JP2004067717A - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- JP2004067717A JP2004067717A JP2002224598A JP2002224598A JP2004067717A JP 2004067717 A JP2004067717 A JP 2004067717A JP 2002224598 A JP2002224598 A JP 2002224598A JP 2002224598 A JP2002224598 A JP 2002224598A JP 2004067717 A JP2004067717 A JP 2004067717A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000004065 semiconductor Substances 0.000 title claims abstract description 32
- -1 phosphate compound Chemical class 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000005011 phenolic resin Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000005538 encapsulation Methods 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 17
- 229910000679 solder Inorganic materials 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 150000001463 antimony compounds Chemical class 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 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 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 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 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000001721 transfer moulding Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 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 4
- 239000000654 additive Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 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 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RMXQRHVIUMSGLJ-UHFFFAOYSA-N O.[Bi]=O Chemical compound O.[Bi]=O RMXQRHVIUMSGLJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 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
- 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
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 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
- 238000009472 formulation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- IHHCJKNEVHNNMW-UHFFFAOYSA-N methane;phenol Chemical compound C.OC1=CC=CC=C1 IHHCJKNEVHNNMW-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 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
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 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
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ハロゲン系難燃剤、アンチモン化合物を含まなくとも難燃性に優れた特性を有する半導体封止用エポキシ樹脂組成物及び半導体装置に関するものである。
【０００２】
【従来の技術】
従来、ダイオード、トランジスタ、集積回路等の電子部品は、主にエポキシ樹脂組成物で封止されている。これらのエポキシ樹脂組成物中には、難燃性を付与するために、通常ハロゲン系難燃剤及び三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等のアンチモン化合物が配合されている。しかしながら、世界的な環境保護の意識の高まりの中、ハロゲン系難燃剤やアンチモン化合物を使用しないで、難燃性を有するエポキシ樹脂組成物の要求が大きくなってきている。又ハロゲン系難燃剤及びアンチモン化合物を含むエポキシ樹脂組成物で封止された半導体装置を高温下で保管した場合、これらの難燃剤成分から熱分解したハロゲン化物が遊離し、半導体素子の接合部を腐食し、半導体装置の信頼性を損なうことが知られており、難燃剤としてハロゲン系難燃剤とアンチモン化合物を使用しなくても難燃グレードがＵＬ９４のＶ−０を達成できるエポキシ樹脂組成物が要求されている。
【０００３】
このように、半導体装置を高温下（例えば、１８５℃等）に保管した後の半導体素子の接合部（ボンディングパッド部）の耐腐食性のことを高温保管特性といい、この高温保管特性を改善する手法としては、五酸化二アンチモンを使用する方法（特開昭５５−１４６９５０号公報）や、酸化アンチモンと有機ホスフィンとを組み合わせる方法（特開昭６１−５３３２１号公報）等が提案され、効果が確認されているが、最近の半導体装置に対する高温保管特性の高い要求レベルに対して、エポキシ樹脂組成物の種類によっては不満足なものもある。
【０００４】
これらの要求に対して、種々の難燃剤が検討されている。例えば水酸化アルミニウムや水酸化マグネシウム等の金属水酸化物、ホウ素系化合物が検討されてきたが、これらは多量に配合しないと難燃性の効果が発現せず、しかも硬化性を低下させる傾向にある。又半導体装置の表面実装化が一般的になってきている現状では、吸湿した半導体装置が半田処理時に高温にさらされ、気化した水蒸気の爆発的応力により半導体装置にクラックが発生したり、或いは半導体素子やリードフレームとエポキシ樹脂組成物の硬化物との界面に剥離が発生することにより、電気的信頼性を大きく損なう不良が生じ、これらの不良の防止、即ち耐半田性の向上が大きな課題となっている。更に近年の環境問題に対して、半導体装置の実装に用いる半田に含まれる有鉛半田を無鉛半田にする方向になってきており、それに伴い半田処理の温度が高くなってきており、要求される耐半田性はより厳しくなると考えられる。
【０００５】
この耐半田性の向上のために、エポキシ樹脂組成物に無機充填材を多量に配合することにより、これを用いて得られる半導体装置の低吸湿化、低熱膨張化、高強度化を図ってきている。このため、樹脂成分としては低粘度型のものや、常温では結晶性であるが融点を越えると極めて低粘性を示す結晶性エポキシ樹脂を使用して、無機充填材の配合量の増加に伴うエポキシ樹脂組成物の成形時の流動性の低下を防止する手法、或いは樹脂骨格自体が疎水性であり、硬化物も低吸湿性を示すようなエポキシ樹脂やフェノール樹脂を用いる等が一般的に手法となっている。
【０００６】
結晶性エポキシ樹脂、疎水性エポキシ樹脂やフェノール樹脂を用いたエポキシ樹脂組成物の硬化物は、ガラス転移温度が低いため、ハロゲン系難燃剤とアンチモン化合物を併用した場合、高温保管特性が低下する傾向にあり、これを向上させるためには、ハロゲン系難燃剤及びアンチモン化合物を使用しないエポキシ樹脂組成物が求められている。又結晶性エポキシ樹脂は低粘度であるがために硬化が遅く、更に疎水性エポキシ樹脂や疎水性フェノール樹脂は架橋点間距離が長い分子構造を含むために、これを用いたエポキシ樹脂組成物の硬化物は柔らかく、離型性を向上し生産性を高めるためには、エポキシ樹脂の硬化阻害を起こすような難燃剤の使用は難しい。即ちハロゲン系難燃剤及びアンチモン化合物を含まないで、難燃性を維持し、成形性、耐半田性、高温保管特性に優れたエポキシ樹脂組成物が求められている。
【０００７】
【発明が解決しようとする課題】
本発明は、ハロゲン系難燃剤及びアンチモン化合物を含まなくとも難燃性に優れ、かつ成形性、耐半田性、高温保管特性に優れた特性を有する半導体封止用エポキシ樹脂組成物及びこれを用いて半導体素子を封止してなる半導体装置を提供するものである。
【０００８】
【課題を解決するための手段】
本発明は、
［１］ （Ａ）一般式（１）〜一般式（３）から選ばれるエポキシ樹脂、（Ｂ）一般式（４）〜一般式（６）から選ばれるフェノール樹脂、（Ｃ）硬化促進剤、（Ｄ）無機充填材及び（Ｅ）一般式（７）で示されるリン酸エステル化合物を含み、リン酸エステル化合物が全エポキシ樹脂組成物中０．０５〜５重量％であることを特徴とする半導体封止用エポキシ樹脂組成物、
【０００９】
【化８】
