JP6152321B2 - Epoxy resin composition for casting ignition coil, ignition coil and method for producing the same - Google Patents
Epoxy resin composition for casting ignition coil, ignition coil and method for producing the same Download PDFInfo
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- JP6152321B2 JP6152321B2 JP2013175735A JP2013175735A JP6152321B2 JP 6152321 B2 JP6152321 B2 JP 6152321B2 JP 2013175735 A JP2013175735 A JP 2013175735A JP 2013175735 A JP2013175735 A JP 2013175735A JP 6152321 B2 JP6152321 B2 JP 6152321B2
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- epoxy resin
- resin composition
- ignition coil
- casting
- cristobalite
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- 239000003822 epoxy resin Substances 0.000 title claims description 94
- 229920000647 polyepoxide Polymers 0.000 title claims description 94
- 239000000203 mixture Substances 0.000 title claims description 63
- 238000005266 casting Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 88
- 229910052906 cristobalite Inorganic materials 0.000 claims description 44
- 239000011342 resin composition Substances 0.000 claims description 31
- 238000001723 curing Methods 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000013007 heat curing Methods 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 description 25
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 239000005350 fused silica glass Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229910002026 crystalline silica Inorganic materials 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- -1 cycloalkane carboxylate Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000007705 chemical test Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- QYFUGNRYZNTHFN-UHFFFAOYSA-N 4-ethenyl-3,7-dioxatricyclo[4.1.0.02,4]heptane Chemical compound C1C2OC2C2OC21C=C QYFUGNRYZNTHFN-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- AUOZNINQGUNWOV-UHFFFAOYSA-N triphenyl borate;triphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 AUOZNINQGUNWOV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Insulating Of Coils (AREA)
Description
本発明は、耐クラック性、電気特性、機械特性及び耐熱性に優れたガソリンエンジン及びハイブリッド自動車に対応することができる点火コイル（Ignition coil）などの絶縁のための注形に好適な点火コイル注形用エポキシ樹脂組成物、同エポキシ樹脂組成物で注形、加熱硬化された点火コイルの製造方法に関する。 INDUSTRIAL APPLICABILITY The present invention provides an ignition coil casting suitable for casting for insulation such as an ignition coil that can be applied to a gasoline engine and a hybrid vehicle having excellent crack resistance, electrical characteristics, mechanical characteristics, and heat resistance. The present invention relates to a molding epoxy resin composition and a method for producing an ignition coil cast and heat-cured with the epoxy resin composition.
従来から、注形用エポキシ樹脂組成物は、自動車やテレビの電子部品である高圧トランス、産業用モジュール、重電用モールド等の絶縁処理に使用されている。そして、自動車用の電子機器用トランス類のうち、点火コイルはエポキシ樹脂組成物で絶縁処理し製造されている。その上、この用途の樹脂組成物では、耐クラック性、熱放散性、電気特性、機械特性の他に耐熱性の要求がますます大きくなっている。近年、小型化による内蔵部品の複雑化等により、絶縁距離が狭くなりつつあり、注形用樹脂組成物には、絶縁破壊に対する要求が高まり、長期信頼性のあるエポキシ樹脂組成物およびその硬化物が求められている。このようなエポキシ樹脂組成物およびその硬化物において、絶縁信頼性を付与する手法としては、樹脂中の不純物若しくは金属異物を低減し、充填材を球状にし、高充填化がおこなわれている。 2. Description of the Related Art Conventionally, casting epoxy resin compositions have been used for insulation treatment of high-voltage transformers, industrial modules, heavy electric molds and the like that are electronic parts for automobiles and televisions. Of the transformers for electronic equipment for automobiles, the ignition coil is manufactured by being insulated with an epoxy resin composition. In addition, the resin composition for this application has an increasing demand for heat resistance in addition to crack resistance, heat dissipation, electrical characteristics, and mechanical characteristics. In recent years, the insulation distance is becoming narrow due to the complexity of internal parts due to miniaturization, and the resin composition for casting has increased the demand for dielectric breakdown, and the epoxy resin composition with long-term reliability and its cured product Is required. In such an epoxy resin composition and a cured product thereof, as a method for imparting insulation reliability, impurities or metal foreign matters in the resin are reduced, the filler is made spherical, and high filling is performed.
しかしながら、上述のような点火コイル等の部品には高電圧が印加されるため、単に通常のエポキシ樹脂組成物を封止樹脂として用いたのみでは、絶縁性が不十分であって絶縁破壊等が生じたり、封止樹脂の硬化物の熱サイクルに起因して発現する熱応力や機械的応力によって、封止樹脂の硬化物にクラックが生じたりしてしまう場合があった。封止樹脂の硬化物にクラックが生じると、点火コイル等の部品に電流を流した際に、前記クラック部分で異常放電等が発生することになり、上記点火コイル等の部品を正常に作動させることができない。
クラックの発生は、エポキシ樹脂組成物に対して可とう性のエポキシ樹脂を配合することによってある程度抑制することができるものの、ガラス転移温度が低下し耐熱性が低下しまい、上述のような高温環境下で使用される点火コイルなどの封止樹脂として用いることができない。
However, since a high voltage is applied to the components such as the ignition coil as described above, simply using a normal epoxy resin composition as a sealing resin is insufficient in insulation properties and causes dielectric breakdown. In some cases, cracks may occur in the cured resin of the sealing resin due to thermal stress or mechanical stress generated due to the thermal cycle of the cured resin of the sealing resin. If cracks occur in the cured product of the sealing resin, an abnormal discharge or the like occurs in the crack portion when a current is passed through the components such as the ignition coil, and the components such as the ignition coil operate normally. I can't.
Although the occurrence of cracks can be suppressed to some extent by blending a flexible epoxy resin with the epoxy resin composition, the glass transition temperature is lowered and the heat resistance is lowered, so that the high temperature environment as described above It cannot be used as a sealing resin such as an ignition coil used in the above.
このような問題に鑑み、特許文献１においては、エポキシ樹脂、フェノール樹脂、および粒子径と粒子形状を規定した結晶性シリカを配合して、さらにエポキシ樹脂組成物の成形温度より２０℃以上高い化合物を併用したエポキシ樹脂組成物が提案されている。
特許文献２においては、メチルテトラヒドロ無水フタル酸及びメチルヘキサヒドロ無水フタル酸を必須成分として含む酸無水物と、平均粒径２μｍ以下の球状シリカを必須成分として含む無機充填剤と、硬化促進剤とを配合したＡ剤と、エポキシ樹脂をＢ剤とした２液型のエポキシ樹脂組成物を得、線膨張率を低減させることによって耐ヒートサイクル性を向上させ、上述した熱応力によるクラックの発生を防止する試みがなされている。
さらに、特許文献３においては、エポキシ樹脂組成物に対して特定範囲の粒径を有するシリカ粒子を所定量含有させることによってトリー経路を形成しにくくし、エポキシ樹脂組成物の絶縁破壊電圧を低下させ、コイル等の部品に高電圧が印加された場合においても絶縁破壊が生じないようにしたモールドコイル含浸用エポキシ樹脂組成物が開示されている。しかしながら、そのような手法でも、耐クラック性、エンジンのダウンサイズに伴う熱放散性（熱伝導率）、コイルへの含浸性の向上ならびに高温度下の硬化物の電気的特性の低下を防止することはできず、これらの諸問題を解決すべき、環境対応新機種コイルに対応した点火コイル注形用エポキシ樹脂組成物のための新規なフィラーの検討が必要となった。一般に、結晶シリカは熱伝導率の向上に有効なフィラーであるが、その反面、結晶シリカが添加された場合でも、熱膨張係数の値を小さくできず、しかも電気特性の誘電正接がほかのフィラーに比較して大きい値を示す。また、溶融シリカはその添加量を増やすことにより、熱膨張係数の値を小さくすることができるが、熱伝導率を大きくすることが難しい。
In view of such a problem, in Patent Document 1, a compound in which an epoxy resin, a phenol resin, and crystalline silica having a defined particle diameter and particle shape are blended, is further 20 ° C. higher than the molding temperature of the epoxy resin composition. An epoxy resin composition using a combination of the above and the like has been proposed.
