JP2024054993A - Thermosetting resin composition, bulk molding compound and molded product thereof - Google Patents
Thermosetting resin composition, bulk molding compound and molded product thereof Download PDFInfo
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 62
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 239000004412 Bulk moulding compound Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 13
- 239000011231 conductive filler Substances 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 10
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 10
- 239000012779 reinforcing material Substances 0.000 claims abstract description 10
- 239000002562 thickening agent Substances 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 238000002347 injection Methods 0.000 abstract description 20
- 239000007924 injection Substances 0.000 abstract description 20
- 230000006835 compression Effects 0.000 abstract description 9
- 238000007906 compression Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 150000001451 organic peroxides Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- -1 alumina Chemical compound 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- MWKGOHCHXBLCSH-UHFFFAOYSA-L [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O MWKGOHCHXBLCSH-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- VCZQCLHBLSUGML-UHFFFAOYSA-K aluminum octacosanoate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O VCZQCLHBLSUGML-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 210000005097 arteria cerebelosa anteroinferior Anatomy 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940061587 calcium behenate Drugs 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- SMBKCSPGKDEPFO-UHFFFAOYSA-L calcium;docosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O SMBKCSPGKDEPFO-UHFFFAOYSA-L 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- OBQVOBQZMOXRAL-UHFFFAOYSA-L magnesium;docosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O OBQVOBQZMOXRAL-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】流動性、射出成形性、圧縮成形性に優れ、熱伝導性に優れる成形品を得ることのできる熱硬化性樹脂組成物、バルクモールディングコンパウンド及びその成形品を提供することである。【解決手段】熱硬化性樹脂（Ａ）、低収縮化剤（Ｂ）、増粘剤（Ｃ）、熱伝導性フィラー（Ｄ）、及び補強材（Ｅ）を含有する熱硬化性樹脂組成物であって、前記熱硬化性樹脂（Ａ）が、不飽和ポリエステル樹脂（ａ１）及びビニルエステル樹脂（ａ２）を含有するものであり、前記増粘剤（Ｃ）が、アクリル樹脂粒子（ｃ１）及び酸化マグネシウム（ｃ２）を含有するものであることを特徴とする熱硬化性樹脂組成物を用いる。【選択図】なし[Problem] To provide a thermosetting resin composition that can give molded articles with excellent flowability, injection moldability, and compression moldability, and excellent thermal conductivity, a bulk molding compound, and a molded article thereof. [Solution] A thermosetting resin composition containing a thermosetting resin (A), a shrinkage reducing agent (B), a thickener (C), a thermally conductive filler (D), and a reinforcing material (E), wherein the thermosetting resin (A) contains an unsaturated polyester resin (a1) and a vinyl ester resin (a2), and the thickener (C) contains acrylic resin particles (c1) and magnesium oxide (c2), is used. [Selected Figure] None
Description
本発明は、熱硬化性樹脂組成物、バルクモールディングコンパウンド及びその成形品に関する。 The present invention relates to a thermosetting resin composition, a bulk molding compound, and a molded article made therefrom.
不飽和ポリエステル樹脂、ビニルエステル樹脂等の熱硬化性樹脂に、低収縮剤、禁止剤、硬化剤、充填材、離型剤、強化材等を加えて、混練機で混練した熱硬化性樹脂組成物は、電気絶縁性、耐熱性、難燃性、高剛性、寸法安定性等の利点があるため、家電、自動車やエネルギー分野等に関連する電子部品へ広く応用されている。前記熱硬化性樹脂組成物の中でも、バルク状にしたバルクモールディングコンパウンド（以下、「ＢＭＣ」と略記することがある。）は、圧縮成形、トランスファー成形、射出成形等の成形方法により、成形品にすることができる。 Thermosetting resin compositions, which are made by adding low-shrinkage agents, inhibitors, curing agents, fillers, release agents, reinforcing materials, etc. to thermosetting resins such as unsaturated polyester resins and vinyl ester resins and kneading them in a kneader, have advantages such as electrical insulation, heat resistance, flame retardancy, high rigidity, and dimensional stability, and are therefore widely used in electronic parts related to home appliances, automobiles, and the energy field. Among the thermosetting resin compositions, bulk molding compounds (hereinafter sometimes abbreviated as "BMC") made into bulk form can be made into molded products by molding methods such as compression molding, transfer molding, and injection molding.
近年、電子部品は、高出力（高密度化）、小型化（軽量化）が進んでいるため、電子部品内部に発生した熱が蓄積され、この熱による電子部品出力低下、寿命短縮等の課題を抱えている。 In recent years, electronic components have become more powerful (higher density) and smaller (lighter weight), which causes heat to build up inside the components, resulting in issues such as reduced output and shorter life spans.
