JP6865592B2 - Manufacturing method of resin varnish, insulated wire and insulated wire - Google Patents
Manufacturing method of resin varnish, insulated wire and insulated wire Download PDFInfo
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- JP6865592B2 JP6865592B2 JP2017007115A JP2017007115A JP6865592B2 JP 6865592 B2 JP6865592 B2 JP 6865592B2 JP 2017007115 A JP2017007115 A JP 2017007115A JP 2017007115 A JP2017007115 A JP 2017007115A JP 6865592 B2 JP6865592 B2 JP 6865592B2
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- Prior art keywords
- resin varnish
- insulated wire
- insulating layer
- polyimide precursor
- mol
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- 229920005989 resin Polymers 0.000 title claims description 129
- 239000011347 resin Substances 0.000 title claims description 129
- 239000002966 varnish Substances 0.000 title claims description 127
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000004642 Polyimide Substances 0.000 claims description 107
- 229920001721 polyimide Polymers 0.000 claims description 107
- 239000002243 precursor Substances 0.000 claims description 73
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 51
- 239000004020 conductor Substances 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 36
- 230000002093 peripheral effect Effects 0.000 claims description 27
- 150000004984 aromatic diamines Chemical class 0.000 claims description 25
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 17
- 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 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 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 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 description 33
- 230000006866 deterioration Effects 0.000 description 29
- 239000003960 organic solvent Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000003495 polar organic solvent Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic diamines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920003055 poly(ester-imide) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RDMFEHLCCOQUMH-UHFFFAOYSA-N 2,4'-Diphenyldiamine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1N RDMFEHLCCOQUMH-UHFFFAOYSA-N 0.000 description 1
- HOLGXWDGCVTMTB-UHFFFAOYSA-N 2-(2-aminophenyl)aniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1N HOLGXWDGCVTMTB-UHFFFAOYSA-N 0.000 description 1
- WRRQKFXVKRQPDB-UHFFFAOYSA-N 2-(2-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC=C1SC1=CC=CC=C1N WRRQKFXVKRQPDB-UHFFFAOYSA-N 0.000 description 1
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 description 1
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-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
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-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
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-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
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 229910000881 Cu alloy Inorganic materials 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
Description
本発明は、樹脂ワニス、絶縁電線及び絶縁電線の製造方法に関する。 The present invention relates to a resin varnish, an insulated electric wire, and a method for manufacturing an insulated electric wire.
モータ等のコイルに用いられる絶縁電線において、導体を被覆する絶縁層には、優れた絶縁性、導体に対する密着性、耐熱性、機械的強度、可撓性等が求められている。この絶縁層の形成に用いる合成樹脂としては、例えばポリイミド、ポリアミドイミド、ポリエステルイミド等が挙げられる。 In an insulated wire used for a coil of a motor or the like, the insulating layer covering the conductor is required to have excellent insulating properties, adhesion to the conductor, heat resistance, mechanical strength, flexibility and the like. Examples of the synthetic resin used for forming the insulating layer include polyimide, polyamide-imide, polyesterimide and the like.
また、適用電圧が高い電気機器、例えば高電圧で使用されるモータ等では、電気機器を構成する絶縁電線に高電圧が印加され、その絶縁層表面で部分放電（コロナ放電）が発生しやすくなる。コロナ放電が発生すると、局部的な温度上昇やオゾン等の発生が引き起こされやすくなり、その結果、絶縁電線の絶縁層が劣化することで早期に絶縁破壊を起こし、電気機器の寿命が短くなる。高電圧が印加される絶縁電線には上記の理由によりコロナ放電開始電圧の向上が求められており、そのためには絶縁層の誘電率を低くすることが有効であることが知られている。 Further, in an electric device having a high applicable voltage, for example, a motor used at a high voltage, a high voltage is applied to an insulated wire constituting the electric device, and a partial discharge (corona discharge) is likely to occur on the surface of the insulating layer. .. When a corona discharge occurs, a local temperature rise and the generation of ozone and the like are likely to occur, and as a result, the insulating layer of the insulated wire deteriorates, causing early dielectric breakdown and shortening the life of the electrical equipment. For the above reason, the insulated wire to which a high voltage is applied is required to improve the corona discharge starting voltage, and it is known that it is effective to lower the dielectric constant of the insulating layer for that purpose.
さらに、絶縁電線は、湿熱環境下に晒される場合がある。このような環境下では、絶縁層を形成する合成樹脂が加水分解を生じてその分子量が著しく低下し、その結果、クラック等が生じて絶縁層としての機能が低下するおそれがある。そのため、絶縁電線の絶縁層には、上記湿熱環境下での機能低下を抑制する性能（耐湿熱劣化性）が要求される場合がある。 Further, the insulated wire may be exposed to a moist heat environment. In such an environment, the synthetic resin forming the insulating layer may be hydrolyzed to significantly reduce its molecular weight, and as a result, cracks or the like may occur and the function as the insulating layer may be deteriorated. Therefore, the insulating layer of the insulated wire may be required to have a performance (moisture heat deterioration resistance) of suppressing functional deterioration in the above-mentioned moist heat environment.
ポリイミドは、絶縁電線の絶縁層に使用される合成樹脂の中では特に耐熱性に優れ、誘電率が低く、かつ機械的強度にも優れるため、高電圧で使用される絶縁電線の絶縁層に用いられている。例えば特開２０１３−２５３１２４号公報には、芳香族ジアミンと芳香族テトラカルボン酸二無水物との反応産物であり、かつイミド化後のイミド基濃度が特定範囲であるポリイミド前駆体を含有する樹脂ワニスを用いて絶縁層を形成することで、耐熱性、耐クレージング性に優れ、コロナ放電し難い絶縁電線が得られると記載されている。 Polyimide is particularly excellent in heat resistance, low dielectric constant, and excellent mechanical strength among synthetic resins used for the insulating layer of insulated wires, so it is used for the insulating layer of insulated wires used at high voltage. Has been done. For example, Japanese Patent Application Laid-Open No. 2013-253124 describes a resin containing a polyimide precursor which is a reaction product of an aromatic diamine and an aromatic tetracarboxylic acid dianhydride and whose imide group concentration after imidization is in a specific range. It is stated that by forming an insulating layer using a varnish, an insulated wire having excellent heat resistance and crazing resistance and which is difficult to discharge from corona can be obtained.
なお、ポリイミドにより絶縁電線の絶縁層を形成する方法としては、ポリイミド前駆体（ポリアミック酸）を含有する樹脂ワニスを導体の外周側に塗工する塗工工程と、得られた塗膜を加熱する加熱工程とを備える方法が一般的である。この加熱工程によってポリイミド前駆体がイミド化してポリイミドが形成される。上記方法では、一回の塗工工程及び加熱工程では数μｍ程度の比較的薄い皮膜しか形成できないため、通常塗工工程及び加熱を繰り返して所定の厚さ（数１０μｍ程度）の皮膜を形成する。この樹脂ワニスには、優れた塗布性が要求され、特に一度の塗工工程及び加熱工程で形成できる皮膜を厚くするために含有するポリイミド前駆体の濃度を高めた場合においても優れた塗布性を維持できることが要求される。 As a method of forming an insulating layer of an insulated wire with polyimide, a coating step of applying a resin varnish containing a polyimide precursor (polyamic acid) to the outer peripheral side of the conductor and heating of the obtained coating film are performed. A method including a heating step is common. By this heating step, the polyimide precursor is imidized to form a polyimide. In the above method, since only a relatively thin film of about several μm can be formed in one coating step and heating step, a film having a predetermined thickness (about several tens of μm) is formed by repeating the normal coating step and heating. .. This resin varnish is required to have excellent coatability, and particularly excellent coatability even when the concentration of the polyimide precursor contained in the resin varnish is increased in order to thicken the film that can be formed in one coating step and heating step. It is required to be sustainable.
ここで、絶縁電線の絶縁層における可撓性を良好なものにするためには、上記絶縁層の主成分として伸張性に優れる材料を用いる必要がある。絶縁層に用いる材料のうち、ポリイミドは比較的伸張性の高い材料であるが、エラストマー等と比較すると伸張性に劣る。また、ポリイミドは、湿熱環境下に長時間曝された場合に加水分解を生じるおそれがある材料である。そのため、上記従来の樹脂ワニスにより形成した絶縁層の可撓性及び耐湿熱劣化性には向上の余地がある。 Here, in order to improve the flexibility of the insulating layer of the insulated wire, it is necessary to use a material having excellent extensibility as the main component of the insulating layer. Among the materials used for the insulating layer, polyimide is a material having relatively high extensibility, but is inferior in extensibility as compared with elastomers and the like. Moreover, polyimide is a material that may cause hydrolysis when exposed to a moist heat environment for a long time. Therefore, there is room for improvement in the flexibility and the moisture resistance and heat deterioration resistance of the insulating layer formed by the conventional resin varnish.
この絶縁層の可撓性及び耐湿熱劣化性を向上する方法として、例えば主成分であるポリイミドを高分子量化し、これによりポリイミドの伸長性を向上すると共に、加水分解後においても一定の分子量を維持し易くすることが考えられる。しかし、この方法は、絶縁層の可撓性向上には有効であるが、絶縁層の耐湿熱劣化性を十分に向上させるためにはポリイミドの分子量を極端に高くする必要があり、そのためには極端に分子量の高い（例えば重量平均分子量１８０，０００超）ポリイミド前駆体を樹脂ワニスに含有させる必要がある。このような樹脂ワニスは、粘度が極めて高くなることで塗布性が低下するおそれがあるため、上記方法だけで上記絶縁層の耐湿熱劣化性を向上することは困難である。 As a method for improving the flexibility and the heat deterioration resistance of the insulating layer, for example, the polyimide as the main component is made high in molecular weight, thereby improving the extensibility of the polyimide and maintaining a constant molecular weight even after hydrolysis. It is possible to make it easier. However, although this method is effective for improving the flexibility of the insulating layer, it is necessary to make the molecular weight of the polyimide extremely high in order to sufficiently improve the moisture resistance and heat deterioration resistance of the insulating layer. It is necessary to include a polyimide precursor having an extremely high molecular weight (for example, a weight average molecular weight of more than 180,000) in the resin varnish. Since such a resin varnish may have an extremely high viscosity and thus a decrease in coatability, it is difficult to improve the moisture resistance and heat deterioration resistance of the insulating layer only by the above method.