In Patent Document 2, an acid anhydride containing methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride as essential components, an inorganic filler containing spherical silica having an average particle size of 2 μm or less as an essential component, a curing accelerator, A two-pack type epoxy resin composition containing the A agent and the epoxy resin B agent is obtained, the heat cycle resistance is improved by reducing the coefficient of linear expansion, and the occurrence of cracks due to the above-described thermal stress. Attempts have been made to prevent it.
Furthermore, in Patent Document 3, it is difficult to form a tree path by containing a predetermined amount of silica particles having a particle size in a specific range with respect to the epoxy resin composition, and the dielectric breakdown voltage of the epoxy resin composition is reduced. Also disclosed is an epoxy resin composition for impregnating a mold coil that does not cause dielectric breakdown even when a high voltage is applied to a component such as a coil. However, even such a technique prevents crack resistance, heat dissipation (heat conductivity) associated with engine downsizing, improved impregnation of coils, and deterioration of electrical properties of cured products at high temperatures. Therefore, it is necessary to investigate a new filler for an epoxy resin composition for casting an ignition coil corresponding to a new environmentally friendly coil that should solve these problems. In general, crystalline silica is an effective filler for improving thermal conductivity, but on the other hand, even when crystalline silica is added, the value of the coefficient of thermal expansion cannot be reduced, and the dielectric loss tangent of electrical characteristics is another filler. A large value is shown in comparison with. Moreover, although the value of a thermal expansion coefficient can be made small by increasing the addition amount of a fused silica, it is difficult to make a thermal conductivity large.
その点、本発明に使用するクリストバライトは熱伝導率を下げることなく熱膨張係数及び誘電正接を溶融シリカと同等に保持することが可能である。
球状溶融シリカ及び／又は球状クリストバライトを特定量配合したエポキシ樹脂組成物は、例えば、特許文献４、５に開示されているが、これらのエポキシ樹脂組成物はいずれも半導体封止用であり、点火コイル注形用に使用することは示唆されていない。
点火コイル注形用エポキシ樹脂組成物は、例えば、特許文献６に開示されているが、特定の数平均粒径を有する破砕溶融シリカと、同じく特定の数平均粒径を有する球状溶融シリカを用いるものであり、クリストバライトを使用することは示唆されていない。
球状クリストバライトを特定の粒子径および球形度に規定して特定量配合したエポキシ樹脂組成物は、例えば、特許文献７に開示されているが、このエポキシ樹脂組成物は半導体封止用であり、点火コイル注形用封止材料として使用することは示唆されていない。
In that respect, the cristobalite used in the present invention can keep the thermal expansion coefficient and dielectric loss tangent equivalent to those of fused silica without lowering the thermal conductivity.
Epoxy resin compositions containing a specific amount of spherical fused silica and / or spherical cristobalite are disclosed in, for example, Patent Documents 4 and 5, and these epoxy resin compositions are all for semiconductor encapsulation, and ignition. It is not suggested for use in coil casting.
The epoxy resin composition for casting an ignition coil is disclosed in, for example, Patent Document 6, and uses crushed fused silica having a specific number average particle size and spherical fused silica having a specific number average particle size. It is not suggested to use cristobalite.
An epoxy resin composition in which a specific amount of spherical cristobalite is prescribed with a specific particle diameter and sphericity is disclosed in, for example, Patent Document 7, but this epoxy resin composition is used for semiconductor encapsulation, ignition There is no suggestion of using it as a sealing material for coil casting.
本発明者らは上記の目的を達成しようと鋭意研究を進めた結果、二酸化ケイ素ではあるが、溶融シリカまたは結晶シリカの替わりに溶融シリカや結晶シリカとは溶融化度の異なるクリストバライトを使用することで熱伝導率の向上と低線膨張率が相反することなく、かつ、作業性を低下させることなくコイルへの高い含浸性を達成することができることを見出した。本発明は作業性に優れた点火コイル注形用エポキシ樹脂組成物及びこのエポキシ樹脂組成物をコイルに含浸させ、加熱硬化させてなる点火コイル、およびその製造方法を提供しようとするものである。 As a result of diligent research to achieve the above object, the present inventors have used cristobalite which is silicon dioxide but has a different degree of melting from fused silica or crystalline silica instead of fused silica or crystalline silica. Thus, it has been found that high impregnation into the coil can be achieved without contradicting the improvement in thermal conductivity and the low linear expansion coefficient and without reducing workability. An object of the present invention is to provide an epoxy resin composition for casting an ignition coil excellent in workability, an ignition coil obtained by impregnating a coil with the epoxy resin composition and heat-curing the coil, and a method for producing the same.
すなわち、本発明は、以下、
（１）（Ａ）エポキシ樹脂（Ｂ）酸無水物、（Ｃ）硬化促進剤および（Ｄ）クリストバライトを含む点火コイル注形用エポキシ樹脂組成物、
（２）（Ａ）エポキシ樹脂および（Ｄ）クリストバライトを主剤成分とし、（Ｂ）酸無水物、（Ｃ）硬化促進剤および（Ｄ）クリストバライトを硬化剤成分とした２液型である上記（１）に記載の点火コイル注形用エポキシ樹脂組成物、
（３）前記（Ｄ）クリストバライトが、前記樹脂組成物中に４０〜８０質量％含まれ、（Ｄ）クリスバライトが数平均粒径３〜１０μｍのクリストバライト（Ｄ−１）と数平均粒径が１０μｍを超え、５０μｍ以下のクリストバライト（Ｄ−２）の配合比、（Ｄ−１）：（Ｄ−２）が質量比で８０：２０〜１００：０である上記（１）又は（２）に記載の点火コイル注形用エポキシ樹脂組成物、
（４）（Ａ）エポキシ樹脂の全量に対して（Ａ−１）液状ビスフェノール型エポキシ樹脂を７０〜１００質量％、（Ａ−２）脂環式エポキシ樹脂を０〜３０質量％含み、（Ｂ）酸無水物の全量に対して、ヘキサヒドロ無水フタル酸またはテトラヒドロ無水フタル酸を７０〜１００質量％含む上記（１）〜（３）のいずれかに記載の点火コイル注形用エポキシ樹脂組成物、
（５）（Ｃ）硬化促進剤がベンジルジメチルアミン又は４級アンモニウム塩である上記（１）〜（４）のいずれかに記載の点火コイル注形用エポキシ樹脂組成物、
（６）上記（１）〜（５）のいずれかに記載の点火コイル注形用エポキシ樹脂組成物をコイルに含浸させ、次いで、加熱硬化させてなる点火コイルおよび
（７）コイルを金型内に固定して金型内を真空状態とし、上記（１）〜（５）のいずれかに記載の点火コイル注形用エポキシ樹脂組成物を金型内に注形し加熱硬化させることを特徴とする点火コイルの製造方法を提供する。
That is, the present invention includes the following:
(1) An epoxy resin composition for casting an ignition coil containing (A) an epoxy resin (B) an acid anhydride, (C) a curing accelerator and (D) cristobalite,
(2) the (A) epoxy resin and (D) cristobalite and a main agent component, (B) an acid anhydride, the (1 a two-liquid type in which the (C) curing accelerator and (D) a curing agent component cristobalite ) Epoxy resin composition for casting an ignition coil according to
(3) The (D) cristobalite is contained in the resin composition in an amount of 40 to 80% by mass, and (D) cristobalite (D-1) having a number average particle diameter of 3 to 10 μm and the number average particle diameter are In the above (1) or (2), the compounding ratio of cristobalite (D-2) exceeding 10 μm and not more than 50 μm, (D-1) :( D-2) is 80:20 to 100: 0 by mass ratio The epoxy resin composition for casting an ignition coil according to the description,
(4) (A-1) 70-100 mass% of liquid bisphenol type epoxy resin with respect to the total amount of epoxy resin, (A-2) 0-30 mass% of alicyclic epoxy resin, (B The epoxy resin composition for casting an ignition coil according to any one of the above (1) to (3), containing 70 to 100% by mass of hexahydrophthalic anhydride or tetrahydrophthalic anhydride with respect to the total amount of acid anhydrides,
(5) (C) the epoxy resin composition for casting an ignition coil according to any one of the above (1) to (4), wherein the curing accelerator is benzyldimethylamine or a quaternary ammonium salt;
(6) The ignition coil casting epoxy resin composition according to any one of the above (1) to (5) is impregnated into a coil, and then heated and cured, and (7) the coil is placed in the mold. The inside of the mold is fixed in a vacuum state, and the epoxy resin composition for casting an ignition coil according to any one of the above (1) to (5) is cast into the mold and heat-cured. A method for manufacturing an ignition coil is provided.
