WO2022149594A1 - 熱硬化性樹脂組成物の製造方法、熱硬化性樹脂組成物、及び電子部品装置 - Google Patents
熱硬化性樹脂組成物の製造方法、熱硬化性樹脂組成物、及び電子部品装置 Download PDFInfo
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- WO2022149594A1 WO2022149594A1 PCT/JP2022/000210 JP2022000210W WO2022149594A1 WO 2022149594 A1 WO2022149594 A1 WO 2022149594A1 JP 2022000210 W JP2022000210 W JP 2022000210W WO 2022149594 A1 WO2022149594 A1 WO 2022149594A1
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- thermosetting resin
- kneading
- resin composition
- temperature
- mass
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- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 1
- ZLVFYUORUHNMBO-UHFFFAOYSA-N 4-bromo-2,6-dimethylphenol Chemical compound CC1=CC(Br)=CC(C)=C1O ZLVFYUORUHNMBO-UHFFFAOYSA-N 0.000 description 1
- SSQQUEKFNSJLKX-UHFFFAOYSA-N 4-bromo-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1O SSQQUEKFNSJLKX-UHFFFAOYSA-N 0.000 description 1
- IWJGMJHAIUBWKT-UHFFFAOYSA-N 4-bromo-2-methylphenol Chemical compound CC1=CC(Br)=CC=C1O IWJGMJHAIUBWKT-UHFFFAOYSA-N 0.000 description 1
- WMUWDPLTTLJNPE-UHFFFAOYSA-N 4-bromo-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Br WMUWDPLTTLJNPE-UHFFFAOYSA-N 0.000 description 1
- GPOQODYGMUTOQL-UHFFFAOYSA-N 4-bromo-3-methylphenol Chemical compound CC1=CC(O)=CC=C1Br GPOQODYGMUTOQL-UHFFFAOYSA-N 0.000 description 1
- LVSPDZAGCBEQAV-UHFFFAOYSA-N 4-chloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=CC=C(Cl)C2=C1 LVSPDZAGCBEQAV-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ZOTKGMAKADCEDH-UHFFFAOYSA-N 5-triethoxysilylpentane-1,3-diamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)CCN ZOTKGMAKADCEDH-UHFFFAOYSA-N 0.000 description 1
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 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
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- RPVOKBZITVQZPD-UHFFFAOYSA-N phenol;hydroiodide Chemical compound I.OC1=CC=CC=C1 RPVOKBZITVQZPD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 125000005496 phosphonium group Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 1
- PSEQWFPWQRZBOO-UHFFFAOYSA-M tetrahexylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC PSEQWFPWQRZBOO-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZYMHKOVQDOFPHH-UHFFFAOYSA-N trimethoxy(oct-1-enyl)silane Chemical compound CCCCCCC=C[Si](OC)(OC)OC ZYMHKOVQDOFPHH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Definitions
- the present disclosure relates to a method for producing a thermosetting resin composition, a thermosetting resin composition, and an electronic component device.
- the mounting method of the surface mount type package is different from that of the conventional pin insertion type package.
- the pin insertion type package after the pin is inserted into the wiring board, soldering is performed from the back surface of the wiring board, so that the package is not directly exposed to high temperature.
- the surface mount type package is temporarily fixed to the surface of the wiring board and processed by a solder bath, a reflow device, or the like, so that it is directly exposed to the soldering temperature (reflow temperature).
- reflow temperature soldering temperature
- the IC package absorbs moisture
- the moisture absorbed during reflow evaporates, and the generated vapor pressure acts as a peeling stress, causing peeling between the insert such as an element or lead frame and the sealing material.
- thermosetting resin such as a biphenyl type epoxy resin or a sulfur atom-containing epoxy resin is preferably used (see, for example, Patent Documents 1 and 2).
- thermosetting resin having a high melting point or softening point such as a biphenyl type epoxy resin or a sulfur atom-containing epoxy resin
- the resin material is sufficiently stirred and mixed at a high temperature while applying shear stress.
- the resin material is thickened and sufficient mixing cannot be performed, which may lead to a decrease in curability.
- the resin is unevenly distributed due to insufficient kneading, the fluidity during molding may decrease.
- the kneading conditions and components must be sufficiently selected, and the degree of freedom in design is limited.
- the present disclosure discloses a method for producing a thermosetting resin composition capable of producing a thermosetting resin composition having excellent fluidity and curability, and a thermosetting resin composition obtained by the production method.
- the present invention relates to an object and an electronic component apparatus including an element sealed with the thermosetting resin composition.
- Means for solving the above problems include the following aspects.
- ⁇ 1> Primary kneading, in which the thermosetting resin is kneaded, and After the primary kneading, a curing accelerator is added and the secondary kneading is further kneaded.
- a method for producing a thermosetting resin composition which comprises.
- ⁇ 2> The production method according to ⁇ 1>, wherein the temperature of the primary kneading is higher than the melting point or the softening point of the thermosetting resin.
- ⁇ 3> The production method according to ⁇ 1> or ⁇ 2>, wherein the temperature of the primary kneading is higher than the onset temperature of the mixture after adding the curing accelerator, which is measured by differential scanning calorimetry.
- ⁇ 4> The production method according to any one of ⁇ 1> to ⁇ 3>, wherein the temperature of the secondary kneading is lower than the temperature of the primary kneading.
- ⁇ 5> In any one of ⁇ 1> to ⁇ 4>, the temperature of the secondary kneading is lower than the onset temperature of the mixture after the addition of the curing accelerator, which is measured by differential scanning calorimetry. The manufacturing method described.
- thermosetting resin contains at least one selected from the group consisting of a biphenyl type epoxy resin and a sulfur atom-containing epoxy resin.
- thermosetting resin composition obtained by the production method according to any one of ⁇ 1> to ⁇ 9>.
- An electronic component device comprising an element sealed with a thermosetting resin composition obtained by the production method according to any one of ⁇ 1> to ⁇ 9>.
- thermosetting resin composition capable of producing a thermosetting resin composition having excellent fluidity and curability, a thermosetting resin composition obtained by the production method, and a thermosetting resin composition.
- An electronic component device including an element sealed with the thermosetting resin composition is provided.
- the term "process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
- the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. ..
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- each component may contain a plurality of applicable substances.
- the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
- a plurality of types of particles corresponding to each component may be contained.
- the particle size of each component means a value for a mixture of the plurality of particles present in the composition, unless otherwise specified.
- solid, solid, liquid, and liquid refer to properties at 25 ° C.
- thermosetting resin composition of the present disclosure (hereinafter, also referred to as the production method of the present disclosure) is a primary kneading in which a thermosetting resin is kneaded, and a further kneading by adding a curing accelerator after the primary kneading. Includes secondary kneading and. According to the manufacturing method of the present disclosure, since the curing accelerator is added after the thermosetting resin is kneaded, it is possible to suitably mix and disperse the thermosetting resin while suppressing the thickening.
- thermosetting resin even when a resin having a high melting point or softening point is used as the thermosetting resin, it can be satisfactorily stirred and mixed while suppressing thickening even if it is kneaded at a high temperature. Further, in the conventional method, when a high shear stress is applied to the thermosetting resin, there is a problem that the temperature of the thermosetting resin rises due to the heat generated by shearing and the thickening further progresses. According to the above, even if a high shear stress is applied, an increase in viscosity can be suppressed, and the resin material can be sufficiently mixed. It is considered that such a method enhances the dispersibility of the resin and obtains good curability. Further, it is considered that the uneven distribution of the resin is unlikely to occur and the fluidity at the time of molding can be improved.
- thermosetting resin is mixed and kneaded.
- an inorganic filler, a coupling agent, and other additives may be further mixed, if necessary.
