されている。 A method for forming a polyimide insulating coating layer by imidizing a polyamic acid using 3,3',4,4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component, in which a polyimide insulating coating layer can be formed without crystallization even when the temperature is raised rapidly, is described in Patent Document 2. Specifically, Patent Document 2 describes a method for producing a polyimide insulating coating layer that includes a step of applying a polyimide precursor composition to a substrate and baking the composition, in which the polyimide precursor composition contains a polyamic acid using 3,3',4,4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component and a basic compound selected from the group consisting of imidazoles and amine compounds, and in which the polyimide precursor composition is heated for 10 to 180 seconds in the baking step, the average heating rate from 100°C to 280°C is 5°C/s or more, and the maximum heating temperature is 300 to 500°C.
本発明は、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を用いたポリアミック酸をイミド化してポリイミド絶縁被覆層を形成する際に、急速な昇温を行っても欠陥なくポリイミド絶縁被覆層を形成できる方法を提供することを目的とする。すなわち、本発明は、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成できるポリイミド前駆体組成物を提供すること、また、このポリイミド前駆体組成物を用いて、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成する工業的に有利な絶縁被覆層の製造方法を提供することを目的とする。 The present invention aims to provide a method for forming a polyimide insulating coating layer without defects even when the temperature is rapidly raised when forming a polyimide insulating coating layer by imidizing a polyamic acid using 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component. That is, the present invention aims to provide a polyimide precursor composition that can form an insulating coating layer of polyimide resin with excellent heat resistance and mechanical properties in a short time without causing crystallization, and to provide an industrially advantageous method for manufacturing an insulating coating layer that uses this polyimide precursor composition to form an insulating coating layer of polyimide resin with excellent heat resistance and mechanical properties in a short time without causing crystallization.
本発明は以下の項に関する。
１． ポリアミック酸と溶媒とを含むポリイミド前駆体組成物であって、
前記ポリアミック酸が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸であり、かつ、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであることを特徴とする、ポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
２． テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
３． テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
４． テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、前記項１に記載のポリイミド絶縁被覆層形成用のポリイミド前駆体組成物。
The present invention relates to the following items:
1. A polyimide precursor composition comprising a polyamic acid and a solvent,
a polyimide precursor composition for forming a polyimide insulating coating layer, the polyamic acid being obtained from a tetracarboxylic acid component containing 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride and a diamine component; and the polyimide precursor composition is capable of producing a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 24 h) by heat treatment under conditions of a maximum heating temperature of 300 to 500°C.
2. A polyimide precursor composition for forming a polyimide insulating coating layer according to item 1, wherein the tetracarboxylic acid component contains 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the diamine component contains 50 to 100 mol % of paraphenylenediamine and 4,4'-diaminodiphenyl ether, or one of them.
3. A polyimide precursor composition for forming a polyimide insulating coating layer according to item 1, wherein the tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the diamine component is made of one or more diamines selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, and contains 30 to 100 mol % of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane.
4. A polyimide precursor composition for forming a polyimide insulating coating layer according to item 1, wherein the tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the diamine component is made of one or more diamines selected from the group consisting of 4,4'-diaminodiphenyl ether and 4,4'-methylenebis(2,6-xylidine), and contains 20 to 100 mol % of 4,4'-methylenebis(2,6-xylidine).
５． 基材にポリイミド前駆体組成物を塗布、焼付けする工程を有するポリイミド絶縁被覆層の製造方法であって、
ポリイミド前駆体組成物が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を含み、かつ、このポリアミック酸が、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであり、
焼付け工程において、
ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、
１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、
最高加熱温度が３００～５００℃であることを特徴とする絶縁被覆層の製造方法。
６． テトラカルボン酸成分が、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含み、ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。
７． テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。
８． テトラカルボン酸成分が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、前記項５に記載の絶縁被覆層の製造方法。
5. A method for producing a polyimide insulating coating layer, comprising the steps of applying a polyimide precursor composition to a substrate and baking the composition,
the polyimide precursor composition contains a polyamic acid obtained from a tetracarboxylic acid component containing 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride and a diamine component, and the polyamic acid is capable of producing a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 24 h) by subjecting the polyamic acid to a heat treatment under conditions of a maximum heating temperature of 300 to 500°C,
In the baking process,
The time for heating the polyimide precursor composition is 10 to 180 seconds;
The average heating rate from 100° C. to 280° C. is 5° C./s or more;
A method for producing an insulating coating layer, characterized in that the maximum heating temperature is 300 to 500°C.
6. The method for producing an insulating coating layer according to item 5, wherein the tetracarboxylic acid component contains 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the diamine component contains 50 to 100 mol % of paraphenylenediamine and 4,4'-diaminodiphenyl ether, or one of them.
7. The method for producing an insulating coating layer according to item 5, wherein the tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the diamine component is made of one or more diamines selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, and contains 30 to 100 mol % of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane.
8. The method for producing an insulating coating layer according to item 5, wherein the tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the diamine component is made of one or more diamines selected from the group consisting of 4,4'-diaminodiphenyl ether and 4,4'-methylenebis(2,6-xylidine), and contains 20 to 100 mol % of 4,4'-methylenebis(2,6-xylidine).
本発明により、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成できるポリイミド前駆体組成物を提供することができる。すなわち、本発明のポリイミド前駆体組成物を用いることにより、耐熱性、機械的特性に優れたポリイミド樹脂の絶縁被覆層を、結晶化を起こすことなく、短時間で形成することができる。本発明のポリイミド前駆体組成物、およびそれを用いた本発明の絶縁被覆層の製造方法は、特に、絶縁電線の製造に好適に適用でき、優れた耐熱性を有するとともに、絶縁被覆層に欠陥がない、信頼性の高い絶縁電線を効率よく製造することができる。 The present invention provides a polyimide precursor composition that can form an insulating coating layer of polyimide resin with excellent heat resistance and mechanical properties in a short time without crystallization. In other words, by using the polyimide precursor composition of the present invention, an insulating coating layer of polyimide resin with excellent heat resistance and mechanical properties can be formed in a short time without crystallization. The polyimide precursor composition of the present invention and the method for producing an insulating coating layer of the present invention using the same can be particularly suitably applied to the production of insulated electric wires, and can efficiently produce highly reliable insulated electric wires that have excellent heat resistance and no defects in the insulating coating layer.
