JP4496778B2 - Curing accelerator, epoxy resin composition, and semiconductor device - Google Patents
Curing accelerator, epoxy resin composition, and semiconductor device Download PDFInfo
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- JP4496778B2 JP4496778B2 JP2004003458A JP2004003458A JP4496778B2 JP 4496778 B2 JP4496778 B2 JP 4496778B2 JP 2004003458 A JP2004003458 A JP 2004003458A JP 2004003458 A JP2004003458 A JP 2004003458A JP 4496778 B2 JP4496778 B2 JP 4496778B2
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- 239000003822 epoxy resin Substances 0.000 title claims description 131
- 229920000647 polyepoxide Polymers 0.000 title claims description 131
- 239000000203 mixture Substances 0.000 title claims description 108
- 239000004065 semiconductor Substances 0.000 title claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 121
- 239000011342 resin composition Substances 0.000 claims description 51
- -1 tri-substituted phosphoniophenolate Chemical class 0.000 claims description 50
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000003700 epoxy group Chemical group 0.000 claims description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 30
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 17
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 229910000679 solder Inorganic materials 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000004305 biphenyl Substances 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000007142 ring opening reaction Methods 0.000 description 9
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000004203 carnauba wax Substances 0.000 description 4
- 235000013869 carnauba wax Nutrition 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LVLZXBIWQHFREA-UHFFFAOYSA-N phenol;phosphane Chemical class [PH4+].[O-]C1=CC=CC=C1 LVLZXBIWQHFREA-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical group 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UZKBSZSTDQSMDR-UHFFFAOYSA-N 1-[(4-chlorophenyl)-phenylmethyl]piperazine Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)N1CCNCC1 UZKBSZSTDQSMDR-UHFFFAOYSA-N 0.000 description 2
- ZUYRZVQAOUOSQI-UHFFFAOYSA-N 2-phosphaniumylphenolate Chemical class OC1=CC=CC=C1P ZUYRZVQAOUOSQI-UHFFFAOYSA-N 0.000 description 2
- FXTKWBZFNQHAAO-UHFFFAOYSA-N 3-iodophenol Chemical compound OC1=CC=CC(I)=C1 FXTKWBZFNQHAAO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NOMRCDXYHTWTNR-UHFFFAOYSA-N diphenylmethanediamine;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 NOMRCDXYHTWTNR-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
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- 108010012137 spleen derived immunosuppressive peptide Proteins 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-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
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
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- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は、硬化促進剤、エポキシ樹脂組成物および半導体装置に関するものである。 The present invention relates to a curing accelerator, an epoxy resin composition, and a semiconductor device.
ＩＣ、ＬＳＩ等の半導体素子を封止して半導体装置を得る方法としては、エポキシ樹脂組成物を用いて、トランスファー成形により封止する方法が、低コスト、大量生産に適しているという点で広く用いられている。また、エポキシ樹脂組成物において、エポキシ樹脂や、硬化剤であるフェノール樹脂などの成分を改良することにより、これを用いた半導体装置の特性および信頼性の向上が図られている。 As a method for obtaining a semiconductor device by sealing semiconductor elements such as IC and LSI, a method of sealing by transfer molding using an epoxy resin composition is widely used in terms of low cost and suitable for mass production. It is used. In addition, in the epoxy resin composition, improvement of properties and reliability of a semiconductor device using the epoxy resin and a phenol resin that is a curing agent are improved.
しかしながら、昨今の電子機器の市場動向において、機器の小型化、軽量化および高性能化に伴い、半導体の高集積化も年々進んでおり、また、製造工程における半導体装置の表面実装化も促進されている。半導体装置の表面実装化においては、エポキシ樹脂組成物の硬化物と半導体装置内部に存在する半導体素子やリードフレーム等の基材との界面の密着性が不十分であると、半田浸漬あるいは半田リフロー工程で、急激に２００℃以上の高温において、この界面で剥離が生じることがあり、剥離により半導体装置にクラックを誘起するとともに、耐湿信頼性の低下も招くこととなる。また、エポキシ樹脂組成物中に揮発成分が存在すれば、それが爆発的に気化する際の応力により、半導体装置にクラックが発生しやすくなり、半導体素子の封止に用いられるエポキシ樹脂組成物への要求は、益々厳しいものとなってきている。このため、従来からのエポキシ樹脂組成物では、解決できない（対応できない）問題も生じている。 However, in recent electronic equipment market trends, along with miniaturization, weight reduction, and high performance of equipment, higher integration of semiconductors has been progressing year by year, and surface mounting of semiconductor devices in the manufacturing process has been promoted. ing. In surface mounting of a semiconductor device, solder dipping or solder reflow may occur if the adhesiveness at the interface between a cured product of the epoxy resin composition and a substrate such as a semiconductor element or a lead frame existing inside the semiconductor device is insufficient. In the process, delamination may occur at this interface at a high temperature of 200 ° C. or more, and the delamination induces cracks in the semiconductor device and also causes a decrease in moisture resistance reliability. In addition, if a volatile component is present in the epoxy resin composition, cracks are likely to occur in the semiconductor device due to the stress when it vaporizes explosively, leading to an epoxy resin composition used for sealing semiconductor elements. The demands are becoming increasingly severe. For this reason, the conventional epoxy resin composition also has a problem that cannot be solved (cannot be handled).
これら耐半田クラック性、耐湿信頼性を改良した硬化促進剤として、付加反応によらない手法で合成されたホスホベタイン構造の硬化促進剤が開示されている（例えば、特許文献３参照。）が、そのようなホスホベタイン化合物は、高融点で結晶性が優れるものが多く、樹脂組成物に添加した際、均一に混合することが難しく、その結果、硬化反応にムラが生じ、粘度が上昇するといった問題があった。 As a curing accelerator with improved solder crack resistance and moisture resistance reliability, a curing accelerator having a phosphobetaine structure synthesized by a method not involving an addition reaction is disclosed (for example, see Patent Document 3). Many of such phosphobetaine compounds have a high melting point and excellent crystallinity, and when added to a resin composition, it is difficult to mix uniformly, resulting in unevenness in the curing reaction and an increase in viscosity. There was a problem.
近年、半導体素子の封止に用いられる材料には、生産効率の向上を目的とした速硬化性の向上と、物流・保管時の取扱い性の向上を目的とした保存性の向上が求められるようになってきている。 In recent years, materials used for sealing semiconductor devices are required to improve fast curing for the purpose of improving production efficiency and to improve storability for the purpose of improving handling during distribution and storage. It is becoming.
電気・電子材料分野向けのエポキシ樹脂組成物には、硬化時における樹脂の硬化反応を促進する目的で、第三ホスフィンとキノン類との付加反応物（例えば、特許文献１参照。）を硬化促進剤として、一般的に添加する。 In the epoxy resin composition for the electric / electronic material field, for the purpose of accelerating the curing reaction of the resin at the time of curing, an addition reaction product of a tertiary phosphine and a quinone (see, for example, Patent Document 1) is accelerated. Generally added as an agent.
ところで、かかる硬化促進剤は、硬化促進効果を示す温度領域が比較的低温にまで及ぶ。このため、例えば硬化前のエポキシ樹脂組成物と他の成分とを混合する際にも、系内に発生する熱や外部から加えられる熱により、エポキシ樹脂組成物の硬化反応は一部進行する。また、混合終了後、このエポキシ樹脂組成物を常温で保管するにあたって、反応はさらに進行する。 By the way, in such a curing accelerator, a temperature range showing a curing acceleration effect extends to a relatively low temperature. For this reason, for example, even when the epoxy resin composition before curing and other components are mixed, the curing reaction of the epoxy resin composition partially proceeds due to heat generated in the system or heat applied from the outside. In addition, the reaction further proceeds when the epoxy resin composition is stored at room temperature after mixing.
この部分的な硬化反応の進行は、エポキシ樹脂組成物が液体の場合には、粘度の上昇や流動性の低下をもたらし、また、エポキシ樹脂組成物が固体の場合には、粘性を発現させる。このような状態の変化は、エポキシ樹脂組成物内に厳密な意味で均一に生じるわけではない。このため、エポキシ樹脂組成物の各部分の硬化性には、ばらつきが生じる。 The progress of the partial curing reaction causes an increase in viscosity or a decrease in fluidity when the epoxy resin composition is a liquid, and develops a viscosity when the epoxy resin composition is a solid. Such a change in state does not occur uniformly in the strict sense within the epoxy resin composition. For this reason, dispersion | variation arises in the sclerosis | hardenability of each part of an epoxy resin composition.
これが原因となり、更に、高温で硬化反応を進行させ、エポキシ樹脂組成物を成形（その他賦形という概念も含んで、以下「成形」と記す）する際に、流動性低下による成形上の障害や、成形品の機械的、電気的あるいは化学的特性の低下をもたらす。 Due to this, further, the curing reaction proceeds at a high temperature, and when molding the epoxy resin composition (including the concept of other shaping, hereinafter referred to as “molding”), the molding troubles due to lower fluidity and , Resulting in deterioration of the mechanical, electrical or chemical properties of the molded product.
したがって、このようにエポキシ樹脂組成物の保存性を低下させる原因となる硬化促進剤を用いる際には、諸成分混合時の厳密な品質管理、低温での保管や運搬、更に成形条件の厳密な管理が必須であり、取扱いが非常に煩雑である。 Therefore, when using a curing accelerator that causes a decrease in the storage stability of the epoxy resin composition in this way, strict quality control during mixing of various components, storage and transportation at low temperatures, and strict molding conditions are required. Management is essential and handling is very complicated.