- a resin material and an inorganic filler are mixed and kneaded, shear heat generation occurs, but by kneading all or part of the curing accelerator by secondary kneading, the effect of thickening due to shear heat generation should be reduced. And there is a tendency that kneading can be performed well.
- a part of the curing accelerator may be mixed as long as the influence of thickening on the kneadability does not pose a practical problem.
- the kneading of is referred to as secondary kneading.
- the mixing amount is preferably 30% by mass or less, preferably 20% by mass or less, of the total curing accelerator to be finally added. More preferably, it is more preferably 10% by mass or less.
- the thermosetting resin and, if necessary, the inorganic filler, the coupling agent, and other additives are kneaded without adding the curing accelerator.
- the kneading method in the primary kneading is not particularly limited.
- a method of melt-kneading with a kneader two-screw kneader, three-screw kneader, etc.
- a roll three-screw roll, etc.
- an extruder or the like that has been heated to a desired temperature in advance can be mentioned.
- the temperature of the primary kneading is preferably adjusted according to the melting temperature of the resin material used.
- the temperature of the primary kneading may be higher than the melting point or softening point of the thermosetting resin (the thermosetting resin having the highest melting point or softening point when a plurality of types of thermosetting resins are used in combination).
- the temperature of the primary kneading is 1 ° C. to 90 ° C. higher than the melting point or softening point of the thermosetting resin (the thermosetting resin having the highest melting point or softening point when a plurality of types of thermosetting resins are used in combination).
- a high temperature is preferable, a temperature 1 ° C. to 70 ° C.
- thermosetting resin can be melted and the fluidity can be maintained, so that stirring and mixing can be performed satisfactorily.
- the temperature of the primary kneading may be higher than the onset temperature measured by differential scanning calorimetry (DSC) of the mixture after the curing accelerator is added in the secondary kneading described later.
- DSC differential scanning calorimetry
- the onset temperature means a temperature corresponding to the intersection of the tangent line at the point where the differential value of the exothermic peak of the DSC chart becomes maximum and the baseline of the exothermic peak of the DSC chart.
- the temperature of the primary kneading is not related to the onset temperature of the mixture after the curing accelerator is added.
- the temperature can be relatively high.
- the thermosetting resin can be sufficiently melted and the primary kneading can be performed, and the dispersibility of the resin can be improved.
- the production method of the present disclosure is particularly useful when the melting point or softening point of the thermosetting resin is higher than the onset temperature of the mixture after the addition of the curing accelerator.
- the temperature of the primary kneading may be 70 ° C. or higher, 80 ° C. or higher, 90 ° C. or higher, 100 ° C. or higher, 110 ° C. or higher. It may be at 120 ° C. or higher. From the viewpoint of more efficiently suppressing the increase in viscosity, the temperature of the primary kneading may be 200 ° C. or lower, 190 ° C. or lower, or 180 ° C. or lower. From this point of view, the temperature of the primary kneading may be 70 ° C. to 200 ° C., 80 ° C. to 200 ° C., 90 ° C. to 200 ° C., or 100 ° C. to 200 ° C. It may be 110 ° C. to 200 ° C., or 120 ° C. to 200 ° C.
- the shearing conditions in the primary kneading are not particularly limited. According to the manufacturing method of the present disclosure, thickening of the thermosetting resin can be suppressed, so that kneading can be suitably performed even if the shear stress and the shear rate are increased as compared with the conventional method. ..
- a curing accelerator is added and further secondary kneading is performed.
- the method of adding the curing accelerator is not particularly limited as long as the curing accelerator can be added afterwards.
- a method (side feed) of adding a curing accelerator to the mixture subjected to the primary kneading as described above from an inlet provided separately from the inlet of the components of the primary kneading can be mentioned.
- the temperature of the secondary kneading is not particularly limited, and may be lower than the temperature of the primary kneading from the viewpoint of suppressing thickening.
- the temperature of the secondary kneading is preferably lower than the onset temperature measured by differential scanning calorimetry (DSC) of the mixture after the curing accelerator is added in the secondary kneading, for example, 1 ° C to 100 ° C lower. It is preferably 2 ° C to 80 ° C lower or 3 ° C to 60 ° C lower.
- kneading is performed at a temperature higher than the onset temperature of the mixture after adding the curing accelerator in the primary kneading, and kneading is performed at a temperature lower than the onset temperature in the secondary kneading.
- the mode of performing the above is mentioned.
- the manufacturing method of the present disclosure may include other steps at any timing in addition to the primary kneading and the secondary kneading.
- the thermosetting resin and other optional components may be mixed at room temperature with a mixer or the like.
- any component other than the thermosetting resin and the curing accelerator may be added at the same time as or at a different time point from one or more components of the thermosetting resin and the curing accelerator and kneaded.
- the composition obtained through the primary kneading and the secondary kneading may be cooled and pulverized to obtain a solid thermosetting resin composition.
- FIG. 1 shows a schematic cross-sectional view of a kneading extruder that can be used in one embodiment.
- the kneading extruder 10 includes a first kneading section A, a second kneading section B arranged downstream in the extrusion direction of the first kneading section A, a main material input port 1 connected to the first kneading section A, and the above.
- a side feeder 2 connected to the second kneading portion B is provided.
- thermosetting resin is charged into the first kneading portion A from the main material charging port 1
- the curing accelerator is charged into the second kneading portion B from the side feeder 2.
- Primary kneading is performed in the first kneading section A, and the kneaded product is extruded and moved to the second kneading section B.
- the transferred kneaded product merges with the curing accelerator and is further kneaded. It is also possible to set the temperature of the primary kneading and the temperature of the secondary kneading, respectively.
- a cooling unit (not shown) may be provided between the first kneading portion A and the second kneading portion B, and the secondary kneading may be performed at a lower temperature than the primary kneading.
- the first kneading portion A may be set to a higher temperature and the second kneading portion B may be set to a lower temperature, and the second kneading portion B employs a mechanism for gradually cooling the contents in the extrusion direction. You may.
- the manufacturing method of the present disclosure is not limited to the aspect of the drawing.
- thermosetting resin composition each component used in the production method of the present disclosure, that is, each component contained in the thermosetting resin composition will be described.
- thermosetting resin The type of the thermosetting resin is not particularly limited, and examples thereof include epoxy resin, phenol resin, urea resin, melamine resin, urethane resin, silicone resin, and unsaturated polyester resin. In the present disclosure, those exhibiting both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups, are included in "thermosetting resins".
- the thermosetting resin may be a solid or a liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably a solid.
- the thermosetting resin may be used alone or in combination of two or more.
- the thermosetting resin preferably contains an epoxy resin.
- the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
- a novolak type epoxy resin (phenol novolak) which is an epoxidation of a novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst.
- Diphenylmethane type epoxy resin which is a diglycidyl ether such as bisphenol A and bisphenol F
- Biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether
- Stilben-type epoxy which is a diglycidyl ether of a stilben-based phenol compound.
- Sulfur atom-containing epoxy resin that is a diglycidyl ether such as bisphenol S
- Epoxide resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol
- a glycidyl ester-type epoxy resin that is a glycidyl ester of a valent carboxylic acid compound
- a glycidylamine-type epoxy resin in which an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid is replaced with a glycidyl group
- Dicyclopentadiene-type epoxy resin which is an epoxide of a cocondensation resin of a phenol compound
- vinylcyclohexene diepoxide which is an epoxide of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-
- An alicyclic epoxy resin such as Lu-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin which is a glycidyl ether of a paraxylylene-modified phenol resin; a glycidyl ether of a metaxylylene-modified phenol resin.
- Metaxylylene-modified epoxy resin Terpen-modified epoxy resin, which is a glycidyl ether of terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified glycidyl ether of cyclopentadiene-modified phenol resin.