このような中、ＢＭＣ成形品には優れた放熱性が求められており、熱伝導性フィラーを用いた熱硬化性樹脂組成物が提案されている（例えば、特許文献１参照。）。しかしながら、この樹脂組成物から得られる成形材料は、フィラーの高充填化により熱伝導性は向上する一方、流動性が不十分である場合があり、射出成形性に劣る問題があった。 In this situation, BMC molded products are required to have excellent heat dissipation properties, and thermosetting resin compositions using thermally conductive fillers have been proposed (see, for example, Patent Document 1). However, while the molding material obtained from this resin composition has improved thermal conductivity due to the high filler loading, it may have insufficient fluidity and suffer from poor injection moldability.
本発明が解決しようとする課題は、流動性、射出成形性、圧縮成形性に優れ、熱伝導性に優れる成形品を得ることのできる熱硬化性樹脂組成物、バルクモールディングコンパウンド及びその成形品を提供することである。 The problem that the present invention aims to solve is to provide a thermosetting resin composition, a bulk molding compound, and a molded article thereof that have excellent flowability, injection moldability, and compression moldability, and that can produce molded articles with excellent thermal conductivity.
本発明者等は、上記の課題を解決するため鋭意研究した結果、特定の熱硬化性樹脂、低収縮化剤、特定の増粘剤、熱伝導性フィラー、及び補強材を含有する熱硬化性樹脂組成物は、上記課題を解決することを見出し、本発明を完成させた。 As a result of intensive research into solving the above problems, the inventors have discovered that a thermosetting resin composition containing a specific thermosetting resin, a shrinkage reducing agent, a specific thickener, a thermally conductive filler, and a reinforcing material solves the above problems, and have completed the present invention.
すなわち、本発明は、熱硬化性樹脂（Ａ）、低収縮化剤（Ｂ）、増粘剤（Ｃ）、熱伝導性フィラー（Ｄ）、及び補強材（Ｅ）を含有する熱硬化性樹脂組成物であって、前記熱硬化性樹脂（Ａ）が、不飽和ポリエステル樹脂（ａ１）及びビニルエステル樹脂（ａ２）を含有するものであり、前記増粘剤（Ｃ）が、アクリル樹脂粒子（ｃ１）及び酸化マグネシウム（ｃ２）を含有するものであることを特徴とする熱硬化性樹脂組成物を提供するものである。 That is, the present invention provides a thermosetting resin composition containing a thermosetting resin (A), a shrinkage reducing agent (B), a thickener (C), a thermally conductive filler (D), and a reinforcing material (E), characterized in that the thermosetting resin (A) contains an unsaturated polyester resin (a1) and a vinyl ester resin (a2), and the thickener (C) contains acrylic resin particles (c1) and magnesium oxide (c2).
本発明の熱硬化性樹脂組成物は、流動性、射出成形性、圧縮成形性に優れ、また、熱伝導性に優れる成形品を得られることから、家電、自動車等に用いられる電気・電子部品の支持体、電気自動車用モーター封止材、ＰＣ・スマートフォン等通信機器の筐体、各種センサー部品、電気自動車バッテリー保持体、ＬＥＤランプのヒートシンク等に非常に有用である。 The thermosetting resin composition of the present invention has excellent flowability, injection moldability, and compression moldability, and can be used to obtain molded products with excellent thermal conductivity. Therefore, it is very useful for applications such as supports for electric and electronic parts used in home appliances and automobiles, motor sealants for electric vehicles, housings for communication devices such as PCs and smartphones, various sensor parts, battery holders for electric vehicles, and heat sinks for LED lamps.
本発明の熱硬化性樹脂組成物は、熱硬化性樹脂（Ａ）、低収縮化剤（Ｂ）、増粘剤（Ｃ）、熱伝導性フィラー（Ｄ）、及び補強材（Ｅ）を含有する熱硬化性樹脂組成物であって、前記熱硬化性樹脂（Ａ）が、不飽和ポリエステル樹脂（ａ１）及びビニルエステル樹脂（ａ２）を含有するものであり、前記増粘剤（Ｃ）が、アクリル樹脂粒子（ｃ１）及び酸化マグネシウム（ｃ２）を含有するものである。 The thermosetting resin composition of the present invention is a thermosetting resin composition containing a thermosetting resin (A), a shrinkage reducing agent (B), a thickener (C), a thermally conductive filler (D), and a reinforcing material (E), in which the thermosetting resin (A) contains an unsaturated polyester resin (a1) and a vinyl ester resin (a2), and the thickener (C) contains acrylic resin particles (c1) and magnesium oxide (c2).
前記熱硬化性樹脂（Ａ）は、不飽和ポリエステル樹脂（ａ１）及びビニルエステル樹脂（ａ２）を含有するものであるが、流動性及び射出成形性がより向上することから、不飽和ポリエステル樹脂（ａ１）及びビニルエステル樹脂（ａ２）の質量比（ａ１／ａ２）は、９０／１０～３０／７０が好ましく、７０／３０～５０/５０がより好ましい。 The thermosetting resin (A) contains an unsaturated polyester resin (a1) and a vinyl ester resin (a2). In order to improve flowability and injection moldability, the mass ratio (a1/a2) of the unsaturated polyester resin (a1) and the vinyl ester resin (a2) is preferably 90/10 to 30/70, and more preferably 70/30 to 50/50.