また、保存性の問題を解決すべく、低温での粘度、流動性の経時変化を抑え、賦形、成形時の加熱によってのみ、硬化反応を起こすような硬化促進剤（いわゆる潜伏性硬化促進剤）の研究が盛んになされており、硬化促進剤の活性点をイオン対により保護することで、潜伏性を発現する研究がなされており、種々の有機酸とホスホニウムイオンとの塩構造を有する潜伏性硬化促進剤が知られている（例えば、特許文献２参照。）が、このホスホニウム塩もまた、表面実装に十分なレベルの耐半田クラック性、耐湿信頼性が得られていない。
また、表面実装に足る耐半田クラック性、耐湿信頼性を得るべく、別の潜伏性硬化促進剤として、種々のホスホニウムベタインの塩構造を有する潜伏性硬化促進剤も提示されている（例えば、特許文献４参照。）が、このホスホニウムベタインの塩は、近年の低分子エポキシ樹脂やフェノールアラルキル樹脂のような硬化剤を用いる半導体封止材料では、硬化が不十分であるという問題が生じている。
In addition, in order to obtain solder crack resistance and moisture resistance reliability sufficient for surface mounting, latent cure accelerators having various phosphonium betaine salt structures have been proposed as other latent cure accelerators (for example, patents). However, this phosphonium betaine salt has a problem of insufficient curing in semiconductor encapsulating materials using a curing agent such as a low-molecular epoxy resin or a phenol aralkyl resin in recent years.
本発明の目的は、各種硬化性樹脂組成物に有用な硬化促進剤、硬化性、保存性や、とりわけ流動性が良好なエポキシ樹脂組成物、および、耐半田クラック性や耐湿信頼性に優れる半導体装置を提供することにある。 An object of the present invention is to provide a curing accelerator useful for various curable resin compositions, an epoxy resin composition having excellent curability and storage stability, and particularly a fluidity, and a semiconductor excellent in solder crack resistance and moisture resistance reliability. To provide an apparatus.
このような目的は、下記（１）〜（６）の本発明により達成される。 Such an object is achieved by the present inventions (1) to ( 6 ) below.
（１） 硬化性樹脂組成物に混合され、該硬化性樹脂組成物の硬化反応を促進し得る硬化促進剤であって、
前記硬化促進剤は、下記一般式（１）で表されるトリ置換ホスホニオフェノラートと、１分子内にエポキシ基を１個以上有する化合物と、１分子内にフェノール性水酸基を１個以上有する化合物とを反応させて得られるものであることを特徴とする硬化促進剤。
［式中、Ｒ 1 、Ｒ 2 およびＲ 3 は、それぞれ、置換もしくは無置換の芳香族基、または、置換もしくは無置換のアルキル基を表し、互いに同一であっても異なっていてもよい。Ａｒは、水酸基以外の置換基により置換もしくは無置換の芳香族基を表す。］
(1) A curing accelerator that is mixed in the curable resin composition and can accelerate the curing reaction of the curable resin composition,
The curing accelerator has a tri-substituted phosphoniophenolate represented by the following general formula (1), a compound having one or more epoxy groups in one molecule, and one or more phenolic hydroxyl groups in one molecule. A curing accelerator characterized by being obtained by reacting with a compound.
[Wherein, R 1 , R 2 and R 3 each represent a substituted or unsubstituted aromatic group or a substituted or unsubstituted alkyl group, and may be the same or different from each other. Ar represents an aromatic group substituted or unsubstituted by a substituent other than a hydroxyl group. ]
（２） 前記トリ置換ホスホニオフェノラートは、下記一般式（２）で表されるものである上記（１）に記載の硬化促進剤。
［式中、Ａｒ1、Ａｒ2およびＡｒ3は、それぞれ、置換もしくは無置換の芳香族基を表し、互いに同一であっても異なっていてもよい。Ａｒは、水酸基以外の置換基により置換もしくは無置換の芳香族基を表す。］
( 2 ) The curing accelerator according to (1), wherein the tri-substituted phosphoniophenolate is represented by the following general formula (2).
[Wherein, Ar 1 , Ar 2 and Ar 3 each represent a substituted or unsubstituted aromatic group, and may be the same or different from each other. Ar represents an aromatic group substituted or unsubstituted by a substituent other than a hydroxyl group. ]
（３） 前記トリ置換ホスホニオフェノラートは、下記一般式（３）で表されるものである上記（１）に記載の硬化促進剤。
［式中、Ｒ4、Ｒ5およびＲ6は、それぞれ、水素原子、メチル基、メトキシ基および水酸基から選択される１種を表し、互いに同一であっても異なっていてもよい。］
( 3 ) The curing accelerator according to (1), wherein the tri-substituted phosphoniophenolate is represented by the following general formula (3).
[Wherein R 4 , R 5 and R 6 each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a hydroxyl group, and may be the same or different from each other. ]
（４） 前記一般式（３）において、オキシアニオンは、リン原子に対してオルト位またはメタ位に位置する上記（３）に記載の硬化促進剤。 ( 4 ) In the said General formula (3), an oxyanion is a hardening accelerator as described in said ( 3 ) located in an ortho position or a meta position with respect to a phosphorus atom.
（５） １分子内にエポキシ基を２個以上有する化合物と、１分子内にフェノール性水酸基を２個以上有する化合物と、上記（１）ないし（４）のいずれかに記載の硬化促進剤とを含むことを特徴とするエポキシ樹脂組成物。 ( 5 ) a compound having two or more epoxy groups in one molecule, a compound having two or more phenolic hydroxyl groups in one molecule, and the curing accelerator according to any one of (1) to ( 4 ) above An epoxy resin composition comprising:
（６） 上記（５）に記載のエポキシ樹脂組成物の硬化物により半導体素子を封止してなることを特徴とする半導体装置。 ( 6 ) A semiconductor device comprising a semiconductor element sealed with a cured product of the epoxy resin composition according to ( 5 ) above.
本発明の硬化促進剤によれば、常温での保存性に優れ，成形時に特に高い流動性を有する硬化性樹脂組成物を得ることができ、前記硬化促進剤を用いたエポキシ樹脂組成物は、硬化性、保存性や、とりわけ流動性が良好であり、また、前記エポキシ樹脂組成物を用いて作製された半導体装置は、高温に曝された場合であっても、この硬化物に欠陥が生じるのを好適に防止することができ、耐半田クラック性や耐湿信頼性など良好な信頼性を発揮することができる。 According to the curing accelerator of the present invention, a curable resin composition having excellent storage stability at room temperature and having particularly high fluidity at the time of molding can be obtained. An epoxy resin composition using the curing accelerator is Curability, storage stability, and particularly fluidity are good, and a semiconductor device manufactured using the epoxy resin composition has defects in the cured product even when exposed to high temperatures. Can be suitably prevented, and good reliability such as solder crack resistance and moisture resistance reliability can be exhibited.
本発明者は、前述したような問題点を解決すべく、鋭意検討を重ねた結果、次のようなＩ〜IIIの事項を見出し、本発明を完成するに至った。
すなわち、Ｉ：特定構造のトリ置換ホスホニオフェノラートの誘導体が、各種硬化性樹脂組成物の硬化反応を促進する硬化促進剤として極めて有用であることを見出した。
As a result of intensive studies to solve the above-described problems, the present inventors have found the following items I to III and have completed the present invention.
That is, it has been found that a derivative of I: trisubstituted phosphoniophenolate having a specific structure is extremely useful as a curing accelerator that accelerates the curing reaction of various curable resin compositions.
II：かかるトリ置換ホスホニオフェノラートの誘導体を硬化性樹脂組成物、特にエポキシ樹脂組成物に硬化促進剤として混合することにより、エポキシ樹脂組成物が、硬化性、保存性および流動性に優れたものとなることを見出した。 II: By mixing such a tri-substituted phosphoniophenolate derivative as a curing accelerator in a curable resin composition, particularly an epoxy resin composition, the epoxy resin composition has excellent curability, storage stability and fluidity. I found out that it would be something.
III：かかるエポキシ樹脂組成物の硬化物により半導体素子を封止してなる半導体装置が、高温に曝された場合であっても、クラックや剥離等の欠陥が発生し難いことを見出した。 III: It has been found that even when a semiconductor device in which a semiconductor element is sealed with a cured product of such an epoxy resin composition is exposed to a high temperature, defects such as cracks and peeling hardly occur.
以下、本発明の硬化促進剤、エポキシ樹脂組成物および半導体装置の好適実施形態について説明する。 Hereinafter, preferred embodiments of the curing accelerator, the epoxy resin composition, and the semiconductor device of the present invention will be described.
本発明の硬化促進剤は、各種硬化性樹脂組成物の硬化促進剤として適用可能であるが、以下では、熱硬化性樹脂組成物の１種であるエポキシ樹脂組成物に適用した場合を代表して説明する。 The curing accelerator of the present invention can be applied as a curing accelerator for various curable resin compositions, but in the following, it represents a case where it is applied to an epoxy resin composition which is a kind of thermosetting resin composition. I will explain.
本実施形態のエポキシ樹脂組成物は、１分子内にエポキシ基を２個以上有する化合物（Ａ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）と、本発明の硬化促進剤であるトリ置換ホスホニオフェノラートの誘導体（Ｃ）とを含むものである。かかるエポキシ樹脂組成物は、硬化性、保存性および流動性に優れたものである。
以下、各成分について、順次説明する。
The epoxy resin composition of the present embodiment includes a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and the curing acceleration of the present invention. And a derivative (C) of a tri-substituted phosphoniophenolate as an agent. Such an epoxy resin composition is excellent in curability, storage stability and fluidity.
Hereinafter, each component will be sequentially described.