- Epoxy resin Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; Naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; Halogenized phenol novolac type epoxy resin; Hydroquinone type epoxy resin Trimethylol propane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; An aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin is epoxidized. Aralkill type epoxy resin; etc. Further, epoxies of silicone resin, epoxies of acrylic resin and the like can also be mentioned as epoxy resins.
- the epoxy resin may be used alone or in combination of two or more.
- the biphenyl type epoxy resin has a low melt viscosity, so even if the inorganic filler is highly filled for the purpose of improving reflow resistance, the problem of wire sweep in the semiconductor package is unlikely to occur. For this reason, biphenyl-type epoxy resins have come to be preferably used as a sealing material for surface-mounted packages in recent years.
- the biphenyl type epoxy resin has a low melt viscosity near 180 ° C., it has a relatively high softening point. Therefore, kneading at a high temperature is desirable in order to sufficiently disperse the resin by kneading. According to the manufacturing method of the present disclosure, even when the thermosetting resin contains a biphenyl type epoxy resin, the thermosetting resin can be suitably kneaded while suppressing an increase in viscosity.
- the biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton.
- an epoxy resin represented by the following general formula (II) is preferable.
- the 3,3', 5,5'positions of R8 where the oxygen atom is substituted are the methyl groups at the 4 and 4'positions.
- the other R 8s are hydrogen atoms YX-4000 and YX-4000H (Mitsubishi Chemical Co., Ltd., trade name), and all R 8s are hydrogen atoms 4,4'-bis (2,3-epoxy).
- R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- thermosetting resin contains a sulfur atom-containing epoxy resin, the increase in viscosity is suppressed.
- the thermosetting resin can be suitably kneaded.
- the sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom.
- an epoxy resin represented by the following general formula (V) can be mentioned.
- the 3,3'position of R13 when the position where the oxygen atom is substituted is the 4th and 4'positions is the t-butyl group.
- YSLV-120TE Nitetsu Chemical & Materials Co., Ltd., trade name
- the 6 and 6'positions are methyl groups and the other R13 is a hydrogen atom, is available as a commercially available product.
- R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- the epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, reflow resistance and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.
- the epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
- the melting point or softening point of the epoxy resin is not particularly limited. From the viewpoint of blocking resistance, the melting point or softening point of the epoxy resin is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. From the viewpoint of suppressing thickening due to kneading, the melting point or softening point of the epoxy resin is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and even more preferably 130 ° C. or lower. From this point of view, the melting point or softening point of the epoxy resin is preferably 40 ° C. to 150 ° C., more preferably 50 ° C.
- epoxy resins having a melting point or softening point of 90 ° C. or higher, 100 ° C. or higher, 110 ° C. or higher, or 120 ° C. or higher are used for the purpose of satisfying the recent demands for high thermal conductivity and reflow resistance. Even when a high crystalline resin having a temperature of ° C. or higher, 100 ° C. or higher, 110 ° C. or higher, or 120 ° C. or higher is used, the production method of the present disclosure can be suitably used.
- the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring ball method) according to JIS K 7234: 1986.
- the content of the epoxy resin is 0.5 with respect to the total mass of the thermosetting resin composition from the viewpoints of strength, fluidity, heat resistance, moldability and the like. It is preferably from mass% to 50% by mass, more preferably from 2% by mass to 30% by mass, and even more preferably from 2% by mass to 20% by mass.
- the thermosetting resin composition may further contain a curing agent.
- the type of the curing agent is not particularly limited as long as it is a compound that causes a curing reaction with the thermosetting resin used in combination.
- the curing agent itself may be a thermosetting resin.
- examples of the curing agent used in combination with the epoxy resin include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, and the like.
- the curing agent one type may be used alone or two or more types may be used in combination.
- the curing agent is preferably a phenol curing agent.
- the curing agent may be a solid or a liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably a solid.
- the phenol curing agent is a compound having a phenolic hydroxyl group in the molecule (hereinafter also referred to as phenol resin).
- phenol resin include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenyl.
- At least one phenolic compound selected from the group consisting of phenol compounds such as phenol and aminophenol and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like.
- a novolak-type phenol resin obtained by condensing or co-condensing an aldehyde compound under an acidic catalyst; a phenol aralkyl resin and naphthol synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like.
- Aralkyl-type phenolic resin such as Aralkyl resin; paraxylylene and / or metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type synthesized by copolymerization of the above phenolic compound and dicyclopentadiene.
- Phenolic resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; the above phenolic compound and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde are acid catalysts.
- the phenolic resin may be used alone or in combination of two or more.
- the hydroxyl group equivalent of the phenol resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the hydroxyl group equivalent of the phenol resin is preferably 70 g / eq to 1000 g / eq, and is preferably 80 g / eq to 500 g / eq. Is more preferable.
- the hydroxyl group equivalent of the phenol resin is a value calculated based on the hydroxyl group value measured in accordance with JIS K0070: 1992.
- the phenol resin When the phenol resin is a solid, its softening point or melting point is not particularly limited.
- the softening point or melting point of the phenol resin is preferably 40 ° C to 180 ° C, and is thermosetting, for example, from the viewpoint of moldability and reflow resistance when the thermosetting resin composition is used as a sealing material. From the viewpoint of handleability during production of the resin composition, the temperature is more preferably 50 ° C to 130 ° C.
- the melting point or softening point of the phenol resin shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.
- the content of the phenol resin is preferably 0.5% by mass to 50% by mass, preferably 2% by mass, based on the total mass of the thermosetting resin composition. It is more preferably to 30% by mass, further preferably 2% by mass to 20% by mass.
- the equivalent ratio of the epoxy resin to the curing agent that is, the ratio of the number of functional groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of functional groups in the curing agent / the number of epoxy groups in the epoxy resin) is not particularly limited.
- the equivalent ratio of the epoxy resin to the curing agent should be set in the range of 0.5 to 2.0 in order to reduce the amount of each unreacted component. Is preferable, and it is more preferable to set it in the range of 0.6 to 1.3.
- the equivalent ratio of the epoxy resin to the curing agent (number of functional groups in the curing agent / number of epoxy groups in the epoxy resin) is 0.8 to. It is more preferable to set it in the range of 1.2.
- the number of functional groups of the curing agent represents, for example, the number of hydroxyl groups in the phenol curing agent when a phenol curing agent is used as the curing agent, and the number of active hydrogens in the amine curing agent when an amine curing agent is used as the curing agent. Represents.
- the type of the curing accelerator is not particularly limited, and is 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), etc.
- Cyclic amidin compounds such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidin compounds; said cyclic amidin compounds or derivatives thereof.
- Phenol novolak salts include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy.
- a quinone compound such as -5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having a ⁇ bond such as diazophenylmethane.
- cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, etc.
- Tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, Ammonium salt compounds such as tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; Secondary phosphine, triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl
- Phenol iodide phenol 2-iodide, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, Halogen such as 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc.
- the curing accelerator may be used alone or in combination of two or more.
- examples of the curing accelerator particularly suitable include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, and the like.
- the content of the curing accelerator is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (that is, the thermosetting resin (including the curing agent when the curing agent is a thermosetting resin)). It is preferably 1 part by mass to 15 parts by mass, and more preferably.
- the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to cure well in a short time.
- the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.
- the thermosetting resin composition may contain an inorganic filler.
- the material of the inorganic filler is not particularly limited. Specifically, as the material of the inorganic filler, molten silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, verilia, and zirconia , Zircon, Fosterite, Steatite, Spinel, Murite, Titania, Tark, Clay, Mica and other inorganic materials. An inorganic filler having a flame-retardant effect may be used.
- Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.
- silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
- the shape of the inorganic filler is not particularly limited, and a spherical shape is preferable from the viewpoint of filling property and mold wear resistance.
- the inorganic filler may be used alone or in combination of two or more.