本発明のポリイミド前駆体組成物は、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を用いたものであり、特定の水蒸気透過係数を有するポリイミドフィルムを与えるポリアミック酸を含むことを特徴とする。 The polyimide precursor composition of the present invention uses 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component, and is characterized by containing a polyamic acid that gives a polyimide film having a specific water vapor permeability coefficient.
本発明で用いるポリアミック酸は、テトラカルボン酸成分（テトラカルボン酸成分にはテトラカルボン酸二無水物も含まれる）とジアミン成分とを溶媒中で、例えば、水又は有機溶媒中で、又は水と有機溶媒の混合溶媒中で反応させることにより得られる。 The polyamic acid used in the present invention is obtained by reacting a tetracarboxylic acid component (including tetracarboxylic dianhydride) with a diamine component in a solvent, for example, in water or an organic solvent, or in a mixed solvent of water and an organic solvent.
このポリアミック酸は、ビフェニルテトラカルボン酸二無水物を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるものである。ビフェニルテトラカルボン酸二無水物とは複数の異性体を含む総称であり、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、および２，２’，３，３’－ビフェニルテトラカルボン酸二無水物がこの中に含まれる。本発明においては、特に、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および／または２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を用いる。 This polyamic acid is obtained from a tetracarboxylic acid component containing 50 to 100 mol% of biphenyltetracarboxylic dianhydride and a diamine component. Biphenyltetracarboxylic dianhydride is a general term that includes multiple isomers, including 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride. In the present invention, in particular, a polyamic acid obtained from a tetracarboxylic acid component containing 50 to 100 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride and a diamine component is used.
また、本発明で用いるポリアミック酸は、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造することができるものである。 Furthermore, the polyamic acid used in the present invention can produce a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 24 h) by heat treating the polyamic acid under conditions of a maximum heating temperature of 300 to 500°C.
本発明で用いるテトラカルボン酸成分は、主成分が、すなわち５０～１００モル％、より好ましくは７０～１００モル％が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方である。特に、耐熱性や機械的特性の観点から、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を主成分として用いるのが好ましい。前述のとおり、通常、テトラカルボン酸成分として、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を用いる場合、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易いが、本発明によれば、すなわち、そのポリアミック酸が、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものである場合、急速な昇温を行っても、結晶化を起こすことなく、ポリイミド層を形成できる。 The tetracarboxylic acid component used in the present invention is mainly composed of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride, i.e., 50 to 100 mol %, more preferably 70 to 100 mol %. In particular, it is preferable to use 3,3',4,4'-biphenyltetracarboxylic dianhydride as the main component from the viewpoint of heat resistance and mechanical properties. As described above, when 3,3',4,4'-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component, partial crystallization is likely to occur when imidization is performed by a short-term heat treatment with rapid heating. However, according to the present invention, i.e., when the polyamic acid is capable of producing a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/(m 2 24 h), a polyimide layer can be formed without crystallization even when the temperature is rapidly raised.
本発明では、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物を５０モル％以下の範囲で用いてもよいし、ビフェニルテトラカルボン酸二無水物以外のテトラカルボン酸成分（テトラカルボン酸二無水物）を５０モル％以下の範囲で用いてもよい。本発明でビフェニルテトラカルボン酸二無水物と組み合わせて用いることができるテトラカルボン酸二無水物は、特に限定するものではないが、得られるポリイミドの特性から芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物が好ましい。例えば、ピロメリット酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、オキシジフタル酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物、ｐ－ターフェニルテトラカルボン酸二無水物、ｍ－ターフェニルテトラカルボン酸二無水物、シクロブタン－１，２，３，４－テトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物などを好適に挙げることができる。ビフェニルテトラカルボン酸二無水物以外のテトラカルボン酸成分を用いる場合、なかでも、得られるポリイミドの特性から、４，４’－オキシジフタル酸二無水物、またはピロメリット酸二無水物を用いることが特に好ましい。前述のテトラカルボン酸二無水物は一種である必要はなく、複数種の混合物であっても構わない。 In the present invention, 2,2',3,3'-biphenyltetracarboxylic dianhydride may be used in a range of 50 mol% or less, or a tetracarboxylic acid component (tetracarboxylic dianhydride) other than biphenyltetracarboxylic dianhydride may be used in a range of 50 mol% or less. The tetracarboxylic dianhydride that can be used in combination with biphenyltetracarboxylic dianhydride in the present invention is not particularly limited, but aromatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides are preferred in terms of the characteristics of the resulting polyimide. For example, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfonetetracarboxylic dianhydride, p-terphenyltetracarboxylic dianhydride, m-terphenyltetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc. can be preferably mentioned. When using a tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride, it is particularly preferable to use 4,4'-oxydiphthalic dianhydride or pyromellitic dianhydride in view of the properties of the resulting polyimide. The above-mentioned tetracarboxylic dianhydride does not have to be one type, and may be a mixture of multiple types.