［化合物（Ａ）］
本発明に用いる１分子内にエポキシ基を２個以上有する化合物（Ａ）は、１分子内にエポキシ基を２個以上有するものであれば、何ら制限はない。
この化合物（Ａ）としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭素化ビスフェノール型エポキシ樹脂等のビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂など、フェノール類やフェノール樹脂、ナフトール類などの水酸基にエピクロロヒドリンを反応させて製造するエポキシ樹脂、エポキシ化合物、または、その他、脂環式エポキシ樹脂のように、オレフィンを過酸を用いて酸化させエポキシ化したエポキシ樹脂や、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等が挙げられ、これらのうちの１種または２種以上を組み合わせて用いることができる。
[Compound (A)]
The compound (A) having two or more epoxy groups in one molecule used in the present invention is not limited as long as it has two or more epoxy groups in one molecule.
Examples of the compound (A) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol type epoxy resins and the like, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and stilbene type epoxy resins. , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dihydroxybenzene type epoxy resin, etc., reacting epichlorohydrin with hydroxyl groups such as phenols, phenol resins, naphthols, etc. Epoxy resins, epoxy compounds, or other alicyclic epoxy resins that are produced by oxidization of olefins with peracids and epoxidized, or glycidyl Ester type epoxy resins, glycidylamine type epoxy resins may be used singly or in combination of two or more of them.
［化合物（Ｂ）］
本発明に用いる１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）は、１分子内にフェノール性水酸基を２個以上有するものであり、前記化合物（Ａ）の硬化剤として作用（機能）するものである。
この化合物（Ｂ）としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノール樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル型フェノール樹脂、トリスフェノール樹脂、キシリレン変性ノボラック樹脂、テルペン変性ノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂が挙げられ、これらのうちの１種または２種以上を組み合わせて用いることができる。
[Compound (B)]
The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention has two or more phenolic hydroxyl groups in one molecule and acts as a curing agent for the compound (A) (function). )
Examples of the compound (B) include phenol novolak resin, cresol novolak resin, bisphenol resin, phenol aralkyl resin, biphenyl aralkyl type phenol resin, trisphenol resin, xylylene modified novolak resin, terpene modified novolak resin, dicyclopentadiene modified phenol. Resins can be used, and one or more of these can be used in combination.
［トリ置換ホスホニオフェノラート誘導体（Ｃ）：本発明の硬化促進剤］
本発明に用いるトリ置換ホスホニオフェノラート誘導体（Ｃ）は、トリ置換ホスホニオフェノラートと、１分子内にエポキシ基を１個以上有する化合物と、１分子内にフェノール性水酸基を１個以上有する化合物とを反応させて得られるものであり、エポキシ樹脂組成物の硬化反応を促進し得る作用（機能）を有するものである。
このうち、トリ置換ホスホニオフェノラートは、前記一般式（１）で表されるものであるのが好ましく、前記一般式（２）で表されるものであるのがより好ましく、前記一般式（３）で表されるものであるのがさらに好ましい。
[Trisubstituted Phosphoniophenolate Derivative (C): Curing Accelerator of the Present Invention]
The tri-substituted phosphoniophenolate derivative (C) used in the present invention has a tri-substituted phosphoniophenolate, a compound having one or more epoxy groups in one molecule, and one or more phenolic hydroxyl groups in one molecule. It is obtained by reacting with a compound and has an action (function) that can accelerate the curing reaction of the epoxy resin composition.
Among these, the tri-substituted phosphoniophenolate is preferably represented by the general formula (1), more preferably represented by the general formula (2), and the general formula ( More preferably, it is represented by 3).
ここで、前記一般式（１）において、リン原子に結合する置換基Ｒ1、Ｒ2およびＲ3としては、置換もしくは無置換の芳香族基または置換もしくは無置換のアルキル基であり、例えば、ベンジル基、メチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基、シクロヘキシル基、ナフチル基、フェニル基、メチルフェニル基、ｐ−ターシャリーブチルフェニル基、メトキシフェニル基、２，６−ジメトキシフェニル基、ヒドロキシフェニル基等が挙げられるが、これらの中でも、前記一般式（２）において、Ａｒ1、Ａｒ2およびＡｒ3で表されるように、ナフチル基、フェニル基、メチルフェニル基、ｐ−ターシャリーブチルフェニル基、メトキシフェニル基、２，６−ジメトキシフェニル基、ヒドロキシフェニル基等の置換もしくは無置換の芳香族基であるのが好ましく、特に、前記一般式（３）において、リン原子に結合する置換基で表されるように、フェニル基、メチルフェニル基の各種異性体、メトキシフェニル基の各種異性体、ヒドロキシフェニル基の各種異性体等であるのがより好ましい。 Here, in the general formula (1), the substituents R 1 , R 2 and R 3 bonded to the phosphorus atom are substituted or unsubstituted aromatic groups or substituted or unsubstituted alkyl groups. Benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, naphthyl group, phenyl group, methylphenyl group, p-tertiarybutylphenyl group, methoxyphenyl group, 2,6-dimethoxyphenyl Group, hydroxyphenyl group, etc., among these, as represented by Ar 1 , Ar 2 and Ar 3 in the general formula (2), naphthyl group, phenyl group, methylphenyl group, p- Tertiary butylphenyl group, methoxyphenyl group, 2,6-dimethoxyphenyl group, hydroxyphenyl group etc. substituted or unsubstituted It is preferably an aromatic group, and in particular, as represented by the substituent bonded to the phosphorus atom in the general formula (3), various isomers of a phenyl group, a methylphenyl group, and various isomers of a methoxyphenyl group And various isomers of a hydroxyphenyl group are more preferable.
また、前記一般式（１）および前記一般式（２）において、Ａｒは、水酸基以外の置換基により置換もしくは無置換の芳香族基を表す。
この置換基Ａｒとしては、例えば、フェニレン基、ビフェニレン基、ナフチレン基、または、これらにハロゲン原子、ニトロ基、シアノ基、炭素数１〜１２のアルキル基やアルコキシ基等の水酸基以外の置換基により置換された芳香族基が挙げられる。
総じて、前記一般式（１）において、置換基Ｒ1、Ｒ2、Ｒ3およびＡｒの組み合わせとしては、置換基Ｒ1、Ｒ2およびＲ3がそれぞれフェニル基であり、Ａｒがフェニレン基であるものが好適である。すなわち、前記一般式（３）において、置換基Ｒ4、Ｒ5およびＲ6がそれぞれ水素原子であるものが好適である。このものは、熱安定性、硬化促進能に特に優れ、製造コストが安価である。
In the general formula (1) and the general formula (2), Ar represents a substituted or unsubstituted aromatic group with a substituent other than a hydroxyl group.
Examples of the substituent Ar include a phenylene group, a biphenylene group, a naphthylene group, or a substituent other than a hydroxyl group such as a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group. A substituted aromatic group may be mentioned.
In general, in the general formula (1), as a combination of the substituents R 1 , R 2 , R 3 and Ar, the substituents R 1 , R 2 and R 3 are each a phenyl group, and Ar is a phenylene group. Those are preferred. That is, in the general formula (3), those in which the substituents R 4 , R 5 and R 6 are each a hydrogen atom are suitable. This product is particularly excellent in thermal stability and curing accelerating ability, and is inexpensive to produce.
更には、前記一般式（３）において、オキシアニオン（解離状態のフェノール性水酸基）は、リン原子に対してオルト位またはメタ位に位置することが好ましい。オルト位またはメタ位のものを硬化促進剤として用いることにより、パラ位のものを硬化促進剤として用いる場合に比較して、エポキシ樹脂組成物は、加熱時の弾性率がより低減する。さらに、かかる弾性率の低いエポキシ樹脂組成物で半導体素子を封止することにより、得られる半導体装置の耐半田クラック性の向上を図ることができる。 Further, in the general formula (3), the oxyanion (dissociated phenolic hydroxyl group) is preferably located in the ortho position or the meta position with respect to the phosphorus atom. By using the ortho-position or meta-position as a curing accelerator, the epoxy resin composition has a lower elastic modulus during heating than when using a para-position as a curing accelerator. Furthermore, by sealing the semiconductor element with such an epoxy resin composition having a low elastic modulus, it is possible to improve the solder crack resistance of the obtained semiconductor device.
本発明の硬化促進剤である、トリ置換ホスホニウムフェノラート誘導体（Ｃ）に用いる１分子内にエポキシ基を１個以上有する化合物は、分子内にエポキシ基を１個以上有するものであれば、その骨格構造などに制限はなく、従来公知のものが使用できる。具体的には、フェニルグリシジルエーテル、ブチルグリシジルエーテルなどの単官能エポキシ化合物、および上記化合物（Ａ）として述べられているような２官能以上のエポキシ化合物が挙げられるが、得られる硬化促進剤がエポキシ樹脂組成物に添加されるときに、良好な溶解性を有するためには、上記化合物（Ａ）として使用するものと、同じものを選択することが好ましい。 The compound having one or more epoxy groups in one molecule used for the tri-substituted phosphonium phenolate derivative (C), which is the curing accelerator of the present invention, can be any compound having one or more epoxy groups in the molecule. There is no restriction | limiting in frame | skeleton structure etc., a conventionally well-known thing can be used. Specific examples include monofunctional epoxy compounds such as phenyl glycidyl ether and butyl glycidyl ether, and bifunctional or higher functional epoxy compounds such as those described as compound (A) above. The resulting curing accelerator is an epoxy. In order to have good solubility when added to the resin composition, it is preferable to select the same one as that used as the compound (A).
また、トリ置換ホスホニウムフェノラート誘導体（Ｃ）に用いる１分子内にフェノール性水酸基を１個以上有する化合物は、分子内にフェノール性水酸基を１つ以上有するものであれば、その骨格構造などに制限はなく、従来公知のものが使用できる。具体的には、フェノール、クレゾール、ブロモフェノールなどの単官能フェノール化合物、および上記化合物（Ｂ）として述べられているような２官能以上のフェノール化合物が挙げられるが、得られる硬化促進剤がエポキシ樹脂組成物に添加されるときに、良好な溶解性を有するためには、上記化合物（Ｂ）として使用するものと、同じものを選択することが好ましい。 In addition, a compound having one or more phenolic hydroxyl groups in one molecule used for the tri-substituted phosphonium phenolate derivative (C) is limited to its skeleton structure as long as it has one or more phenolic hydroxyl groups in the molecule. There are no known ones. Specific examples include monofunctional phenolic compounds such as phenol, cresol, and bromophenol, and bifunctional or higher functional phenolic compounds as described in the above compound (B). The obtained curing accelerator is an epoxy resin. In order to have good solubility when added to the composition, it is preferable to select the same compound as that used as the compound (B).