本発明は上述のような事情に基づいてなされたものであり、塗布性に優れ、かつ形成される絶縁層の耐湿熱劣化性及び可撓性に優れる樹脂ワニスと、この樹脂ワニスを用いた絶縁電線及びその製造方法とを提供することを目的とする。 The present invention has been made based on the above circumstances, and is a resin varnish having excellent coatability and excellent moisture-heat deterioration resistance and flexibility of the insulating layer to be formed, and insulation using this resin varnish. It is an object of the present invention to provide an electric wire and a method for manufacturing the electric wire.
上記課題を解決するためになされた本発明の一態様に係る樹脂ワニスは、芳香族テトラカルボン酸二無水物と芳香族ジアミンとの反応生成物であるポリイミド前駆体を含有する樹脂ワニスであって、上記ポリイミド前駆体の重量平均分子量が１０，０００以上１８０，０００以下であり、上記芳香族テトラカルボン酸二無水物がビフェニルテトラカルボン酸二無水物を含み、上記芳香族テトラカルボン酸二無水物１００モル％に対するビフェニルテトラカルボン酸二無水物の含有量が２５モル％以上９５モル％以下である。 The resin varnish according to one aspect of the present invention made to solve the above problems is a resin varnish containing a polyimide precursor which is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine. The weight average molecular weight of the polyimide precursor is 10,000 or more and 180,000 or less, the aromatic tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride. The content of biphenyltetracarboxylic dianhydride with respect to 100 mol% is 25 mol% or more and 95 mol% or less.
上記課題を解決するためになされた本発明の別の態様に係る絶縁電線は、導体と、この導体の外周側に積層される１又は複数の絶縁層とを備える絶縁電線であって、上記１又は複数の絶縁層のうち少なくとも１層が上述の樹脂ワニスの硬化物である。 The insulated wire according to another aspect of the present invention made to solve the above problem is an insulated wire including a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor. Alternatively, at least one of the plurality of insulating layers is a cured product of the above-mentioned resin varnish.
上記課題を解決するためになされた本発明のさらに別の態様に係る絶縁電線の製造方法は、導体と、この導体の外周側に積層される１又は複数の絶縁層とを備える絶縁電線の製造方法であって、導体の外周側に上述の樹脂ワニスを塗工する塗工工程と、上記塗工された樹脂ワニスを加熱する加熱工程とを備える。 A method for manufacturing an insulated wire according to still another aspect of the present invention, which has been made to solve the above problems, is to manufacture an insulated wire including a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor. The method includes a coating step of applying the above-mentioned resin varnish on the outer peripheral side of the conductor and a heating step of heating the coated resin varnish.
本発明の一態様に係る樹脂ワニスは、塗布性に優れ、かつ耐湿熱劣化性及び可撓性に優れる絶縁層を形成できる。本発明の別の一態様に係る絶縁電線及びその製造方法は、耐湿熱劣化性及び可撓性に優れる絶縁層を備える絶縁電線を提供できる。 The resin varnish according to one aspect of the present invention can form an insulating layer having excellent coatability and excellent moisture-heat deterioration resistance and flexibility. An insulated wire according to another aspect of the present invention and a method for manufacturing the same can provide an insulated wire provided with an insulating layer having excellent moisture resistance and heat deterioration resistance and flexibility.
［本発明の実施形態の説明］
本発明の一態様に係る樹脂ワニスは、芳香族テトラカルボン酸二無水物と芳香族ジアミンとの反応生成物であるポリイミド前駆体を含有する樹脂ワニスであって、上記ポリイミド前駆体の重量平均分子量が１０，０００以上１８０，０００以下であり、上記芳香族テトラカルボン酸二無水物がビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）を含み、上記芳香族テトラカルボン酸二無水物１００モル％に対するビフェニルテトラカルボン酸二無水物の含有量が２５モル％以上９５モル％以下である。
[Explanation of Embodiments of the Present Invention]
The resin varnish according to one aspect of the present invention is a resin varnish containing a polyimide precursor which is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine, and has a weight average molecular weight of the polyimide precursor. Is 10,000 or more and 180,000 or less, the aromatic tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride (BPDA), and biphenyltetra is contained in an amount of 100 mol% of the aromatic tetracarboxylic dianhydride. The content of the carboxylic dianhydride is 25 mol% or more and 95 mol% or less.
当該樹脂ワニスは、上記構成を有することにより、塗布性に優れ、かつ耐湿熱劣化性及び可撓性に優れる絶縁層を形成できる。当該樹脂ワニスが上記構成を有することにより上記効果を奏する理由は定かではないが、例えば以下のように推察される。すなわち、当該樹脂ワニスは、重量平均分子量が上記下限以上と比較的高分子量であるポリイミド前駆体を含有するため、導体の外周側への塗工及び加熱により、比較的高分子量のポリイミドを主成分とする絶縁層を形成できる。このような比較的高分子量のポリイミドは、伸長性に優れ、かつ加水分解を生じたとしても一定の分子量を維持し易いため、上記絶縁層の可撓性及び耐湿熱劣化性を向上すると考えられる。また、当該樹脂ワニスは、加水分解性の低いＢＰＤＡを上記ポリイミド前駆体の原料として特定量用いることで、形成される絶縁層の主成分であるポリイミドに加水分解性の低い構造を導入できる。その結果、当該樹脂ワニスは、上記ポリイミド前駆体を極端に高分子量化せず、その重量平均分子量を上記上限以下としても上記絶縁層の耐湿熱劣化性を十分に向上できると考えられる。さらに、当該樹脂ワニスは、上記ポリイミド前駆体の重量平均分子量を上記上限以下とすることで、極端な粘度の増大を抑制して塗布性を向上でき、特にポリイミド前駆体の濃度を高めた場合においても優れた塗布性を維持できる。さらに、当該樹脂ワニスは、上記ポリイミド前駆体の原料である芳香族テトラカルボン酸二無水物に対するＢＰＤＡの含有量を上記上限以下とすることで、上記ＢＰＤＡの結晶化に由来する塗布欠陥の発生を抑制できる。これらにより、当該樹脂ワニスは、塗布性に優れ、かつ耐湿熱劣化性及び可撓性に優れる絶縁層を形成できると考えられる。ここで「重量平均分子量」とは、ＪＩＳ−Ｋ７２５２−１：２００８「プラスチック−サイズ排除クロマトグラフィーによる高分子の平均分子量及び分子量分布の求め方−第１部：通則」に準拠し、ゲル浸透クロマトグラフィー（ＧＰＣ）を用いて測定した値をいう。 By having the above structure, the resin varnish can form an insulating layer having excellent coatability, moisture resistance and heat deterioration resistance, and flexibility. The reason why the resin varnish has the above-mentioned effect is not clear, but it is presumed as follows, for example. That is, since the resin varnish contains a polyimide precursor having a weight average molecular weight equal to or higher than the above lower limit and a relatively high molecular weight, the resin varnish contains a relatively high molecular weight polyimide as a main component by coating and heating the outer peripheral side of the conductor. An insulating layer can be formed. Such a polyimide having a relatively high molecular weight is excellent in extensibility and easily maintains a constant molecular weight even if hydrolysis occurs, so that it is considered that the flexibility of the insulating layer and the resistance to moisture and heat deterioration are improved. .. Further, in the resin varnish, a structure having low hydrolyzability can be introduced into the polyimide which is the main component of the insulating layer to be formed by using a specific amount of BPDA having low hydrolyzability as a raw material of the polyimide precursor. As a result, it is considered that the resin varnish can sufficiently improve the moisture resistance and heat deterioration resistance of the insulating layer even if the polyimide precursor is not extremely high molecular weight and the weight average molecular weight is set to the upper limit or less. Further, in the resin varnish, by setting the weight average molecular weight of the polyimide precursor to the above upper limit or less, it is possible to suppress an extreme increase in viscosity and improve the coatability, especially when the concentration of the polyimide precursor is increased. Can maintain excellent coatability. Further, the resin varnish causes the occurrence of coating defects due to the crystallization of the BPDA by setting the content of BPDA in the aromatic tetracarboxylic dianhydride which is the raw material of the polyimide precursor to the above upper limit or less. Can be suppressed. From these, it is considered that the resin varnish can form an insulating layer having excellent coatability and excellent moisture-heat deterioration resistance and flexibility. Here, the "weight average molecular weight" is based on JIS-K7252-1: 2008 "Plastic-How to obtain the average molecular weight and molecular weight distribution of a polymer by size exclusion chromatography-Part 1: General rules" and gel permeation chromatography. A value measured using graphics (GPC).
上記芳香族テトラカルボン酸二無水物がピロメリット酸二無水物をさらに含むとよく、この場合、上記芳香族テトラカルボン酸二無水物１００モル％に対するピロメリット酸二無水物の含有量としては、５モル％以上７５モル％以下が好ましい。このように、上記芳香族テトラカルボン酸二無水物がピロメリット酸二無水物を特定量含むことで、形成される絶縁層の主成分であるポリイミドに剛直な構造を導入できるため、上記絶縁層の耐熱性を向上できる。 It is preferable that the aromatic tetracarboxylic dianhydride further contains a pyromellitic dianhydride. In this case, the content of the pyromellitic dianhydride with respect to 100 mol% of the aromatic tetracarboxylic dianhydride is determined. It is preferably 5 mol% or more and 75 mol% or less. As described above, when the aromatic tetracarboxylic dianhydride contains a specific amount of pyromellitic dianhydride, a rigid structure can be introduced into the polyimide which is the main component of the insulating layer to be formed, so that the insulating layer can be introduced. Heat resistance can be improved.
上記芳香族ジアミンがジアミノジフェニルエーテルを含むとよい。このように、上記芳香族ジアミンがジアミノジフェニルエーテルを含むことで、形成される絶縁層の靭性を向上できる。 The aromatic diamine may contain diaminodiphenyl ether. As described above, when the aromatic diamine contains diaminodiphenyl ether, the toughness of the formed insulating layer can be improved.