（Ｒは、炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ａは０又は１〜３。ｎは平均値で、１〜１０の正数）
【００１１】
【化９】
（Ｒは、炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ａは０又は１〜３。ｎは平均値で、１〜１０の正数）
【００１３】
【化１０】
（Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ｂは１又は２。ｎは平均値で、１〜１０の正数。）
【００１５】
【化１１】
（Ｒは、炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ａは０又は１〜３。ｎは平均値で、１〜１０の正数）
【００１７】
【化１２】
（Ｒは、炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ａは０又は１〜３。ｎは平均値で、１〜１０の正数）
【００１９】
【化１３】
（Ｒは、炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。Ｒ１は、水素原子又は炭素数１〜４のアルキル基を表し、互いに同一もしくは異なっていてもよい。ｂは１又は２。ｎは平均値で、１〜１０の正数。）
【００２１】
【化１４】
（Ｒは、有機基を表し、互いに同一もしくは異なっていてもよい）
［２］ 一般式（７）で示されるリン酸エステル化合物のＲが、置換又は無置換アリール基である第［１］項記載の半導体封止用エポキシ樹脂組成物、
［３］ 第［１］項又は［２］項記載のエポキシ樹脂組成物を用いて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、
である。
【００２３】
【発明の実施の形態】
本発明に用いられる一般式（１）〜一般式（３）で示されるエポキシ樹脂は、疎水性の樹脂骨格を有しているので、これを用いたエポキシ樹脂組成物の硬化物は低吸湿性となると共に、硬化物の架橋点間距離が長くなるため半田処理温度での弾性率が低くなる特徴を有している。このため発生する応力が小さく、密着性に優れるため、耐半田性が良好である。又一般式（１）〜一般式（３）で示されるエポキシ樹脂は、樹脂中の芳香族環含有率が高いために、樹脂自体が耐燃性の特性を有しており、難燃剤の配合量を低く抑えることができる。
一般式（１）〜一般式（３）で示されるエポキシ樹脂の特性を損なわない範囲で、他のエポキシ樹脂を併用してもよい。併用するエポキシ樹脂としては、１分子内にエポキシ基を２個以上有するモノマー、オリゴマー、ポリマー全般を言い、例えばビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、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、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂等が挙げられ、これらは単独でも混合して用いても差し支えない。
【００２４】
本発明に用いられる一般式（４）〜一般式（６）で示されるフェノール樹脂は、疎水性の樹脂骨格を有しているので、これを用いたエポキシ樹脂組成物の硬化物は低吸湿性となると共に、硬化物の架橋点間距離が長くなるため半田処理温度での弾性率が低くなる特徴を有している。このため発生する応力が小さく、密着性に優れるため、耐半田性が良好である。又一般式（４）〜一般式（６）で示されるエポキシ樹脂は、樹脂中の芳香族環含有率が高いために、樹脂自体が耐燃性の特性を有しており、難燃剤の配合量を低く抑えることができる。
一般式（４）〜一般式（６）で示されるフェノール樹脂の特性を損なわない範囲で、他のフェノール樹脂を併用してもよい。併用するフェノール樹脂としては、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般を言い、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、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂樹脂等が挙げられ、これらは単独でも混混合して用いても差し支えない。
又一般式（１）〜一般式（３）で示されるエポキシ樹脂及び一般式（４）〜一般式（６）で示されるフェノール樹脂は、前記したように優れた特徴を有しているが、硬化性や離型性等の成形性において、若干劣る傾向にあり、成形性を阻害する添加物は極力少なくする必要がある。
これらの配合量としては、全エポキシ樹脂のエポキシ基数と全フェノール樹脂のフェノール性水酸基数の比が０．８〜１．３の範囲が好ましい。０．８未満であれば硬化性と硬化物の耐熱性が低下し、吸湿率が増大するという問題があり、１．３を越えると硬化物の耐熱性と耐燃性が低下すると傾向にある。
【００２５】