前記トリ置換ホスホニウムフェノラート誘導体（Ｃ）において、これらの３つの成分を反応させる際の、各成分の比率は、トリ置換ホスホニオフェノラートの硬化促進能力が発揮され、成分がゲル化しないような比率であれば、何ら制限はない。具体的には、トリ置換ホスホニオフェノラート１モルに対し、エポキシ基およびフェノール性水酸基が各々１モルとなるような比率であることが好ましい。トリ置換ホスホニオフェノラートが他成分に対して少ない場合、エポキシとフェノール性水酸基の反応が主として進行し、この２成分がゲルを形成してしまうことがある。また、エポキシがフェノール性水酸基に対して大過剰に存在する場合、エポキシ基が開環して生じたアルコラートアニオンに、フェノール性水酸基がプロトン供与できないことから、エポキシ基同士の反応が促進し、ゲル化してしまうことがある。
これらの３成分を反応させる方法としては、例えば、各成分を常温で混合後、成分の少なくとも１つ以上が溶融する温度まで加熱し、混合しながら反応する方法や、各成分が溶解するような溶媒中で、穏やかに加温し反応させる方法などが挙げられるが、これに限定されるものではない。また、３つの成分のうち、２つをあらかじめ反応させ、さらに３つ目の成分を加えて反応をさせることもできる。
In the tri-substituted phosphonium phenolate derivative (C), when these three components are reacted, the ratio of each component is such that the ability to accelerate curing of the tri-substituted phosphoniophenolate is exhibited and the component does not gel. If it is a ratio, there is no limit. Specifically, the ratio is preferably such that each of the epoxy group and the phenolic hydroxyl group is 1 mole per mole of the tri-substituted phosphoniophenolate. When the amount of the tri-substituted phosphoniophenolate is smaller than that of the other components, the reaction between the epoxy and the phenolic hydroxyl group proceeds mainly, and the two components may form a gel. In addition, when the epoxy is present in a large excess with respect to the phenolic hydroxyl group, the phenolic hydroxyl group cannot be protonated to the alcoholate anion generated by the ring opening of the epoxy group. It may become.
As a method of reacting these three components, for example, after mixing each component at room temperature, it is heated to a temperature at which at least one of the components is melted and reacted while mixing, or each component is dissolved. A method of gently warming and reacting in a solvent is exemplified, but the method is not limited thereto. Also, two of the three components can be reacted in advance, and a third component can be added to react.
このようにして得られるトリ置換ホスホニウムフェノラート誘導体（Ｃ）は、トリ置換ホスホニウムフェノラートのフェノール性水酸基と、エポキシ化合物のエポキシ基が反応して得られるホスホニウム化合物と、フェノール性水酸基を有する化合物との塩を形成していると考えられる。 The tri-substituted phosphonium phenolate derivative (C) thus obtained includes a phenolic hydroxyl group of the tri-substituted phosphonium phenolate, a phosphonium compound obtained by reacting an epoxy group of the epoxy compound, a compound having a phenolic hydroxyl group, It is thought that the salt is formed.
本発明のエポキシ樹脂組成物において、トリ置換ホスホニオフェノラート誘導体（Ｃ）の含有量（配合量）は、特に限定されないが、０．０１〜１５重量％程度であるのが好ましい。これにより、エポキシ樹脂組成物の硬化性、保存性、流動性、他特性がバランスよく発揮される。
また、前記化合物（Ａ）と、前記化合物（Ｂ）との配合比率も、特に限定されないが、前記化合物（Ａ）のエポキシ基１モルに対し、前記化合物（Ｂ）のフェノール性水酸基が０．５〜２モル程度となるように用いるのが好ましく、０．７〜１．５モル程度となるように用いるのがより好ましい。これにより、エポキシ樹脂組成物の諸特性のバランスを好適なものに維持しつつ、諸特性がより向上する。
In the epoxy resin composition of the present invention, the content (blending amount) of the tri-substituted phosphoniophenolate derivative (C) is not particularly limited, but is preferably about 0.01 to 15% by weight. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and other characteristics of an epoxy resin composition are exhibited with sufficient balance.
Moreover, the compounding ratio of the compound (A) and the compound (B) is not particularly limited, but the phenolic hydroxyl group of the compound (B) is 0.1% with respect to 1 mol of the epoxy group of the compound (A). It is preferably used so as to be about 5 to 2 mol, and more preferably used so as to be about 0.7 to 1.5 mol. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.
本発明の樹脂組成物には、得られる半導体装置の補強を目的として、無機充填材を配合することができる。その種類については、特に制限はなく、一般に封止材料に用いられているものを使用することができる。
この無機充填材としては、例えば、溶融破砕シリカ、溶融シリカ、結晶シリカ、２次凝集シリカ、アルミナ、チタンホワイト、水酸化アルミニウム、タルク、クレー、ガラス繊維等が挙げられ、これらのうちの１種または２種以上を組み合わせて用いることができる。
また、無機充填材の形状としては、例えば、粒状、塊状、鱗片状等のいかなるものであってもよいが、粒状（特に、球状）であるのが好ましい。
この無機充填材の含有量（配合量）は、特に限定されないが、前記化合物（Ａ）と前記化合物（Ｂ）との合計量１００重量部あたり、２００〜２４００重量部程度であるのが好ましく、４００〜１４００重量部程度であるのがより好ましい。無機充填材の含有量（配合量）が、前記化合物（Ａ）と前記化合物（Ｂ）との合計量１００重量部あたり、４００〜１４００重量部であれば、エポキシ樹脂組成物の硬化物の吸湿率が低くなり、半田クラックの発生を防止することができる。また、かかるエポキシ樹脂組成物は、加熱溶融時の流動性も良好であるため、半導体装置内部の金線変形を引き起こすことが好適に防止される。
また、無機充填材の含有量（配合量）は、前記化合物（Ａ）、前記化合物（Ｂ）や無機充填材自体の比重を、それぞれ考慮し、重量部を体積％に換算して取り扱うようにしてもよい。
An inorganic filler can be blended with the resin composition of the present invention for the purpose of reinforcing the obtained semiconductor device. There is no restriction | limiting in particular about the kind, The thing generally used for the sealing material can be used.
Examples of the inorganic filler include fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber, and the like. Alternatively, two or more kinds can be used in combination.
Moreover, as a shape of an inorganic filler, what kind of things, such as a granular form, a block shape, and a scale shape, may be sufficient, for example, It is preferable that it is granular (especially spherical shape).
The content (blending amount) of the inorganic filler is not particularly limited, but is preferably about 200 to 2400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B). More preferably, it is about 400 to 1400 parts by weight. If the content (blending amount) of the inorganic filler is 400 to 1400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B), the moisture absorption of the cured product of the epoxy resin composition The rate is lowered, and the occurrence of solder cracks can be prevented. Moreover, since the epoxy resin composition has good fluidity when heated and melted, it is suitably prevented from causing deformation of the gold wire inside the semiconductor device.
In addition, the content (blending amount) of the inorganic filler is handled by converting the weight parts into volume%, taking into consideration the specific gravity of the compound (A), the compound (B) and the inorganic filler itself. May be.
また、本発明のエポキシ樹脂組成物中には、前記（Ａ）〜（Ｃ）成分と、無機充填材の他に、必要に応じて、例えば、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、臭素化エポキシ樹脂、酸化アンチモン、リン化合物等の難燃剤、シリコーンオイル、シリコーンゴム等の低応力成分、天然ワックス、合成ワックス、高級脂肪酸またはその金属塩類、パラフィン等の離型剤、酸化防止剤等の各種添加剤を配合（混合）するようにしてもよい。 Further, in the epoxy resin composition of the present invention, in addition to the components (A) to (C) and the inorganic filler, if necessary, for example, a cup of γ-glycidoxypropyltrimethoxysilane or the like. Ringing agents, coloring agents such as carbon black, flame retardants such as brominated epoxy resins, antimony oxides and phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural waxes, synthetic waxes, higher fatty acids or their metal salts, paraffins Various additives such as mold release agents and antioxidants may be blended (mixed).
また、本発明において硬化促進剤として機能するトリ置換ホスホニオフェノラート誘導体（Ｃ）の特性を損なわない範囲で、エポキシ樹脂組成物中には、例えば、トリフェニルホスフィン、１，８−ジアザビシクロ（５，４，０）−７−ウンデセン、２−メチルイミダゾール等の他の公知の硬化促進剤を配合（混合）するようにしても、何ら問題はない。 In the present invention, the epoxy resin composition contains, for example, triphenylphosphine, 1,8-diazabicyclo (5) as long as the properties of the tri-substituted phosphoniophenolate derivative (C) that functions as a curing accelerator are not impaired. , 4, 0) -7-undecene, other known curing accelerators such as 2-methylimidazole may be blended (mixed) without any problem.
本発明のエポキシ樹脂組成物は、前記（Ａ）〜（Ｃ）の化合物（成分）、および、必要に応じて、その他の添加剤等をミキサーを用いて常温混合し、熱ロール、加熱ニーダー等を用いて加熱混練し、冷却、粉砕することにより得られる。 The epoxy resin composition of the present invention is prepared by mixing the above-mentioned compounds (components) (A) to (C) and, if necessary, other additives at room temperature using a mixer, a heat roll, a heating kneader, etc. It is obtained by kneading with heat, cooling and pulverizing.