本発明の点火コイル注形用エポキシ樹脂組成物は点火コイルを構成する複合部品（特に、巻き線部、すなわち、コイル）への含浸性に優れ、硬化物の機械的強度及び通電状態における絶縁破壊電圧が向上した、優れた硬化物を得ることができ、ガソリン又はＨＥＶ自動車に対応することができる、絶縁信頼性に優れた高性能点火コイルを安価にかつ歩留まり良く製造することができる。
また、本発明の製造方法によれば、本発明の樹脂組成物を用いてコイルに含浸、加熱硬化させることにより機械的強度及び絶縁信頼性に優れた点火コイルとすることができ、低温から高温下（−４０〜１５０℃）での動作信頼性の高い点火コイルを用いた耐久性のある製品を提供することができる。
The epoxy resin composition for casting an ignition coil according to the present invention is excellent in impregnation to a composite part (in particular, a coiled portion, that is, a coil) constituting the ignition coil, and has a mechanical strength of a cured product and a dielectric breakdown in an energized state. An excellent cured product with improved voltage can be obtained, and a high-performance ignition coil excellent in insulation reliability that can be applied to gasoline or HEV automobiles can be manufactured at low cost and with high yield.
Further, according to the production method of the present invention, an ignition coil having excellent mechanical strength and insulation reliability can be obtained by impregnating and heat-curing the coil using the resin composition of the present invention. It is possible to provide a durable product using an ignition coil with high operation reliability at a lower temperature (−40 to 150 ° C.).
成分（Ａ）
本発明に用いる成分（Ａ）のエポキシ樹脂としては、（Ａ−１）液状ビスフェノール型エポキシ樹脂が好ましい。（Ａ−１）液状ビスフェノール型エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂などがあり、市販品ではＥＰ４１００Ｅ〔アデカ（株）製〕、８３０−Ｓ〔ＤＩＣ社製〕、Ｒ７１０〔三井石油化学（株）製〕などがある。
（Ａ−１）液状ビスフェノール型エポキシ樹脂とともに、より粘度の低い（Ａ−２）脂環式エポキシ樹脂を併用してもよい。
Ingredient (A)
The component (A) epoxy resin used in the present invention is preferably (A-1) a liquid bisphenol type epoxy resin. (A-1) As liquid bisphenol type epoxy resins, there are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, etc., and commercially available products are EP4100E [manufactured by Adeka Corporation], 830-S [ DIC Corporation], R710 [Mitsui Petrochemical Co., Ltd.] and the like.
(A-1) An alicyclic epoxy resin having a lower viscosity may be used in combination with the liquid bisphenol type epoxy resin.
（Ａ−２）脂環式エポキシ樹脂としては、ビニルシクロペンタジエンジオキシド、ビニルシクロヘキセンモノ乃至ジオキシド、ジシクロペンタジエンオキシド、３，４−エポキシ−１−［８，９−エポキシ−２，４−ジオキサスピロ［５．５］ウンデカン−３−イル］−シクロヘキサンなどのエポキシ−［エポキシ−オキサスピロＣ8-15アルキル］−シクロＣ5-12アルカン、３，４−エポキシシクロヘキシルメチル−３′，４′−エポキシシクロヘキサンカルボキシレート、４，５−エポキシシクロオクチルメチル−４′，５′−エポキシシクロオクタンカルボキシレートなどのエポキシＣ5-12シクロアルキルＣ1-3アルキル−エポキシＣ5-12シクロアルカンカルボキシレート、ビス（２−メチル−３，４−エポキシシクロヘキシルメチル）アジペートなどのビス（Ｃ1-3アルキルエポキシＣ5-12シクロアルキルＣ1-3アルキル）ジカルボキシレートなどが挙げられる。
３，４−エポキシシクロヘキシルメチル−３′，４′−エポキシシクロヘキサンカルボキシレートの市販品としては〔（株）ダイセル製、商品名：セロキサイド＃２０２１Ｐ、エポキシ当量：１２８〜１４０〕、があり、好ましく用いられる。
(A-2) As the alicyclic epoxy resin, vinylcyclopentadiene dioxide, vinylcyclohexene mono- to dioxide, dicyclopentadiene oxide, 3,4-epoxy-1- [8,9-epoxy-2,4-dioxaspiro [5.5] Epoxy- [epoxy-oxaspiro C 8-15 alkyl] -cycloC 5-12 alkane, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy, such as undecan-3-yl] -cyclohexane Epoxy C 5-12 cycloalkyl C 1-3 alkyl-epoxy C 5-12 cycloalkane carboxylate such as cyclohexane carboxylate, 4,5-epoxycyclooctylmethyl-4 ′, 5′-epoxycyclooctanecarboxylate, bis (2-Methyl-3,4-epoxycyclohexylmethyl) azi Bis (C 1-3 alkyl epoxy C 5-12 cycloalkyl C 1-3 alkyl) dicarboxylate, such as over bets and the like.
Commercially available 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate includes [manufactured by Daicel Corporation, trade name: Celoxide # 2021P, epoxy equivalent: 128-140], preferably used. It is done.
（Ａ−１）と（Ａ−２）の配合比率は下記の通りである。
（Ａ−１）が、好ましくは７０〜１００質量％、より好ましくは８０〜９０質量％であり、（Ａ−２）が、好ましくは０〜３０質量％、より好ましくは１０〜２０質量％である。（Ａ−１）と（Ａ−２）の合計は１００質量％である。
（Ａ−２）を添加することにより、樹脂組成物が適度な粘度となり、コイルへの含浸性が向上する。また、（Ａ−２）の添加量を３０質量％以下とすることにより、適度な硬化性と硬化物の優れた機械的物性を確保することができる。
The blending ratio of (A-1) and (A-2) is as follows.
(A-1) is preferably 70 to 100% by mass, more preferably 80 to 90% by mass, and (A-2) is preferably 0 to 30% by mass, more preferably 10 to 20% by mass. is there. The sum of (A-1) and (A-2) is 100% by mass.
By adding (A-2), the resin composition has an appropriate viscosity, and the impregnation into the coil is improved. Moreover, moderate sclerosis | hardenability and the outstanding mechanical physical property of hardened | cured material are securable by making the addition amount of (A-2) into 30 mass% or less.