- "using two or more kinds of inorganic fillers together" means, for example, when two or more kinds of inorganic fillers having the same component but different average particle diameters are used, two inorganic fillers having the same average particle diameter but different components are used. There are cases where more than one type is used and cases where two or more types of inorganic fillers having different average particle diameters and types are used.
- the content of the inorganic filler is not particularly limited. From the viewpoint of further improving the properties such as the coefficient of thermal expansion, the coefficient of thermal conductivity, and the elastic coefficient of the cured product, the content of the inorganic filler is preferably 30% by volume or more of the total amount of the heat-curable resin composition. It is more preferably 5% by volume or more, further preferably 50% by volume or more, particularly preferably 60% by volume or more, and extremely preferably 70% by volume or more. From the viewpoint of improving the fluidity and reducing the viscosity, the content of the inorganic filler is preferably 99% by volume or less, preferably 98% by volume or less, and 97 by volume of the entire thermosetting resin composition. More preferably, it is by volume or less.
- the content of the inorganic filler may be 70% by volume to 99% by volume of the entire thermosetting resin composition, and may be 80% by volume to 80% by volume. It may be 99% by volume, 83% by volume to 99% by volume, or 85% by volume to 99% by volume.
- the content of the inorganic filler in the cured product of the thermosetting resin composition can be measured as follows. First, the total mass of the cured product is measured, and the cured product is fired at 400 ° C. for 2 hours and then at 700 ° C. for 3 hours to evaporate the resin component, and the mass of the remaining inorganic filler is measured. The volume is calculated from each obtained mass and each specific gravity, and the ratio of the volume of the inorganic filler to the total volume of the cured product is obtained and used as the content of the inorganic filler.
- the flow of a mixture of each component during kneading and molding tends to be able to keep the sex low. Therefore, according to the manufacturing method of the present disclosure, even if the composition cannot increase the content of the inorganic filler due to the influence of the increase in viscosity according to the conventional method, for example, the concern about the occurrence of wire flow, the inorganic filler It is considered possible to increase the filling rate.
- the inorganic filler When the inorganic filler is in the form of particles, its average particle size is not particularly limited.
- the volume average particle size of the entire inorganic filler is preferably 80 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less. May be good.
- the volume average particle size of the entire inorganic filler is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more. When the volume average particle size of the inorganic filler is 0.1 ⁇ m or more, the increase in the viscosity of the thermosetting resin composition tends to be further suppressed.
- the volume average particle size of the inorganic filler When the volume average particle size of the inorganic filler is 80 ⁇ m or less, the filling property into a narrow gap tends to be further improved.
- the volume average particle size of the inorganic filler shall be measured as the particle size (D50) when the cumulative amount from the small diameter side is 50% in the volume-based particle size distribution measured by the laser scattering diffraction method particle size distribution measuring device. Can be done.
- thermosetting resin composition contains an inorganic filler
- a coupling agent may be contained in order to enhance the adhesiveness between the resin component and the inorganic filler.
- the coupling agent include known coupling agents such as silane compounds, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.
- silane compound examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(.
- titanium compounds include isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, and tetra (2,2).
- the amount of the coupling agent is preferably 0.05 part by mass to 20 parts by mass, and 0.1 part by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably to 15 parts by mass.
- the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the metal member tends to be further improved.
- the amount of the coupling agent is 20 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability tends to be improved.
- thermosetting resin composition may contain various additives such as an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent.
- the thermosetting resin composition may contain various additives generally used in the art, if necessary, in addition to the additives exemplified below.
- the thermosetting resin composition may contain an ion exchanger.
- the thermosetting resin composition when used as a molding material for sealing, it contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device provided with the element to be sealed.
- the ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth.
- the ion exchanger one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
- thermosetting resin composition contains an ion exchanger
- the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions.
- it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component.
- the thermosetting resin composition may contain a mold release agent from the viewpoint of obtaining good mold release property from the mold at the time of molding.
- the release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene.
- the release agent may be used alone or in combination of two or more.
- the amount thereof is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin component. ..
- the amount of the mold release agent is 0.01 part by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained.
- it is 10 parts by mass or less, better adhesiveness and curability tend to be obtained.
- the thermosetting resin composition may contain a flame retardant.
- the flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like.
- the flame retardant may be used alone or in combination of two or more.
- the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
- it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component.
- thermosetting resin composition may further contain a colorant.
- a colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red ocher.
- the content of the colorant can be appropriately selected according to the purpose and the like.
- the colorant one type may be used alone or two or more types may be used in combination.
- the thermosetting resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles.
- a stress relaxation agent such as silicone oil and silicone rubber particles.
- the stress relaxation agent include commonly used known stress relaxation agents (flexible agents).
- thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic.
- Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc.
- MFS methyl methacrylate-styrene-butadiene copolymer
- Examples include rubber particles having a structure.
- the stress relaxation agent one type may be used alone or two or more types may be used in combination.
- thermosetting resin composition of the present disclosure is obtained by the above-mentioned production method of the present disclosure.
- the thermosetting resin composition may be solid or liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably solid.
- the shape is not particularly limited, and examples thereof include powder, granules, and tablets.
- the thermosetting resin composition is in the form of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.
- the viscosity of the thermosetting resin composition is not particularly limited. It is preferable to adjust the viscosity to a desired value according to the molding method, the composition of the thermosetting resin composition, and the like. When the thermosetting resin composition is used as a sealing material, it is preferable to adjust the composition according to the susceptibility of wire flow during molding. For example, when the thermosetting resin composition is used as a sealing material, the viscosity of the thermosetting resin composition is preferably 200 Pa ⁇ s or less at 175 ° C., preferably 150 Pa / s, from the viewpoint of reducing wire flow.
- thermosetting resin composition is more preferable, 100 Pa ⁇ s or less is further preferable, 70 Pa ⁇ s or less is particularly preferable, and 50 Pa ⁇ s or less is extremely preferable.
- the lower limit of the viscosity of the thermosetting resin composition is not particularly limited, and may be, for example, 2 Pa ⁇ s or more at 175 ° C.
- the viscosity of the thermosetting resin composition can be measured by a high-grade flow tester (for example, manufactured by Shimadzu Corporation).
- the flow distance of the spiral flow obtained by the following method is not particularly limited, and is preferably 70 cm or more, more preferably 80 cm or more, and further preferably 90 cm or more.
- a thermosetting resin composition is molded using a spiral flow measuring die according to EMMI-1-66, and the flow distance is determined. Molding shall be performed by a transfer molding machine under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds.
- the distance of the disk flow obtained by the following test is not particularly limited, and is preferably 125 mm or more, more preferably 130 mm or more, and further preferably 135 mm or more.
- the upper mold is used. 5 g of the thermosetting resin composition weighed on a dish balance is placed on the center of the lower mold heated to 180 ° C. After 5 seconds, the upper mold heated to 180 ° C.
- the thermal hardness measured by the following method is preferably 50 or more, more preferably 60 or more, and further preferably 70 or more.
- the thermosetting resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm, and immediately after molding, a Shore D type hardness tester (for example, HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.) is used to heat hardness.
- a Shore D type hardness tester for example, HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.
- Molding shall be performed by a transfer molding machine under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds.
- the gel time is preferably 20 seconds or longer, more preferably 30 seconds or longer, and even more preferably 40 seconds or longer. From the viewpoint of curability, the gel time is preferably 120 seconds or less, more preferably 100 seconds or less, and further preferably 90 seconds or less.
- the gel time is a value measured by the following method. A measurement using a curast meter (for example, manufactured by JSR Trading Co., Ltd.) is carried out on 3 g of the thermosetting resin composition at a temperature of 180 ° C., and the time until the rise of the torque curve is defined as the gel time.