本発明で用いることができるジアミンとしては、特に限定するものではないが、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，３’－ジクロロベンジジン、４，４’－ジアミノジフェニルスルフィド、３，３’－ジアミノジフェニルスルホン、１，５－ジアミノナフタレン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、３，３’－ジメチル－４，４’－ビフェニルジアミン、ベンジジン、３，３’－ジメチルベンジジン、３，３’－ジメトキシベンジジン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルプロパン、２，４－ジアミノトルエン、ビス（４－アミノ－３－カルボキシフェニル）メタン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、ビス〔４－（４－アミノフェノキシ）フェニル〕スルホン、２，４－ビス（β－アミノ－第三ブチル）トルエン、ビス（ｐ－β－アミノ－第三ブチルフェニル）エーテル、ビス（ｐ－β－メチル－６－アミノフェニル）ベンゼン、ビス－ｐ－（１，１－ジメチル－５－アミノ－ペンチル）ベンゼン、１－イソプロピル－２，４－ｍ－フェニレンジアミン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、４，４’－メチレンビス（２，６－キシリジン）、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼンなどの芳香族ジアミン、ジ（ｐ－アミノシクロヘキシル）メタン、１，４－ジアミノシクロヘキサンなどの脂環式構造を含むジアミン、へキサメチレンジアミン、へプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ジアミノプロピルテトラメチレン、３－メチルヘプタメチレンジアミン、４，４－ジメチルヘプタメチレンジアミン、２，１１－ジアミノドデカン、１，２－ビス－３－アミノプロポキシエタン、２，２－ジメチルプロピレンジアミン、３－メトキシヘキサメチレンジアミン、２，５－ジメチルヘキサメチレンジアミン、２，５－ジメチルヘプタメチレンジアミン、３－メチルへプタメチレンジアミン、５－メチルノナメチレンジアミン、２，１７－ジアミノエイコサデカン、１，１０－ジアミノ－１，１０－ジメチルデカン、１，１２－ジアミノオクタデカンなどの脂肪族ジアミン等を好適に挙げることができる。前述のジアミンは一種である必要はなく、複数種の混合物であっても構わない。 Diamines that can be used in the present invention are not particularly limited, but include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenyl sulfone, 4, 4'-diaminodiphenylpropane, 2,4-diaminotoluene, bis(4-amino-3-carboxyphenyl)methane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,4-bis(β-amino-tert-butyl)toluene, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-6-aminophenyl)benzene, bis-p-(1,1-dimethyl-5-amino-pentyl)benzene, Aromatic diamines such as 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-methylenebis(2,6-xylidine), α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, diamines containing an alicyclic structure such as di(p-aminocyclohexyl)methane and 1,4-diaminocyclohexane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetraamine, etc. Preferred examples of the diamine include aliphatic diamines such as lamethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoeicosadecane, 1,10-diamino-1,10-dimethyldecane, and 1,12-diaminooctadecane. The diamines mentioned above do not have to be of one type, and may be a mixture of multiple types.
上記のうち、芳香族ジアミンとして、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、２，４－ジアミノトルエン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、４，４’－メチレンビス（２，６－キシリジン）、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼンがより好ましく、脂肪族ジアミンとして、へキサメチレンジアミン、へプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ジアミノプロピルテトラメチレン、３－メチルヘプタメチレンジアミン、２，１１－ジアミノドデカン、１，１２－ジアミノオクタデカンがより好ましい。なかでも、得られるポリイミドの特性から、ｐ－フェニレンジアミン、または４，４’－ジアミノジフェニルエーテルのいずれか一種以上を用いることが特に好ましい。 Among the above, the aromatic diamines are 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, m-xylylenediamine, p-xylylenediamine, 2,2-bis[4-(4-aminophenoxy) More preferred are 4,4'-methylenebis(2,6-xylidine) and α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, and more preferred are aliphatic diamines such as hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 2,11-diaminododecane, and 1,12-diaminooctadecane. Of these, it is particularly preferred to use at least one of p-phenylenediamine and 4,4'-diaminodiphenyl ether in view of the properties of the resulting polyimide.
本発明で用いるポリアミック酸は、最高加熱温度を３００～５００℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できることが必要である。特に水蒸気透過係数が１．８ｇ・ｍｍ／（ｍ2・２４ｈ）以上のポリイミドフィルムを製造できることが好ましい。得られるポリイミドフィルムの水蒸気透過係数がこれより小さい値である場合、ポリイミド絶縁被覆層の製造において、急速な昇温による短時間の熱処理によりイミド化を行おうとすると、部分的な結晶化を起こし易い。 The polyamic acid used in the present invention must be capable of producing a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 ·24 h) by heat treatment under conditions of a maximum heating temperature of 300 to 500° C. It is particularly preferable to produce a polyimide film having a water vapor permeability coefficient of 1.8 g mm/( m2 ·24 h) or more. If the water vapor permeability coefficient of the resulting polyimide film is smaller than this value, partial crystallization is likely to occur when imidization is performed by short-term heat treatment with rapid temperature increase in the production of a polyimide insulating coating layer.
ここで、イミド化過程における結晶化について説明する。イミド化過程においては、溶媒の蒸発とイミド化反応が平行して起こる。昇温速度が大きいと、イミド化反応の進行に対して溶媒の蒸発量が少なくなり、残存溶媒量が比較的多くなる。ポリアミック酸のイミド化が進行してイミド結合が生成すると、分子鎖の溶媒に対する溶解性が小さくなる。そのため、残存溶媒量が比較的多い状態では、分子鎖が結晶化して析出しやすくなる。一方、昇温速度が小さい場合、イミド化反応の進行に対して溶媒の蒸発量が多くなり、残存溶媒が少ないため、結晶化が起こりにくい。本発明のポリイミド前駆体組成物に用いるポリアミック酸からは気体を透過しやすいポリイミド樹脂が得られるため、溶媒が蒸発し易く、昇温速度が大きい条件における結晶化の問題が起こりにくくなる。 Here, crystallization during the imidization process will be explained. In the imidization process, the evaporation of the solvent and the imidization reaction occur in parallel. When the temperature rise rate is high, the amount of solvent evaporated is small relative to the progress of the imidization reaction, and the amount of remaining solvent is relatively large. When the imidization of the polyamic acid progresses and imide bonds are formed, the solubility of the molecular chain in the solvent decreases. Therefore, in a state where the amount of remaining solvent is relatively large, the molecular chain is likely to crystallize and precipitate. On the other hand, when the temperature rise rate is low, the amount of solvent evaporated is large relative to the progress of the imidization reaction, and the remaining solvent is small, so crystallization is unlikely to occur. The polyamic acid used in the polyimide precursor composition of the present invention produces a polyimide resin that is easily permeable to gas, so the solvent is easily evaporated and the problem of crystallization is unlikely to occur under conditions where the temperature rise rate is high.
最高加熱温度を３００～５００℃とする条件下で加熱処理することにより得られるポリイミドフィルムの水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリアミック酸としては、例えば、テトラカルボン酸成分として２，３，３’，４’－ビフェニルテトラカルボン酸二無水物を含むポリアミック酸が挙げられる。この場合、ジアミン成分として、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはそのいずれか一方を５０～１００モル％含むことが好ましい。 An example of a polyamic acid that can produce a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 24 h) by heat treatment under conditions of a maximum heating temperature of 300 to 500° C. is a polyamic acid containing 2,3,3',4'-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component. In this case, the diamine component preferably contains 50 to 100 mol % of paraphenylenediamine and/or 4,4'-diaminodiphenyl ether.