上記ポリイミド前駆体の樹脂ワニス中の濃度としては、２５質量％以上５０質量％以下が好ましい。このように、上記ポリイミド前駆体の樹脂ワニス中の濃度を上記範囲とすること、つまり比較的高濃度とすることで、一回の塗工工程及び加熱工程で形成される皮膜を厚くできるため、塗工工程及び加熱工程を繰り返す場合にその回数を低減でき、かつ製造工程全体での樹脂ワニスの合計使用量を低減でき、これらの結果、絶縁電線の製造コストを低減できる。 The concentration of the polyimide precursor in the resin varnish is preferably 25% by mass or more and 50% by mass or less. As described above, by setting the concentration of the polyimide precursor in the resin varnish within the above range, that is, setting it to a relatively high concentration, the film formed in one coating step and heating step can be thickened. When the coating process and the heating process are repeated, the number of times can be reduced, and the total amount of resin varnish used in the entire manufacturing process can be reduced. As a result, the manufacturing cost of the insulated wire can be reduced.
上記ポリイミド前駆体の重量平均分子量としては、１３０，０００以下が好ましい。このように、上記ポリイミド前駆体の重量平均分子量を上記上限以下とすることで、より塗布性を向上できる。 The weight average molecular weight of the polyimide precursor is preferably 130,000 or less. As described above, by setting the weight average molecular weight of the polyimide precursor to the above upper limit or less, the coatability can be further improved.
上記課題を解決するためになされた本発明の別の態様に係る絶縁電線は、導体と、この導体の外周側に積層される１又は複数の絶縁層とを備える絶縁電線であって、上記１又は複数の絶縁層のうち少なくとも１層が上述の樹脂ワニスの硬化物である。 The insulated wire according to another aspect of the present invention made to solve the above problem is an insulated wire including a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor. Alternatively, at least one of the plurality of insulating layers is a cured product of the above-mentioned resin varnish.
当該絶縁電線は、当該樹脂ワニスを用いて絶縁層を形成するため、耐湿熱劣化性及び可撓性に優れる絶縁層を備える。 Since the insulating wire forms an insulating layer using the resin varnish, the insulated wire includes an insulating layer having excellent moisture resistance and heat deterioration resistance and flexibility.
本発明の別の態様に係る絶縁電線の製造方法は、導体と、この導体の外周側に積層される１又は複数の絶縁層とを備える絶縁電線の製造方法であって、導体の外周側に上述の樹脂ワニスを塗工する塗工工程と、上記塗工された樹脂ワニスを加熱する加熱工程とを備える。 A method for manufacturing an insulated wire according to another aspect of the present invention is a method for manufacturing an insulated wire including a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor, on the outer peripheral side of the conductor. It includes a coating step of applying the above-mentioned resin varnish and a heating step of heating the above-mentioned coated resin varnish.
当該絶縁電線の製造方法は、当該樹脂ワニスを用いて絶縁層を形成するため、耐湿熱劣化性及び可撓性に優れる絶縁層を備える絶縁電線を容易かつ確実に製造できる。 Since the insulating layer is formed by using the resin varnish in the method for manufacturing the insulated wire, it is possible to easily and surely manufacture an insulated wire having an insulating layer having excellent moisture resistance and heat deterioration resistance and flexibility.
［本発明の実施形態の詳細］
以下、本発明の一態様に係る樹脂ワニスと、本発明の別の態様に係る絶縁電線及びその製造方法とをこの順番で説明する。
[Details of Embodiments of the present invention]
Hereinafter, the resin varnish according to one aspect of the present invention, the insulated wire according to another aspect of the present invention, and the method for manufacturing the same will be described in this order.
＜樹脂ワニス＞
当該樹脂ワニスはポリイミド前駆体（ポリアミック酸）を含有する。また、当該樹脂ワニスは通常有機溶剤をさらに含有する。以下、各成分について説明する。
<Resin varnish>
The resin varnish contains a polyimide precursor (polyamic acid). In addition, the resin varnish usually further contains an organic solvent. Hereinafter, each component will be described.
［ポリイミド前駆体］
当該樹脂ワニスが含有するポリイミド前駆体は、芳香族テトラカルボン酸二無水物と芳香族ジアミンとの重合によって得られる反応生成物である。つまり、上記ポリイミド前駆体は、芳香族テトラカルボン酸二無水物と芳香族ジアミンとを原料とする。
[Polyimide precursor]
The polyimide precursor contained in the resin varnish is a reaction product obtained by polymerizing an aromatic tetracarboxylic dianhydride and an aromatic diamine. That is, the polyimide precursor uses aromatic tetracarboxylic dianhydride and aromatic diamine as raw materials.
上記ポリイミド前駆体の重量平均分子量の下限としては、１０，０００であり、１５，０００が好ましい。一方、上記重量平均分子量の上限としては、１８０，０００であり、１３０，０００が好ましい。上記重量平均分子量が上記下限より小さい場合、当該樹脂ワニスにより形成される絶縁層の耐湿熱劣化性及び可撓性が不十分となるおそれがある。逆に、上記重量平均分子量が上記上限を超える場合、当該樹脂ワニスが顕著に増粘し、塗布性が不十分となるおそれがある。 The lower limit of the weight average molecular weight of the polyimide precursor is 10,000, preferably 15,000. On the other hand, the upper limit of the weight average molecular weight is 180,000, preferably 130,000. If the weight average molecular weight is smaller than the above lower limit, the moisture resistance and heat deterioration resistance and flexibility of the insulating layer formed by the resin varnish may be insufficient. On the contrary, when the weight average molecular weight exceeds the upper limit, the resin varnish may be remarkably thickened and the coatability may be insufficient.
上記ポリイミド前駆体の原料として用いる芳香族テトラカルボン酸二無水物と芳香族ジアミンとのモル比（芳香族テトラカルボン酸二無水物／芳香族ジアミン）としては、ポリイミド前駆体の合成容易性の観点から、例えば９５／１０５以上１０５／９５以下とすることができる。 The molar ratio of the aromatic tetracarboxylic dianhydride used as the raw material of the polyimide precursor to the aromatic diamine (aromatic tetracarboxylic dianhydride / aromatic diamine) is from the viewpoint of easiness of synthesizing the polyimide precursor. Therefore, for example, it can be 95/105 or more and 105/95 or less.
（芳香族テトラカルボン酸二無水物）
上記ポリイミド前駆体の原料として用いる芳香族テトラカルボン酸二無水物は、ＢＰＤＡを含む。ＢＰＤＡとしては、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（３，３’，４，４’−ＢＤＰＡ）、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（２，３，３’，４’−ＢＤＰＡ）、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物（２，２’，３，３’−ＢＤＰＡ）等が挙げられ、これらの中で、３，３’，４，４’−ＢＤＰＡが好ましい。
(Aromatic tetracarboxylic dianhydride)
The aromatic tetracarboxylic dianhydride used as a raw material for the polyimide precursor contains BPDA. BPDA includes 3,3', 4,4'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-BDPA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride. Anhydrides (2,3,3', 4'-BDPA), 2,2', 3,3'-biphenyltetracarboxylic dianhydrides (2,2', 3,3'-BDPA) and the like can be mentioned. Of these, 3,3', 4,4'-BDPA is preferable.
上記芳香族テトラカルボン酸二無水物１００モル％に対するＢＰＤＡの含有量の下限としては、２５モル％であり、３５モル％が好ましく、６０モル％がより好ましい。一方、上記ＢＰＤＡの含有量の上限としては、９５モル％であり、８０モル％が好ましい。上記ＢＰＤＡの含有量を上記範囲とすることで、当該樹脂ワニスにより形成される絶縁層の耐湿熱劣化性をより向上できる。上記ＢＰＤＡの含有量が上記下限より小さい場合、当該樹脂ワニスにより形成される絶縁層の耐湿熱劣化性が不十分となるおそれがある。逆に、上記ＢＰＤＡの含有量が上記上限を超える場合、当該樹脂ワニスにより形成される絶縁層の主成分であるポリイミドが結晶構造を取り易くなるため、結晶化に伴う不透明化や、部位毎の結晶化のバラツキによる色ムラ等の塗布欠陥が生じるおそれがある。 The lower limit of the content of BPDA with respect to 100 mol% of the aromatic tetracarboxylic dianhydride is 25 mol%, preferably 35 mol%, and more preferably 60 mol%. On the other hand, the upper limit of the content of BPDA is 95 mol%, preferably 80 mol%. By setting the content of BPDA in the above range, the moisture resistance and heat deterioration resistance of the insulating layer formed by the resin varnish can be further improved. If the content of the BPDA is smaller than the above lower limit, the moisture resistance and heat deterioration resistance of the insulating layer formed by the resin varnish may be insufficient. On the contrary, when the content of BPDA exceeds the above upper limit, the polyimide which is the main component of the insulating layer formed by the resin varnish easily takes a crystal structure, so that opacity due to crystallization and each part are opaque. There is a risk of coating defects such as color unevenness due to variations in crystallization.
上記ポリイミド前駆体の原料として用いる芳香族テトラカルボン酸二無水物のうち、ＢＰＤＡ以外の芳香族テトラカルボン酸二無水物としては、例えばピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、４，４’−オキシジフタル酸二無水物、２，２’，３，３’−ベンゾフェノンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物等が挙げられる。上記その他の芳香族テトラカルボン酸二無水物は、単独で用いても２種以上を併用してもよい。 Among the aromatic tetracarboxylic dianhydrides used as the raw material of the above-mentioned polyimide precursor, the aromatic tetracarboxylic dianhydrides other than BPDA include, for example, pyromellitic dianhydride (PMDA), 3,3', 4 , 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4) -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3) , 4-dicarboxyphenyl) sulfonate dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7 − Naphthalenetetracarboxylic dianhydride and the like can be mentioned. The other aromatic tetracarboxylic dianhydride may be used alone or in combination of two or more.
上記ポリイミド前駆体の原料として用いる芳香族テトラカルボン酸二無水物は、ＰＭＤＡをさらに含むことが好ましい。ポリイミド前駆体の原料として剛直な構造を有するＰＭＤＡを用いることで、イミド化後のポリイミドに剛直な構造を導入できるため、当該樹脂ワニスにより形成される絶縁層の耐熱性を向上できる。 The aromatic tetracarboxylic dianhydride used as a raw material for the polyimide precursor preferably further contains PMDA. By using PMDA having a rigid structure as a raw material of the polyimide precursor, a rigid structure can be introduced into the polyimide after imidization, so that the heat resistance of the insulating layer formed by the resin varnish can be improved.