- thermosetting resin composition The use of the thermosetting resin composition of the present disclosure is not particularly limited, and it can be used in various mounting techniques, for example, as a sealing material for electronic component devices. Further, the thermosetting resin composition of the present disclosure has a good flow of resin compositions such as resin molded bodies for various modules, resin molded bodies for motors, resin molded bodies for automobiles, and encapsulants for protective materials for electronic circuits. It can be used in various applications where it is desirable to have properties and curability.
- the electronic component apparatus of the present disclosure includes an element sealed with a thermosetting resin composition obtained by the above-mentioned manufacturing method of the present disclosure.
- Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, and resistors. , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a thermosetting resin composition. More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a thermosetting resin composition or the like.
- DIP Device Inline Package
- PLCC Physical Readed Chip Carrier
- QFP Quad Flat Package
- SOP Small Outline Package
- SOJ SmallOdlinePack
- TCP Teape Carrier Package having a structure in which an element connected to a tape carrier with a bump is sealed with a thermosetting resin composition.
- a COB Chip On Board
- a hybrid IC or a multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like to a wiring formed on a support member is sealed with a thermosetting resin composition.
- thermosetting resin composition examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the thermosetting resin composition can also be preferably used in the printed wiring board.
- thermosetting resin composition examples include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like.
- thermosetting resin composition First, each component shown below was prepared.
- Epoxy resin 1 Epoxy equivalent 180 g / eq to 192 g / eq, biphenyl type epoxy resin with a melting point of 105 ° C.
- Epoxy resin 2 Epoxy equivalent 238 g / eq to 254 g / eq, melting point 116 ° C to 126 ° C.
- -Curing agent 1 Phenolic novolak type phenol resin having a hydroxyl group equivalent of 103 g / eq, softening point 85 ° C.
- -Curing agent 2 Xylylene-type phenol resin having a hydroxyl group equivalent of 175 g / eq and a softening point of 70 ° C.
- thermosetting resin compositions of Examples 1 to 4 were prepared by the following method (referred to as "manufacturing method A").
- a twin-screw kneader kneading extruder outlined in FIG. 1 was used.
- the main material input port is connected to the first kneading portion, and the side feeder is connected to the second kneading portion downstream in the extrusion direction.
- the components other than the curing accelerator were sufficiently mixed with a mixer.
- the mixture was charged from the main material charging port of the twin-screw kneader, a curing accelerator was charged from the side feeder, and kneading extrusion was performed.
- the primary kneading temperature in the first kneading section was the temperature shown in Tables 1 and 2.
- the temperature is gradually lowered from the side feeder connecting portion to the outlet so that the temperature is about 70 ° C. near the side feeder connecting portion and about 30 ° C. near the outlet of the twin-screw kneader.
- the melt was cooled and the solid state was pulverized into a powder to prepare a powdery thermosetting resin composition.
- thermosetting resin compositions of Comparative Examples 1 to 4 were prepared by the following method (referred to as "manufacturing method B"). After sufficiently mixing each component shown in Tables 1 and 2 with a mixer, the mixture was melt-kneaded at the kneading temperatures shown in Tables 1 and 2 using a twin-screw kneader. Then, the melt was cooled and the solid state was pulverized into a powder to prepare a powdery thermosetting resin composition.
- thermosetting resin composition was evaluated by various tests shown below. The evaluation results are shown in Tables 1 and 2. Unless otherwise specified, the thermosetting resin composition was molded by a transfer molding machine under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds.
- thermosetting resin composition was molded under the above conditions using a spiral flow measuring die according to EMMI-1-66, and the flow distance (cm) was determined.
- thermosetting resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, it is heated using a Shore D type hardness tester (HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.). The hardness was measured.