前記成分（Ａ−１）と（Ａ−２）以外に、その他のエポキシ樹脂を併用することが可能であり、１分子中に２個以上のエポキシ基を有する化合物であればよく、フェノールノボラック型またはクレゾールノボラック型エポキシ樹脂、ビフェニル型等芳香族系のエポキシ樹脂のような汎用エポキシ樹脂、固形エポキシ樹脂等、一般に封止用材料として使用されるエポキシ樹脂を特に制限なく使用されることできる。また、これらのほかに必要に応じて液状のモノエポキシ樹脂を使用することができる。
点火コイル注形用エポキシ樹脂組成物中の成分（Ａ）の割合は樹脂組成物のコイルへの含浸性および硬化物の諸物性の観点から２０〜５０質量％程度であることが好ましい。
In addition to the components (A-1) and (A-2), other epoxy resins can be used in combination, and any compound having two or more epoxy groups in one molecule may be used. Or an epoxy resin generally used as a sealing material, such as a general-purpose epoxy resin such as an aromatic epoxy resin such as a cresol novolac type epoxy resin or a biphenyl type, or a solid epoxy resin, can be used without particular limitation. In addition to these, a liquid monoepoxy resin can be used as necessary.
The proportion of the component (A) in the epoxy resin composition for casting an ignition coil is preferably about 20 to 50% by mass from the viewpoint of impregnation of the resin composition into the coil and various physical properties of the cured product.
成分（Ｂ）
本発明において硬化剤として用いる成分（Ｂ）の酸無水物としては、通常、エポキシ樹脂の硬化剤として使用されるものであればよく、特に制限されるものではないが、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。成分（Ｂ）の酸無水物中ヘキサヒドロ無水フタル酸またはテトラヒドロ無水フタル酸は樹脂組成物の硬化性の観点から７０〜１００質量％であることが好ましい。
成分（Ｂ）の酸無水物の配合量は前記成分（Ａ）のエポキシ樹脂中のエポキシ基１当量に対して酸無水物基を０．８〜１．３当量、好ましくは０．９５〜１．２当量程度になるように調整する。
０．８当量より少ないと硬化が不十分となり、１．３当量を超えると硬化物の機械的物性が低下するので好ましくない。
点火コイル注形用エポキシ樹脂組成物中の成分（Ｂ）の割合は樹脂組成物のコイルへの含浸性および硬化物の諸物性の観点から２０〜５０質量％程度であることが好ましい。
Ingredient (B)
The acid anhydride of component (B) used as a curing agent in the present invention is not particularly limited as long as it is usually used as a curing agent for epoxy resins, but phthalic anhydride, tetrahydroanhydride are not particularly limited. Examples include phthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. In the acid anhydride of component (B), hexahydrophthalic anhydride or tetrahydrophthalic anhydride is preferably 70 to 100% by mass from the viewpoint of curability of the resin composition.
The compounding amount of the acid anhydride of component (B) is 0.8 to 1.3 equivalents, preferably 0.95 to 1, equivalents of acid anhydride groups to 1 equivalent of epoxy groups in the epoxy resin of component (A). Adjust to about 2 equivalents.
If it is less than 0.8 equivalent, curing will be insufficient, and if it exceeds 1.3 equivalent, the mechanical properties of the cured product will deteriorate, such being undesirable.
The proportion of the component (B) in the epoxy resin composition for casting an ignition coil is preferably about 20 to 50% by mass from the viewpoint of the impregnation property of the resin composition into the coil and various physical properties of the cured product.
成分（Ｃ）
本発明に用いる成分（Ｃ）の硬化促進剤は、一般的に用いられるもの、例えば、第３級アミン、４級アンモニウム塩、イミダゾール類、有機ホスフィン、ルイス酸触媒等が挙げられる。
第３級アミンとしては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、ベンジルジメチルアミン等、４級アンモニウム塩としては、ＤＢＵ〔１，８−ジアザビシクロ［５．４．０］ウンデセン−７〕のオクチル酸塩〔サンアプロ（株）製、商品名：ＳＡ１０２）、ＤＢＮ〔１，５−ジアザビシクロ［４．３．０］−５−ノネン〕や３級アミンとカルボン酸との塩である４級アンモニム塩系〔サンアプロ（株）製、商品名：Ｕ−ＣＡＴ２３１３〕、オクタデシルトリメチルアンモニウムクロライド〔日油株式会社製、商品名：ニッサンカチオンRＡＢ−６００、凝固点６０〜６６℃〕、テトラアルキル（各アルキル基の炭素数１〜１８）アンモニウム塩［例えばテトラエチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、テトラアルキルアンモニウムカルボン酸塩（カルボン酸の炭素数１〜１２）、イミダゾール類としては、１−ベンジル−２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１，２−ジメチルイミダゾール、１−ベンジル−２−フェニルイミダゾール等、有機ホスフィンとしては、トリフェニルホスフィン、トリフェニルホスフィン−トリフェニルボレート、トリス（ｐ−メトキシフェニル）ホスフィン、テトラフェニルホスフォニウム・テトラフェニルボレート等、ルイス酸触媒としては、具体的には、例えば、三フッ化ホウ素アミン錯体、三塩化ホウ素アミン錯体、三フッ化ホウ素エチルアミン錯体などのルイス酸触媒などが挙げられる。
中でも、硬化性の観点からベンジルジメチルアミン又は４級アンモニム塩を使用することが好ましい。
これらは単独又は２種類以上を混合して使用することができる。
この成分（Ｃ）硬化促進剤の配合量は、前記成分（Ｂ）酸無水物の１００質量部に対して、０．３〜５質量部の範囲であることが好ましく、配合量が０．３質量部未満であると、硬化時間が長く機械的特性を十分に向上させることができないおそれがあり、５質量部を超えると、反応が速く、ポットライフが短くなるため好ましくない。
Ingredient (C)
Examples of the component (C) curing accelerator used in the present invention include commonly used ones such as tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, and Lewis acid catalysts.
Tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, benzyldimethylamine and the like, and quaternary ammonium salts include octyl of DBU [1,8-diazabicyclo [5.4.0] undecene-7]. Quaternary ammonium salts which are salts of acid salts (manufactured by San Apro Co., Ltd., trade name: SA102), DBN [1,5-diazabicyclo [4.3.0] -5-nonene] and tertiary amines and carboxylic acids System [manufactured by San Apro Co., Ltd., trade name: U-CAT2313], octadecyltrimethylammonium chloride [manufactured by NOF Corporation, trade name: NISSAN CATION R AB-600, freezing point 60-66 ° C.], tetraalkyl (each alkyl group 1-18) ammonium salt [eg tetraethylammonium bromide, tetra As tylammonium bromide, tetraalkylammonium carboxylate (carbon number 1 to 12 of carboxylic acid), and imidazoles, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, Examples of organic phosphines such as 1,2-dimethylimidazole and 1-benzyl-2-phenylimidazole include triphenylphosphine, triphenylphosphine-triphenylborate, tris (p-methoxyphenyl) phosphine, tetraphenylphosphonium tetra Specific examples of the Lewis acid catalyst such as phenyl borate include Lewis acid catalysts such as boron trifluoride amine complex, boron trichloride amine complex, and boron trifluoride ethylamine complex.
Among these, benzyldimethylamine or quaternary ammonium salt is preferably used from the viewpoint of curability.
These can be used individually or in mixture of 2 or more types.
The blending amount of this component (C) curing accelerator is preferably in the range of 0.3 to 5 parts by weight with respect to 100 parts by weight of the component (B) acid anhydride, and the blending amount is 0.3. If the amount is less than part by mass, the curing time may be long and the mechanical properties may not be sufficiently improved. If the amount exceeds 5 parts by mass, the reaction is fast and the pot life is shortened, such being undesirable.