上記ポリイミド前駆体の原料として用いる芳香族テトラカルボン酸二無水物１００モル％に対するＰＭＤＡの含有量の下限としては、５モル％が好ましく、２０モル％がより好ましい。一方、上記ＰＭＤＡの含有量の上限としては、７５モル％が好ましく、６５モル％がより好ましく、４０モル％がさらに好ましい。上記ＰＭＤＡの含有量が上記下限より小さい場合、当該樹脂ワニスにより形成される絶縁層の耐熱性が不十分となるおそれがある。逆に、上記ＰＭＤＡの含有量が上記上限を超える場合、当該樹脂ワニスにより形成される絶縁層の主成分であるポリイミドにＢＰＤＡに由来する構造を十分に導入することができず、その結果、上記絶縁層の耐湿熱劣化性が低下するおそれがある。 The lower limit of the content of PMDA with respect to 100 mol% of the aromatic tetracarboxylic dianhydride used as the raw material of the polyimide precursor is preferably 5 mol%, more preferably 20 mol%. On the other hand, as the upper limit of the content of PMDA, 75 mol% is preferable, 65 mol% is more preferable, and 40 mol% is further more preferable. If the PMDA content is smaller than the lower limit, the heat resistance of the insulating layer formed by the resin varnish may be insufficient. On the contrary, when the content of PMDA exceeds the above upper limit, the structure derived from BPDA cannot be sufficiently introduced into the polyimide which is the main component of the insulating layer formed by the resin varnish, and as a result, the above The moisture resistance and heat deterioration resistance of the insulating layer may decrease.
（芳香族ジアミン）
上記ポリイミド前駆体の原料として用いる芳香族ジアミンとしては、例えば４，４’−ジアミノジフェニルエーテル（４，４’−ＯＤＡ）、３，４’−ジアミノジフェニルエーテル（３，４’−ＯＤＡ）、３，３’−ジアミノジフェニルエーテル（３，３’−ＯＤＡ）、２，４’−ジアミノジフェニルエーテル（２，４’−ＯＤＡ）、２，２’−ジアミノジフェニルエーテル（２，２’−ＯＤＡ）等のジアミノジフェニルエーテル（ＯＤＡ）、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）、４，４’−ジアミノジフェニルメタン、３，４’−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、２，４’−ジアミノジフェニルメタン、２，２’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、２，４’−ジアミノジフェニルスルホン、２，２’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルフィド、３，４’−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フィド、２，４’−ジアミノジフェニルスルフィド、２，２’−ジアミノジフェニルスルフィド、パラフェニレンジアミン、メタフェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、２，２’−ジメチル−４，４’−ジアミノビフェニル、１，５−ジアミノナフタレン、４，４’−ベンゾフェノンジアミン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン等が挙げられる。これらの芳香族ジアミンは、単独で用いても２種以上を併用してもよい。
(Aromatic diamine)
Examples of the aromatic diamine used as the raw material of the polyimide precursor include 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether (3,4'-ODA), 3,3. Diaminodiphenyl ethers (ODA) such as'-diaminodiphenyl ether (3,3'-ODA), 2,4'-diaminodiphenyl ether (2,4'-ODA), 2,2'-diaminodiphenyl ether (2,2'-ODA) ), 2,2-Bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,4 '-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, 2 , 2'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfide, 2,4′-diaminodiphenylsulfide, 2,2′-diamino Diphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylene diamine, m-xylylene diamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 4,4'- Examples thereof include benzophenonediamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and the like. These aromatic diamines may be used alone or in combination of two or more.
上記ポリイミド前駆体の原料として用いる芳香族ジアミンは、ＯＤＡを含むことが好ましい。上記ポリイミド前駆体の原料としてＯＤＡを用いることで、当該樹脂ワニスにより形成される絶縁層の靭性を向上できる。上記ＯＤＡとしては、４，４’−ＯＤＡが好ましい。 The aromatic diamine used as a raw material for the polyimide precursor preferably contains ODA. By using ODA as a raw material for the polyimide precursor, the toughness of the insulating layer formed by the resin varnish can be improved. As the ODA, 4,4'-ODA is preferable.
上記芳香族ジアミン１００モル％に対するＯＤＡの含有量の下限としては、５０モル％が好ましく、９０モル％がより好ましく、９９モル％がさらに好ましい。このように、上記ＯＤＡの含有量を上記下限以上とすることで、当該樹脂ワニスにより形成される絶縁層の靭性をより向上できる。また、上記ＯＤＡの含有量としては、１００モル％が特に好ましい。 The lower limit of the content of ODA with respect to 100 mol% of the aromatic diamine is preferably 50 mol%, more preferably 90 mol%, still more preferably 99 mol%. By setting the content of the ODA to the above lower limit or more in this way, the toughness of the insulating layer formed by the resin varnish can be further improved. The content of the ODA is particularly preferably 100 mol%.
なお、上記ポリイミド前駆体は、芳香族テトラカルボン酸二無水物及び芳香族ジアミンと、その他の原料との重合によって得られる反応生成物であってもよい。上記その他の原料としては、例えば１，２，４，５−シクロヘキサンテトラカルボン酸二無水物等の脂肪族テトラカルボン酸二無水物、ヘキサメチレンジアミン等の脂肪族ジアミンなどが挙げられる。 The polyimide precursor may be a reaction product obtained by polymerizing an aromatic tetracarboxylic dianhydride or an aromatic diamine with other raw materials. Examples of the other raw materials include aliphatic tetracarboxylic dianhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and aliphatic diamines such as hexamethylenediamine.
上記ポリイミド前駆体は、実質的にＢＰＤＡ、ＰＭＤＡ及びＯＤＡのみを原料として得られる反応生成物であることが好ましい。具体的には、上記ポリイミド前駆体の全原料におけるＢＰＤＡ、ＰＭＤＡ及びＯＤＡの合計割合の下限としては、９５モル％が好ましく、９９モル％がより好ましい。また、上記合計割合は、１００モル％が最も好ましい。 The polyimide precursor is preferably a reaction product obtained by using substantially only BPDA, PMDA and ODA as raw materials. Specifically, the lower limit of the total ratio of BPDA, PMDA and ODA in all the raw materials of the polyimide precursor is preferably 95 mol%, more preferably 99 mol%. The total ratio is most preferably 100 mol%.
上記ポリイミド前駆体の当該樹脂ワニス中の濃度の下限としては、２５質量％が好ましく、３０質量％がより好ましい。一方、上記濃度の上限としては、５０質量％が好ましく、４０質量％がより好ましい。上記濃度が上記下限未満である場合、当該樹脂ワニスを用いて絶縁層を形成する際に、所望の厚さの絶縁層を得るために製造工程全体で必要となる樹脂ワニス量が増加するおそれや、塗工工程及び加熱工程の回数が増加するおそれがある。逆に、上記濃度が上記上限を超える場合、当該樹脂ワニスの粘度が増大することで塗布性が低下するおそれがある。 The lower limit of the concentration of the polyimide precursor in the resin varnish is preferably 25% by mass, more preferably 30% by mass. On the other hand, the upper limit of the concentration is preferably 50% by mass, more preferably 40% by mass. If the above concentration is less than the above lower limit, the amount of resin varnish required in the entire manufacturing process in order to obtain an insulating layer having a desired thickness may increase when forming an insulating layer using the resin varnish. , The number of coating steps and heating steps may increase. On the contrary, when the above concentration exceeds the above upper limit, the viscosity of the resin varnish may increase and the coatability may decrease.
（ポリイミド前駆体の合成方法）
上記ポリイミド前駆体は、上述した芳香族テトラカルボン酸二無水物と芳香族ジアミンとの重合反応により得ることができる。上記重合反応の方法としては、従来のポリイミド前駆体の合成と同様とすることができる。上記重合反応の具体的な方法としては、例えば芳香族テトラカルボン酸二無水物と芳香族ジアミンとを有機溶剤中で混合し、この混合液を加熱する方法等が挙げられる。この方法により、芳香族テトラカルボン酸二無水物と芳香族ジアミンとが重合し、ポリイミド前駆体が有機溶剤に溶解した溶液を得ることができる。
(Method for synthesizing polyimide precursor)
The polyimide precursor can be obtained by a polymerization reaction of the above-mentioned aromatic tetracarboxylic dianhydride and an aromatic diamine. The method of the polymerization reaction can be the same as that of the conventional synthesis of the polyimide precursor. Specific methods of the above-mentioned polymerization reaction include, for example, a method of mixing an aromatic tetracarboxylic dianhydride and an aromatic diamine in an organic solvent and heating the mixed solution. By this method, the aromatic tetracarboxylic dianhydride and the aromatic diamine are polymerized, and a solution in which the polyimide precursor is dissolved in an organic solvent can be obtained.
上記重合の際の反応条件としては、使用する原料等により適宜設定すればよいが、例えば反応温度を１０℃以上１００℃以下、反応時間を０．５時間以上２４時間以下とすることができる。 The reaction conditions for the above polymerization may be appropriately set depending on the raw materials used and the like. For example, the reaction temperature can be 10 ° C. or higher and 100 ° C. or lower, and the reaction time can be 0.5 hours or longer and 24 hours or lower.
上記重合に用いる芳香族テトラカルボン酸二無水物と芳香族ジアミンとのモル比（芳香族テトラカルボン酸二無水物／芳香族ジアミン）は、重合反応を効率的に進行させる観点から、１００／１００に近いほど好ましい。上記モル比としては、例えば９５／１０５以上１０５／９５以下とすることができる。このように、上記モル比を上記範囲とすることで、得られるポリイミド前駆体の重量平均分子量を増加させ易くなる。 The molar ratio of aromatic tetracarboxylic dianhydride to aromatic diamine (aromatic tetracarboxylic dianhydride / aromatic diamine) used in the above polymerization is 100/100 from the viewpoint of efficiently advancing the polymerization reaction. The closer it is, the more preferable. The molar ratio can be, for example, 95/105 or more and 105/95 or less. By setting the molar ratio in the above range in this way, it becomes easy to increase the weight average molecular weight of the obtained polyimide precursor.