前記熱硬化性樹脂（Ａ）には、不飽和ポリエステル樹脂（ａ１）、ビニルエステル樹脂（ａ２）以外の熱硬化性樹脂を含有することもできる。 The thermosetting resin (A) may contain a thermosetting resin other than the unsaturated polyester resin (a1) and the vinyl ester resin (a2).
本発明の熱硬化性樹脂組成物は、熱硬化性樹脂（Ａ）及び低収縮化剤（Ｂ）を必須成分とする樹脂成分を含有するものであるが、成形収縮率とその他の物性のバランスから、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の質量比（Ａ／Ｂ）は、９５／５～５０／５０が好ましく、９０／１０～７０/３０がより好ましい。 The thermosetting resin composition of the present invention contains resin components that essentially include a thermosetting resin (A) and a low-shrinkage agent (B). In view of the balance between the molding shrinkage rate and other physical properties, the mass ratio (A/B) of the thermosetting resin (A) and the low-shrinkage agent (B) is preferably 95/5 to 50/50, and more preferably 90/10 to 70/30.
前記低収縮化剤（Ｂ）は、熱硬化性樹脂組成物の硬化収縮を抑制するために配合するものであるが、例えば、ポリメチルメタクリレート、ポリスチレン、飽和ポリエステル、スチレン－ブタジエン系ゴム、ポリ酢酸ビニル等が挙げられる。これらの低収縮化剤は、１種で用いることも２種以上併用することもできる。 The shrinkage reducing agent (B) is added to suppress the cure shrinkage of the thermosetting resin composition, and examples of such agents include polymethyl methacrylate, polystyrene, saturated polyester, styrene-butadiene rubber, polyvinyl acetate, etc. These shrinkage reducing agents can be used alone or in combination of two or more.
前記増粘剤（Ｃ）は、アクリル樹脂粒子（ｃ１）及び酸化マグネシウム（ｃ２）を含有するものであるが、これらを併用することにより、後述するＢＭＣの流動性が良くなり、射出成形性（計量性）、射出成形性（充填性）の確保ができる。 The thickener (C) contains acrylic resin particles (c1) and magnesium oxide (c2). By using these in combination, the fluidity of the BMC (described below) is improved, and injection moldability (measurement ability) and injection moldability (filling ability) can be ensured.
前記アクリル樹脂粒子（ｃ１）は特に限定されないが、ＢＭＣの流動性が良くなり、射出成形性（計量性）、射出成形性（充填性）をより向上することから、平均粒子径が０．１～８μｍが好ましく、０．１～３μｍがより好ましい。なお、本発明において、アクリル樹脂粒子の平均粒子径は動的光散乱法で測定したものである。 The acrylic resin particles (c1) are not particularly limited, but the average particle size is preferably 0.1 to 8 μm, and more preferably 0.1 to 3 μm, because this improves the fluidity of the BMC and further improves the injection moldability (measurement ability) and injection moldability (filling ability). In the present invention, the average particle size of the acrylic resin particles is measured by dynamic light scattering.
前記アクリル樹脂粒子（ｃ１）は、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、１～２０質量部が好ましく、１～１０質量部がより好ましい。 The amount of the acrylic resin particles (c1) is preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the shrinkage reducing agent (B) combined.
前記酸化マグネシウム（ｃ２）は、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、０．０５～５質量部が好ましく、０．１～２質量部がより好ましい。 The amount of the magnesium oxide (c2) is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the shrinkage reducing agent (B) combined.
前記熱伝導性フィラー（Ｄ）としては、例えば、銀、銅、アルミニウム、鉄、ステンレス等の金属系フィラー；アルミナ、マグネシア、ベリリア、シリカ、窒化ホウ素、窒化アルミニウム、炭化ケイ素、炭化ホウ素、炭化チタン等の無機系フィラー；ダイヤモンド、黒鉛、グラファイト、炭素繊維等の炭素系フィラーなどが挙げられる。これらの中でも、熱伝導性向上と軽量化の観点から、炭素系フィラーが好ましく、黒鉛がより好ましい。これらの熱伝導性フィラーは、単独で用いることも、２種以上を併用することもできる。 Examples of the thermally conductive filler (D) include metal-based fillers such as silver, copper, aluminum, iron, and stainless steel; inorganic fillers such as alumina, magnesia, beryllia, silica, boron nitride, aluminum nitride, silicon carbide, boron carbide, and titanium carbide; and carbon-based fillers such as diamond, graphite, and carbon fiber. Among these, carbon-based fillers are preferred, and graphite is more preferred, from the viewpoints of improving thermal conductivity and reducing weight. These thermally conductive fillers can be used alone or in combination of two or more types.