- a Shore D type hardness tester HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.
- thermosetting resin composition The minimum melt viscosity of the thermosetting resin composition at 175 ° C. was measured using a high-grade flow tester (manufactured by Shimadzu Corporation).
- the onset temperature of the compositions in Examples 1 to 4 is lower than the temperature of the primary kneading and higher than the temperature of the secondary kneading.
- thermosetting resin composition obtained by the production method A has excellent fluidity and a low melt viscosity at 175 ° C. Further, according to the production method A, even if the thermosetting resin is kneaded at a relatively high temperature, the gel time can be satisfactorily kneaded without shortening the gel time too much. Further, as can be seen from the evaluation of the hardness at the time, the thermosetting resin composition obtained by the production method A tends to have suitable curability. In particular, it can be seen that good curability and fluidity can be obtained when the kneading temperature before the addition of the curing accelerator is relatively high.
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Abstract
Description
<1> 熱硬化性樹脂を混練する一次混練と、
前記一次混練の後に硬化促進剤を添加してさらに混練する二次混練と、
を含む、熱硬化性樹脂組成物の製造方法。
<2> 前記一次混練の温度が、前記熱硬化性樹脂の融点又は軟化点よりも高い、<1>に記載の製造方法。
<3> 前記一次混練の温度が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より高い、<1>又は<2>に記載の製造方法。
<4> 前記二次混練の温度が、前記一次混練の温度よりも低い、<1>~<3>のいずれか1項に記載の製造方法。
<5> 前記二次混練の温度が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より低い、<1>~<4>のいずれか1項に記載の製造方法。
<6> 前記熱硬化性樹脂の融点又は軟化点が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より高い、<1>~<5>のいずれか1項に記載の製造方法。
<7> 前記熱硬化性樹脂の融点又は軟化点が60℃以上である、<1>~<6>のいずれか1項に記載の製造方法。
<8> 前記熱硬化性樹脂が、ビフェニル型エポキシ樹脂及び硫黄原子含有型エポキシ樹脂からなる群より選択される少なくとも1つを含む、<1>~<7>のいずれか1項に記載の製造方法。
<9> 前記一次混練においてさらに無機充填材を混練する、<1>~<8>のいずれか1項に記載の製造方法。
<10> <1>~<9>のいずれか1項に記載の製造方法により得られた熱硬化性樹脂組成物。
<11> <1>~<9>のいずれか1項に記載の製造方法により得られた熱硬化性樹脂組成物により封止された素子を備える電子部品装置。
本開示において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含まれていてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本開示において、固形、固体、液状、及び液体とは、25℃での性状をいう。
本開示において実施形態を図面を参照して説明する場合、当該実施形態の構成は図面に示された構成に限定されない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。
本開示の熱硬化性樹脂組成物の製造方法(以下、本開示の製造方法ともいう)は、熱硬化性樹脂を混練する一次混練と、前記一次混練の後に硬化促進剤を添加してさらに混練する二次混練と、を含む。
本開示の製造方法によれば、熱硬化性樹脂を混練した後に硬化促進剤を添加することから、増粘を抑えつつ、熱硬化性樹脂を好適に混合及び分散させることが可能となる。特に、熱硬化性樹脂として融点又は軟化点の高い樹脂を用いる場合であっても、高温で混練しても増粘を抑えつつ良好に撹拌混合することができる。また、従来の方法では、熱硬化性樹脂に高せん断応力を付加すると、せん断発熱により熱硬化性樹脂の温度が上昇し、さらに増粘が進行するという問題があったが、本開示の製造方法によれば、高せん断応力を付加しても粘度の上昇を抑えることができ、樹脂材料を十分に混合することができる。かかる方法により樹脂の分散性が高まり、良好な硬化性が得られると考えられる。また、樹脂の偏在化が起こりにくく、成形時の流動性も良好なものとすることができると考えられる。
一次混練では、熱硬化性樹脂を混合し、混練する。このとき、さらに無機充填材、カップリング剤、及びその他の添加剤を必要に応じて混合してもよい。一般的に樹脂材料と無機充填材を混合して混練するとせん断発熱が起こるが、硬化促進剤の全量又は一部を二次混練で混練することで、せん断発熱による増粘の影響を低減することができ、混練を良好に行うことができる傾向にある。一次混練において、増粘による混練性への影響が実用上問題とならない範囲であれば、硬化促進剤のうちの一部を混合してもよい。なお、本開示において、硬化促進剤を複数回に分けて添加する場合には、便宜上、最終的に添加する全硬化促進剤のうちの過半、すなわち50質量%以上の硬化促進剤を添加した後の混練を二次混練と称するものとする。一次混練において硬化促進剤の一部を混合する場合には、当該混合する量は、最終的に添加する全硬化促進剤のうち、30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることがさらに好ましい。好ましくは、一次混練では熱硬化性樹脂、並びに必要に応じて無機充填材、カップリング剤、及びその他の添加剤を、硬化促進剤を添加しない状態で混練する。
本開示の製造方法によれば、一次混練と硬化促進剤を添加して行う二次混練とを順次行うため、一次混練の温度を、硬化促進剤を添加した後の混合物のオンセット温度に関わらず比較的高い温度とすることができる。これにより、例えば熱硬化性樹脂を十分に溶融させて一次混練を行うことができ、樹脂の分散性を高めることができる。本開示の製造方法は、熱硬化性樹脂の融点又は軟化点が、硬化促進剤を添加した後の混合物のオンセット温度より高い場合に特に有用である。
一次混練に引き続き、硬化促進剤を添加してさらに二次混練を行う。硬化促進剤の添加方法は、硬化促進剤が後添加できる方法であれば、特に制限されない。例えば、上述のように一次混練を行った混合物に対して、一次混練の成分の投入口とは別に設けられた投入口から硬化促進剤を添加する方法(サイドフィード)が挙げられる。
熱硬化性樹脂の種類は特に制限されず、エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ウレタン樹脂、シリコーン樹脂、不飽和ポリエステル樹脂等が挙げられる。本開示では、エポキシ基を含有するアクリル樹脂等の、熱可塑性と熱硬化性の両方の性質を示すものは「熱硬化性樹脂」に含めるものとする。熱硬化性樹脂は、常温常圧下(例えば、25℃、大気圧下)で固体であっても液体であってもよく、固体であることが好ましい。熱硬化性樹脂は1種を単独で用いても2種以上を組み合わせて用いてもよい。
エポキシ樹脂の融点は示差走査熱量測定(DSC)で測定される値とし、エポキシ樹脂の軟化点はJIS K 7234:1986に準じた方法(環球法)で測定される値とする。
硬化剤の官能基数とは、例えば、硬化剤としてフェノール硬化剤を用いる場合にはフェノール硬化剤中の水酸基数を表し、硬化剤としてアミン硬化剤を用いる場合にはアミン硬化剤中の活性水素数を表す。