上記重合に用いる有機溶剤としては、例えばＮ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、γ−ブチロラクトン等の非プロトン性極性有機溶剤を使用できる。これらの有機溶剤は単独で用いても２種以上を併用しても良い。ここで「非プロトン性極性有機溶剤」とは、プロトンを放出する基を持たない極性有機溶剤をいう。 Examples of the organic solvent used for the above-mentioned polymerization include aprotic polar organic solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. Can be used. These organic solvents may be used alone or in combination of two or more. Here, the "aprotic polar organic solvent" refers to a polar organic solvent having no group that releases a proton.
上記有機溶剤の使用量は、芳香族テトラカルボン酸二無水物及び芳香族ジアミンを均一に溶解、分散させることができる使用量であれば特に制限されない。上記有機溶剤の使用量としては、例えば芳香族テトラカルボン酸二無水物及び芳香族ジアミンの合計１００質量部に対し、１００質量部以上１，０００質量部以下とすることができる。 The amount of the organic solvent used is not particularly limited as long as it can uniformly dissolve and disperse the aromatic tetracarboxylic dianhydride and the aromatic diamine. The amount of the organic solvent used may be, for example, 100 parts by mass or more and 1,000 parts by mass or less with respect to 100 parts by mass in total of the aromatic tetracarboxylic dianhydride and the aromatic diamine.
上記重合では、反応系に分子量調整剤を添加してもよい。このように、上記重合で反応系に分子量調整剤を添加することで、得られるポリイミド前駆体の重量平均分子量を適度に低減することができる。上記分子量調整剤としては、例えばモノアミンやジカルボン酸無水物等が挙げられ、具体的には、アニリン、トルイジン、クロロアニリン等の芳香族モノアミンや、フタル酸無水物等の芳香族ジカルボン酸無水物などが挙げられる。上記重合における分子量調整剤の添加量としては、例えば芳香族テトラカルボン酸二無水物及び芳香族ジアミンの合計使用量１００モル％に対し、１モル％以上１００モル％以下とすることができる。 In the above polymerization, a molecular weight modifier may be added to the reaction system. As described above, by adding the molecular weight adjusting agent to the reaction system in the above polymerization, the weight average molecular weight of the obtained polyimide precursor can be appropriately reduced. Examples of the molecular weight adjusting agent include monoamines and dicarboxylic acid anhydrides, and specifically, aromatic monoamines such as aniline, toluidine and chloroaniline, and aromatic dicarboxylic acid anhydrides such as phthalic acid anhydrides. Can be mentioned. The amount of the molecular weight adjusting agent added in the above polymerization may be, for example, 1 mol% or more and 100 mol% or less with respect to 100 mol% of the total amount of the aromatic tetracarboxylic dianhydride and the aromatic diamine used.
［有機溶剤］
当該樹脂ワニスに用いる有機溶剤は、当該樹脂ワニスの塗布性を向上する。また、上記有機溶剤を含有する当該樹脂ワニスは、導体の周面側への塗工工程及び加熱工程を繰り返して複数の絶縁層を形成する際、２回目以降の塗工工程において当該樹脂ワニス中の有機溶剤が前回の工程で形成された絶縁層中のポリイミドを若干溶解するため、形成される複数の絶縁層の各層間の密着力を向上させることができる。
[Organic solvent]
The organic solvent used for the resin varnish improves the coatability of the resin varnish. Further, when the resin varnish containing the organic solvent is formed by repeating the coating step and the heating step on the peripheral surface side of the conductor to form a plurality of insulating layers, the resin varnish is contained in the resin varnish in the second and subsequent coating steps. Since the organic solvent of the above slightly dissolves the polyimide in the insulating layer formed in the previous step, the adhesion between each layer of the plurality of insulating layers formed can be improved.
上記有機溶剤としては、非プロトン性極性有機溶剤が好ましい。ポリイミド前駆体は非プロトン性極性有機溶剤に対する溶解性が高いため、上記有機溶剤として非プロトン性極性有機溶剤を用いることにより、上記ポリイミド前駆体の当該樹脂ワニス中の濃度を高める場合においても上記ポリイミド前駆体を確実に溶解させることができる。また、上記有機溶剤として非プロトン性極性有機溶剤を用いることにより、上述の２回目以降の塗工工程において当該樹脂ワニス中の有機溶剤が前回の工程で形成された絶縁層中のポリイミドを溶解し易くなるため、形成される複数の絶縁層の各層間の密着力をより向上させることができる。 As the organic solvent, an aprotic polar organic solvent is preferable. Since the polyimide precursor has high solubility in an aprotic polar organic solvent, the polyimide is used even when the concentration of the polyimide precursor in the resin varnish is increased by using the aprotic polar organic solvent as the organic solvent. The precursor can be reliably dissolved. Further, by using an aprotic polar organic solvent as the organic solvent, the organic solvent in the resin varnish in the second and subsequent coating steps described above dissolves the polyimide in the insulating layer formed in the previous step. Since it becomes easy, the adhesion between each layer of the plurality of insulating layers to be formed can be further improved.
上記非プロトン性極性有機溶剤としては、ポリイミド前駆体の溶解性向上及び絶縁層間の密着力向上の観点から、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、γ−ブチロラクトン及びこれらの組み合わせが好ましく、ＮＭＰがより好ましい。 The aprotic polar organic solvent includes N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N- from the viewpoint of improving the solubility of the polyimide precursor and the adhesion between the insulating layers. Dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and combinations thereof are preferable, and NMP is more preferable.
有機溶剤は、上述したポリイミド前駆体の重合反応に使用した有機溶剤をそのまま使用してもよく、ポリイミド前駆体を得た後、別途添加してもよいが、作業性の観点から、ポリイミド前駆体の重合反応に使用した有機溶剤をそのまま使用することが好ましい。当該樹脂ワニスにおける有機溶剤の含有量としては、例えばポリイミド前駆体１００質量部に対して１００質量部以上３００質量部以下の範囲とすることができる。 As the organic solvent, the organic solvent used for the polymerization reaction of the polyimide precursor described above may be used as it is, or may be added separately after obtaining the polyimide precursor. However, from the viewpoint of workability, the polyimide precursor may be used. It is preferable to use the organic solvent used for the polymerization reaction as it is. The content of the organic solvent in the resin varnish can be, for example, in the range of 100 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the polyimide precursor.
当該樹脂ワニスは、上述した成分以外に顔料、染料、無機又は有機のフィラー、潤滑剤、密着向上剤等の各種添加剤や反応性低分子などを含有しても良い。この中で、密着向上剤としてメラミン化合物を含有することで、形成される絶縁層と導体との密着力を向上できる。さらに、当該樹脂ワニスは、本発明の趣旨を損ねない範囲で他の樹脂を含有してもよい。当該樹脂ワニスに上述の成分を含有させる場合、当該樹脂ワニスにおける上述の成分の含有量としては、ポリイミド前駆体１００質量部に対し、例えば０．５質量部以上３０質量部以下とすることができる。 The resin varnish may contain various additives such as pigments, dyes, inorganic or organic fillers, lubricants, adhesion improvers, and reactive small molecules in addition to the above-mentioned components. Among these, by containing a melamine compound as an adhesion improver, the adhesion between the formed insulating layer and the conductor can be improved. Further, the resin varnish may contain other resins as long as the gist of the present invention is not impaired. When the resin varnish contains the above-mentioned components, the content of the above-mentioned components in the resin varnish can be, for example, 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor. ..
＜樹脂ワニスの製造方法＞
当該樹脂ワニスの製造方法としては、例えばポリイミド前駆体の合成方法で説明したポリイミド前駆体が有機溶剤に溶解した溶液をそのまま当該樹脂ワニスとする方法が挙げられる。また、当該樹脂ワニスの製造方法としては、例えば上記ポリイミド前駆体が有機溶剤に溶解した溶液からポリイミド前駆体を精製した後に、得られた精製ポリイミド前駆体と有機溶剤等の他の成分とを混合する方法も挙げられる。
<Manufacturing method of resin varnish>
Examples of the method for producing the resin varnish include a method in which the solution in which the polyimide precursor is dissolved in an organic solvent, which has been described in the method for synthesizing a polyimide precursor, is used as it is as the resin varnish. Further, as a method for producing the resin varnish, for example, after purifying the polyimide precursor from a solution in which the polyimide precursor is dissolved in an organic solvent, the obtained purified polyimide precursor is mixed with other components such as an organic solvent. There is also a way to do it.
＜絶縁電線＞
次に、当該樹脂ワニスを用いて絶縁層を形成した当該絶縁電線について説明する。当該絶縁電線は、導体と、この導体の外周側に積層される１又は複数の絶縁層とを備え、この複数の絶縁層のうち少なくとも１層が上述の当該樹脂ワニスの硬化物である。当該絶縁電線は、当該樹脂ワニスにより形成される絶縁層を備えるため、耐湿熱劣化性及び可撓性に優れる。
<Insulated wire>
Next, the insulated wire having an insulating layer formed by using the resin varnish will be described. The insulated wire includes a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor, and at least one of the plurality of insulating layers is the cured product of the resin varnish described above. Since the insulated wire includes an insulating layer formed of the resin varnish, it is excellent in moisture and heat deterioration resistance and flexibility.
当該樹脂ワニスの硬化物である上記絶縁層は、ポリイミドを主成分とする。示差走査熱量計で２０℃／ｍｉｎの昇温条件において測定される上記ポリイミドの結晶融解ピークの熱量の上限としては、５Ｊ／ｇが好ましく、３Ｊ／ｇがより好ましい。上記ポリイミドの結晶融解ピークの熱量は、０Ｊ／ｇが最も好ましい。 The insulating layer, which is a cured product of the resin varnish, contains polyimide as a main component. As the upper limit of the calorific value of the crystal melting peak of the polyimide measured under the temperature rising condition of 20 ° C./min with a differential scanning calorimeter, 5 J / g is preferable, and 3 J / g is more preferable. The calorific value of the crystal melting peak of the polyimide is most preferably 0 J / g.