得られたエポキシ樹脂組成物をモールド樹脂として用いて、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の成形方法で硬化成形することにより、半導体素子等の電子部品を封止する。これにより、本発明の半導体装置が得られる。 The obtained epoxy resin composition is used as a mold resin, and is cured and molded by a molding method such as transfer molding, compression molding, injection molding, and the like, thereby sealing electronic components such as semiconductor elements. Thereby, the semiconductor device of the present invention is obtained.
本発明の半導体装置の形態としては、特に限定されないが、例えば、ＳＩＰ（Single Inline Package）、ＨＳＩＰ（SIP with Heatsink）、ＺＩＰ（Zig-zag Inline Package）、ＤＩＰ（Dual Inline Package）、ＳＤＩＰ（Shrink Dual Inline Package）、ＳＯＰ（Small Outline Package）、ＳＳＯＰ（Shrink Small Outline Package）、ＴＳＯＰ（Thin Small Outline Package）、ＳＯＪ（Small Outline J-leaded Package）、ＱＦＰ（Quad Flat Package）、ＱＦＰ(ＦＰ）（QFP Fine Pitch）、ＴＱＦＰ（Thin Quad Flat Package）、ＱＦＪ（ＰＬＣＣ）（Quad Flat J-leaded Package）、ＢＧＡ（Ball Grid Array）等が挙げられる。 The form of the semiconductor device of the present invention is not particularly limited. For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink) Dual Inline Package), SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline J-leaded Package), QFP (Quad Flat Package), QFP (FP) ( QFP Fine Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), BGA (Ball Grid Array), and the like.
なお、本実施形態では、本発明の硬化促進剤を、エポキシ樹脂組成物に用いる場合を代表して説明したが、本発明の硬化促進剤は、ホスフィンまたはホスホニウム塩を硬化促進剤として好適に使用し得る熱硬化性樹脂組成物に対して使用可能である。かかる熱硬化性樹脂組成物としては、例えばエポキシ化合物、マレイミド化合物、シアネート化合物、イソシアネート化合物、アクリレート化合物、または、アルケニルおよびアルキニル化合物等を含む樹脂組成物が挙げられる。 In the present embodiment, the case where the curing accelerator of the present invention is used as an epoxy resin composition has been described as a representative. However, the curing accelerator of the present invention preferably uses a phosphine or a phosphonium salt as a curing accelerator. The thermosetting resin composition can be used. Examples of such a thermosetting resin composition include a resin composition containing an epoxy compound, a maleimide compound, a cyanate compound, an isocyanate compound, an acrylate compound, or an alkenyl and alkynyl compound.
また、本発明の硬化促進剤は、熱硬化性樹脂組成物の他、例えば反応硬化性樹脂組成物、光硬化性樹脂組成物、嫌気硬化性樹脂組成物等の各種硬化性樹脂組成物に対しても使用可能である。 In addition to the thermosetting resin composition, the curing accelerator of the present invention is used for various curable resin compositions such as a reactive curable resin composition, a photocurable resin composition, and an anaerobic curable resin composition. Can be used.
また、本実施形態では、本発明のエポキシ樹脂組成物を、半導体装置の封止材料として用いる場合について説明したが、本発明のエポキシ樹脂組成物の用途としては、これに限定されるものではない。また、エポキシ樹脂組成物の用途等に応じて、本発明のエポキシ樹脂組成物では、無機充填材の混合（配合）を省略することもできる。
以上、本発明の硬化促進剤、エポキシ樹脂組成物および半導体装置の好適実施形態について説明したが、本発明は、これに限定されるものではない。
In the present embodiment, the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described. However, the use of the epoxy resin composition of the present invention is not limited thereto. . Further, in the epoxy resin composition of the present invention, mixing (compounding) of the inorganic filler can be omitted depending on the use of the epoxy resin composition.
As mentioned above, although preferred embodiment of the hardening accelerator of this invention, an epoxy resin composition, and a semiconductor device was described, this invention is not limited to this.
次に、本発明の具体的実施例について説明する。
１．トリ置換ホスホニオフェノラート誘導体（Ｃ）の合成
まず、硬化促進剤として使用する、本発明の硬化促進剤である化合物Ｃ１〜Ｃ８、比較用の硬化促進剤である化合物Ｃ９、Ｃ１０、およびトリフェニルホスフィンを用意した。
Next, specific examples of the present invention will be described.
1. Synthesis of Tri-Substituted Phosphoniophenolate Derivative (C) First, compounds C1 to C8 which are curing accelerators of the present invention, compounds C9 and C10 which are comparative curing accelerators, and triphenyl are used as curing accelerators. Phosphine was prepared.
（化合物Ｃ１の合成）
冷却管および撹拌装置付きのセパラブルフラスコ（容量：５００ｍＬ）に、３−ヨードフェノール２２．０ｇ（０．１００ｍｏｌ）と、トリフェニルホスフィン３１．４ｇ（０．１００ｍｏｌ）、塩化ニッケル０．５ｇ、エタノール１００ｍＬを仕込み、還流するように加熱し２４時間反応させた。
反応終了後、反応液を室温まで冷却した後、純水５００ｍＬに滴下し、反応物を析出させた。析出した反応物は、ろ過後にヘキサン１００ｍＬで洗浄し、乾燥して、ホスホニウムハロゲン塩３６．２ｇ（収率８３％）を得た。このハロゲン塩を、等モルの水酸化ナトリウムで中和して合成した下記式（４）で表されるトリ置換ホスホニウムフェノラート３５．４ｇ（０．１ｍｏｌ）、下記式（５）で表される構造のビフェニル型エポキシ樹脂 １９．３ｇ（エポキシ基０．１ｍｏｌ相当）を、攪拌装置付きのセパラブルフラスコにしこみ、常温で混合後、内温が１４０℃になるよう加熱し、９０分間反応させた。反応後に、フェノール９．４ｇ（フェノール水酸基０．１ｍｏｌ相当）を加え、さらに１００℃で６０分反応させ、樹脂状の化合物Ｃ１を得た。
(Synthesis of Compound C1)
In a separable flask (capacity: 500 mL) equipped with a condenser and a stirrer, 22.0 g (0.100 mol) of 3-iodophenol, 31.4 g (0.100 mol) of triphenylphosphine, 0.5 g of nickel chloride, ethanol 100 mL was charged and heated to reflux for 24 hours.
After completion of the reaction, the reaction solution was cooled to room temperature and then added dropwise to 500 mL of pure water to precipitate the reaction product. The precipitated reaction product was filtered, washed with 100 mL of hexane, and dried to obtain 36.2 g (yield 83%) of a phosphonium halogen salt. 35.4 g (0.1 mol) of a tri-substituted phosphonium phenolate represented by the following formula (4) synthesized by neutralizing this halogen salt with an equimolar amount of sodium hydroxide, and represented by the following formula (5) 19.3 g of biphenyl type epoxy resin (corresponding to 0.1 mol of epoxy group) was put into a separable flask equipped with a stirrer, mixed at room temperature, heated to 140 ° C. and reacted for 90 minutes. . After the reaction, 9.4 g of phenol (equivalent to 0.1 mol of phenol hydroxyl group) was added, and the mixture was further reacted at 100 ° C. for 60 minutes to obtain a resinous compound C1.
＜式（５）の化合物の物性＞
融点 ：１０５℃
水酸基当量 ：１９３
１５０℃のＩＣＩ溶融粘度：０．１５ｐｏｉｓｅ
<Physical properties of compound of formula (5)>
Melting point: 105 ° C
Hydroxyl equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise
上記で得た樹脂状の化合物Ｃ１を、ＤＳＣにより測定を行ったところ、９０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C1 obtained above was measured by DSC, endotherm due to a wide softening point was confirmed at around 90 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ２の合成）
前記同様にして合成した式（４）で表されるトリ置換ホスホニウムフェノラート３５．４ｇ（０．１ｍｏｌ）、下記式（６）で表される構造のビフェニルアラルキル型エポキシ樹脂２７．２ｇ（エポキシ基０．１ｍｏｌ相当）を、攪拌装置付きのセパラブルフラスコにしこみ、常温で混合後、内温が１４０℃になるよう加熱し、９０分間反応させた。反応後に、下記式（７）で表される構造のビフェニルアラルキル樹脂１９．９ｇ（フェノール水酸基０．１ｍｏｌ相当）を加え、さらに１００℃で６０分反応させ、樹脂状の化合物Ｃ２を得た。
(Synthesis of Compound C2)
35.4 g (0.1 mol) of a tri-substituted phosphonium phenolate represented by the formula (4) synthesized in the same manner as described above, and 27.2 g of an epoxy resin having a structure represented by the following formula (6) (epoxy group) 0.1 mol equivalent) was placed in a separable flask equipped with a stirrer, mixed at room temperature, heated to an internal temperature of 140 ° C., and reacted for 90 minutes. After the reaction, 19.9 g (corresponding to 0.1 mol of phenol hydroxyl group) of a biphenyl aralkyl resin having a structure represented by the following formula (7) was added and further reacted at 100 ° C. for 60 minutes to obtain a resinous compound C2.