本発明に用いられる硬化促進剤としては、エポキシ基とフェノール性水酸基との硬化反応を促進させるものであればよく、一般に封止材料に使用するものを用いることができる。例えば１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリフェニルホスフィン、２−メチルイミダゾール、テトラフェニルホスホニウム・テトラフェニルボレート等が挙げられ、これらは単独でも混合して用いても差し支えない。
【００２６】
本発明に用いられる無機充填材としては、一般に封止材料に使用されているものを用いることができる。例えば溶融シリカ、結晶シリカ、タルク、アルミナ、窒化珪素等が挙げられ、これらは単独でも混合して用いても差し支えない。無機充填材の配合量としては、成形性と耐半田性のバランスから、全エポキシ樹脂組成物中に６０〜９５重量％が好ましい。６０重量％未満だと、吸湿率の上昇に伴う耐半田性が低下し、９５重量％を越えると、ワイヤースィープ及びパッドシフト等の成形性の問題が生じ好ましくない。
【００２７】
本発明に用いられる一般式（７）で示されるリン酸エステル化合物は、リンによる炭化促進、即ちエポキシ樹脂組成物の硬化物の表面に不燃性の炭化層を形成することにより、硬化物表面の保護及び酸素を遮断することにより、高い難燃性を付与するものと推定されている。式中のＲは、互いに同一もしくは異なる有機基を示すが、耐熱性、耐湿性の点から置換又は無置換のアリール基が好ましい。一般式（７）で示されるリン酸エステル化合物の具体例としては、トリフェニルホスフェート、トリキシレニルホスフェート、トリクレジニル、クレジニルジフェニルホスフェート、レゾルシノールビス（ジフェニル）ホスフェート、ビスフェノールＡビス（ジフェニル）ホスフェート、２−エチルヘキシルジフェニルホスフェート等が挙げられる。
本発明に用いられる一般式（７）で示されるリン酸エステル化合物には、一般式（８）で示される複数のリン酸エステル化合物が、二価の有機基（Ｒ１）を介して結合した構造の化合物も含まれる。リン酸エステル化合物同士を結合する二価の有機基としては、ハイドロキノン、４，４’−ビスフェノール、ビスフェノールＡ等の二官能フェノール化合物の水酸基から２個の水素原子を除いた残基等が好ましい。結合しているリン酸エステル化合物は同一でも異なっていてもよい。
【００２８】
【化１５】
本発明におけるリン酸エステル化合物は、単独でも併用してもよい。リン酸エステル化合物の配合量としては、全エポキシ樹脂組成物中の０．０５〜５重量％が好ましく、更に好ましくは０．３〜３重量％が望ましい。下限値未満であると難燃性向上の効果を得ることが出来ず、上限値を越えると強度の低下、吸水率の増大等による半田耐熱性の低下や硬化性の悪化により成形性が低下する。この範囲内ならば、本発明に用いられるエポキシ樹脂とフェノール樹脂の組み合わせでも成形性、耐半田性に優れたエポキシ樹脂組成物を得ることができる。
【００３０】
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｅ）成分の他、必要に応じて他の難燃剤、酸化ビスマス水和物等の無機イオン交換体、カーボンブラック、ベンガラ等の着色剤、シリコーンオイル、シリコーンゴム等の低応力化剤、天然ワックス、合成ワックス、高級脂肪酸及びその金属塩類もしくは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することができる。
【００３１】
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｅ）成分、及びその他の添加剤等をミキサーを用いて混合後、熱ロール、加熱ニーダー、押出機等の混練機で溶融混練し、冷却後粉砕して得られる。
本発明のエポキシ樹脂組成物を用いて、半導体素子等の電子部品を封止し、半導体装置を製造するには、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ればよい。
【００３２】
【実施例】
以下、本発明を実施例で具体的に説明するが、本発明はこれらに限定されるものではない。配合割合は重量部とする。
実施例１
式（９）のエポキシ樹脂（軟化点６０℃、エポキシ当量２７０ｇ／ｅｑ．）６．３重量部
【００３３】
【化１６】
式（１０）のフェノール樹脂（軟化点７３℃、水酸基当量１９９ｇ／ｅｑ．）４．７重量部
【００３５】
【化１７】
溶融球状シリカ（平均粒径２０μｍ） ８６．０重量部
式（１１）のリン酸エステル化合物 ２．０重量部
【００３７】
【化１８】
トリフェニルホスフィン ０．２重量部
エポキシシラン（γ−グリシドキシプロピルトリメトキシシラン）０．２重量部
カーボンブラック ０．３重量部
カルナバワックス ０．３重量部
をミキサーを用いて常温で混合した後、表面温度が９０℃と４５℃の２本ロールを用いて混練し、冷却後粉砕して、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を以下の方法で評価した。結果を表１に示す。
【００３９】
評価方法
スパイラルフロー：ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用の金型を用いて、金型温度１７５℃、注入圧力６．９ＭＰａ、硬化時間１２０秒で測定した。単位はｃｍ。