前記熱伝導性フィラー（Ｄ）は、本発明の熱硬化性樹脂組成物の流動性及び成形品の熱伝導性向上の観点から、粒子状のものが好ましく、その平均粒径は、１０～５００μｍが好ましく、３０～４００μｍがより好ましい。 From the viewpoint of improving the flowability of the thermosetting resin composition of the present invention and the thermal conductivity of the molded product, the thermally conductive filler (D) is preferably particulate, and its average particle size is preferably 10 to 500 μm, and more preferably 30 to 400 μm.
前記熱伝導性フィラー（Ｄ）は、流動性及び射出成形性と熱伝導性のバランスがより向上することから、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、１００～５００質量部が好ましく、１５０～３５０質量部がより好ましい。 The thermally conductive filler (D) is preferably present in an amount of 100 to 500 parts by mass, more preferably 150 to 350 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the low shrinkage agent (B) in total, because this improves the balance between fluidity, injection moldability, and thermal conductivity.
前記補強材（Ｅ）としては、例えば、ガラス繊維、ビニロン繊維、フェノール繊維、炭素繊維、ポリエステル繊維等の繊維状の材料が挙げられる。これらの中でも、入手容易性、ＢＭＣ低流動性、及びＢＭＣ成形品強度物性向上の観点からガラス繊維が好ましい。このガラス繊維は、ガラスチョップドストランド、ミルドガラス等のいずれのものも用いることができる。ＢＭＣの流動性が良くなり、射出成形性（計量性）、射出成形性（充填性）またＢＭＣ成形品の物性をより向上することから、繊維長１．５～１２ｍｍのものが用いられるが好ましく、１．５～９ｍｍのものがより好ましい。 Examples of the reinforcing material (E) include fibrous materials such as glass fiber, vinylon fiber, phenol fiber, carbon fiber, and polyester fiber. Among these, glass fiber is preferred from the viewpoints of availability, low BMC fluidity, and improved strength properties of BMC molded products. Any glass fiber such as glass chopped strands or milled glass can be used. Since this improves the fluidity of the BMC and further improves injection moldability (measurement ability), injection moldability (filling ability), and the physical properties of the BMC molded products, a fiber length of 1.5 to 12 mm is preferably used, and 1.5 to 9 mm is more preferred.
前記補強材の配合量は、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、１０～８０質量部が好ましく、１５～５０質量部がより好ましい。 The amount of the reinforcing material is preferably 10 to 80 parts by mass, and more preferably 15 to 50 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the shrinkage reducing agent (B) combined.
本発明の熱硬化性樹脂組成物には、上記の成分（Ａ）～（Ｅ）以外に、本発明の効果を損なわない範囲で、熱可塑性樹脂、重合禁止剤、硬化剤、硬化促進剤、分散剤、離型剤、、顔料、着色剤、消泡剤等を配合してもよい。 In addition to the above components (A) to (E), the thermosetting resin composition of the present invention may contain thermoplastic resins, polymerization inhibitors, curing agents, curing accelerators, dispersants, release agents, pigments, colorants, defoamers, etc., within the scope of the invention.
前記重合禁止剤としては、例えば、トルハイドロキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、１，４－ナフトキノン、パラベンゾキノン、ｐ－ｔ－ブチルカテコール、２，６－ｔ－ブチル－４－メチルフェノール等が挙げられる。本発明の熱硬化性樹脂組成物に重合禁止剤を配合する際の配合量は、本発明の熱硬化性樹脂組成物中１０～１５００ｐｐｍの範囲が好ましい。 Examples of the polymerization inhibitor include toluhydroquinone, hydroquinone, hydroquinone monomethyl ether, 1,4-naphthoquinone, parabenzoquinone, p-t-butylcatechol, 2,6-t-butyl-4-methylphenol, etc. When a polymerization inhibitor is blended into the thermosetting resin composition of the present invention, the blending amount is preferably in the range of 10 to 1500 ppm in the thermosetting resin composition of the present invention.
前記硬化剤としては、有機過酸化物が好ましく、例えば、ジアシルパーオキサイド系有機過酸化物、パーオキシエステル系有機過酸化物、ハイドロパーオキサイド系有機過酸化物、ジアルキルパーオキサイド系有機過酸化物、ケトンパーオキサイド系有機過酸化物、パーオキシケタール系有機過酸化物、アルキルパーエステル系有機過酸化物、パーカーボネート系有機過酸化物等が挙げられる。なお、これらの硬化剤は、単独で用いることも、２種以上併用することもできる。 The curing agent is preferably an organic peroxide, such as diacyl peroxide-based organic peroxides, peroxyester-based organic peroxides, hydroperoxide-based organic peroxides, dialkyl peroxide-based organic peroxides, ketone peroxide-based organic peroxides, peroxyketal-based organic peroxides, alkyl perester-based organic peroxides, and percarbonate-based organic peroxides. These curing agents can be used alone or in combination of two or more.