成分（Ｄ）
成分（Ｄ）のクリストバライトとしては、破砕したクリストバライト及び、球状のクリストバライトなどを用いることができる。例えば、破砕したクリストバライトとして、クリストバライトＢＦ-１１５、ＢＦ−０７〔以上、福島窯業（株）製、商品名〕等が挙げられる。これらは単独又は２種以上混合して使用することができる。一般に、破砕したクリストバライトはアスペクト比が１に近いほど作業性が優れており、点火コイルへの樹脂組成物の含浸性が良好になる。
なお、クリストバライトまたはクリストバル石（cristobalite）は、二酸化ケイ素(ＳｉＯ2)の結晶多形の一つで、石英の高温結晶形のものであり、方珪石（ほうけいせき）とも称されている。球状溶融シリカまたは結晶シリカを原料とし加熱処理にてクリストバライト化したものであり、クリストバライトは溶融シリカまたは結晶シリカとは溶融化度が異なっている。クリストバライトの溶融化度（測定法：Ｘ線回折）は７５％程度であり、溶融シリカまたは結晶シリカの溶融化度はそれぞれ１００％と０％である。
Ingredient (D)
As the cristobalite of the component (D), crushed cristobalite, spherical cristobalite, and the like can be used. For example, cristobalite BF-115, BF-07 [above, product name, manufactured by Fukushima Ceramics Co., Ltd.] and the like are listed as crushed cristobalite. These can be used alone or in admixture of two or more. Generally, the crushed cristobalite has better workability as the aspect ratio is closer to 1, and the impregnation property of the resin composition into the ignition coil becomes better.
Note that cristobalite or cristobalite is one of the crystal polymorphs of silicon dioxide (SiO 2 ), which is a high-temperature crystal form of quartz, and is also referred to as quarkite. Spherical fused silica or crystalline silica is used as a raw material to be cristobalite by heat treatment, and cristobalite has a different degree of melting from fused silica or crystalline silica. The degree of melting of cristobalite (measurement method: X-ray diffraction) is about 75%, and the degree of melting of fused silica or crystalline silica is 100% and 0%, respectively.
本発明の点火コイル注形用エポキシ樹脂組成物に配合される好ましいクリストバライトは数平均粒径３〜１０μｍのクリストバライト（Ｄ−１）と数平均粒径が１０μｍを超え、５０μｍ以下のクリストバライト（Ｄ−２）を合わせて全クリストバライト中３０質量％以上であることが好ましく、さらに好ましくは５０〜１００質量％である。さらに、両者の配合比（Ｄ−１）：（Ｄ−２）が質量比で８０：２０〜１００：０であることが好ましく、８０：２０〜９０：１０であることがより好ましい。
これによって、硬化物は高熱伝導性、低線膨張性、高強度という優れた機械的特性および体積抵抗率を示す。数平均粒径以外には特に制限なく広く使用できる。成分（Ｄ）のクリストバライトの配合量はエポキシ樹脂組成物中において４０〜８０質量％範囲であることが好ましく、より好ましくは、４５〜５５質量％の範囲である。配合量を４０質量％以上とすることにより強度を十分に確保ができ、８０質量％以下とすることにより粘度が上昇し、作業性およびコイルへの含浸性が低下してしまう恐れがある。
Preferred cristobalite blended in the epoxy resin composition for casting an ignition coil of the present invention is cristobalite (D-1) having a number average particle diameter of 3 to 10 μm and cristobalite (D−) having a number average particle diameter of more than 10 μm and 50 μm or less. It is preferable that it is 30 mass% or more in all cristobalite combining 2), More preferably, it is 50-100 mass%. Furthermore, it is preferable that both compounding ratio (D-1) :( D-2) is 80: 20-100: 0 by mass ratio, and it is more preferable that it is 80: 20-90: 10.
Accordingly, the cured product exhibits excellent mechanical properties such as high thermal conductivity, low linear expansion, and high strength, and volume resistivity. Other than the number average particle diameter, it can be used widely without any particular limitation. The blending amount of cristobalite as component (D) is preferably in the range of 40 to 80% by mass, more preferably in the range of 45 to 55% by mass in the epoxy resin composition. If the blending amount is 40% by mass or more, sufficient strength can be secured, and if it is 80% by mass or less, the viscosity increases, and workability and impregnation into the coil may be reduced.
また、成分（Ｄ）のクリストバライトは、樹脂組成物中へのカップリング剤の添加処理により、その表面改質を施すことで、さらに優れた硬化物の絶縁信頼性、機械的強度を得ることができる。ここで用いることができるカップリング剤としては、シランカップリング剤、チタン系カップリング剤、アルミニウム系カップリング剤等が挙げられ、耐湿性などの特性向上に優れていることから特にシランカップリング剤が好ましい。
これらシランカップリング剤としては、例えば、3- グリシドキシプロピルトリメトキシシラン、γ―アミノプロピルトリエトキシシラン、γ―アミノプロピルトリメトキシシラン、Ｎ−アミノエチルアミノプロピルトリメトキシシラン、Ｎ−フェニルーγ―アミノプロピルトリメトキシシラン、Ｎ−３−（４−（３−アミノプロポキシ）ブトキシ）プロピル−３−アミノプロピルトリメトキシシランが挙げられ、これらは単独でも２種類以上併用してもよい。
さらに、本発明の目的に反しない範囲において、クリストバライト以外の無機質充填剤、カップリング剤、消泡剤、沈降防止剤及びその他の成分を添加配合することができる。無機質充填剤としては、アルミナ、結晶シリカ、タルク、炭酸カルシウム等が上げられ、これらは単独または、２種以上混合して使用することができる。
In addition, the cristobalite component (D) can be further improved in the insulation reliability and mechanical strength of the cured product by surface modification by adding a coupling agent to the resin composition. it can. Examples of coupling agents that can be used here include silane coupling agents, titanium-based coupling agents, aluminum-based coupling agents, and the like, and are particularly excellent in improving properties such as moisture resistance. Is preferred.
Examples of these silane coupling agents include 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-aminoethylaminopropyltrimethoxysilane, N-phenyl-γ. -Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane may be mentioned, and these may be used alone or in combination of two or more.
Furthermore, an inorganic filler other than cristobalite, a coupling agent, an antifoaming agent, an antisettling agent, and other components can be added and blended within a range not departing from the object of the present invention. Examples of the inorganic filler include alumina, crystalline silica, talc, calcium carbonate and the like, and these can be used alone or in combination of two or more.
本発明の点火コイル注形用エポキシ樹脂組成物は、常法により上述した各成分、すなわちエポキシ樹脂、硬化剤、硬化促進剤、クリストバライト及びその他の成分を加えて、十分に混合、撹拌して製造することができる。
通常は、主剤成分と硬化剤成分の２液型として注形直前に両者を混合することが好ましい。その一例として、前記成分（Ａ）のエポキシ樹脂と成分（Ｄ）のクリストバライトを混合して調製した主剤成分と、別途前記成分（Ｂ）の硬化剤、成分（Ｃ）の硬化促進剤および成分（Ｄ）のクリストバライトを混合して調製した硬化剤成分の２液型として注形直前に両者を混合するのが好ましい。成分（Ｄ）のクリストバライトを主剤成分と硬化剤成分の双方に分けて混合するのは両者の粘度に大きな差がないようにして混合を容易にするためである。
なお、主剤成分および/または硬化剤成分に結晶シリカ、タルク、炭酸カルシウム等の無機質充填剤を配合してもよい。こうして得られた点火コイル注形用エポキシ樹脂組成物は、ガソリン又はＨＥＶ自動車に対応することができる点火コイル等の高熱伝導コイル注型用樹脂組成物として使用することができる。
本発明のコイル注形用エポキシ樹脂組成物を含浸後、加熱硬化させてなる点火コイルを有する装置としては、ペンタイプのイグニションコイルが挙げられる。これは、直径２．０ｃｍ以下のプラスチックケース中に配置された、直径５０μｍ程度の被覆導線を鉄心に巻いたコイルに前記エポキシ樹脂組成物を含浸させ、次いで加熱硬化させてなるものである。このイグニションコイルにおける樹脂組成物の占有体積は３０％以下であることが好ましい。
本発明の点火コイル注形用エポキシ樹脂組成物はガソリン又はＨＥＶ自動車に対応することができる
The epoxy resin composition for casting an ignition coil according to the present invention is manufactured by adding the above-described components, that is, an epoxy resin, a curing agent, a curing accelerator, cristobalite, and other components by a conventional method, and thoroughly mixing and stirring. can do.