＜式（６）の化合物の物性＞
軟化点 ：６０℃
エポキシ当量 ：２７２
１５０℃のＩＣＩ溶融粘度：１．３ｐｏｉｓｅ
<Physical Properties of Compound of Formula (6)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise
＜式（７）の化合物の物性＞
軟化点 ：６８℃
水酸基当量 ：１９９
１５０℃のＩＣＩ溶融粘度：０．９ｐｏｉｓｅ
<Physical properties of compound of formula (7)>
Softening point: 68 ° C
Hydroxyl equivalent: 199
ICI melt viscosity at 150 ° C .: 0.9 poise
上記で得た樹脂状の化合物Ｃ２を、ＤＳＣにより測定を行ったところ、６０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C2 obtained above was measured by DSC, endotherm due to a wide softening point was confirmed around 60 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ３の合成）
前記同様にして合成した式（４）で表されるトリ置換ホスホニウムフェノラート３５．４ｇ（０．１ｍｏｌ）、フェニルグリシジルエーテル１５．０ｇ（エポキシ基０．１ｍｏｌ）を、攪拌装置付きのセパラブルフラスコにしこみ、常温で混合後、内温が１４０℃になるよう加熱し、９０分間反応させた。反応後に、下記式（８）で表される構造のフェノールアラルキル樹脂１７．２ｇ（フェノール水酸基０．１ｍｏｌ相当）を加え、さらに１００℃で６０分反応させ、樹脂状の化合物Ｃ３を得た。
(Synthesis of Compound C3)
A separable flask equipped with a stirrer was prepared in the same manner as above by synthesizing 35.4 g (0.1 mol) of the tri-substituted phosphonium phenolate represented by formula (4) and 15.0 g of phenylglycidyl ether (0.1 mol of epoxy group). After squeezing and mixing at room temperature, the mixture was heated to an internal temperature of 140 ° C and reacted for 90 minutes. After the reaction, 17.2 g of phenol aralkyl resin having a structure represented by the following formula (8) (corresponding to 0.1 mol of phenol hydroxyl group) was added and reacted at 100 ° C. for 60 minutes to obtain a resinous compound C3.
＜式（８）の化合物の物性＞
軟化点 ：７７℃
水酸基当量 ：１７２
１５０℃のＩＣＩ溶融粘度：３．６ｐｏｉｓｅ
<Physical Properties of Compound of Formula (8)>
Softening point: 77 ° C
Hydroxyl equivalent: 172
ICI melt viscosity at 150 ° C .: 3.6 poise
上記で得た樹脂状の化合物Ｃ３を、ＤＳＣにより測定を行ったところ、７０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C3 obtained above was measured by DSC, endotherm due to a wide softening point was confirmed around 70 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ４の合成）
前記同様にして合成した式（４）表されるトリ置換ホスホニウムフェノラート３５．４ｇ（０．１ｍｏｌ）、前記式（５）で表される構造のビフェニル型エポキシ樹脂１９．３ｇ（エポキシ基０．１ｍｏｌ）を、攪拌装置付きのセパラブルフラスコにしこみ、常温で混合後、内温が１００℃になるよう加熱し、６０分間反応させた。反応後に、前記式（８）で表される構造のフェノールアラルキル樹脂１７．２ｇ（フェノール水酸基０．１ｍｏｌ相当）を加え、さらに１００℃で６０分反応させ、樹脂状の化合物Ｃ４を得た。
(Synthesis of Compound C4)
35.4 g (0.1 mol) of the tri-substituted phosphonium phenolate represented by the formula (4) synthesized in the same manner as described above, and 19.3 g of the biphenyl type epoxy resin having the structure represented by the formula (5) 1 mol) was placed in a separable flask equipped with a stirrer, mixed at room temperature, heated to an internal temperature of 100 ° C., and reacted for 60 minutes. After the reaction, 17.2 g of phenol aralkyl resin having a structure represented by the above formula (8) (equivalent to 0.1 mol of phenol hydroxyl group) was added, and the mixture was further reacted at 100 ° C. for 60 minutes to obtain a resinous compound C4.
上記で得た樹脂状の化合物Ｃ４を、ＤＳＣにより測定を行ったところ、７５℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C4 obtained above was measured by DSC, endotherm due to a wide softening point was confirmed around 75 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ５の合成）
３−ブロモフェノールの代わりに、２−ブロモ−６−ナフトール２２．３ｇ（０．１ｍｏｌ）を用いて、化合物Ｃ１と同様の手法で合成した下記式（９）で表されるトリ置換ホスホニウムフェノラート４０．４ｇ（０．１ｍｏｌ）を用いた以外は、化合物Ｃ１の合成と同様に行い、樹脂状の化合物Ｃ５を得た。
(Synthesis of Compound C5)
Trisubstituted phosphonium phenolate represented by the following formula (9) synthesized in the same manner as compound C1 using 22.3 g (0.1 mol) of 2-bromo-6-naphthol instead of 3-bromophenol A resinous compound C5 was obtained in the same manner as in the synthesis of Compound C1, except that 40.4 g (0.1 mol) was used.
上記で得た樹脂状の化合物Ｃ５を、ＤＳＣにより測定を行ったところ、９０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C5 obtained above was measured by DSC, endotherm due to a wide softening point was confirmed at around 90 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ６の合成）
前記式（４）で表されるトリ置換ホスホニウムフェノラートの代わりに、前記同様にして合成した式（９）で表されるトリ置換ホスホニウムフェノラート４０．４ｇ（０．１ｍｏｌ）を用いた以外は、化合物Ｃ２の合成と同様に行い、樹脂状の化合物Ｃ６を得た。
上記で得た樹脂状の化合物Ｃ６を、ＤＳＣにより測定を行ったところ、６０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。
(Synthesis of Compound C6)
Instead of the tri-substituted phosphonium phenolate represented by the formula (4), 40.4 g (0.1 mol) of the tri-substituted phosphonium phenolate represented by the formula (9) synthesized in the same manner as described above was used. In the same manner as in the synthesis of compound C2, resinous compound C6 was obtained.
When the resinous compound C6 obtained above was measured by DSC, an endotherm due to a wide softening point was confirmed around 60 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ７の合成）
トリフェニルホスフィンの代わりに、トリ−ｐ−トリルホスフィン３０．４ｇ（０．１ｍｏｌ）、３−ヨードフェノールの代わりに、２−ヨードフェノールを用いて合成した下記式（１０）で表されるトリ置換ホスホニウムフェノラート３９．７ｇ（０．１ｍｏｌ）を用いた以外は、化合物Ｃ２の合成と同様に行い、樹脂状の化合物Ｃ７を得た。
(Synthesis of Compound C7)
Tri-p-tolylphosphine 30.4 g (0.1 mol) instead of triphenylphosphine, tri-substituted represented by the following formula (10) synthesized using 2-iodophenol instead of 3-iodophenol Except that 39.7 g (0.1 mol) of phosphonium phenolate was used, a resinous compound C7 was obtained in the same manner as the synthesis of compound C2.
上記で得た樹脂状の化合物Ｃ７を、ＤＳＣにより測定を行ったところ、６０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C7 obtained above was measured by DSC, an endotherm due to a wide softening point was confirmed around 60 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ８の合成）
トリフェニルホスフィンの代わりに、トリ−ｎ−ブチルホスフィン２０．２ｇ（０．１ｍｏｌ）を用いて合成した下記式（１１）で表されるトチ置換ホスホニウムフェノラート２９．５ｇ（０．１ｍｏｌ）を用いた以外は、化合物Ｃ２の合成と同様に行い、樹脂状の化合物Ｃ８を得た。
(Synthesis of Compound C8)
Instead of triphenylphosphine, 29.5 g (0.1 mol) of toti-substituted phosphonium phenolate represented by the following formula (11) synthesized using 20.2 g (0.1 mol) of tri-n-butylphosphine was used. Except that, resin-like compound C8 was obtained in the same manner as in the synthesis of compound C2.
上記で得た樹脂状の化合物Ｃ８を、ＤＳＣにより測定を行ったところ、６０℃付近に幅広い軟化点による吸熱を確認した。また、高温域で、エポキシ基の開環反応による発熱は見られなかった。これより、仕込んだ原料が適切な反応を起こしていることが確認できた。 When the resinous compound C8 obtained above was measured by DSC, an endotherm due to a wide softening point was confirmed around 60 ° C. Further, no heat generation due to the ring-opening reaction of the epoxy group was observed at a high temperature range. From this, it was confirmed that the charged raw material had caused an appropriate reaction.
（化合物Ｃ９、Ｃ１０の合成）
前記同様にして合成した式（４）で表されるトリ置換ホスホニウムフェノラートを化合物Ｃ９とし、前記同様にして合成した式（９）で表されるトリ置換ホスホニウムフェノラートをＣ１０とした。
(Synthesis of compounds C9 and C10)
The tri-substituted phosphonium phenolate represented by the formula (4) synthesized in the same manner as above was designated as Compound C9, and the tri-substituted phosphonium phenolate represented by the formula (9) synthesized in the same manner as above was designated as C10.
２．エポキシ樹脂組成物の調製および半導体装置の製造
以下のようにして、前記化合物Ｃ１〜Ｃ８、比較用の化合物Ｃ９、Ｃ１０、およびトリフェニルホスフィンを含むエポキシ樹脂組成物を調製し、半導体装置を製造した。
2. Preparation of Epoxy Resin Composition and Manufacturing of Semiconductor Device An epoxy resin composition containing the compounds C1 to C8, comparative compounds C9 and C10, and triphenylphosphine was prepared as follows to manufacture a semiconductor device. .
（実施例１）
まず、化合物（Ａ）として前記式（５）で表されるビフェニル型エポキシ樹脂、化合物（Ｂ）として前記式（８）で表されるフェノールアラルキル樹脂（ただし、繰り返し単位数：３は、平均値を示す。）、硬化促進剤（Ｃ）として化合物Ｃ１、その他の添加剤として、無機充填材の溶融球状シリカ（平均粒径１５μｍ）、カーボンブラック、臭素化ビスフェノールＡ型エポキシ樹脂およびカルナバワックスを、それぞれ用意した。
Example 1
First, the biphenyl type epoxy resin represented by the formula (5) as the compound (A), the phenol aralkyl resin represented by the formula (8) as the compound (B) (however, the number of repeating units: 3 is an average value) The compound C1 as a curing accelerator (C), and as other additives, fused spherical silica (average particle size 15 μm), carbon black, brominated bisphenol A epoxy resin and carnauba wax as inorganic fillers, Each prepared.