前記硬化剤の配合量は、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、０．５～５質量部が好ましく、１～３質量部がより好ましい。 The amount of the curing agent is preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the low shrinkage agent (B) combined.
前記離型剤は、本発明の熱硬化性樹脂組成物を、金型を用いて成形した後、金型から得られた成形品の取り出しを容易にするためのものである。前記離型剤としては、例えば、不飽和脂肪酸アミド系離型剤、ポリエチレンワックス系離型剤、金属石鹸系離型剤、シリコーン系離型剤、フッ素系離型剤等が挙げられる。また、前記金属石鹸系離型剤としては、例えば、ラウリル酸亜鉛、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸マグネシウム、ミリスチン酸亜鉛、モンタン酸カルシウム、モンタン酸亜鉛、モンタン酸アルミニウム、ベヘン酸カルシウム、ベヘン酸マグネシウム、ベヘン酸亜鉛等が挙げられる。なお、これらの離型剤は、単独で用いることも、２種以上併用することもできる。 The release agent is intended to facilitate removal of the molded product obtained by molding the thermosetting resin composition of the present invention using a mold. Examples of the release agent include unsaturated fatty acid amide-based release agents, polyethylene wax-based release agents, metal soap-based release agents, silicone-based release agents, and fluorine-based release agents. Examples of the metal soap-based release agents include zinc laurate, calcium laurate, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc myristate, calcium montanate, zinc montanate, aluminum montanate, calcium behenate, magnesium behenate, and zinc behenate. These release agents can be used alone or in combination of two or more.
前記離型剤の配合量は、前記熱硬化性樹脂（Ａ）及び前記低収縮化剤（Ｂ）の合計１００質量部に対して、１～１０質量部が好ましく、３～８質量部がより好ましい。 The amount of the release agent is preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, per 100 parts by mass of the thermosetting resin (A) and the shrinkage reducing agent (B) combined.
本発明の熱硬化性樹脂組成物は、上記の各成分をニーダー等の混練機を用いて混練することにより製造することができる。また、得られる樹脂組成物がバルク状になるように、配合組成を調整することで、バルクモールディングコンパウンド（ＢＭＣ）とすることができる。 The thermosetting resin composition of the present invention can be produced by kneading the above-mentioned components using a kneader or other kneading machine. In addition, by adjusting the compounding composition so that the resulting resin composition is in a bulk form, it can be made into a bulk molding compound (BMC).
本発明の熱硬化性樹脂組成物をＢＭＣとすることで、圧縮成形、トランスファー成形、射出成形等の成形方法により、容易に成形品にすることができる。 By using the thermosetting resin composition of the present invention as a BMC, it can be easily made into a molded product by molding methods such as compression molding, transfer molding, and injection molding.
以下に実施例により本発明をより具体的に説明する。なお、樹脂の酸価は、ＪＩＳ Ｋ６９０１に準拠し測定した。 The present invention will be explained in more detail below with reference to the following examples. The acid value of the resin was measured in accordance with JIS K6901.
（製造例１：不飽和ポリエステル樹脂（ａ１）の合成）
窒素ガス導入管、温度計、還流コンデンサ、攪拌機を備えた２Ｌのガラス製フラスコに、ネオペンチルグリコール２０６質量部、プロピレングリコール５３質量部、水素化ビスフェノールＡ ２６６質量部、イソフタル酸２８８質量部を仕込み窒素気流下、加熱を開始した。内温２１５℃、常法にて脱水縮合反応を行い、固形分酸価が６（ｍｇＫＯＨ／ｇ）になったところで、１９０℃まで冷却した。次いで、マレイン酸１９８質量部を添加し脱水縮合反応を継続し、固形分酸価２８（ｍｇＫＯＨ／ｇ）になったところで、トルハイドロキノン０．４質量部を添加した。不飽和ポリエステル濃度が６５質量％となるようスチレンモノマーに溶解させ、不飽和ポリエステル樹脂（ａ１）を得た。
(Production Example 1: Synthesis of Unsaturated Polyester Resin (a1))
A 2L glass flask equipped with a nitrogen gas inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 206 parts by mass of neopentyl glycol, 53 parts by mass of propylene glycol, 266 parts by mass of hydrogenated bisphenol A, and 288 parts by mass of isophthalic acid, and heating was started under a nitrogen stream. At an internal temperature of 215°C, a dehydration condensation reaction was carried out in a conventional manner, and when the solid acid value became 6 (mgKOH/g), the reaction was cooled to 190°C. Next, 198 parts by mass of maleic acid was added to continue the dehydration condensation reaction, and when the solid acid value became 28 (mgKOH/g), 0.4 parts by mass of toluhydroquinone was added. The unsaturated polyester was dissolved in styrene monomer so that the concentration of the unsaturated polyester was 65% by mass, and an unsaturated polyester resin (a1) was obtained.