Usually, it is preferable to mix the two components immediately before casting as a two-component type of a main component and a curing agent component. As an example, a main component prepared by mixing the epoxy resin of component (A) and cristobalite of component (D), a curing agent of component (B), a curing accelerator of component (C), and a component ( It is preferable that the two components are mixed immediately before casting as a two-component curing agent component prepared by mixing cristobalite of D). The reason why the cristobalite of component (D) is divided into the main component and the hardener component is mixed to facilitate mixing so that there is no great difference in viscosity between the two.
In addition, you may mix | blend inorganic fillers, such as a crystalline silica, a talc, and a calcium carbonate, with a main ingredient component and / or a hardening | curing agent component. The epoxy resin composition for casting an ignition coil thus obtained can be used as a resin composition for casting a high thermal conductivity coil such as an ignition coil that can be used for gasoline or HEV automobiles.
Examples of the apparatus having an ignition coil that is impregnated with the epoxy resin composition for casting a coil according to the present invention and then cured by heating include a pen type ignition coil. This is obtained by impregnating the above-mentioned epoxy resin composition into a coil, which is disposed in a plastic case having a diameter of 2.0 cm or less and in which a coated conductor having a diameter of about 50 μm is wound around an iron core, and then heat-curing. The occupied volume of the resin composition in the ignition coil is preferably 30% or less.
The epoxy resin composition for casting an ignition coil of the present invention can be applied to gasoline or HEV automobiles.
次に、本発明の点火コイルの製造方法について説明する。
まず、コイルを金型内に固定して金型内を真空状態とし、得られた点火コイル注形用エポキシ樹脂組成物を金型内に注形してコイル内に含浸させ、１００〜３００℃、好ましくは１５０〜２００℃程度の温度で、０．５〜５時間、好ましくは１〜３時間程度加熱硬化させることにより本発明の点火コイルを得ることができる。後で説明する＜京セラケミカル式テストコイル法＞による含浸率は８０％以上であることが好ましい。
Next, the manufacturing method of the ignition coil of this invention is demonstrated.
First, the coil is fixed in a mold and the mold is evacuated, and the resulting epoxy resin composition for casting an ignition coil is cast in a mold and impregnated in the coil, and 100 to 300 ° C. The ignition coil of the present invention can be obtained by heat curing preferably at a temperature of about 150 to 200 ° C. for 0.5 to 5 hours, preferably about 1 to 3 hours. The impregnation rate by <Kyocera Chemical Test Coil Method> described later is preferably 80% or more.
次に本発明を実施例によって説明する。本発明はこれらの実施例によって限定されるものではない。以下の実施例及び比較例において「部」とは「質量部」を意味する。 Next, the present invention will be described by way of examples. The present invention is not limited by these examples. In the following Examples and Comparative Examples, “part” means “part by mass”.
＜実施例１＞
成分（Ａ）として、液状のビスフェノールＡジグリシジルエーテル型エポキシ樹脂〔アデカ（株）製、商品名：ＥＰ４１００Ｅ、エポキシ当量１９０〕１００部、消泡剤〔モメンティブ・パフォーマンス・マテリアルズ（株）製、商品名：ＴＳＡ７２０〕０．１部、シランカップリング剤〔モメンティブ・パフォーマンス・マテリアルズ（株）製、製品名：Ａ−１８７〕０．５部、成分（Ｄ−１）として、数平均粒径７μｍのクリストバライト〔福島窯業（株）製、商品名：ＢＦ−０７〕１６０部、成分（Ｄ−２）として、数平均粒径１５μｍのクリストバライト〔福島窯業（株）製、商品名：ＢＦ−１１５〕２０部、沈降防止剤として１,３：２,４−ビス−Ｏ−ベンジリデン−Ｄ−グルシトール（ジベンジリデンソルビトール）〔新日本理化（株）製、製品名：ゲルオールＤ〕０．５部を混合して主剤とした。
これとは別に、成分（Ｂ）の酸無水物としてメチルヘキサヒドロ無水フタル酸〔日立化成（株）製、商品名：ＨＮ７０００〕１００部、成分（Ｃ）の硬化促進剤として４級アンモニウム塩〔日油（株）製、商品名：Ｍ２−１００〕０．５部を混合して硬化剤とした。上記主剤と硬化剤を混合してガソリン又はＨＥＶ自動車に対応することができる点火コイル注形用エポキシ樹脂組成物を製造した。
<Example 1>
As component (A), liquid bisphenol A diglycidyl ether type epoxy resin [manufactured by Adeka Co., Ltd., trade name: EP4100E, epoxy equivalent 190] 100 parts, antifoaming agent [Momentive Performance Materials Co., Ltd., Product name: TSA720] 0.1 part, Silane coupling agent [Mentive Performance Materials, product name: A-187] 0.5 part, number average particle size as component (D-1) Cristobalite 7 [mu] m [Fukushima Ceramics Co., Ltd., trade name: BF-07] 160 parts, component (D-2), number average particle size 15 [mu] m cristobalite [Fukushima Ceramics Co., Ltd., trade name: BF-115 ] 20 parts, 1,3: 2,4-bis-O-benzylidene-D-glucitol (dibenzylidene sorbitol) as anti-settling agent [Shin Nippon Rika Ltd.), product name: GEL ALL D] were mixed 0.5 parts of a main agent.
Separately, 100 parts of methylhexahydrophthalic anhydride [manufactured by Hitachi Chemical Co., Ltd., trade name: HN7000] as the acid anhydride of component (B), quaternary ammonium salt as the curing accelerator of component (C) [ Nippon Oil Co., Ltd., trade name: M2-100] 0.5 part was mixed to obtain a curing agent. An epoxy resin composition for casting an ignition coil that can be used for gasoline or HEV automobiles was prepared by mixing the main agent and the curing agent.
＜実施例２〜６、比較例１〜５＞
表１に示した配合組成によって実施例１と同様に点火コイル注形用エポキシ樹脂組成物および比較用のエポキシ樹脂組成物を製造した。これらの点火コイル注形用エポキシ樹脂組成物の粘度およびゲルタイムを測定して表１に示した。
<Examples 2-6, Comparative Examples 1-5>
An epoxy resin composition for casting an ignition coil and an epoxy resin composition for comparison were produced in the same manner as in Example 1 with the formulation shown in Table 1. The viscosities and gel times of these ignition coil casting epoxy resin compositions were measured and shown in Table 1.