硬化促進剤の種類は、特に制限されず、1,5-ジアザビシクロ[4.3.0]ノネン-5(DBN)、1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)等のジアザビシクロアルケン、2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-ヘプタデシルイミダゾール等の環状アミジン化合物;前記環状アミジン化合物の誘導体;前記環状アミジン化合物又はその誘導体のフェノールノボラック塩;これらの化合物に無水マレイン酸、1,4-ベンゾキノン、2,5-トルキノン、1,4-ナフトキノン、2,3-ジメチルベンゾキノン、2,6-ジメチルベンゾキノン、2,3-ジメトキシ-5-メチル-1,4-ベンゾキノン、2,3-ジメトキシ-1,4-ベンゾキノン、フェニル-1,4-ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどの、π結合をもつ化合物を付加してなる分子内分極を有する化合物;DBUのテトラフェニルボレート塩、DBNのテトラフェニルボレート塩、2-エチル-4-メチルイミダゾールのテトラフェニルボレート塩、N-メチルモルホリンのテトラフェニルボレート塩等の環状アミジニウム化合物;ピリジン、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の三級アミン化合物;前記三級アミン化合物の誘導体;酢酸テトラ-n-ブチルアンモニウム、リン酸テトラ-n-ブチルアンモニウム、酢酸テトラエチルアンモニウム、安息香酸テトラ-n-ヘキシルアンモニウム、水酸化テトラプロピルアンモニウム等のアンモニウム塩化合物;エチルホスフィン、フェニルホスフィン等の一級ホスフィン、ジメチルホスフィン、ジフェニルホスフィン等の二級ホスフィン、トリフェニルホスフィン、ジフェニル(p-トリル)ホスフィン、トリス(アルキルフェニル)ホスフィン、トリス(アルコキシフェニル)ホスフィン、トリス(アルキルアルコキシフェニル)ホスフィン、トリス(ジアルキルフェニル)ホスフィン、トリス(トリアルキルフェニル)ホスフィン、トリス(テトラアルキルフェニル)ホスフィン、トリス(ジアルコキシフェニル)ホスフィン、トリス(トリアルコキシフェニル)ホスフィン、トリス(テトラアルコキシフェニル)ホスフィン、トリアルキルホスフィン、ジアルキルアリールホスフィン、アルキルジアリールホスフィン、トリナフチルホスフィン、トリス(ベンジル)ホスフィン等の三級ホスフィンなどの、有機ホスフィン;前記有機ホスフィンと有機ボロン類との錯体等のホスフィン化合物;前記有機ホスフィン又は前記ホスフィン化合物と無水マレイン酸、1,4-ベンゾキノン、2,5-トルキノン、1,4-ナフトキノン、2,3-ジメチルベンゾキノン、2,6-ジメチルベンゾキノン、2,3-ジメトキシ-5-メチル-1,4-ベンゾキノン、2,3-ジメトキシ-1,4-ベンゾキノン、フェニル-1,4-ベンゾキノン、アントラキノン等のキノン化合物、ジアゾフェニルメタンなどの、π結合をもつ化合物を付加してなる分子内分極を有する化合物;前記有機ホスフィン又は前記ホスフィン化合物と4-ブロモフェノール、3-ブロモフェノール、2-ブロモフェノール、4-クロロフェノール、3-クロロフェノール、2-クロロフェノール、4-ヨウ化フェノール、3-ヨウ化フェノール、2-ヨウ化フェノール、4-ブロモ-2-メチルフェノール、4-ブロモ-3-メチルフェノール、4-ブロモ-2,6-ジメチルフェノール、4-ブロモ-3,5-ジメチルフェノール、4-ブロモ-2,6-ジ-t-ブチルフェノール、4-クロロ-1-ナフトール、1-ブロモ-2-ナフトール、6-ブロモ-2-ナフトール、4-ブロモ-4’-ヒドロキシビフェニル等のハロゲン化フェノール化合物を反応させた後に、脱ハロゲン化水素の工程を経て得られる、分子内分極を有する化合物;テトラフェニルホスホニウム等のテトラ置換ホスホニウム、テトラフェニルホスホニウムテトラ-p-トリルボレート等のテトラ置換ホスホニウムのテトラフェニルボレート塩、テトラ置換ホスホニウムとフェノール化合物との塩などの、テトラ置換ホスホニウム化合物;ホスホベタイン化合物;ホスホニウム化合物とシラン化合物との付加物などが挙げられる。硬化促進剤は1種を単独で用いても2種以上を組み合わせて用いてもよい。
熱硬化性樹脂組成物は無機充填材を含有してもよい。無機充填材の材質は特に制限されない。
無機充填材の材質として具体的には、溶融シリカ、結晶シリカ、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化ケイ素、窒化アルミニウム、窒化ホウ素、酸化マグネシウム、炭化ケイ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカ等の無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。
無機充填材の中でも、線膨張係数低減の観点からは溶融シリカ等のシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。
また、例えば、熱硬化性樹脂組成物を圧縮成形用に用いる場合には、無機充填材の含有率は熱硬化性樹脂組成物全体の70体積%~99体積%としてもよく、80体積%~99体積%としてもよく、83体積%~99体積%としてもよく、85体積%~99体積%としてもよい。
熱硬化性樹脂組成物が無機充填材を含む場合は、樹脂成分と無機充填材との接着性を高めるために、カップリング剤を含んでもよい。カップリング剤としては、シラン系化合物、チタン系化合物、アルミニウムキレート化合物、アルミニウム/ジルコニウム系化合物等の公知のカップリング剤が挙げられる。
熱硬化性樹脂組成物は、上述の成分に加えて、イオン交換体、離型剤、難燃剤、着色剤、応力緩和剤等の各種添加剤を含有してもよい。熱硬化性樹脂組成物は、以下に例示する添加剤以外にも必要に応じて当技術分野で一般的に用いられる各種添加剤を含有してもよい。
熱硬化性樹脂組成物は、イオン交換体を含有してもよい。特に、熱硬化性樹脂組成物を封止用成形材料として用いる場合には、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、イオン交換体を含有することが好ましい。イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、ハイドロタルサイト化合物、並びにマグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスからなる群より選ばれる少なくとも1種の元素の含水酸化物等が挙げられる。イオン交換体は、1種を単独で用いても2種以上を組み合わせて用いてもよい。中でも、下記一般式(A)で表されるハイドロタルサイトが好ましい。
(0<X≦0.5、mは正の数)
熱硬化性樹脂組成物は、成形時における金型との良好な離型性を得る観点から、離型剤を含有してもよい。離型剤は特に制限されず、従来公知のものを用いることができる。具体的には、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。離型剤は、1種を単独で用いても2種以上を組み合わせて用いてもよい。
熱硬化性樹脂組成物は、難燃剤を含有してもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。具体的には、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む有機又は無機の化合物、金属水酸化物等が挙げられる。難燃剤は、1種を単独で用いても2種以上を組み合わせて用いてもよい。
熱硬化性樹脂組成物は、着色剤をさらに含有してもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、1種を単独で用いても2種以上を組み合わせて用いてもよい。
熱硬化性樹脂組成物は、シリコーンオイル、シリコーンゴム粒子等の応力緩和剤を含有してもよい。応力緩和剤を含有することにより、熱硬化性樹脂組成物を封止材用途で使用する場合のパッケージの反り変形及びパッケージクラックの発生を低減させることができる。応力緩和剤としては、一般に使用されている公知の応力緩和剤(可とう剤)が挙げられる。具体的には、シリコーン系、スチレン系、オレフィン系、ウレタン系、ポリエステル系、ポリエーテル系、ポリアミド系、ポリブタジエン系等の熱可塑性エラストマー、NR(天然ゴム)、NBR(アクリロニトリル-ブタジエンゴム)、アクリルゴム、ウレタンゴム、シリコーンパウダー等のゴム粒子、メタクリル酸メチル-スチレン-ブタジエン共重合体(MBS)、メタクリル酸メチル-シリコーン共重合体、メタクリル酸メチル-アクリル酸ブチル共重合体等のコア-シェル構造を有するゴム粒子などが挙げられる。応力緩和剤は、1種を単独で用いても2種以上を組み合わせて用いてもよい。
本開示の熱硬化性樹脂組成物は、上述の本開示の製造方法により得られる。
熱硬化性樹脂組成物は、常温常圧下(例えば、25℃、大気圧下)において固体であっても液状であってもよく、固体であることが好ましい。熱硬化性樹脂組成物が固体である場合の形状は特に制限されず、粉状、粒状、タブレット状等が挙げられる。熱硬化性樹脂組成物がタブレット状である場合の寸法及び質量は、パッケージの成形条件に合うような寸法及び質量となるようにすることが取り扱い性の観点から好ましい。
熱硬化性樹脂組成物の粘度は、特に制限されない。成形方法、熱硬化性樹脂組成物の組成等に応じて所望の粘度となるよう調整することが好ましい。熱硬化性樹脂組成物を封止材用途で使用する場合には、成形時のワイヤ流れの起こりやすさに応じて調整することが好ましい。
例えば、熱硬化性樹脂組成物を封止材用途で使用する場合、ワイヤ流れの低減等の観点から、熱硬化性樹脂組成物の粘度は175℃で200Pa・s以下であることが好ましく、150Pa・s以下であることがより好ましく、100Pa・s以下であることがさらに好ましく、70Pa・s以下であることが特に好ましく、50Pa・s以下であることが極めて好ましい。熱硬化性樹脂組成物の粘度の下限値は特に限定されず、例えば、175℃で2Pa・s以上であってもよい。
熱硬化性樹脂組成物の粘度は、高化式フローテスター(例えば、株式会社島津製作所製)によって測定することができる。
以下の方法により求められるスパイラルフローの流動距離は、特に制限されず、70cm以上であることが好ましく、80cm以上であることがより好ましく、90cm以上であることがさらに好ましい。
EMMI-1-66に準じたスパイラルフロー測定用金型を用いて、熱硬化性樹脂組成物を成形し、流動距離を求める。成形はトランスファー成形機により金型温度180℃、成形圧力6.9MPa、硬化時間90秒の条件で行うものとする。
200mm(W)×200mm(D)×25mm(H)の上型と200mm(W)×200mm(D)×15mm(H)の下型を有する円板フロー測定用平板金型を用いて、上皿天秤にて秤量した熱硬化性樹脂組成物5gを、180℃に加熱した下型の中心部にのせる。5秒後に、180℃に加熱した上型を閉じて、荷重78N、硬化時間90秒の条件で圧縮成形し、ノギスで成形品の長径(mm)及び短径(mm)を測定して、その平均値(mm)を円板フローとする。
以下の方法により測定される熱時硬度は、50以上であることが好ましく、60以上であることがより好ましく、70以上であることがさらに好ましい。
熱硬化性樹脂組成物を直径50mm×厚み3mmの円板に成形し、成形後直ちにショアD型硬度計(例えば、株式会社上島製作所製、HD-1120(タイプD))を用いて熱時硬度を測定する。成形はトランスファー成形機により金型温度180℃、成形圧力6.9MPa、硬化時間90秒の条件で行うものとする。
流動性の観点からは、ゲルタイムは、20秒以上であることが好ましく、30秒以上であることがより好ましく、40秒以上であることがさらに好ましい。また、硬化性の観点からは、ゲルタイムは120秒以下であることが好ましく、100秒以下であることがより好ましく、90秒以下であることがさらに好ましい。ゲルタイムは以下の方法により測定される値とする。