当該絶縁電線は、上記ポリイミドの結晶融解ピークの熱量を上記上限以下とすること、つまりポリイミドの結晶化を抑制することで、後述する理由により絶縁層の曲げ加工性及び外観性を向上できる。ここで、上記ポリイミドの結晶融解ピークの熱量はポリイミドの構造と絶縁層の形成条件とによって決まるが、ＢＰＤＡに由来する構造を過剰に含むポリイミドは、ＢＰＤＡが有するビフェニル構造により分子同士のパッキングが促進されるため結晶化し易く、絶縁層の形成条件の制御だけで結晶融解ピークの熱量を上記上限以下とすることは困難である。一方、当該絶縁電線は、上記ポリイミド前駆体の原料におけるＢＰＤＡの含有量を上記上限以下とし、ポリイミドに含まれるＢＰＤＡに由来する構造を一定以下とするため、容易かつ確実に結晶融解ピークの熱量を上記上限以下とすることができる。 In the insulated wire, the amount of heat of the crystal melting peak of the polyimide is set to be equal to or less than the above upper limit, that is, the crystallization of the polyimide is suppressed, so that the bending workability and appearance of the insulating layer can be improved for the reason described later. Here, the calorific value of the crystal melting peak of the polyimide is determined by the structure of the polyimide and the formation conditions of the insulating layer, but in the polyimide containing an excess of the structure derived from BPDA, the packing of molecules is promoted by the biphenyl structure of BPDA. Therefore, it is easy to crystallize, and it is difficult to set the calorific value of the crystal melting peak to the above upper limit or less only by controlling the formation conditions of the insulating layer. On the other hand, in the insulated wire, the content of BPDA in the raw material of the polyimide precursor is set to the above upper limit or less, and the structure derived from BPDA contained in the polyimide is set to a certain level or less. It can be less than or equal to the above upper limit.
当該絶縁電線が上記結晶融解ピークの熱量を上記上限以下とすることで絶縁層の曲げ加工性及び外観性に優れる理由は以下の通りであると考えられる。すなわち、ポリイミドを主成分とする絶縁層を形成する方法としては、ポリイミド前駆体（ポリアミック酸）を含有する樹脂ワニスを導体の外周側に塗工する塗工工程と、得られた塗膜を加熱する加熱工程とを備える方法が一般的である。上記方法では、一回の塗工工程及び加熱工程では数μｍ程度の比較的薄い絶縁層しか形成できないため、通常塗工工程及び加熱工程を繰り返して所定の厚さ（数１０μｍ程度）となるまで複数の絶縁層を順次積層する。この２回目以降の塗工工程の際、樹脂ワニスに含まれる溶剤が下地層（前回の塗工工程及び加熱工程で形成された絶縁層）に含まれるポリイミドを若干溶解する場合には、上記下地層と新たに積層する絶縁層とが馴染み易くなるため、各層間の密着力が向上すると考えられる。ここで、結晶化度が高いポリイミドは結晶部に溶剤が浸透し難いため耐溶剤性が過度に高くなる傾向にあると考えられる。 It is considered that the reason why the insulating electric wire is excellent in bending workability and appearance of the insulating layer by setting the calorific value of the crystal melting peak to the above upper limit or less is as follows. That is, as a method for forming an insulating layer containing polyimide as a main component, a coating step of applying a resin varnish containing a polyimide precursor (polyamic acid) to the outer peripheral side of the conductor and a coating step of heating the obtained coating film are performed. A method including a heating step is generally provided. In the above method, since only a relatively thin insulating layer of about several μm can be formed in one coating step and heating step, the normal coating step and heating step are repeated until the thickness reaches a predetermined thickness (about several tens of μm). A plurality of insulating layers are sequentially laminated. In the case where the solvent contained in the resin varnish slightly dissolves the polyimide contained in the base layer (the insulating layer formed in the previous coating step and the heating step) in the second and subsequent coating steps, the above is described below. It is considered that the adhesion between the layers is improved because the stratum and the newly laminated insulating layer become more familiar with each other. Here, it is considered that the polyimide having a high degree of crystallinity tends to have an excessively high solvent resistance because the solvent does not easily permeate into the crystal portion.
当該絶縁電線は、上記ポリイミドの結晶融解ピークの熱量を上記上限以下とすることで、その耐溶剤性を適度に低減でき、その結果、上述のポリイミドの溶解に起因する絶縁層の各層間の密着力向上効果を発揮させることができる。これにより、当該絶縁電線に曲げ加工等によって絶縁層に大きな変形を施した際に、絶縁層の各層間の剥離による絶縁性等の低下が抑制され、優れた曲げ加工性が発揮されると考えられる。また、結晶化度が高いポリイミドは、その結晶部及び非晶部の界面で生じる光の散乱によって白濁するおそれがある。当該絶縁電線は、上記ポリイミドの結晶融解ピークの熱量を上記上限以下とすることで、上記白濁を抑制でき、その結果、絶縁層の外観性を向上できると考えられる。 The solvent resistance of the insulated wire can be appropriately reduced by setting the calorific value of the crystal melting peak of the polyimide to the above upper limit or less, and as a result, the adhesion between the layers of the insulating layer due to the dissolution of the polyimide is adhered to. It is possible to exert the effect of improving power. As a result, when the insulating wire is significantly deformed by bending or the like, deterioration of the insulating property due to peeling between the layers of the insulating layer is suppressed, and excellent bending workability is exhibited. Be done. Further, a polyimide having a high degree of crystallinity may become cloudy due to light scattering generated at the interface between the crystalline portion and the amorphous portion. It is considered that the insulating electric wire can suppress the white turbidity by setting the calorific value of the crystal melting peak of the polyimide to the upper limit or less, and as a result, the appearance of the insulating layer can be improved.
上記導体の材質としては、導電率が高く、かつ機械的強度が大きい金属が好ましい。このような金属としては、例えば銅、銅合金、アルミニウム、ニッケル、銀、軟鉄、鋼、ステンレス鋼等が挙げられる。当該絶縁電線の導体は、これらの金属を線状に形成した材料や、このような線状の材料にさらに別の金属を被覆した多層構造のもの、例えばニッケル被覆銅線、銀被覆銅線、銅被覆アルミニウム線、銅被覆鋼線等を用いることができる。 As the material of the conductor, a metal having high conductivity and high mechanical strength is preferable. Examples of such metals include copper, copper alloys, aluminum, nickel, silver, soft iron, steel, stainless steel and the like. The conductor of the insulated wire is a material obtained by forming these metals in a linear shape, or a material having a multi-layer structure in which such a linear material is coated with another metal, for example, a nickel-coated copper wire or a silver-coated copper wire. Copper-coated aluminum wire, copper-coated steel wire and the like can be used.
当該絶縁電線の導体の平均断面積の下限としては、０．０１ｍｍ２が好ましく、０．１ｍｍ２がより好ましい。一方、上記導体の平均断面積の上限としては、１０ｍｍ２が好ましく、５ｍｍ２がより好ましい。上記導体の平均断面積が上記下限より小さい場合、抵抗値が増大するおそれがある。逆に、上記導体の平均断面積が上記上限を超える場合、誘電率を十分に低下させるために絶縁層を厚く形成しなければならず、当該絶縁電線が不必要に大径化するおそれがある。 As the lower limit of the average cross-sectional area of the conductor of the insulated wire, 0.01 mm 2 is preferable, and 0.1 mm 2 is more preferable. On the other hand, as the upper limit of the average cross-sectional area of the conductor, 10 mm 2 is preferable, and 5 mm 2 is more preferable. If the average cross-sectional area of the conductor is smaller than the lower limit, the resistance value may increase. On the contrary, when the average cross-sectional area of the conductor exceeds the upper limit, the insulating layer must be formed thick in order to sufficiently reduce the dielectric constant, and the diameter of the insulated wire may be unnecessarily increased. ..
当該絶縁電線の１又は複数の絶縁層は、導体の外周側に積層され、少なくとも１層が当該樹脂ワニスにより形成される。当該絶縁電線が複数の絶縁層を備える場合、各絶縁層は上記導体の外周側に断面視で同心円状に順次積層される。この場合、各絶縁層の平均厚さとしては、例えば１μｍ以上５μｍ以下とすることができる。また、上記複数の絶縁層の平均合計厚さとしては、例えば１０μｍ以上２００μｍ以下とすることができる。さらに、複数の絶縁層の合計層数としては、例えば２層以上２００層以下とすることができる。なお、上記複数の絶縁層は、全ての絶縁層が当該樹脂ワニスより形成されることが好ましいが、一部の絶縁層が当該樹脂ワニス以外の他の樹脂ワニスにより形成される層であってもよい。上記他の樹脂ワニスに用いる合成樹脂としては、例えばポリアミドイミド、ポリエステルイミド、ポリウレタン、ポリエーテルイミド等が使用できる。 One or more insulating layers of the insulated wire are laminated on the outer peripheral side of the conductor, and at least one layer is formed of the resin varnish. When the insulating wire includes a plurality of insulating layers, the insulating layers are sequentially laminated concentrically on the outer peripheral side of the conductor in a cross-sectional view. In this case, the average thickness of each insulating layer can be, for example, 1 μm or more and 5 μm or less. The average total thickness of the plurality of insulating layers can be, for example, 10 μm or more and 200 μm or less. Further, the total number of layers of the plurality of insulating layers can be, for example, two or more and 200 or less. In the plurality of insulating layers, it is preferable that all the insulating layers are formed of the resin varnish, but even if some of the insulating layers are formed of a resin varnish other than the resin varnish. Good. As the synthetic resin used for the other resin varnish, for example, polyamide-imide, polyesterimide, polyurethane, polyetherimide and the like can be used.
当該絶縁電線は、１又は複数の絶縁層の外周側にさらに他の層が積層されていてもよい。上記他の層としては、例えば表面潤滑層等が挙げられる。 In the insulated wire, another layer may be laminated on the outer peripheral side of one or a plurality of insulating layers. Examples of the other layer include a surface lubrication layer and the like.