また、前記ポリアミック酸としては、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分として、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含むポリアミック酸が挙げられる。 The polyamic acid may be a polyamic acid that contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, and 30 to 100 mol % of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane as a diamine component, and is composed of one or more diamines selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane.
さらに、前記ポリアミック酸としては、テトラカルボン酸成分として３，３’，４，４’－ビフェニルテトラカルボン酸二無水物を５０～１００モル％含み、ジアミン成分として、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含むポリアミック酸が挙げられる。 The polyamic acid further includes a polyamic acid that contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, and one or more diamines selected from the group consisting of 4,4'-diaminodiphenyl ether and 4,4'-methylenebis(2,6-xylidine) as a diamine component, and contains 20 to 100 mol % of 4,4'-methylenebis(2,6-xylidine).
本発明で用いるポリアミック酸は、略等モルのテトラカルボン酸二無水物とジアミンとを、溶媒中で、イミド化反応を抑制するために１００℃以下、好ましくは８０℃以下の比較的低温で反応させることにより、ポリアミック酸溶液として得ることができる。 The polyamic acid used in the present invention can be obtained as a polyamic acid solution by reacting approximately equimolar amounts of tetracarboxylic dianhydride and diamine in a solvent at a relatively low temperature of 100°C or less, preferably 80°C or less, to suppress the imidization reaction.
限定するものではないが、通常、反応温度は２５℃～１００℃、好ましくは４０℃～８０℃、より好ましくは５０℃～８０℃であり、反応時間は０．１～２４時間程度、好ましくは２～１２時間程度である。反応温度及び反応時間を前記範囲内とすることによって、生産効率よく高分子量のポリアミック酸溶液を容易に得ることができる。 Although not limited thereto, the reaction temperature is usually 25°C to 100°C, preferably 40°C to 80°C, and more preferably 50°C to 80°C, and the reaction time is about 0.1 to 24 hours, and preferably about 2 to 12 hours. By setting the reaction temperature and reaction time within the above ranges, a high molecular weight polyamic acid solution can be easily obtained with high production efficiency.
なお、反応は、空気雰囲気下でも行うことができるが、通常は不活性ガス、好ましくは窒素ガス雰囲気下で好適に行われる。 Although the reaction can be carried out in an air atmosphere, it is usually carried out in an inert gas atmosphere, preferably nitrogen gas atmosphere.
略等モルのテトラカルボン酸二無水物とジアミンとは、具体的には、これらのモル比［テトラカルボン酸二無水物／ジアミン］で０．９０～１．１０程度、好ましくは０．９５～１．０５程度である。 The approximately equimolar amounts of tetracarboxylic dianhydride and diamine are, specifically, in a molar ratio [tetracarboxylic dianhydride/diamine] of about 0.90 to 1.10, preferably about 0.95 to 1.05.
本発明で用いる溶媒としては、ポリアミック酸を重合可能であればいずれの溶媒でもよく、水溶媒であっても、有機溶媒であってもよい。溶媒は２種以上の混合物であってもよく、２種以上の有機溶媒の混合溶媒、又は水と１種以上の有機溶媒の混合溶媒も好適に用いることができる。 The solvent used in the present invention may be any solvent capable of polymerizing polyamic acid, and may be either an aqueous solvent or an organic solvent. The solvent may be a mixture of two or more types, and a mixed solvent of two or more types of organic solvents, or a mixed solvent of water and one or more types of organic solvents, may also be suitably used.
本発明で用いることができる有機溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン、Ｎ－メチルカプロラクタム、ヘキサメチルホスホロトリアミド、１，２－ジメトキシエタン、ビス（２－メトキシエチル）エーテル、１，２－ビス（２－メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２－（２－メトキシエトキシ）エチル］エーテル、１，４－ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、ｍ－クレゾール、フェノール、γ－ブチロラクトンなどが挙げられる。 Organic solvents that can be used in the present invention are not particularly limited, but examples include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl]ether, 1,4-dioxane, dimethylsulfoxide, dimethylsulfone, diphenyl ether, sulfolane, diphenylsulfone, tetramethylurea, anisole, m-cresol, phenol, and γ-butyrolactone.
なお、この反応に用いた溶媒が、本発明のポリイミド前駆体組成物に含まれる溶媒であることができる。 The solvent used in this reaction may be the solvent contained in the polyimide precursor composition of the present invention.
本発明で用いるポリアミック酸は、限定されないが、温度３０℃、濃度０．５ｇ／１００ｍＬで測定した対数粘度が０．２以上、好ましくは０．４以上、特に好ましくは０．６以上であることが好適である。対数粘度が前記範囲よりも低い場合には、ポリアミック酸の分子量が低いことから、高い特性のポリイミドを得ることが難しくなることがある。 The polyamic acid used in the present invention is not limited, but preferably has a logarithmic viscosity of 0.2 or more, preferably 0.4 or more, and particularly preferably 0.6 or more, measured at a temperature of 30°C and a concentration of 0.5 g/100 mL. If the logarithmic viscosity is lower than the above range, it may be difficult to obtain a polyimide with high properties because the molecular weight of the polyamic acid is low.
本発明で用いるポリイミド前駆体組成物は、ポリアミック酸に起因する固形分濃度が、限定されないが、ポリアミック酸と溶媒との合計量に対して、好ましくは５質量％～４５質量％、より好ましくは５質量％～４０質量％、さらに好ましくは５質量％超～３０質量％であることが好適である。固形分濃度が５質量％より低いと使用時の取り扱いが悪くなることがあり、４５質量％より高いと溶液の流動性がなくなることがある。 The polyimide precursor composition used in the present invention has a solids concentration attributable to polyamic acid that is not limited, but is preferably 5% to 45% by mass, more preferably 5% to 40% by mass, and even more preferably more than 5% to 30% by mass, based on the total amount of polyamic acid and solvent. If the solids concentration is lower than 5% by mass, handling during use may be poor, and if it is higher than 45% by mass, the solution may lose fluidity.