実施例２〜６、比較例１〜５で用いた成分は以下の通りである。
（1）エポキシ樹脂―成分（Ａ）
液状ビスフェノールＡ型エポキシ樹脂：アデカ（株）製〔商品名：ＥＰ４１００Ｅ、エポキシ当量１９０〕
脂環式エポキシ樹脂：（株）ダイセル製〔商品名：セロキサイド＃２０２１Ｐ、エポキシ当量：１２８〜１４０〕
（2）酸無水物―成分（Ｂ）
メチルヘキサヒドロ無水フタル酸 日立化成（株）製、商品名：ＨＮ７０００
メチルテトラヒドロ無水フタル酸：日立化成（株）製、商品名：ＨＮ２０００
（3）硬化促進剤―成分（Ｃ）
三級アミン：花王（株）製のベンジルジメチルアミン〔ＢＤＭＡ〕
４級アンモニウム塩：日油（株）製のテトラデシルジメチルベンジルアンモニウムクロライド〔Ｍ２-１００Ｒ〕
イミダゾール：四国化成（株）製の２−エチル−４−メチルイミダゾール〔２Ｅ４ＭＺ〕
（4）クリストバライト―成分（Ｄ）
クリストバライトＤ-１：福島窯業（株）製、数平均粒子径７ｕｍ（Ｄ−１）、溶融化度７５％、商品名：ＢＦ−０７
クリストバライトＤ-２：福島窯業（株）製、数平均粒子径１５ｕｍ（Ｄ−２）、溶融化度７５％、商品名：ＢＦ−１１５
（5）充填材―成分（Ｄ）に対する比較材料
溶融シリカ１：龍森（株）製、数平均粒径７μｍの溶融シリカ〔Ｅ−２〕、溶融化度１００％
溶融シリカ２：龍森（株）製、数平均粒径１５μｍの溶融シリカ〔ＺＡ−２０〕、溶融化度１００％
結晶シリカ：龍森（株）製、数平均粒径６μｍの結晶シリカ〔Ａ−ＡＣ〕、溶融化度０％
（6）沈降防止剤
新日本理化（株）製の１,３：２,４−ビス−Ｏ−ベンジリデン−Ｄ−グルシトール（ジベンジリデンソルビトール）〔ゲルオールＤ〕
（7）シランカップリング剤
モメンティブ・パフォーマンス・マテリアルズ（株）製のエポキシシラン系カップリング剤〔Ａ-１８７〕
（8）消泡剤
モメンティブ・パフォーマンス・マテリアルズ（株）製のシリコーン系消泡剤〔ＴＳＡ７２０〕
The components used in Examples 2 to 6 and Comparative Examples 1 to 5 are as follows.
(1) Epoxy resin-Component (A)
Liquid bisphenol A type epoxy resin: manufactured by ADEKA Corporation [trade name: EP4100E, epoxy equivalent 190]
Alicyclic epoxy resin: manufactured by Daicel Corporation [trade name: Celoxide # 2021P, epoxy equivalent: 128-140]
(2) Acid anhydride-component (B)
Methylhexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd., trade name: HN7000
Methyltetrahydrophthalic anhydride: manufactured by Hitachi Chemical Co., Ltd., trade name: HN2000
(3) Curing accelerator-Component (C)
Tertiary amine: Benzyldimethylamine [BDMA] manufactured by Kao Corporation
Quaternary ammonium salt: tetradecyldimethylbenzylammonium chloride [M2-100R] manufactured by NOF Corporation
Imidazole: 2-ethyl-4-methylimidazole [2E4MZ] manufactured by Shikoku Kasei Co., Ltd.
(4) Cristobalite-ingredient (D)
Cristobalite D-1: manufactured by Fukushima Ceramics Co., Ltd., number average particle size 7um (D-1), degree of melting 75%, trade name: BF-07
Cristobalite D-2: manufactured by Fukushima Ceramics Co., Ltd., number average particle size 15um (D-2), degree of melting 75%, product name: BF-115
(5) Filler—Comparative material for component (D) Fused silica 1: Tatsumori Co., Ltd., fused silica with a number average particle size of 7 μm [E-2], degree of melting 100%
Fused silica 2: manufactured by Tatsumori Co., Ltd., fused silica with a number average particle size of 15 μm [ZA-20], degree of melting 100%
Crystalline silica: manufactured by Tatsumori Co., Ltd., crystalline silica [A-AC] having a number average particle diameter of 6 μm, degree of melting 0%
(6) Anti-settling agent 1,3: 2,4-bis-O-benzylidene-D-glucitol (dibenzylidene sorbitol) [Gelol D] manufactured by Shin Nippon Rika Co., Ltd.
(7) Silane coupling agent Epoxysilane coupling agent [A-187] manufactured by Momentive Performance Materials Co., Ltd.
(8) Antifoaming agent Silicone antifoaming agent manufactured by Momentive Performance Materials Co., Ltd. [TSA720]
実施例１〜６及び比較例１〜５で製造した点火コイル注形用エポキシ樹脂組成物および比較用のエポキシ樹脂組成物を用いて加熱硬化させて評価用硬化物を製造した。製造された樹脂組成物について粘度、ゲルタイム、接着性および京セラケミカル式テストコイル法によるコイルへの含浸性を測定して表１に示した。
次に、製造された樹脂組成物の硬化物について、ガラス転移点、熱膨張率、曲げ強さ、曲げ弾性率および熱伝導率を測定して表１に示した。
次に、コイルを金型内に固定して点火コイル注形用エポキシ樹脂組成物および比較用のエポキシ樹脂組成物を真空下で注形して含浸させ、１００℃で３時間、１５０℃で３時間加熱硬化させて点火コイルを作製し、電気特性、絶縁破壊電圧、熱伝導率、テストコイル法による含浸性を試験して、その結果を表１と図１に示した。
図１は樹脂組成物のコイル巻き線部への含浸性を試験する際の手順と巻き線部における樹脂組成物の含浸状態を示す写真である。従来の点火コイルでは得られない高電圧下での体積抵抗率が安定性を有していることが証明され、実施例１〜６のいずれにおいても、点火コイル注形用エポキシ樹脂組成物、その硬化物および点火コイルの特性が優れており、本発明による効果を確認することができた。
A cured product for evaluation was produced by heat curing using the epoxy resin composition for casting an ignition coil produced in Examples 1 to 6 and Comparative Examples 1 to 5 and the comparative epoxy resin composition. Table 1 shows the viscosity, gel time, adhesion, and impregnation of the resin composition produced by the Kyocera Chemical test coil method.
Next, the cured product of the produced resin composition was measured for glass transition point, coefficient of thermal expansion, bending strength, bending elastic modulus and thermal conductivity and shown in Table 1.
Next, the coil is fixed in a mold, and the epoxy resin composition for casting an ignition coil and the epoxy resin composition for comparison are cast and impregnated under vacuum, and 3 hours at 100 ° C. and 3 hours at 150 ° C. Ignition coils were produced by heat-curing for hours, and electrical characteristics, dielectric breakdown voltage, thermal conductivity, and impregnation by a test coil method were tested, and the results are shown in Table 1 and FIG.
FIG. 1 is a photograph showing a procedure for testing the impregnation property of a coiled portion of a resin composition and an impregnation state of the resin composition in the wound portion. It has been proved that the volume resistivity under high voltage that cannot be obtained by a conventional ignition coil has stability, and in any of Examples 1 to 6, an epoxy resin composition for casting an ignition coil, its The properties of the cured product and the ignition coil were excellent, and the effects of the present invention could be confirmed.