＜絶縁電線の製造方法＞
次に、当該絶縁電線の製造方法について説明する。当該絶縁電線の製造方法は、導体の外周側に当該樹脂ワニスを塗工する塗工工程と、上記塗工された当該樹脂ワニスを加熱する加熱工程とを備える。当該絶縁電線の製造方法は、上記塗工工程及び加熱工程を繰り返すことが好ましい。当該絶縁電線の製造方法によれば、当該絶縁電線を容易かつ確実に製造できる。以下、本実施形態の各工程について説明する。
<Manufacturing method of insulated wire>
Next, a method of manufacturing the insulated wire will be described. The method for manufacturing the insulated wire includes a coating step of applying the resin varnish on the outer peripheral side of the conductor and a heating step of heating the coated resin varnish. As for the method for manufacturing the insulated wire, it is preferable to repeat the above coating step and heating step. According to the method for manufacturing the insulated wire, the insulated wire can be easily and reliably manufactured. Hereinafter, each step of this embodiment will be described.
［塗工工程］
本工程では、導体の外周側に当該樹脂ワニスを塗工する。塗工方法としては、特に限定されないが、例えば当該樹脂ワニスを貯留した樹脂ワニス槽と塗工ダイスとを備える塗工装置を用いた方法等が挙げられる。この塗工装置によれば、導体が樹脂ワニス槽内を挿通することで当該樹脂ワニスが導体外周面に付着した後、塗工ダイスを通過することで当該樹脂ワニスが導体外周面に均一な厚さで塗工される。なお、本工程では、導体の外周面に当該樹脂ワニスを直接塗工してもよく、導体の外周面に予め密着改良層等の中間層を設けておき、その中間層の外周側に当該樹脂ワニスを塗工してもよい。
[Coating process]
In this step, the resin varnish is applied to the outer peripheral side of the conductor. The coating method is not particularly limited, and examples thereof include a method using a coating device including a resin varnish tank for storing the resin varnish and a coating die. According to this coating device, the resin varnish adheres to the outer peripheral surface of the conductor by inserting the conductor into the resin varnish tank, and then passes through the coating die so that the resin varnish has a uniform thickness on the outer peripheral surface of the conductor. It is coated with resin. In this step, the resin varnish may be directly applied to the outer peripheral surface of the conductor, and an intermediate layer such as an adhesion improving layer is provided in advance on the outer peripheral surface of the conductor, and the resin is provided on the outer peripheral side of the intermediate layer. Varnish may be applied.
なお、当該絶縁電線の製造方法で上記塗工工程及び加熱工程を繰り返す場合、複数の塗工工程のうち一部の塗工工程では、当該樹脂ワニス以外の樹脂ワニスを用いてもよい。 When the coating step and the heating step are repeated in the method for manufacturing the insulated wire, a resin varnish other than the resin varnish may be used in some of the coating steps among the plurality of coating steps.
［加熱工程］
本工程では、例えば当該樹脂ワニスを塗工した導体を加熱炉内で走行させる方法等により、導体に塗工された当該樹脂ワニスを加熱する。この加熱工程によって、当該樹脂ワニスが含有するポリイミド前駆体がイミド化されると共に有機溶剤等の揮発成分が除去され、導体の外周側に焼付層である絶縁層が積層される。加熱方法としては、特に限定されず、例えば熱風加熱、赤外線加熱、高周波加熱等の従来公知の方法により行うことができる。加熱温度としては、例えば３５０℃以上５００℃以下とすることができる。加熱時間としては、通常５秒以上１００秒以下とすることができる。なお、当該樹脂ワニスを塗工した導体を加熱炉内で走行させることで加熱する場合、加熱炉内の設定温度を上記加熱温度と見なすものとする。
[Heating process]
In this step, the resin varnish coated on the conductor is heated by, for example, a method of running the conductor coated with the resin varnish in a heating furnace. By this heating step, the polyimide precursor contained in the resin varnish is imidized, volatile components such as an organic solvent are removed, and an insulating layer which is a baking layer is laminated on the outer peripheral side of the conductor. The heating method is not particularly limited, and can be performed by a conventionally known method such as hot air heating, infrared heating, or high frequency heating. The heating temperature can be, for example, 350 ° C. or higher and 500 ° C. or lower. The heating time can usually be 5 seconds or more and 100 seconds or less. When the conductor coated with the resin varnish is heated by running it in the heating furnace, the set temperature in the heating furnace shall be regarded as the heating temperature.
当該絶縁電線の製造方法で上記塗工工程及び加熱工程を繰り返す場合、上記塗工工程及び加熱工程を繰り返す回数としては、例えば２回以上２００回以下とすることができる。 When the coating process and the heating process are repeated in the method for manufacturing the insulated wire, the number of times the coating process and the heating process are repeated can be, for example, 2 times or more and 200 times or less.
［その他の実施形態］
上記開示された実施形態は全ての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
[Other Embodiments]
It should be considered that the disclosed embodiments are exemplary in all respects and not restrictive. The scope of the present invention is not limited to the configuration of the above embodiment, but is indicated by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims. To.
以下、実施例によって本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
なお、実施例中、ポリイミド前駆体の重量平均分子量は、ＪＩＳ−Ｋ７２５２−１：２００８「プラスチック−サイズ排除クロマトグラフィーによる高分子の平均分子量及び分子量分布の求め方−第１部：通則」に準拠し、ゲル浸透クロマトグラフィー（ＧＰＣ）を用いて測定される。 In the examples, the weight average molecular weight of the polyimide precursor is based on JIS-K7252-1: 2008 "Plastic-How to obtain the average molecular weight and molecular weight distribution of a polymer by size exclusion chromatography-Part 1: General rules". Then, it is measured using gel permeation chromatography (GPC).
［樹脂ワニスＮｏ．８］
４，４’−ＯＤＡ１００モル％をＮ−メチル−２−ピロリドンに溶解させた後、得られた溶液にＰＭＤＡ１０モル％と、３，３’，４，４’−ＢＰＤＡ９０モル％と、分子量調整剤としての適量のジカルボン酸無水物（フタル酸無水物）とを加え、窒素雰囲気下で撹拌する。その後、撹拌しながら８０℃で３時間反応させた後、室温に冷却することにより、有機溶剤としてのＮ−メチル−２−ピロリドンにポリイミド前駆体が溶解している樹脂ワニスＮｏ．８が製造できる。この樹脂ワニスＮｏ．８中のポリイミド前駆体濃度は３０質量％である。また、樹脂ワニスＮｏ．８が含有するポリイミド前駆体の重量平均分子量は９，０００とする。
[Resin varnish No. 8]
After dissolving 100 mol% of 4,4'-ODA in N-methyl-2-pyrrolidone, PMDA 10 mol%, 3,3', 4,4'-BPDA 90 mol% and a molecular weight modifier were added to the obtained solution. Add an appropriate amount of dicarboxylic acid anhydride (phthalic acid anhydride) and stir in a nitrogen atmosphere. Then, after reacting at 80 ° C. for 3 hours with stirring, the resin varnish No. 1 in which the polyimide precursor was dissolved in N-methyl-2-pyrrolidone as an organic solvent was cooled to room temperature. 8 can be manufactured. This resin varnish No. The polyimide precursor concentration in 8 is 30% by mass. In addition, the resin varnish No. The weight average molecular weight of the polyimide precursor contained in 8 is 9,000.
［樹脂ワニスＮｏ．１〜７及び９〜３５］
ＰＭＤＡ、３，３’，４，４’−ＢＰＤＡ及び４，４’−ＯＤＡの使用量と重量平均分子量とを表１に示す通りとした以外は、樹脂ワニスＮｏ．８と同様に操作し、樹脂ワニスＮｏ．１〜７及び９〜３５を製造する。なお、ポリイミド前駆体の重量平均分子量を９，０００超に増大する場合、分子量調整剤の使用量を樹脂ワニスＮｏ．８よりも適宜減量する。
[Resin varnish No. 1-7 and 9-35]
Resin varnish No. 1 except that the amounts of PMDA, 3,3', 4,4'-BPDA and 4,4'-ODA and the weight average molecular weights were as shown in Table 1. The same operation as in No. 8 was carried out, and the resin varnish No. 1 to 7 and 9 to 35 are manufactured. When the weight average molecular weight of the polyimide precursor is increased to more than 9,000, the amount of the molecular weight adjusting agent used is changed to Resin Varnish No. The weight should be reduced as appropriate from 8.
＜評価＞
樹脂ワニスＮｏ．１〜３５を用いて以下の通り絶縁電線の絶縁層を形成し、各樹脂ワニスの塗布性と、形成される絶縁層の耐湿熱劣化性及び可撓性とを評価する。評価結果を表１に示す。
<Evaluation>
Resin varnish No. The insulating layer of the insulated wire is formed using 1 to 35 as follows, and the applicability of each resin varnish and the moisture and heat deterioration resistance and flexibility of the formed insulating layer are evaluated. The evaluation results are shown in Table 1.
［絶縁電線の製造］
銅を主成分とする平均厚さ１．５ｍｍ、平均幅３ｍｍの平角導体を用意する。樹脂ワニスＮｏ．１〜３５を上記導体の外周面に塗工する工程と、上記樹脂ワニスを塗工した導体を加熱炉の設定温度４００℃、加熱時間３０秒の条件で加熱する工程とを１０回ずつ繰り返し行うことで、上記導体と、この導体の外周面に積層される平均厚さ３５μｍの絶縁層とを備える絶縁電線を得る。
[Manufacturing of insulated wires]
Prepare a flat conductor containing copper as a main component, having an average thickness of 1.5 mm and an average width of 3 mm. Resin varnish No. The steps of coating the outer peripheral surfaces of the conductors 1 to 35 and heating the conductor coated with the resin varnish under the conditions of a set temperature of a heating furnace of 400 ° C. and a heating time of 30 seconds are repeated 10 times each. As a result, an insulated wire having the conductor and an insulating layer having an average thickness of 35 μm laminated on the outer peripheral surface of the conductor is obtained.