また、本発明で用いるポリイミド前駆体組成物の３０℃における溶液粘度は、限定されないが、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは０．５～５００Ｐａ・ｓｅｃ、さらに好ましくは１～３００Ｐａ・ｓｅｃ、特に好ましくは２～２００Ｐａ・ｓｅｃであることが取り扱い上好適である。 The solution viscosity of the polyimide precursor composition used in the present invention at 30°C is not limited, but is preferably 1000 Pa·sec or less, more preferably 0.5 to 500 Pa·sec, even more preferably 1 to 300 Pa·sec, and particularly preferably 2 to 200 Pa·sec, for ease of handling.
ポリイミド前駆体組成物は、加熱処理によって溶媒を除去するとともにイミド化（脱水閉環）することによってポリイミドとなるが、上記のような本発明のポリイミド前駆体組成物を用いることにより、ポリイミド絶縁被覆層の形成のために、短時間で昇温し高温で焼付ける工程を採用することが可能となる。ここで、短時間で昇温して高温で焼付けをするとは、例えば、ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、且つ、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上となる条件で昇温し、最高加熱温度が３００～５００℃である工程である。 The polyimide precursor composition becomes polyimide by removing the solvent and imidizing (dehydration ring closure) by heat treatment. By using the polyimide precursor composition of the present invention as described above, it is possible to adopt a process of heating in a short time and baking at a high temperature to form a polyimide insulating coating layer. Here, heating in a short time and baking at a high temperature refers to a process in which the polyimide precursor composition is heated for 10 to 180 seconds, the temperature is raised under conditions where the average heating rate from 100°C to 280°C is 5°C/s or more, and the maximum heating temperature is 300 to 500°C.
本発明では、公知の方法により基材に上記のようなポリイミド前駆体組成物を塗布し、加熱（焼付け）することによりポリイミド絶縁被覆層を形成する。この焼付け工程においては、ポリイミド前駆体組成物を加熱する時間（加熱炉で加熱する場合、加熱炉内にある時間）を１０～１８０秒間とし、１００℃から２８０℃までの平均昇温速度を５℃／ｓ以上とし、最高加熱温度を３００～５００℃とすることができる。１００℃から２８０℃までの平均昇温速度の上限は、特に限定されないが、例えば、５０℃／ｓ以下が好ましい。 In the present invention, the polyimide insulating coating layer is formed by applying the polyimide precursor composition as described above to a substrate by a known method and heating (baking). In this baking step, the time for heating the polyimide precursor composition (time in the heating furnace when heating in a heating furnace) is set to 10 to 180 seconds, the average heating rate from 100°C to 280°C is set to 5°C/s or more, and the maximum heating temperature can be set to 300 to 500°C. There is no particular limit to the upper limit of the average heating rate from 100°C to 280°C, but for example, 50°C/s or less is preferable.
本発明においては、さらに、１００℃から３００℃までの平均昇温速度を５℃／ｓ以上（すなわち、１００℃～３００℃まで４０秒以内）としてもよく、１００℃から最高加熱温度（３００～５００℃）までの平均昇温速度を５℃／ｓ以上としてもよい。１００℃までの平均昇温速度も、特に限定されないが、５℃／ｓ以上としてもよい。 In the present invention, the average heating rate from 100°C to 300°C may be 5°C/s or more (i.e., from 100°C to 300°C within 40 seconds), and the average heating rate from 100°C to the maximum heating temperature (300 to 500°C) may be 5°C/s or more. The average heating rate up to 100°C is not particularly limited, but may be 5°C/s or more.
本発明においては、１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上（すなわち、１００℃～２８０℃まで３６秒以内）であれば、室温から最高加熱温度までの昇温条件に制限はなく、一定の昇温速度で昇温してもよく、また加熱処理中に昇温速度を変更してもよく、段階的に昇温してもよい。 In the present invention, there are no limitations on the heating conditions from room temperature to the maximum heating temperature, so long as the average heating rate from 100°C to 280°C is 5°C/s or more (i.e., within 36 seconds from 100°C to 280°C), and the temperature may be raised at a constant heating rate, or the heating rate may be changed during the heat treatment, or the temperature may be raised in stages.
このイミド化のための加熱処理は、例えば、空気雰囲気下、あるいは不活性ガス雰囲気下で行うことができる。 The heat treatment for this imidization can be carried out, for example, in an air atmosphere or in an inert gas atmosphere.
なお、上記以外の条件で、本発明のポリイミド前駆体組成物を加熱処理してポリイミド絶縁被覆層を形成することもできる。 The polyimide precursor composition of the present invention can also be heat-treated under conditions other than those described above to form a polyimide insulating coating layer.
なお、基材は、特に限定されず、用途に応じて適宜選択される。また、形成するポリイミド絶縁被覆層の厚みも、特に限定されず、用途に応じて適宜選択される。 The substrate is not particularly limited and is selected appropriately depending on the application. The thickness of the polyimide insulating coating layer to be formed is also not particularly limited and is selected appropriately depending on the application.
本発明により得られるポリイミド絶縁被覆層は、高度の耐電圧性、耐熱性、及び耐湿熱性を有する絶縁部材（被覆層）である。したがって、電気・電子部品関連、自動車分野、航空宇宙分野等に特に好適に使用でき、ＨＶ車モーター用コイルや超小型モーターの分野にも使用可能である。 The polyimide insulating coating layer obtained by the present invention is an insulating member (coating layer) that has high voltage resistance, heat resistance, and moist heat resistance. Therefore, it can be particularly suitably used in electrical and electronic parts, the automotive field, the aerospace field, etc., and can also be used in the fields of coils for hybrid vehicle motors and ultra-small motors.
以下、本発明を実施例により更に具体的に説明するが、本発明は、これら実施例に限定されるものではない。 The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.
以下の例で用いた特性の測定方法を以下に示す。
＜固形分濃度＞
試料溶液（その質量をｗ1とする）を、熱風乾燥機中１２０℃で１０分間、２５０℃で１０分間、次いで３５０℃で３０分間加熱処理して、加熱処理後の質量（その質量をｗ2とする）を測定する。固形分濃度［質量％］は、次式によって算出した。
The methods for measuring the properties used in the following examples are as follows.
<Solid content>
The sample solution ( w1 ) was heated in a hot air dryer at 120°C for 10 minutes, 250°C for 10 minutes, and then 350°C for 30 minutes, and the mass after the heat treatment ( w2 ) was measured. The solid content concentration [mass%] was calculated by the following formula.