熱硬化性樹脂組成物3gに対し、キュラストメータ(例えば、JSRトレーディング株式会社製)を用いた測定を温度180℃で実施し、トルク曲線の立ち上がりまでの時間をゲルタイムとする。
〔熱硬化性樹脂組成物の用途〕
本開示の熱硬化性樹脂組成物の用途は特に制限されず、例えば電子部品装置の封止材として種々の実装技術に用いることができる。また、本開示の熱硬化性樹脂組成物は、各種モジュール用樹脂成形体、モーター用樹脂成形体、車載用樹脂成形体、電子回路用保護材用封止材等、樹脂組成物が良好な流動性及び硬化性を有することが望ましい種々の用途に用いることができる。
本開示の電子部品装置は、上述の本開示の製造方法により得られた熱硬化性樹脂組成物により封止された素子を備える。
より具体的には、リードフレーム上に素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング、バンプ等で接続した後、熱硬化性樹脂組成物を用いてトランスファー成形等によって封止した構造を有するDIP(Dual Inline Package)、PLCC(Plastic Leaded Chip Carrier)、QFP(Quad Flat Package)、SOP(Small Outline Package)、SOJ(Small Outline J-lead package)、TSOP(Thin Small Outline Package)、TQFP(Thin Quad Flat Package)等の一般的な樹脂封止型IC;テープキャリアにバンプで接続した素子を熱硬化性樹脂組成物で封止した構造を有するTCP(Tape Carrier Package);支持部材上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した素子を、熱硬化性樹脂組成物で封止した構造を有するCOB(Chip On Board)モジュール、ハイブリッドIC、マルチチップモジュール等;裏面に配線板接続用の端子を形成した支持部材の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と支持部材に形成された配線とを接続した後、熱硬化性樹脂組成物で素子を封止した構造を有するBGA(Ball Grid Array)、CSP(Chip Size Package)、MCP(Multi Chip Package)などが挙げられる。また、プリント配線板においても熱硬化性樹脂組成物を好適に使用することができる。
まず、下記に示す各成分を準備した。
・エポキシ樹脂1:エポキシ当量180g/eq~192g/eq、融点105℃のビフェニル型エポキシ樹脂
・エポキシ樹脂2:エポキシ当量238g/eq~254g/eq、融点116℃~126℃のチオエーテル型エポキシ樹脂
・硬化剤2:水酸基当量175g/eq、軟化点70℃のキシリレン型フェノール樹脂
・硬化促進剤:リン系硬化促進剤
・カップリング剤:N-フェニル-3-アミノプロピルトリメトキシシラン
・離型剤:ヘキストワックス
・着色剤:カーボンブラック
・イオン交換体:ハイドロタルサイト類化合物
・無機充填材:体積平均粒子径15μmの球状シリカ
まず、表1及び表2に示される成分のうち、硬化促進剤以外の成分をミキサーで十分混合した。当該混合物を二軸混練機の主材投入口から投入し、サイドフィーダーから硬化促進剤を投入し、混練押出を行った。第1混練部における一次混練温度は表1及び表2に示される温度とした。第2混練部では、サイドフィーダー連結部付近では約70℃、二軸混練機の出口付近では約30℃となるように、サイドフィーダー連結部から出口に向けて徐々に温度を下げる機構とした。その後、溶融物を冷却し、固体状になったものを粉末状に粉砕することにより、粉末状の熱硬化性樹脂組成物を調製した。
表1及び表2に示される各成分をミキサーで十分混合した後、二軸混練機を用いて表1及び表2に記載の混練温度で溶融混練した。その後、溶融物を冷却し、固体状になったものを粉末状に粉砕することにより、粉末状の熱硬化性樹脂組成物を調製した。
作製された熱硬化性樹脂組成物を、以下に示す各種試験によって評価した。評価結果を表1及び表2に示す。なお、熱硬化性樹脂組成物の成形は、明記しない限りトランスファー成形機により、金型温度180℃、成形圧力6.9MPa、硬化時間90秒の条件で成形した。
EMMI-1-66に準じたスパイラルフロー測定用金型を用いて、熱硬化性樹脂組成物を上記条件で成形し、流動距離(cm)を求めた。
熱硬化性樹脂組成物を上記条件で直径50mm×厚み3mmの円板に成形し、成形後直ちにショアD型硬度計(株式会社上島製作所製、HD-1120(タイプD))を用いて熱時硬度を測定した。
高化式フローテスター(株式会社島津製作所製)を用いて、175℃における熱硬化性樹脂組成物の最低溶融粘度を測定した。
熱硬化性樹脂組成物3gに対し、JSRトレーディング株式会社のキュラストメータを用いた測定を温度180℃で実施し、トルク曲線の立ち上がりまでの時間をゲルタイム(秒)とした。
200mm(W)×200mm(D)×25mm(H)の上型と200mm(W)×200mm(D)×15mm(H)の下型を有する円板フロー測定用平板金型を用いて、上皿天秤にて秤量した熱硬化性樹脂組成物5gを、180℃に加熱した下型の中心部にのせる。5秒後に、180℃に加熱した上型を閉じて、荷重78N、硬化時間90秒の条件で圧縮成形し、ノギスで成形品の長径(mm)及び短径(mm)を測定して、その平均値(mm)を円板フローとした。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。
2 サイドフィーダー
10 混練押出機
A 第1混練部
B 第2混練部
Claims (11)
- 熱硬化性樹脂を混練する一次混練と、
前記一次混練の後に硬化促進剤を添加してさらに混練する二次混練と、
を含む、熱硬化性樹脂組成物の製造方法。 - 前記一次混練の温度が、前記熱硬化性樹脂の融点又は軟化点よりも高い、請求項1に記載の製造方法。
- 前記一次混練の温度が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より高い、請求項1又は請求項2に記載の製造方法。
- 前記二次混練の温度が、前記一次混練の温度よりも低い、請求項1~請求項3のいずれか1項に記載の製造方法。
- 前記二次混練の温度が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より低い、請求項1~請求項4のいずれか1項に記載の製造方法。
- 前記熱硬化性樹脂の融点又は軟化点が、前記硬化促進剤を添加した後の混合物の、示差走査熱量測定により測定されるオンセット温度より高い、請求項1~請求項5のいずれか1項に記載の製造方法。
- 前記熱硬化性樹脂の融点又は軟化点が60℃以上である、請求項1~請求項6のいずれか1項に記載の製造方法。
- 前記熱硬化性樹脂が、ビフェニル型エポキシ樹脂及び硫黄原子含有型エポキシ樹脂からなる群より選択される少なくとも1つを含む、請求項1~請求項7のいずれか1項に記載の製造方法。
- 前記一次混練においてさらに無機充填材を混練する、請求項1~請求項8のいずれか1項に記載の製造方法。
- 請求項1~請求項9のいずれか1項に記載の製造方法により得られた熱硬化性樹脂組成物。
- 請求項1~請求項9のいずれか1項に記載の製造方法により得られた熱硬化性樹脂組成物により封止された素子を備える電子部品装置。
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JP2004346101A (ja) * | 2003-05-20 | 2004-12-09 | Nippon Kayaku Co Ltd | 成型方法、及びその硬化物 |
JP2009127012A (ja) * | 2007-11-27 | 2009-06-11 | Panasonic Electric Works Co Ltd | 封止用エポキシ樹脂組成物の製造方法および半導体装置 |
JP2009203292A (ja) * | 2008-02-26 | 2009-09-10 | Panasonic Electric Works Co Ltd | 液状エポキシ樹脂組成物と封止半導体装置並びに封止方法 |
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Patent Citations (8)
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JPH03211A (ja) * | 1989-05-26 | 1991-01-07 | Matsushita Electric Works Ltd | 半導体封止用エポキシ樹脂成形材料の製造方法 |
JPH0853532A (ja) * | 1994-08-10 | 1996-02-27 | Arakawa Chem Ind Co Ltd | エポキシ樹脂、その製造方法およびエポキシ樹脂組成物 |
JP2002179807A (ja) * | 2000-12-18 | 2002-06-26 | Nitto Denko Corp | 光半導体素子封止用エポキシ樹脂組成物の製造方法 |
JP2003160642A (ja) * | 2001-11-27 | 2003-06-03 | Matsushita Electric Works Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2004346101A (ja) * | 2003-05-20 | 2004-12-09 | Nippon Kayaku Co Ltd | 成型方法、及びその硬化物 |
JP2009127012A (ja) * | 2007-11-27 | 2009-06-11 | Panasonic Electric Works Co Ltd | 封止用エポキシ樹脂組成物の製造方法および半導体装置 |
JP2009203292A (ja) * | 2008-02-26 | 2009-09-10 | Panasonic Electric Works Co Ltd | 液状エポキシ樹脂組成物と封止半導体装置並びに封止方法 |
JP2020145424A (ja) * | 2019-02-28 | 2020-09-10 | 京セラ株式会社 | 炭化ケイ素、酸化ガリウム、窒化ガリウム及びダイヤモンド素子封止用成形材料組成物、並びに電子部品装置 |
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