硬化性：低圧トランスファー成形機を用いて金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で成形した。金型が開いて１０秒後のランナーの表面硬度をバコール硬度計＃９３５で測定した。バコール硬度は硬化性の指標であり、数値が大きい方が硬化性が良好である。
吸湿率：低圧トランスファー成形機を用いて金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で直径５０ｍｍ、厚さ３ｍｍの円板を成形し、１７５℃、８時間で後硬化し、８５℃、相対湿度８５％の環境下で１６８時間放置し、重量変化を測定して吸湿率を求めた。単位は重量％。
熱時曲げ強度：ＪＩＳ Ｋ ６９１１に準じて２４０℃での曲げ強度を測定した。単位はＭＰａ。
難燃性：低圧トランスファー成形機を用いて金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で試験片（１２７ｍｍ×１２．７ｍｍで厚みは１．０ｍｍ、１．６ｍｍ、３．２ｍｍの３種類）を成形し、１７５℃、８時間で後硬化した後、ＵＬ−９４垂直法に準じてΣＦ、Ｆｍａｘを測定し、難燃性を判定した。
【００４０】
耐湿信頼性：低圧トランスファー成形機を用いて金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で１６ｐＳＯＰ（模擬素子のＴＥＧ３使用、配線幅２０μｍ）を成形し、１７５℃、８時間で後硬化した後、耐湿信頼性評価（１４０℃／相対湿度８５％で１０Ｖの印加電圧をかけて処理）を行い、配線間のオープン不良を確認した。２０個のパッケージについて、処理５００時間後と１０００時間後での不良パッケージ個数を不良率として百分率で示した。単位は％。
耐半田性：低圧トランスファー成形機を用いて、金型温度１７５℃、注入圧力８．３ＭＰａ、硬化時間１２０秒で８０ｐＱＦＰ（２ｍｍ厚、チップサイズ９．０ｍｍ×９．０ｍｍ）を成形し、１７５℃、８時間で後硬化し、８５℃、相対湿度８５％で１６８時間放置し、その後２４０℃の半田槽に１０秒間浸漬した。顕微鏡で観察し、クラック発生率［（クラック発生率）＝｛（外部クラック発生パッケージ数）／（全パッケージ数）｝×１００］を求めた。単位は％。又半導体素子とエポキシ樹脂組成物の硬化物との界面の剥離面積を超音波探傷装置を用いて測定し、剥離率［（剥離率）＝｛（剥離面積）／（半導体素子面積）｝×１００］を求めた。単位は％。
高温保管特性：低圧トランスファー成形機を用いて金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で１６ｐＤＩＰ（チップサイズ３．０ｍｍ×３．５ｍｍ）を成形し、１７５℃、８時間で後硬化した後、高温保管試験（１８５℃、１０００時間）を行い、配線間の電気抵抗値が初期値に対し２０％増加したパッケージを不良と判定した。１５個のパッケージ中の不良なパッケージ個数の率（不良率）を百分率で示した。単位は％。
キュラストメーターのトルク値：キュラストメーターＶ型（（株）オリエンテック・製）を用い、３５φのダイス、振幅角１度、温度１７５℃で測定した。９０秒後のトルク値を測定し、硬化性を評価した。キュラストトルクという。単位はＮｍ。
【００４１】
実施例２〜７、比較例１〜４
表１の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得、実施例１と同様にして評価した。結果を表１、表２に示す。
【００４２】
式（１２）のエポキシ樹脂（軟化点６２℃、エポキシ当量２２７ｇ／ｅｑ．）
【００４３】
【化１９】
式（１３）のエポキシ樹脂（軟化点７３℃、エポキシ当量２６９ｇ／ｅｑ．）
【００４５】
【化２０】
式（１４）のエポキシ樹脂（軟化点８１℃、エポキシ当量２６５ｇ／ｅｑ．）
【００４７】
【化２１】
式（１５）のフェノール樹脂（軟化点７７℃、水酸基当量１７４ｇ／ｅｑ．）
【００４９】
【化２２】
式（１６）のフェノール樹脂（軟化点８７℃、水酸基当量２１０ｇ／ｅｑ．）
【００５１】
【化２３】
式（１７）のリン酸エステル化合物
【００５３】
【化２４】
式（１８）のリン酸エステル化合物
【００５５】
【化２５】
比較例４で用いた臭素化ビスフェノールＡ型エポキシ樹脂は、エポキシ当量３６５ｇ／ｅｑ．、臭素原子含有率４８重量％である。
【００５７】
【表１】
【表２】
【発明の効果】
本発明に従うと、ハロゲン系難燃剤及びアンチモン化合物を含まなくとも難燃性に優れ、かつ硬化性や離型性等の成形性、耐半田性、高温保管特性に優れた特性を有する半導体封止用エポキシ樹脂組成物が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device having excellent flame retardancy even without containing a halogen-based flame retardant and an antimony compound.