固形分濃度［質量％］＝（ｗ2／ｗ1）×１００
＜溶液粘度（回転粘度）＞
トキメック社製Ｅ型粘度計を用いて３０℃で測定した。
＜絶縁被覆層の状態観察（被覆膜評価）＞
得られた被覆層について目視により状態観察を行った。濁りが全くないものを良好、濁りがある領域が１０％を越えているものを濁りありとした。「濁りがある」ということは、ポリイミド樹脂が少なくとも一部結晶化していることを示している。
＜昇温速度の測定＞
被覆層形成工程において、キーエンス株式会社製の計測ユニットＮＲ－ＴＨ０８と解析ソフトＷＡＶＥ ＬＯＧＧＥＲを用いて、サンプル温度が１００℃から２８０℃に変化するまでの所要時間を測定した。
＜水蒸気透過係数＞
ＪＩＳ Ｋ７１２９のＢ法に準拠して、４０℃、相対湿度９０％で測定を行った。
＜弾性率、引張強度、引張伸度＞
調製したポリイミド前駆体組成物をガラス基板上に塗工し、熱風オーブン中、８０℃で３０分加熱し、続いて３５０℃で３０分加熱して硬化させ、厚さがおよそ２５μｍのポリイミドフィルムを作製した。得られたポリイミドフィルムを幅１０ｍｍ、長さ１００ｍｍに切り出して試験片とした。この試験片について、引張試験機（オリエンテック製；テンシロンＲＴＧ－１２２５）を使用して、温度２５℃、湿度５０％ＲＨ、クロスヘッド速度５０ｍｍ／分、チャック間距離５０ｍｍの条件で、引張弾性率、引張強度、及び引張伸度を測定した。
Solid content concentration [mass%] = (w 2 /w 1 ) x 100
<Solution Viscosity (Rotational Viscosity)>
The measurement was performed at 30° C. using an E-type viscometer manufactured by Tokimec Corporation.
<Observation of the state of the insulating coating layer (coating film evaluation)>
The state of the resulting coating layer was visually observed. A coating layer with no turbidity was rated as good, and a coating layer with a turbid area of more than 10% was rated as turbid. "Turbidity" indicates that at least a portion of the polyimide resin was crystallized.
<Measurement of heating rate>
In the coating layer forming step, the time required for the sample temperature to change from 100° C. to 280° C. was measured using a measurement unit NR-TH08 manufactured by Keyence Corporation and analysis software WAVE LOGGER.
<Water vapor permeability coefficient>
The measurement was carried out in accordance with JIS K7129, Method B, at 40° C. and a relative humidity of 90%.
<Elastic modulus, tensile strength, tensile elongation>
The prepared polyimide precursor composition was applied onto a glass substrate, heated in a hot air oven at 80°C for 30 minutes, and then heated at 350°C for 30 minutes to cure the composition, producing a polyimide film having a thickness of approximately 25 μm. The obtained polyimide film was cut into a width of 10 mm and a length of 100 mm to prepare a test piece. The tensile modulus, tensile strength, and tensile elongation of the test piece were measured using a tensile tester (manufactured by Orientec; Tensilon RTG-1225) under conditions of a temperature of 25°C, a humidity of 50% RH, a crosshead speed of 50 mm/min, and a chuck distance of 50 mm.
以下の例で使用した化合物の略号について説明する。
ｓ－ＢＰＤＡ：３，３’，４，４’－ビフェニルテトラカルボン酸二無水物
ａ-ＢＰＤＡ：２，３，３’，４’－ビフェニルテトラカルボン酸二無水物
ＯＤＡ：４，４’－ジアミノジフェニルエーテル
ＰＰＤ：ｐ－フェニレンジアミン
ＢＡＰＰ：２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン
ＭＤＸ：４，４’－メチレンビス（２，６－キシリジン）
ＮＭＰ：Ｎ－メチル－２－ピロリドン
The abbreviations for compounds used in the following examples are explained below.
s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride ODA: 4,4'-diaminodiphenyl ether PPD: p-phenylenediamine BAPP: 2,2'-bis[4-(4-aminophenoxy)phenyl]propane MDX: 4,4'-methylenebis(2,6-xylidine)
NMP: N-methyl-2-pyrrolidone
〔実施例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 1
396 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 40.05 g (0.2 mol) of ODA was added thereto and dissolved by stirring at 50° C. for 1 hour. 58.84 g (0.2 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を、膜厚５０μｍのポリイミドフィルム上に塗工した。得られたサンプルを事前に３８０℃に熱したＳＵＳ板の上に置いて１分間保持し、厚さがおよそ２５μｍの絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 This polyimide precursor composition was applied onto a polyimide film with a thickness of 50 μm. The obtained sample was placed on a SUS plate that had been preheated to 380°C and held there for 1 minute to create an insulating coating layer with a thickness of approximately 25 μm. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔実施例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４７．０８ｇ（０．１６モル）、ａ－ＢＰＤＡの１１．７７ｇ（０．０４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 2
396 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 40.05 g (0.2 mol) of ODA was added thereto and dissolved by stirring at 50° C. for 1 hour. 47.08 g (0.16 mol) of s-BPDA and 11.77 g (0.04 mol) of a-BPDA were added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔比較例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）、ａ－ＢＰＤＡの５．８８ｇ（０．０２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 1
396 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 40.05 g (0.2 mol) of ODA was added thereto and dissolved by stirring at 50° C. for 1 hour. 52.96 g (0.18 mol) of s-BPDA and 5.88 g (0.02 mol) of a-BPDA were added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔比較例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９６ｇを加え、これにＯＤＡの４０．０５ｇ（０．２モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 2
396 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 40.05 g (0.2 mol) of ODA was added thereto and dissolved by stirring at 50° C. for 1 hour. 58.84 g (0.2 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔実施例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にａ－ＢＰＤＡの７０．６１ｇ（０．２４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 3
386 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 25.95 g (0.24 mol) of PPD was added thereto and dissolved by stirring at 50° C. for 1 hour. 70.61 g (0.24 mol) of a-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.2 mass% and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔実施例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの３５．３１ｇ（０．１２モル）、ａ－ＢＰＤＡの３５．３１ｇ（０．１２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 4
386 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 25.95 g (0.24 mol) of PPD was added thereto and dissolved by stirring at 50° C. for 1 hour. 35.31 g (0.12 mol) of s-BPDA and 35.31 g (0.12 mol) of a-BPDA were added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.2 mass% and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔比較例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４２．３７ｇ（０．１４モル）、ａ－ＢＰＤＡの２８．２５ｇ（０．１０モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 3
386 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 25.95 g (0.24 mol) of PPD was added thereto and dissolved by stirring for 1 hour at 50° C. 42.37 g (0.14 mol) of s-BPDA and 28.25 g (0.10 mol) of a-BPDA were added to this solution and stirred for 3 hours at 50° C. to obtain a polyimide precursor composition having a solid content of 18.2 mass % and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔比較例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＰＰＤの２５．９５ｇ（０．２４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの７０．６１ｇ（０．２４モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．２質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 4
386 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 25.95 g (0.24 mol) of PPD was added thereto and dissolved by stirring at 50° C. for 1 hour. 70.61 g (0.24 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.2 mass% and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表１に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 1.