（製造例２：ビニルエステル樹脂（ａ２）の合成）
窒素導入管、温度計、撹拌機を設けた２Ｌフラスコに、エポキシ樹脂（ＤＩＣ株式会社製「エピクロン８６０－Ｃ」、ビスフェノールＡ型エポキシ樹脂、エポキシ当量２４０）２４６質量部、エポキシ樹脂（ＤＩＣ株式会社製「エピクロン１０５０」、ビスフェノールＡ型エポキシ樹脂、エポキシ当量４７０）７３０質量部、メタクリル酸２１５質量部、及びジブチルヒドロキシトルエン０．４５質量部添加し、窒素と空気とを１対１で混合したガス流通下で、１００℃まで昇温した。ここに２－メチルイミダゾール０．９６質量部を添加し、１１０℃まで昇温し、反応を行った。固形分酸価が６（ｍｇＫＯＨ／ｇ）以下になったところで、トルハイドロキノン０．４６質量部を添加し、ビニルエステル濃度が７０質量％となるようスチレンモノマーに溶解させ、ビニルエステル樹脂（ａ２）を得た。
(Production Example 2: Synthesis of vinyl ester resin (a2))
In a 2L flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer, 246 parts by mass of epoxy resin (DIC Corporation's "Epicron 860-C", bisphenol A type epoxy resin, epoxy equivalent 240), 730 parts by mass of epoxy resin (DIC Corporation's "Epicron 1050", bisphenol A type epoxy resin, epoxy equivalent 470), 215 parts by mass of methacrylic acid, and 0.45 parts by mass of dibutylhydroxytoluene were added, and the temperature was raised to 100 ° C. under a gas flow in which nitrogen and air were mixed in a ratio of 1:1. 0.96 parts by mass of 2-methylimidazole was added thereto, and the temperature was raised to 110 ° C. to carry out the reaction. When the solid acid value became 6 (mgKOH / g) or less, 0.46 parts by mass of toluhydroquinone was added, and the vinyl ester concentration was dissolved in styrene monomer to 70 mass%, to obtain a vinyl ester resin (a2).
（製造例３：低収縮化剤（Ｂ）の製造）
窒素導入管、温度計、撹拌機を設けた２Ｌフラスコに、スチレンモノマー９００質量部、ポリスチレン（ＤＩＣ株式会社製「ディックスチレンＣＲ－３５００」）６００質量部、トルハイドロキノン０．２５質量部を添加し、窒素ガスを流通下で、５０℃まで昇温した。熱可塑性樹脂ポリスチレンを完全に溶融するまで撹拌、その後４０℃以下に降温し、ポリスチレン濃度４０質量％の低収縮化剤（Ｂ）を得た。
(Production Example 3: Production of Low Profile Agent (B))
A 2 L flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer was charged with 900 parts by mass of styrene monomer, 600 parts by mass of polystyrene (DIC Corporation's "DIC Styrene CR-3500"), and 0.25 parts by mass of toluhydroquinone, and the temperature was raised to 50° C. under a nitrogen gas flow. The thermoplastic resin polystyrene was stirred until completely melted, and then the temperature was lowered to 40° C. or lower, to obtain a low shrinkage agent (B) with a polystyrene concentration of 40% by mass.
（実施例１：熱硬化性樹脂組成物（１）の調製）
製造例１で得られた不飽和ポリエステル樹脂（ａ１）５０質量部、製造例２で得られたビニルエステル樹脂（ａ２）３０質量部、製造例３で得られたポリスチレン低収縮化剤（Ｂ）２０質量部、アクリル樹脂粒子（ｃ１）（アイカ工業株式会社製「ゼフィアックＦ３０３」；平均粒径２μｍ）５質量部、酸化マグネシウム（ｃ２）（協和化学工業株式会社製「キョーワマグ４０」）０．５質量部、硬化剤（１）（日油株式会社製「パーブチルＯ」；パーオキシエステル系有機過酸化物）０．６質量部、硬化剤（２）（日油株式会社製「パーブチルＺ」；パーオキシエステル系有機過酸化物）１．２質量部、離型剤（１）（堺化学工業株式会社製「ステアリン酸亜鉛」）４質量部、離型剤（２）（日油株式会社製「カルシウムステアレート」）１．２質量部、黒鉛粉末（Ｄ１）（伊藤黒鉛工業株式会社製「ＡＧＢ－３２」；平均粒径２００～３００μｍ）１００質量部、及び黒鉛粉末（Ｄ２）（伊藤黒鉛工業株式会社製「ＡＧＢ－１００」；平均粒径１１０μｍ）１６０質量部を、プラネタリーミキサーを用いて９分間混練した後、補強材（Ｅ）（ガラス繊維／チョップドストランド；重慶国際複合材料有限公司製「ＥＣＳ４０４－６」；繊維長６ｍｍ）３３質量部を加えて、さらに６分間混練することで、バルク状物を得た。得られたバルク状物をアルミ蒸着フィルムで梱包し、４０℃恒温槽中に１２時間放置し、ＢＭＣとして、熱硬化性樹脂組成物（１）を得た。
(Example 1: Preparation of thermosetting resin composition (1))