次に、ビフェニル型エポキシ樹脂：５２重量部、フェノールアラルキル樹脂：４８重量部、化合物Ｃ１：３．２１重量部、溶融球状シリカ：７３０重量部、カーボンブラック：２重量部、臭素化ビスフェノールＡ型エポキシ樹脂：２重量部、カルナバワックス：２重量部を、まず室温で混合し、次いで熱ロールを用いて８５℃で８分間混練した後、冷却粉砕して、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得た。 Next, biphenyl type epoxy resin: 52 parts by weight, phenol aralkyl resin: 48 parts by weight, compound C1: 3.21 parts by weight, fused spherical silica: 730 parts by weight, carbon black: 2 parts by weight, brominated bisphenol A type epoxy 2 parts by weight of resin and 2 parts by weight of carnauba wax were first mixed at room temperature, then kneaded at 85 ° C. for 8 minutes using a hot roll, then cooled and crushed to obtain an epoxy resin composition (thermosetting resin composition) Product).
次に、このエポキシ樹脂組成物をモールド樹脂として用い、１００ピンＴＱＦＰのパッケージ（半導体装置）を８個、および、１６ピンＤＩＰのパッケージ（半導体装置）を１５個、それぞれ製造した。
１００ピンＴＱＦＰは、金型温度１７５℃、注入圧力７．４ＭＰａ、硬化時間２分でトランスファーモールド成形し、１７５℃、８時間で後硬化させることにより製造した。
なお、この１００ピンＴＱＦＰのパッケージサイズは、１４×１４ｍｍ、厚み１．４ｍｍ、シリコンチップ（半導体素子）サイズは、８．０×８．０ｍｍ、リードフレームは、４２アロイ製とした。
また、１６ピンＤＩＰは、金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分でトランスファーモールド成形し、１７５℃、８時間で後硬化させることにより製造した。
なお、この１６ピンＤＩＰのパッケージサイズは、６．４×１９．８ｍｍ、厚み３．５ｍｍ、シリコンチップ（半導体素子）サイズは、３．５×３．５ｍｍ、リードフレームは、４２アロイ製とした。
Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.
The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.
The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .
（実施例２）
まず、化合物（Ａ）として前記式（６）で表されるビフェニルアラルキル型エポキシ樹脂（ただし、繰り返し単位数：３は、平均値を示す。）、化合物（Ｂ）として前記式（７）で表されるビフェニルアラルキル型フェノール樹脂（ただし、繰り返し単位数：３は、平均値を示す。）、硬化促進剤（Ｃ）として化合物Ｃ１、その他の添加剤として、無機充填材である溶融球状シリカ（平均粒径１５μｍ）、カーボンブラック、臭素化ビスフェノールＡ型エポキシ樹脂およびカルナバワックスを、それぞれ用意した。
(Example 2)
First, a biphenyl aralkyl type epoxy resin represented by the above formula (6) as the compound (A) (however, the number of repeating units: 3 shows an average value), and a compound (B) represented by the above formula (7). Biphenyl aralkyl type phenolic resin (however, the number of repeating units: 3 indicates an average value), compound C1 as a curing accelerator (C), and fused spherical silica (average) as an inorganic additive as other additives Particle size 15 μm), carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared.
次に、ビフェニルアラルキル型エポキシ樹脂：５７重量部、ビフェニルアラルキル型フェノール樹脂：４３重量部、化合物Ｃ１：３．２１重量部、溶融球状シリカ：６５０重量部、カーボンブラック：２重量部、臭素化ビスフェノールＡ型エポキシ樹脂：２重量部、カルナバワックス：２重量部を、まず室温で混合し、次いで熱ロールを用いて９５℃で８分間混練した後、冷却粉砕して、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得た。
次に、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
Next, biphenyl aralkyl type epoxy resin: 57 parts by weight, biphenyl aralkyl type phenol resin: 43 parts by weight, compound C1: 3.21 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized, and an epoxy resin composition (thermosetting) Resin composition).
Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（実施例３）
化合物Ｃ１に代わり、化合物Ｃ２：４．１３重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 4.13 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例４）
化合物Ｃ１に代わり、化合物Ｃ２：４．１３重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
Example 4
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 4.13 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例５）
化合物Ｃ１に代わり、化合物Ｃ３：３．３８重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.38 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例６）
化合物Ｃ１に代わり、化合物Ｃ３：３．３８重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.38 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例７）
化合物Ｃ１に代わり、化合物Ｃ４：３．６０重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 7)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1, except that 3.60 parts by weight of compound C4 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例８）
化合物Ｃ１に代わり、化合物Ｃ４：３．６０重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, except that 3.60 parts by weight of compound C4 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例９）
化合物Ｃ１に代わり、化合物Ｃ５：３．４６重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
Example 9
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.46 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例１０）
化合物Ｃ１に代わり、化合物Ｃ５：３．４６重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 10)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.46 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例１１）
化合物Ｃ１に代わり、化合物Ｃ６：４．３８重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 11)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 4.38 parts by weight of compound C6 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例１２）
化合物Ｃ１に代わり、化合物Ｃ６：４．３８重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 12)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, except that 4.38 parts by weight of compound C6 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例１３）
化合物Ｃ１に代わり、化合物Ｃ７：３．６３重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 13)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.63 parts by weight of compound C7 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例１４）
化合物Ｃ１に代わり、化合物Ｃ７：３．６３重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 14)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.63 parts by weight of compound C7 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（実施例１５）
化合物Ｃ１に代わり、化合物Ｃ８：３．８５重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 15)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.85 parts by weight of compound C8 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例１６）
化合物Ｃ１に代わり、化合物Ｃ８：３．８５重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Example 16)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.85 parts by weight of compound C8 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（比較例１）
化合物Ｃ１に代わり、化合物Ｃ９：１．７７重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 1)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.77 parts by weight of compound C9 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（比較例２）
化合物Ｃ１に代わり、化合物Ｃ９：１．７７重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.77 parts by weight of compound C9 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（比較例３）
化合物Ｃ１に代わり、化合物Ｃ１０：２．０２重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.02 parts by weight of compound C10 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（比較例４）
化合物Ｃ１に代わり、化合物Ｃ１０：２．０２重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.02 parts by weight of compound C10 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（比較例５）
化合物Ｃ１に代わり、トリフェニルホスフィン：１．００重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（比較例６）
化合物Ｃ１に代わり、トリフェニルホスフィン：１．００重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 2.
３．特性評価
各実施例および各比較例で得られたエポキシ樹脂組成物の特性評価Ｉ〜III、および、各実施例および各比較例で得られた半導体装置の特性評価IVおよびＶを、それぞれ、以下のようにして行った。
Ｉ：スパイラルフロー
ＥＭＭＩ−Ｉ−６６に準じたスパイラルフロー測定用の金型を用い、金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分で測定した。
このスパイラルフローは、流動性のパラメータであり、数値が大きい程、流動性が良好であることを示す。
II：硬化トルク
キュラストメーター（オリエンテック（株）製、ＪＳＲキュラストメーターＩＶ ＰＳ型）を用い、１７５℃、４５秒後のトルクを測定した。
この硬化トルクは、数値が大きい程、硬化性が良好であることを示す。
III：フロー残存率
得られたエポキシ樹脂組成物を、大気中３０℃で１週間保存した後、前記Ｉと同様にしてスパイラルフローを測定し、調製直後のスパイラルフローに対する百分率（％）を求めた。
このフロー残存率は、数値が大きい程、保存性が良好であることを示す。
IV：耐半田クラック性
１００ピンＴＱＦＰを８５℃、相対湿度８５％の環境下で１６８時間放置し、その後、２６０℃の半田槽に１０秒間浸漬した。
その後、顕微鏡下に、外部クラックの発生の有無を観察し、クラック発生率＝（クラックが発生したパッケージ数）／（全パッケージ数）×１００として、百分率（％）で表示した。
また、シリコンチップとエポキシ樹脂組成物の硬化物との剥離面積の割合を、超音波探傷装置を用いて測定し、剥離率＝（剥離面積）／（シリコンチップの面積）×１００として、８個のパッケージの平均値を求め、百分率（％）で表示した。
これらのクラック発生率および剥離率は、それぞれ、数値が小さい程、耐半田クラック性が良好であることを示す。
Ｖ：耐湿信頼性
１６ピンＤＩＰに、１２５℃、相対湿度１００％の水蒸気中で、２０Ｖの電圧を印加し、断線不良を調べた。１５個のパッケージのうち８個以上に不良が出るまでの時間を不良時間とした。
なお、測定時間は、最長で５００時間とし、その時点で不良パッケージ数が８個未満であったものは、不良時間を５００時間超（＞５００）と示す。
この不良時間は、数値が大きい程、耐湿信頼性に優れることを示す。
3. Characteristic Evaluation Characteristic evaluations I to III of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluations IV and V of the semiconductor device obtained in each example and each comparative example are as follows. I went as follows.
I: Spiral Flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 2 minutes.
This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.
II: Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.
III: Flow residual ratio After the obtained epoxy resin composition was stored in the atmosphere at 30 ° C. for 1 week, the spiral flow was measured in the same manner as I above, and the percentage (%) with respect to the spiral flow immediately after preparation was determined. .
This flow residual ratio indicates that the larger the numerical value, the better the storage stability.
IV: Resistance to solder cracking 100 pin TQFP was left in an environment of 85 ° C. and 85% relative humidity for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds.
Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.
Further, the ratio of the peeled area between the silicon chip and the cured epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).
These crack occurrence rate and peeling rate indicate that the smaller the numerical value, the better the solder crack resistance.
V: Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100% to examine disconnection defects. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.
Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
各特性評価Ｉ〜Ｖの結果を、表１に示す。
表１に示すように、各実施例で得られたエポキシ樹脂組成物（本発明のエポキシ樹脂組成物）は、いずれも、硬化性、保存性、流動性が極めて良好であり、さらに、この硬化物で封止された各実施例のパッケージ（本発明の半導体装置）は、いずれも、耐半田クラック性、耐湿信頼性が良好なものであった。
これに対し、比較例１ないし比較例４で得られたエポキシ樹脂組成物は、いずれも流動性に劣るものであった。また、比較例５および比較例６で得られたエポキシ樹脂組成物は、いずれも、硬化性、保存性、流動性が極めて悪く、これらの比較例で得られたパッケージは、いずれも、耐半田クラック性に劣るものであった。
As shown in Table 1, each of the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in each example has extremely good curability, storage stability, and fluidity. Each of the packages of the examples (semiconductor device of the present invention) sealed with an object had good solder crack resistance and moisture resistance reliability.
On the other hand, the epoxy resin compositions obtained in Comparative Examples 1 to 4 were all poor in fluidity. In addition, the epoxy resin compositions obtained in Comparative Example 5 and Comparative Example 6 are extremely poor in curability, storage stability, and fluidity, and the packages obtained in these Comparative Examples are all solder resistant. It was inferior to cracking property.
４．他の熱硬化性樹脂組成物の調製と半導体装置の製造およびその評価
（実施例１７〜２４および比較例７）
ジアミノジフェニルメタンのビスマレイミド樹脂（ケイ・アイ化成製ＢＭＩ−Ｈ）１００重量部に、硬化促進剤として化合物Ｃ１〜Ｃ８およびトリフェニルホスフィンを、それぞれ、表２に示す配合比で配合し、これらを均一に混合した樹脂組成物（熱硬化性樹脂組成物）を得た。
実施例１７〜２４および比較例７で得られた樹脂組成物に対して、１９０℃におけるゲル化時間を測定した。
4). Preparation of other thermosetting resin compositions, manufacture of semiconductor devices and evaluation thereof (Examples 17 to 24 and Comparative Example 7)
In 100 parts by weight of diaminodiphenylmethane bismaleimide resin (K-I Kasei BMI-H), compounds C1 to C8 and triphenylphosphine as curing accelerators were blended at the blending ratios shown in Table 2, respectively. A resin composition (thermosetting resin composition) mixed with was obtained.
The gelation time at 190 ° C. was measured for the resin compositions obtained in Examples 17 to 24 and Comparative Example 7.
この結果を、各硬化促進剤の配合比と合わせて、表２に示す。
表２に示すように、各実施例で得られた樹脂組成物は、いずれも、速やかに硬化に至るものであった。これに対し、比較例で得られた樹脂組成物は、硬化には至らず、ミクロゲル化した。 As shown in Table 2, all of the resin compositions obtained in the respective examples rapidly cured. On the other hand, the resin composition obtained in the comparative example did not reach curing but was microgelled.
本発明の硬化促進剤は、熱硬化性樹脂組成物、特に、エポキシ樹脂組成物に、特に優れた流動性を与えることができ、また、良好な保存性と硬化性も兼ね備えている。一方、常温保管性の向上による、各種コストの低減及びハンドリング性の向上にも寄与することができる。また、該熱硬化性樹脂組成物を用い、その硬化物により封止された半導体素子などの電子部品を封止した電子部品装置は、耐半田クラック性や耐湿信頼性に優れるものとなる。 The curing accelerator of the present invention can give particularly excellent fluidity to a thermosetting resin composition, particularly an epoxy resin composition, and also has good storage stability and curability. On the other hand, it is possible to contribute to the reduction of various costs and the improvement of handling properties by improving the storage stability at room temperature. In addition, an electronic component device using the thermosetting resin composition and encapsulating an electronic component such as a semiconductor element sealed with the cured product has excellent solder crack resistance and moisture resistance reliability.
Claims (6)
であって、
前記硬化促進剤は、下記一般式（１）で表されるトリ置換ホスホニオフェノラートと、１分子内にエポキシ基を１個以上有する化合物と、１分子内にフェノール性水酸基を１個以上有する化合物とを反応させて得られるものであることを特徴とする硬化促進剤。
［式中、Ｒ 1 、Ｒ 2 およびＲ 3 は、それぞれ、置換もしくは無置換の芳香族基、または、置換もしくは無置換のアルキル基を表し、互いに同一であっても異なっていてもよい。Ａｒは、水酸基以外の置換基により置換もしくは無置換の芳香族基を表す。］ A curing accelerator that is mixed in the curable resin composition and can accelerate the curing reaction of the curable resin composition,
The curing accelerator has a tri-substituted phosphoniophenolate represented by the following general formula (1), a compound having one or more epoxy groups in one molecule, and one or more phenolic hydroxyl groups in one molecule. A curing accelerator characterized by being obtained by reacting with a compound.
[Wherein, R 1 , R 2 and R 3 each represent a substituted or unsubstituted aromatic group or a substituted or unsubstituted alkyl group, and may be the same or different from each other. Ar represents an aromatic group substituted or unsubstituted by a substituent other than a hydroxyl group. ]
項１に記載の硬化促進剤。
［式中、Ａｒ1、Ａｒ2およびＡｒ3は、それぞれ、置換もしくは無置換の芳香族基を表し、互いに同一であっても異なっていてもよい。Ａｒは、水酸基以外の置換基により置換もしくは無置換の芳香族基を表す。］ The curing accelerator according to claim 1, wherein the tri-substituted phosphoniophenolate is represented by the following general formula (2).
[Wherein, Ar 1 , Ar 2 and Ar 3 each represent a substituted or unsubstituted aromatic group, and may be the same or different from each other. Ar represents an aromatic group substituted or unsubstituted by a substituent other than a hydroxyl group. ]
項１に記載の硬化促進剤。
［式中、Ｒ4、Ｒ5およびＲ6は、それぞれ、水素原子、メチル基、メトキシ基および水酸基から選択される１種を表し、互いに同一であっても異なっていてもよい。］ The curing accelerator according to claim 1, wherein the tri-substituted phosphoniophenolate is represented by the following general formula (3).
[Wherein R 4 , R 5 and R 6 each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a hydroxyl group, and may be the same or different from each other. ]
位に位置する請求項３に記載の硬化促進剤。 In the said General formula (3), the oxyanion is a hardening accelerator of Claim 3 located in an ortho position or a meta position with respect to a phosphorus atom.
個以上有する化合物と、請求項１ないし４のいずれかに記載の硬化促進剤とを含むことを特徴とするエポキシ樹脂組成物。 A compound having two or more epoxy groups in one molecule and two phenolic hydroxyl groups in one molecule
The epoxy resin composition characterized by including the compound which has more than one, and the hardening accelerator in any one of Claims 1 thru | or 4 .
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| JP4747584B2 (en) * | 2005-01-18 | 2011-08-17 | 住友ベークライト株式会社 | Liquid encapsulating resin composition for semiconductor and semiconductor device encapsulated using the same |
| JP6111708B2 (en) * | 2013-02-04 | 2017-04-12 | 日立化成株式会社 | Curable resin composition and electronic component device |
| JP6111710B2 (en) * | 2013-02-04 | 2017-04-12 | 日立化成株式会社 | Curable resin composition and electronic component device |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000273155A (en) * | 1999-03-25 | 2000-10-03 | Sumitomo Bakelite Co Ltd | Semiconductor sealing epoxy resin molding material and semiconductor device using the same |
| JP2004115742A (en) * | 2002-09-27 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Curing agent composition for epoxy resin, epoxy resin composition using curing agent composition, and semiconductor device |
| JP2004156036A (en) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | Curing accelerator for curable resin, curable resin composition, electronic component device and method for producing phosphine derivative |
| JP2004176039A (en) * | 2002-06-05 | 2004-06-24 | Sumitomo Bakelite Co Ltd | Curing accelerator, epoxy resin composition, and semiconductor device |
| JP2004211007A (en) * | 2003-01-07 | 2004-07-29 | Sumitomo Bakelite Co Ltd | Curing accelerator, epoxy resin composition and semiconductor device |
| JP2005082722A (en) * | 2003-09-09 | 2005-03-31 | Sumitomo Bakelite Co Ltd | Hardening accelerator, epoxy resin composition and semiconductor device |
| JP2005154717A (en) * | 2003-10-31 | 2005-06-16 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1051031A (en) * | 1974-06-21 | 1979-03-20 | The Dow Chemical Company | Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids |
| JPH0340459A (en) * | 1989-07-07 | 1991-02-21 | Nitto Denko Corp | Semiconductor device |
| JP2765420B2 (en) * | 1992-12-10 | 1998-06-18 | 信越化学工業株式会社 | Manufacturing method of curing agent for epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000273155A (en) * | 1999-03-25 | 2000-10-03 | Sumitomo Bakelite Co Ltd | Semiconductor sealing epoxy resin molding material and semiconductor device using the same |
| JP2004176039A (en) * | 2002-06-05 | 2004-06-24 | Sumitomo Bakelite Co Ltd | Curing accelerator, epoxy resin composition, and semiconductor device |
| JP2004115742A (en) * | 2002-09-27 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Curing agent composition for epoxy resin, epoxy resin composition using curing agent composition, and semiconductor device |
| JP2004156036A (en) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | Curing accelerator for curable resin, curable resin composition, electronic component device and method for producing phosphine derivative |
| JP2004211007A (en) * | 2003-01-07 | 2004-07-29 | Sumitomo Bakelite Co Ltd | Curing accelerator, epoxy resin composition and semiconductor device |
| JP2005082722A (en) * | 2003-09-09 | 2005-03-31 | Sumitomo Bakelite Co Ltd | Hardening accelerator, epoxy resin composition and semiconductor device |
| JP2005154717A (en) * | 2003-10-31 | 2005-06-16 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
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