〔実施例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９５ｇを加え、これにＢＡＰＰの５７．４７ｇ（０．１４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４１．１９ｇ（０．１４モル）を加え、５０℃で３時間撹拌して、固形分濃度１９．０質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 5
395 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 57.47 g (0.14 mol) of BAPP was added thereto and dissolved by stirring at 50° C. for 1 hour. 41.19 g (0.14 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 19.0 mass % and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔実施例６〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４０１ｇを加え、これにＢＡＰＰの２２．１７ｇ（０．０５モル）、ＯＤＡの２５．２３ｇ（０．１３モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．７質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 6
In a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, 401 g of NMP was added as a solvent, to which 22.17 g (0.05 mol) of BAPP and 25.23 g (0.13 mol) of ODA were added, and the mixture was stirred at 50° C. for 1 hour to dissolve. 52.96 g (0.18 mol) of s-BPDA was added to this solution, and the mixture was stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.7% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔比較例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３８６ｇを加え、これにＢＡＰＰの１４．７８ｇ（０．０４モル）、ＯＤＡの２８．８３ｇ（０．１４モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５２．９６ｇ（０．１８モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．７質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 5
386 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 14.78 g (0.04 mol) of BAPP and 28.83 g (0.14 mol) of ODA were added thereto and dissolved by stirring at 50° C. for 1 hour. 52.96 g (0.18 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.7% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔実施例７〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９３ｇを加え、これにＢＡＰＰの４５．９８ｇ（０．１１モル）、ＰＰＤの５．１９ｇ（０．０５モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの４７．０８ｇ（０．１６モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．８質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 7
393 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 45.98 g (0.11 mol) of BAPP and 5.19 g (0.05 mol) of PPD were added thereto and dissolved by stirring at 50° C. for 1 hour. 47.08 g (0.16 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.8% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔比較例６〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９７ｇを加え、これにＢＡＰＰの４１．８７ｇ（０．１０モル）、ＰＰＤの７．３５ｇ（０．０７モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５０．０２ｇ（０．１７モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．８質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 6
397 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 41.87 g (0.10 mol) of BAPP and 7.35 g (0.07 mol) of PPD were added thereto and dissolved by stirring at 50° C. for 1 hour. 50.02 g (0.17 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.8% by mass and a solution viscosity of 5.0 Pa s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔実施例８〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４０４ｇを加え、これにＭＤＸの１０．１８ｇ（０．０４モル）、ＯＤＡの３２．０４ｇ（０．１６モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．６質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Example 8
404 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 10.18 g (0.04 mol) of MDX and 32.04 g (0.16 mol) of ODA were added thereto and dissolved by stirring at 50° C. for 1 hour. 58.84 g (0.2 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.6% by mass and a solution viscosity of 5.0 Pa·s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔比較例７〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＭＤＸの５．０９ｇ（０．０２モル）、ＯＤＡの３６．０４ｇ（０．１８モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２０モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．６質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 7
400 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 5.09 g (0.02 mol) of MDX and 36.04 g (0.18 mol) of ODA were added thereto and dissolved by stirring at 50° C. for 1 hour. 58.84 g (0.20 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.6% by mass and a solution viscosity of 5.0 Pa·s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔比較例８〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９２ｇを加え、これにＭＤＸの３０．５３ｇ（０．１２モル）、ＰＰＤの８．６５ｇ（０．０８モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの５８．８４ｇ（０．２モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 8
392 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 30.53 g (0.12 mol) of MDX and 8.65 g (0.08 mol) of PPD were added thereto and dissolved by stirring at 50° C. for 1 hour. 58.84 g (0.2 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa·s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
〔比較例９〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの３９９ｇを加え、これにＭＤＸの２６．７１ｇ（０．１１モル）、ＰＰＤの１１．３５ｇ（０．１１モル）を加え、５０℃で１時間攪拌し、溶解させた。この溶液にｓ－ＢＰＤＡの６１．７９ｇ（０．２１モル）を加え、５０℃で３時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．０Ｐａ・ｓのポリイミド前駆体組成物を得た。
Comparative Example 9
399 g of NMP was added as a solvent to a 500 mL glass reaction vessel equipped with a stirrer and nitrogen gas inlet/outlet tubes, and 26.71 g (0.11 mol) of MDX and 11.35 g (0.11 mol) of PPD were added thereto and dissolved by stirring at 50° C. for 1 hour. 61.79 g (0.21 mol) of s-BPDA was added to this solution and stirred at 50° C. for 3 hours to obtain a polyimide precursor composition having a solid content of 18.5% by mass and a solution viscosity of 5.0 Pa·s.
このポリイミド前駆体組成物を用いて実施例１と同様にして絶縁被覆層を作成した。その際のサンプル温度が１００℃から２８０℃へ昇温する時間は１２秒であった（昇温速度１５℃／ｓ）。得られたポリイミド前駆体組成物及び絶縁被覆層について、状態観察及び特性の評価結果を表２に示した。 Using this polyimide precursor composition, an insulating coating layer was produced in the same manner as in Example 1. The time it took for the sample temperature to rise from 100°C to 280°C was 12 seconds (heating rate 15°C/s). The state observation and property evaluation results for the obtained polyimide precursor composition and insulating coating layer are shown in Table 2.