［塗布性］
樹脂ワニスの塗布性は、形成された絶縁層を目視で観察し、厚さが不均一な箇所、かすれ、色ムラ、剥離、窪み、ピンホール等の欠陥が観察されなかった場合を「Ａ（良好）」とする。上記欠陥が観察された樹脂ワニスについては、塗布性を向上するための工夫を加えた上で再度絶縁電線の製造を行い、塗布性を再評価する。塗布性を向上するための工夫としては、例えば塗工の際、変質しない温度範囲で樹脂ワニスを加温して粘度を低減する等の操作を行う。上記工夫により上記欠陥が解消された場合を「Ｂ（条件付きで良好）」、上記工夫によっても上記欠陥が解消されなかった場合を「Ｃ（良好でない）」とする。
[Applicability]
Regarding the applicability of the resin varnish, when the formed insulating layer is visually observed and no defects such as uneven thickness, faintness, color unevenness, peeling, dents, and pinholes are observed, "A ( Good) ”. For the resin varnish in which the above-mentioned defects are observed, the insulating electric wire is manufactured again after devising a device for improving the coatability, and the coatability is re-evaluated. As a device for improving the coatability, for example, at the time of coating, the resin varnish is heated in a temperature range that does not deteriorate to reduce the viscosity. The case where the defect is eliminated by the above-mentioned ingenuity is defined as "B (conditionally good)", and the case where the above-mentioned defect is not eliminated by the above-mentioned ingenuity is defined as "C (not good)".
［耐湿熱劣化性］
絶縁層の耐湿熱劣化性は、絶縁電線を長手方向に１０％伸長しつつ、温度８５℃、相対湿度９５％、７５０時間の条件で湿熱処理を行う。処理後の絶縁電線を目視で観察して表面に亀裂が観察されなかった場合を「Ａ（良好）」、表面に亀裂が観察されたが、その数及び大きさが顕著でない場合を「Ｂ（あまり良好でない）」、表面に亀裂が観察され、その数及び大きさが顕著な場合を「Ｃ（良好でない）」とする。
[Moisture and heat deterioration resistance]
As for the moisture and heat deterioration resistance of the insulating layer, the insulating wire is stretched by 10% in the longitudinal direction, and the wet heat treatment is performed under the conditions of a temperature of 85 ° C., a relative humidity of 95%, and 750 hours. When the treated insulated wire is visually observed and no cracks are observed on the surface, it is "A (good)", and when cracks are observed on the surface, but the number and size are not remarkable, "B (" (Not very good) ”, when cracks are observed on the surface and the number and size are remarkable, it is defined as“ C (not good) ”.
［引張伸び］
電気分解処理により絶縁電線から導体を除去し、チューブ状の絶縁層を採取する。絶縁層の引張伸びは、この絶縁層について、引張試験機（島津製作所社の「ＡＧ−ＩＳ」）を用いて引張速度１０ｍｍ／分の引張条件で測定する。引張伸び（％）は、その数値が大きいほど伸長性に優れるため絶縁層の可撓性が良好であることを示し、１０％以上の場合を「Ａ（良好）」、１０％未満の場合を「Ｂ（良好でない）」とする。
[Tension elongation]
The conductor is removed from the insulated wire by electrolysis treatment, and a tubular insulating layer is collected. The tensile elongation of the insulating layer is measured for this insulating layer using a tensile tester (“AG-IS” manufactured by Shimadzu Corporation) at a tensile speed of 10 mm / min. The larger the value of tensile elongation (%), the better the extensibility, indicating that the flexibility of the insulating layer is good. When it is 10% or more, it is "A (good)", and when it is less than 10% Let it be "B (not good)".
樹脂ワニスＮｏ．９〜１３、１６〜２０及び２３〜２７は、ポリイミド前駆体の重合において芳香族テトラカルボン酸二無水物１００モル％に対してＢＰＤＡを２５モル％以上９５モル％以下使用し、かつ上記ポリイミド前駆体のＭｗを１０，０００以上１８０，０００以下とすることで、良好な塗布性、可撓性及び耐湿熱劣化性が発揮される。また、樹脂ワニス９〜１２、１６〜１９及び２３〜２６は、上記Ｍｗを１３０，０００以下とすることで、塗布性をさらに向上することができる。 Resin varnish No. 9 to 13, 16 to 20 and 23 to 27 use 25 mol% or more and 95 mol% or less of BPDA with respect to 100 mol% of aromatic tetracarboxylic dianhydride in the polymerization of the polyimide precursor, and the above-mentioned polyimide precursor. By setting the Mw of the body to 10,000 or more and 180,000 or less, good coatability, flexibility and moisture and heat deterioration resistance are exhibited. Further, the resin varnishes 9 to 12, 16 to 19 and 23 to 26 can be further improved in coatability by setting the Mw to 130,000 or less.
一方、樹脂ワニスＮｏ．１〜７は、芳香族テトラカルボン酸二無水物１００モル％に対するＢＰＤＡの含有量を９５モル％超としたため、十分な塗布性を発揮できない。また、樹脂ワニスＮｏ．２９〜３５は、上記ＢＰＤＡの含有量を２５モル％未満としたため、ＢＰＤＡを用いることによる耐湿熱劣化性の向上効果を十分に得られない。 On the other hand, the resin varnish No. In Nos. 1 to 7, since the content of BPDA with respect to 100 mol% of aromatic tetracarboxylic dianhydride was more than 95 mol%, sufficient coatability could not be exhibited. In addition, the resin varnish No. In Nos. 29 to 35, since the content of BPDA was less than 25 mol%, the effect of improving the moisture resistance and heat deterioration resistance by using BPDA could not be sufficiently obtained.
樹脂ワニスＮｏ．８、１５及び２２は、上記ポリイミド前駆体のＭｗを１０，０００未満としたため、耐湿熱劣化性及び可撓性のうち少なくとも一方が良好でない。また、樹脂ワニスＮｏ．１４、２１及び２８は、上記ポリイミド前駆体のＭｗを１８０，０００超としたため、塗布性が良好でない。 Resin varnish No. In Nos. 8, 15 and 22, since the Mw of the polyimide precursor was less than 10,000, at least one of the moisture resistance and heat deterioration resistance and the flexibility was not good. In addition, the resin varnish No. In Nos. 14, 21 and 28, since the Mw of the polyimide precursor was more than 180,000, the coatability was not good.
本発明の樹脂ワニスは、塗布性に優れ、かつ耐湿熱劣化性及び可撓性に優れる絶縁層を形成できる。本発明の絶縁電線及びその製造方法によれば、耐湿熱劣化性及び可撓性に優れる絶縁層を備える絶縁電線を提供できる。 The resin varnish of the present invention can form an insulating layer having excellent coatability and excellent moisture-heat deterioration resistance and flexibility. According to the insulated wire of the present invention and the method for manufacturing the same, it is possible to provide an insulated wire provided with an insulating layer having excellent moisture resistance and heat deterioration resistance and flexibility.
Claims (4)
上記ポリイミド前駆体の重量平均分子量が１５，０００以上１３０，０００以下であり、
上記芳香族テトラカルボン酸二無水物がビフェニルテトラカルボン酸二無水物を含み、
上記芳香族テトラカルボン酸二無水物１００モル％に対するビフェニルテトラカルボン酸二無水物の含有量が６０モル％以上８０モル％以下であり、
上記芳香族テトラカルボン酸二無水物がピロメリット酸二無水物をさらに含み、
上記芳香族テトラカルボン酸二無水物１００モル％に対するピロメリット酸二無水物の含有量が２０モル％以上３０モル％以下であり、
上記ポリイミド前駆体の樹脂ワニス中の濃度が２５質量％以上５０質量％以下であ
る樹脂ワニス。 A resin varnish containing a polyimide precursor which is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine.
The weight average molecular weight of the polyimide precursor is 15,000 or more and 130,000 or less .
The aromatic tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride.
80 mol% der less content of more than 60 mol% of the aromatic tetracarboxylic dianhydride biphenyltetracarboxylic dianhydride for 100 mol% is,
The aromatic tetracarboxylic dianhydride further comprises pyromellitic dianhydride.
The content of pyromellitic dianhydride with respect to 100 mol% of the aromatic tetracarboxylic dianhydride is 20 mol% or more and 30 mol% or less.
A resin varnish in which the concentration of the polyimide precursor in the resin varnish is 25% by mass or more and 50% by mass or less .
上記１又は複数の絶縁層のうち少なくとも１層が請求項１又は請求項２に記載の樹脂ワニスの硬化物である絶縁電線。 An insulated wire including a conductor and one or more insulating layers laminated on the outer peripheral side of the conductor.
An insulated wire in which at least one of the above one or a plurality of insulating layers is a cured product of the resin varnish according to claim 1 or 2.
導体の外周側に請求項１に記載の樹脂ワニスを塗工する塗工工程と、
上記塗工された樹脂ワニスを加熱する加熱工程と
を備える絶縁電線の製造方法。 A method for manufacturing an insulated wire including a conductor and one or a plurality of insulating layers laminated on the outer peripheral side of the conductor.
The coating process of applying the resin varnish according to claim 1 to the outer peripheral side of the conductor, and
A method for manufacturing an insulated wire, which comprises a heating step of heating the coated resin varnish.
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| JPS59204619A (en) * | 1983-05-09 | 1984-11-20 | Ube Ind Ltd | Aromatic polyamic acid solution composition |
| JP5029003B2 (en) * | 2006-10-17 | 2012-09-19 | 日立化成工業株式会社 | Polyimide resin heat-resistant resin, seamless tubular body, coating film, coating plate and heat-resistant paint using this resin |
| US8796411B2 (en) * | 2008-02-25 | 2014-08-05 | Hitachi Chemical Dupont Microsystems, Ltd. | Polyimide precursor composition, polyimide film, and transparent flexible film |
| JP5464838B2 (en) * | 2008-10-31 | 2014-04-09 | 三菱電線工業株式会社 | Insulating member manufacturing method |
| US20130184406A1 (en) * | 2010-09-28 | 2013-07-18 | Toray Industries, Inc. | Resin composition and manufacturing process therefor |
| JP5761151B2 (en) * | 2012-10-16 | 2015-08-12 | 日立金属株式会社 | Insulated wires and coils |
| JP2014136743A (en) * | 2013-01-16 | 2014-07-28 | Hitachi Metals Ltd | Polyamic acid coating material, method of producing the same, and insulated wire using the same |
| JP2016183228A (en) * | 2015-03-25 | 2016-10-20 | 住友精化株式会社 | Application liquid composition, coating layer formation method, and coil having coating layer formed by coating layer formation method |
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2017
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