＜評価項目＞
（1）粘度
Ｂ型粘度計を使用して２５℃で測定した。
（2）ゲルタイム
試験管法により１１０℃で測定した。
（3）樹脂組成物（主剤＋硬化剤）のコイルへの含浸性
図１に示すような方法＜京セラケミカル式テストコイル法＞で樹脂組成物のコイル巻き線部への含浸率の測定を行なった。測定温度は２５℃である。
直径５０μｍの被覆導線をアルミナ製ボビンに２２０００回巻きつけたものについて、樹脂組成物の含浸性を、コイル巻き線部に樹脂が浸透した部位（含浸部位）の割合（含浸率）を下記式により計算して数値化して下記の基準で評価した。
使用したボビンの幅は１０ｍｍ、コイル巻き線部のボビン直径方法の厚さは５ｍｍである。ボビンを入れる容器の高さはボビンの幅１０ｍｍより高い約１５ｍｍである。容器の内径はボビンのコイル巻き線部の外径３０ｍｍより大きい５０ｍｍである。図１におけるボビンの中心孔の上部を真空ライン（図１には示さず）に連結して、樹脂組成物を容器の高さまで流し込み、約２分真空ラインを稼動させて樹脂組成物をコイル巻き線部に含浸させた。
含浸率＝（含浸部位面積）×１００/（含浸部位面積＋未含浸部位面積）
含浸性の評価基準
○：含浸率が８０％以上
△：含浸率が６０％以上８０％未満
×：含浸率が６０％未満
含浸率が低いと、巻線に欠落が生じる。
（4）ガラス転移点
点火コイル注形用エポキシ樹脂組成物を１００℃で３時間、次いで１５０℃で３時間加熱硬化後、ＴＭＡ法により、昇温速度１５℃／分として室温から２５０℃まで昇温させて測定した。
（5）熱膨張率
樹脂組成物を１００℃で３時間、次いで１５０℃で３時間加熱硬化後、ＴＭＡ法により、昇温速度１５℃／分として室温から２５０℃まで昇温させて測定した。
（6）曲げ強さおよび曲げ弾性率
樹脂組成物を１００℃で３時間、次いで１５０℃で３時間加熱硬化させてサンプル片（幅：１０ｍｍ、高さ：４ｍｍ、長さ：８０ｍｍ）を作製し、ＪＩＳ Ｋ６９１１に準じ、温度２５℃において測定した。
（7）接着性＜被着面積および試験条件＞
樹脂組成物を被接着材であるＰＢＴ板（厚さ２ｍｍ）上に被着面積（幅５ｍｍ×長さ７ｍｍ）になるように塗布（厚さ：１ｍｍ）し、１００℃で３時間、次いで１５０℃で３時間加熱硬化させて接着性評価用サンプル片を作製した。
ＪＩＳ Ｋ６８５０に準じ、引張速度２．５ｍｍ/分、温度２５℃において接着強度を測定した。
（8）熱伝導率
樹脂組成物を１００℃で３時間、次いで１５０℃で３時間加熱硬化させてサンプル片（幅：８００ｍｍ、高さ：１０ｍｍ、長さ：１０００ｍｍ）を作製し、プローグ法にて室温で測定した。
（9）比誘電率：ＪＩＳ Ｃ２１０５、測定周波数５０Ｈｚ、測定温度２５℃
（10）誘電正接：ＪＩＳ Ｃ２１０５、測定周波数５０Ｈｚ、測定温度２５℃
（11）体積抵抗率：ＪＩＳ Ｃ２１０５、測定電圧ＤＣ５００Ｖ、測定温度２５℃
体積抵抗率等の測定には試験片厚さ２ｍｍのもの、主電極として６０φのものを用いた。
<Evaluation items>
(1) Viscosity The viscosity was measured at 25 ° C. using a B-type viscometer.
(2) Gel time It measured at 110 degreeC by the test tube method.
(3) Impregnation of the resin composition (main agent + curing agent) into the coil The impregnation ratio of the resin composition into the coil winding portion was measured by the method <Kyocera Chemical Test Coil Method> as shown in FIG. It was. The measurement temperature is 25 ° C.
For a coated conductor having a diameter of 50 μm wound around an alumina bobbin 22,000 times, the impregnating property of the resin composition, and the ratio (impregnation ratio) of the portion (impregnation portion) where the resin penetrated into the coil winding portion is expressed by the following formula: Calculations and numerical values were made and evaluated according to the following criteria.
The width of the used bobbin is 10 mm, and the thickness of the bobbin diameter method of the coil winding portion is 5 mm. The height of the container into which the bobbin is placed is about 15 mm, which is higher than the width of the bobbin 10 mm. The inner diameter of the container is 50 mm, which is larger than the outer diameter of 30 mm of the coil winding portion of the bobbin. The upper part of the bobbin center hole in FIG. 1 is connected to a vacuum line (not shown in FIG. 1), the resin composition is poured to the height of the container, and the vacuum line is operated for about 2 minutes to coil the resin composition. The wire part was impregnated.
Impregnation rate = (impregnated part area) × 100 / (impregnated part area + unimpregnated part area)
Evaluation standard for impregnation ○: Impregnation ratio is 80% or more Δ: Impregnation ratio is 60% or more and less than 80% ×: Impregnation ratio is less than 60% If the impregnation ratio is low, the winding is missing.
(4) Glass transition point After curing the epoxy resin composition for casting an ignition coil at 100 ° C. for 3 hours and then at 150 ° C. for 3 hours, the temperature was increased from room temperature to 250 ° C. at a temperature increase rate of 15 ° C./min by the TMA method. Measured by warming.
(5) Coefficient of thermal expansion The resin composition was heated and cured at 100 ° C. for 3 hours and then at 150 ° C. for 3 hours, and then measured by a TMA method by raising the temperature from room temperature to 250 ° C. at a rate of temperature increase of 15 ° C./min.
(6) Bending strength and flexural modulus The resin composition was heat-cured at 100 ° C. for 3 hours and then at 150 ° C. for 3 hours to prepare a sample piece (width: 10 mm, height: 4 mm, length: 80 mm). According to JIS K6911, the temperature was measured at 25 ° C.
(7) Adhesiveness <Application area and test conditions>
The resin composition was applied (thickness: 1 mm) on a PBT plate (thickness: 2 mm), which is an adherend, so as to have a deposition area (width: 5 mm × length: 7 mm). A sample piece for adhesion evaluation was prepared by heat curing at 3 ° C. for 3 hours.
According to JIS K6850, the adhesive strength was measured at a tensile speed of 2.5 mm / min and a temperature of 25 ° C.
(8) Thermal conductivity The resin composition is heated and cured at 100 ° C. for 3 hours and then at 150 ° C. for 3 hours to produce a sample piece (width: 800 mm, height: 10 mm, length: 1000 mm). And measured at room temperature.
(9) Relative permittivity: JIS C2105, measurement frequency 50Hz, measurement temperature 25 ° C
(10) Dissipation factor: JIS C2105, measurement frequency 50 Hz, measurement temperature 25 ° C.
(11) Volume resistivity: JIS C2105, measurement voltage DC500V, measurement temperature 25 ° C
For the measurement of volume resistivity and the like, a specimen having a thickness of 2 mm and a main electrode having a diameter of 60 mm were used.
表１には各実施例および比較例の上記物性の測定結果に応じて、評価が高い順にＡ、Ｂ、Ｃ、Ｄの総合評価を記載している。
表１から、実施例１〜６の成分（Ｄ）のクリストバライトを含む樹脂組成物は溶融シリカまたは結晶シリカを同量配合した比較例の樹脂組成物に比べて、樹脂組成物のコイルへの含浸性、接着強度、硬化物の機械的強度、体積抵抗率の全てがバランスよく、優れていることがわかる。
Table 1 shows the overall evaluation of A, B, C, and D in descending order of evaluation according to the measurement results of the physical properties of the examples and comparative examples.
From Table 1, the resin composition containing cristobalite of components (D) of Examples 1 to 6 was impregnated into the coil of the resin composition as compared with the resin composition of the comparative example in which the same amount of fused silica or crystalline silica was blended. It can be seen that the properties, adhesive strength, mechanical strength of the cured product, and volume resistivity are all well balanced.
本発明の点火コイル注形用エポキシ樹脂組成物はガソリン又はＨＥＶ自動車用の点火コイルの分野において、絶縁および封止材料として極めて有用である。 The epoxy resin composition for casting an ignition coil of the present invention is extremely useful as an insulating and sealing material in the field of ignition coils for gasoline or HEV automobiles.
Claims (7)
The coil is fixed in a mold and the mold is evacuated, and the epoxy resin composition for casting an ignition coil according to any one of claims 1 to 5 is cast into the mold and heat-cured. A manufacturing method of an ignition coil characterized by the above.
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