50 parts by mass of unsaturated polyester resin (a1) obtained in Production Example 1, 30 parts by mass of vinyl ester resin (a2) obtained in Production Example 2, 20 parts by mass of polystyrene shrinkage reducing agent (B) obtained in Production Example 3, 5 parts by mass of acrylic resin particles (c1) ("Zefiac F303" manufactured by AICA Corporation; average particle size 2 μm), 0.5 parts by mass of magnesium oxide (c2) ("Kyowamag 40" manufactured by Kyowa Chemical Industry Co., Ltd.), 0.6 parts by mass of curing agent (1) ("Perbutyl O" manufactured by NOF Corporation; peroxyester-based organic peroxide), 1.2 parts by mass of curing agent (2) ("Perbutyl Z" manufactured by NOF Corporation; peroxyester-based organic peroxide), and a release agent (1) ("zinc stearate" manufactured by Sakai Chemical Industry Co., Ltd.) 4 parts by mass, release agent (2) ("calcium stearate" manufactured by NOF Corporation) 1.2 parts by mass, graphite powder (D1) ("AGB-32" manufactured by Ito Graphite Industry Co., Ltd.; average particle size 200 to 300 μm) 100 parts by mass, and graphite powder (D2) ("AGB-100" manufactured by Ito Graphite Industry Co., Ltd.; average particle size 110 μm) 160 parts by mass were kneaded for 9 minutes using a planetary mixer, and then 33 parts by mass of reinforcing material (E) (glass fiber / chopped strand; "ECS404-6" manufactured by Chongqing International Composite Materials Co., Ltd.; fiber length 6 mm) were added and kneaded for another 6 minutes to obtain a bulk-like material. The obtained bulk-like material was packed in an aluminum deposition film and left in a 40 ° C. constant temperature bath for 12 hours, and a thermosetting resin composition (1) was obtained as BMC.
（実施例２～５）
表１に示した配合組成に変更した以外は実施例１と同様にして、ＢＭＣとして、熱硬化性樹脂組成物（２）～（５）を得た。
(Examples 2 to 5)
Thermosetting resin compositions (2) to (5) were obtained as BMC in the same manner as in Example 1, except that the blending composition was changed to that shown in Table 1.
（比較例１～２）
表１に示した配合組成に変更した以外は実施例１と同様にして、ＢＭＣとして、熱硬化性樹脂組成物（Ｒ１）～（Ｒ２）を得た。
(Comparative Examples 1 to 2)
Thermosetting resin compositions (R1) to (R2) were obtained as BMC in the same manner as in Example 1, except that the blending composition was changed to that shown in Table 1.
上記の実施例１～５及び比較例１～２で得られた熱硬化性樹脂組成物（１）～（５）及び（Ｒ１）～（Ｒ２）を用いて、それぞれ下記の評価を行った。 The following evaluations were carried out using the thermosetting resin compositions (1) to (5) and (R1) to (R2) obtained in the above Examples 1 to 5 and Comparative Examples 1 to 2.
［流動性の評価］
上記で得られた熱硬化性樹脂組成物の初期粘度を測定した。粘度測定は、キャピラリー粘度計（細管型レオメータ）により以下の条件で行った。樹脂組成物投入量（サンプル量）：７５ｇ、測定温度条件：５０℃、押出速度：５０ｍｍ／分、ノズル径：６ｍｍ、ノズル長さ：１０ｍｍ
なお、高粘度のため測定できないものは、測定不可とした。
[Evaluation of Liquidity]
The initial viscosity of the thermosetting resin composition obtained above was measured. The viscosity measurement was performed using a capillary viscometer (thin tube type rheometer) under the following conditions: resin composition input amount (sample amount): 75 g, measurement temperature conditions: 50° C., extrusion speed: 50 mm/min, nozzle diameter: 6 mm, nozzle length: 10 mm
In addition, those that could not be measured due to high viscosity were marked as not measurable.
［射出成形性（計量性）の評価］
上記で得られた熱硬化性樹脂組成物の所定量（７５ｃｍ３）について、所定時間（３０秒間）で、スクリューにより材料庫（押込みホッパー）からシリンダーへの移動が可能な量を測定し、下記の基準により射出成形性（計量性）を評価した。
測定条件：押込め圧力５ＭＰａ、スクリュー回転数２０ｒｐｍ、押込みホッパーとシリンダー温度３５℃
○：３０秒未満で、７５ｃｍ３
△：３０秒間で、４０～７５ｃｍ３
×：３０秒間で、４０ｃｍ３未満
[Evaluation of injection moldability (measureability)]
For a given amount (75 cm3 ) of the thermosetting resin composition obtained above, the amount that could be moved by the screw from the material storage (push-in hopper) to the cylinder in a given time (30 seconds) was measured, and the injection moldability (measurability) was evaluated according to the following criteria.