Claims (9)
前記ポリアミック酸が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸であり、かつ、１００℃から２８０℃までの昇温時間１２秒で、最高加熱温度を３８０℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ２・２４ｈ）より大きいポリイミドフィルムを製造できるものであり、前記ポリイミド前駆体組成物が、イミダゾール類およびアミン化合物からなる群より選択される塩基性化合物を含まず、且つ前記ジアミン成分が、下記式（１）：
で表される化合物を０．５～４０モル％の量で含まないことを特徴とする、電線絶縁被覆層形成用のポリイミド前駆体組成物。 A polyimide precursor composition comprising a polyamic acid and a solvent,
The polyamic acid is a polyamic acid obtained from a tetracarboxylic acid component containing 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride and a diamine component, and by heat treatment under conditions of a temperature increase time from 100°C to 280°C of 12 seconds and a maximum heating temperature of 380°C, a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/( m2 24h) can be produced, the polyimide precursor composition does not contain a basic compound selected from the group consisting of imidazoles and amine compounds, and the diamine component is a polyamic acid represented by the following formula (1):
The polyimide precursor composition for forming an electric wire insulating coating layer is characterized in that it does not contain a compound represented by the following formula (1) in an amount of 0.5 to 40 mol %.
ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、請求項１に記載の、電線絶縁被覆層形成用のポリイミド前駆体組成物。 the tetracarboxylic acid component comprises 2,3,3',4'-biphenyltetracarboxylic dianhydride;
2. The polyimide precursor composition for forming an electric wire insulating coating layer according to claim 1, wherein the diamine component contains 50 to 100 mol % of paraphenylenediamine and 4,4'-diaminodiphenyl ether, or either one of them.
ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、請求項１に記載の、電線絶縁被覆層形成用のポリイミド前駆体組成物。 The tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2. The polyimide precursor composition for forming a wire insulating coating layer according to claim 1, wherein the diamine component comprises one or more diamines selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, and contains 30 to 100 mol % of 2,2' -bis[4-(4-aminophenoxy)phenyl]propane.
ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、請求項１に記載の、電線絶縁被覆層形成用のポリイミド前駆体組成物。 The tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2. The polyimide precursor composition for forming a wire insulating coating layer according to claim 1 , wherein the diamine component comprises one or more diamines selected from the group consisting of 4,4'-diaminodiphenyl ether and 4,4'-methylenebis(2,6-xylidine), and contains 20 to 100 mol % of 4,4'- methylenebis(2,6-xylidine).
ポリイミド前駆体組成物が、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物および２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、またはそのいずれか一方を５０～１００モル％含むテトラカルボン酸成分とジアミン成分とから得られるポリアミック酸を含み、イミダゾール類およびアミン化合物からなる群より選択される塩基性化合物を含まず、かつ、このポリアミック酸が、１００℃から２８０℃までの昇温時間１２秒で、最高加熱温度を３８０℃とする条件下で加熱処理することにより、水蒸気透過係数が１．７ｇ・ｍｍ／（ｍ2・２４ｈ）より大きいポリイミドフィルムを製造できるものであり、
焼付け工程において、
ポリイミド前駆体組成物を加熱する時間が１０～１８０秒間であり、
１００℃から２８０℃までの平均昇温速度が５℃／ｓ以上であり、
最高加熱温度が３００～５００℃であることを特徴とする、電線絶縁被覆層の製造方法。 A method for producing an electric wire insulating coating layer, comprising a step of applying a polyimide precursor composition to a substrate, which is an electric wire, and baking the composition,
the polyimide precursor composition contains a polyamic acid obtained from a tetracarboxylic acid component containing 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride and a diamine component, and does not contain a basic compound selected from the group consisting of imidazoles and amine compounds, and a polyimide film having a water vapor permeability coefficient of more than 1.7 g mm/(m2 24 h) can be produced by heat-treating this polyamic acid under conditions of a temperature rise time from 100°C to 280°C of 12 seconds and a maximum heating temperature of 380°C,
In the baking process,
The time for heating the polyimide precursor composition is 10 to 180 seconds;
The average heating rate from 100° C. to 280° C. is 5° C./s or more;
A method for producing a wire insulating coating layer, characterized in that the maximum heating temperature is 300 to 500°C.
ジアミン成分が、パラフェニレンジアミンおよび４，４’－ジアミノジフェニルエーテル、またはこれらのいずれか一方を５０～１００モル％含む、請求項６に記載の、電線絶縁被覆層の製造方法。 the tetracarboxylic acid component comprises 2,3,3',4'-biphenyltetracarboxylic dianhydride;
7. The method for producing a wire insulating covering layer according to claim 6, wherein the diamine component contains 50 to 100 mol % of paraphenylenediamine and/or 4,4'-diaminodiphenyl ether.
ジアミン成分が、パラフェニレンジアミン、４，４’－ジアミノジフェニルエーテルおよび２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンからなる群から選択される１種以上のジアミンからなり、２，２’－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンを３０～１００モル％含む、請求項６に記載の、電線絶縁被覆層の製造方法。 The tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride,
7. The method for producing a wire insulating coating layer according to claim 6, wherein the diamine component comprises one or more diamines selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, and contains 30 to 100 mol % of 2,2'-bis[ 4-(4-aminophenoxy)phenyl]propane.
ジアミン成分が、４，４’－ジアミノジフェニルエーテルおよび４，４’－メチレンビス（２，６－キシリジン）からなる群から選択される１種以上のジアミンからなり、４，４’－メチレンビス（２，６－キシリジン）を２０～１００モル％含む、請求項６に記載の、電線絶縁被覆層の製造方法。 The tetracarboxylic acid component contains 50 to 100 mol % of 3,3',4,4'-biphenyltetracarboxylic dianhydride,
The method for producing a wire insulating coating layer according to claim 6 , wherein the diamine component comprises one or more diamines selected from the group consisting of 4,4'-diaminodiphenyl ether and 4,4'-methylenebis(2,6-xylidine), and contains 20 to 100 mol% of 4,4'- methylenebis(2,6-xylidine).
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| TW201619303A (en) | 2016-06-01 |
| JPWO2016056595A1 (en) | 2017-07-20 |
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