Measurement conditions: compression pressure 5 MPa, screw rotation speed 20 rpm, compression hopper and cylinder temperature 35°C
○: Less than 30 seconds, 75 cm3
△: 40 to 75 cm3 in 30 seconds
×: Less than 40 cm3 in 30 seconds
［射出成形性（充填性）の評価］
上記計量評価結果が○となった熱硬化性樹脂組成物について、流動性評価用金型を用い、射出成形を行い、成形品の外観を目視観察し、下記の基準により射出成形性（充填性）を評価した。
成形条件：金型温度１６０℃、型締力７５０ｋＮ、射出速度７０ｍｍ／秒、硬化時間５５秒
○：ショートなし、成形品表面にボイドなし
△：ショートなし、成形品表面にボイドあり
×：ショートあり、成形品表面にボイドあり
[Evaluation of injection moldability (filling ability)]
For the thermosetting resin compositions for which the above-mentioned weighing evaluation result was ◯, injection molding was performed using a mold for fluidity evaluation, and the appearance of the molded product was visually observed, and the injection moldability (filling property) was evaluated according to the following criteria.
Molding conditions: mold temperature 160°C, mold clamping force 750 kN, injection speed 70 mm/sec, curing time 55 sec. ◯: no shorts, no voids on the molded product surface △: no shorts, voids on the molded product surface ×: shorts, voids on the molded product surface
［圧縮成形性の評価］
上記で得られた熱硬化性樹脂組成物について、圧縮成形を行い、下記の基準により圧縮成形性を評価した。
成形条件：成形温度１４５℃、圧力１０ＭＰａ、加圧時間３００秒、金型２２０ｍｍ×２２０ｍｍ
○：厚み３ｍｍ、４ｍｍ、１０ｍｍの成形品全てでショートなし
△：厚み３ｍｍの成形品でショートあり、４ｍｍ及び１０ｍｍの成形品でショートなし
×：厚み３ｍｍ及び４ｍｍの成形品でショートあり、１０ｍｍの成形品でショートなし
[Evaluation of compression moldability]
The thermosetting resin composition obtained above was subjected to compression molding, and the compression moldability was evaluated according to the following criteria.
Molding conditions: Molding temperature 145°C, pressure 10 MPa, pressure time 300 seconds, mold 220 mm x 220 mm
○: No short circuit in any of the molded products with thicknesses of 3 mm, 4 mm, and 10 mm. △: Short circuit occurred in the molded product with a thickness of 3 mm, and no short circuit occurred in the molded products with a thickness of 4 mm and 10 mm. ×: Short circuit occurred in the molded products with thicknesses of 3 mm and 4 mm, and no short circuit occurred in the molded product with a thickness of 10 mm.
［熱伝導性の評価］
成形温度１４５℃、成形圧力１０ＭＰａ、成形保圧時間３００秒の条件で圧縮成形して、２２０ｍｍ×２２０ｍｍ×厚さ１０ｍｍの平板を作製し、熱線法（ＪＩＳ Ｒ２６１６）に準拠し熱伝導率を測定し、熱伝導性を評価した。
[Evaluation of thermal conductivity]
The mixture was compression molded under conditions of a molding temperature of 145°C, a molding pressure of 10 MPa, and a molding pressure holding time of 300 seconds to prepare a flat plate of 220 mm x 220 mm x 10 mm thickness. The thermal conductivity was measured according to the hot wire method (JIS R2616) to evaluate the thermal conductivity.
上記で得られた熱硬化性樹脂組成物の組成及び評価結果を表１及び２に示す。 The composition and evaluation results of the thermosetting resin composition obtained above are shown in Tables 1 and 2.
表中の「黒鉛粉末（Ｄ３）」は、伊藤黒鉛工業株式会社製「ＡＧＢ－６０４」（平均粒径５５μｍ）である。 The "graphite powder (D3)" in the table is "AGB-604" (average particle size 55 μm) manufactured by Ito Graphite Industries Co., Ltd.
実施例１～５の本発明の熱硬化性樹脂組成物は、流動性、射出成形性、圧縮成形性に優れ、熱伝導性に優れる成形品を得られることが確認された。 It was confirmed that the thermosetting resin compositions of the present invention in Examples 1 to 5 have excellent flowability, injection moldability, and compression moldability, and can produce molded products with excellent thermal conductivity.
一方、比較例１は、不飽和ポリエステルを含有しない例であるが、流動性、射出成形性が不十分であることが確認された。 On the other hand, Comparative Example 1 is an example that does not contain unsaturated polyester, but it was confirmed that the flowability and injection moldability were insufficient.
比較例２は、ビニルエステルを含有しない例であるが、流動性、射出成形性が不十分であることが確認された。 Comparative Example 2 is an example that does not contain vinyl ester, but it was confirmed that the flowability and injection moldability were insufficient.
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