[0002]
[Prior art]
Conventionally, electronic components such as diodes, transistors, and integrated circuits have been mainly sealed with an epoxy resin composition. These epoxy resin compositions usually contain a halogen-based flame retardant and an antimony compound such as antimony trioxide, antimony tetroxide, or antimony pentoxide in order to impart flame retardancy. However, with increasing awareness of environmental protection worldwide, there is an increasing demand for epoxy resin compositions having flame retardancy without using halogen-based flame retardants or antimony compounds. In addition, when semiconductor devices sealed with an epoxy resin composition containing a halogen-based flame retardant and an antimony compound are stored at a high temperature, a thermally decomposed halide is released from these flame retardant components, and a junction of the semiconductor element is formed. Corrosion is known to impair the reliability of semiconductor devices, and an epoxy resin composition capable of achieving a flame retardant grade of UL94 V-0 without using a halogen-based flame retardant and an antimony compound as a flame retardant is known. Is required.
[0003]
As described above, the corrosion resistance of the bonding portion (bonding pad portion) of the semiconductor element after the semiconductor device is stored at a high temperature (for example, 185 ° C.) is called a high-temperature storage characteristic, and the high-temperature storage characteristic is improved. As a method of performing this, a method using diantimony pentoxide (JP-A-55-146950), a method of combining antimony oxide with an organic phosphine (JP-A-61-53321), and the like have been proposed. However, some types of epoxy resin compositions are not satisfactory with respect to the recent high level of high-temperature storage characteristics required for semiconductor devices.
[0004]
To meet these requirements, various flame retardants have been studied. For example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and boron-based compounds have been studied. However, unless these are blended in a large amount, the flame-retardant effect does not appear, and the curability tends to decrease. is there. In the current situation where surface mounting of semiconductor devices is becoming common, a semiconductor device that has absorbed moisture is exposed to high temperatures during soldering, and cracks occur in the semiconductor device due to the explosive stress of vaporized water vapor. The occurrence of peeling at the interface between the element and the lead frame and the cured product of the epoxy resin composition causes defects that greatly impair the electrical reliability.Prevention of these defects, that is, improvement of solder resistance is a major issue. Has become. Furthermore, in response to recent environmental problems, the trend has been to change leaded solder contained in solder used for mounting semiconductor devices to lead-free solder, and accordingly, the temperature of solder processing has been increased, which is required. It is believed that the solder resistance will be more severe.
[0005]
In order to improve the soldering resistance, a large amount of an inorganic filler is added to the epoxy resin composition to reduce the moisture absorption, lower the thermal expansion, and increase the strength of the semiconductor device obtained using the same. I have. For this reason, as a resin component, a low-viscosity type resin or a crystalline epoxy resin which is crystalline at room temperature but exhibits an extremely low viscosity above the melting point is used. Techniques to prevent a decrease in fluidity during molding of the resin composition, or a method in which the resin skeleton itself is hydrophobic and the cured product also uses an epoxy resin or a phenol resin that exhibits low moisture absorption, etc. Has become.
[0006]
The cured product of the epoxy resin composition using crystalline epoxy resin, hydrophobic epoxy resin or phenol resin has a low glass transition temperature, so when a halogen-based flame retardant and an antimony compound are used in combination, the high-temperature storage characteristics tend to decrease. In order to improve this, an epoxy resin composition that does not use a halogen-based flame retardant and an antimony compound is required. In addition, crystalline epoxy resin has low viscosity, but cures slowly because it has a low viscosity. In addition, hydrophobic epoxy resin and hydrophobic phenol resin have a molecular structure with a long distance between cross-linking points. The cured product is soft, and it is difficult to use a flame retardant that inhibits the curing of the epoxy resin in order to improve the releasability and increase the productivity. That is, there is a need for an epoxy resin composition that does not contain a halogen-based flame retardant and an antimony compound, maintains flame retardancy, and is excellent in moldability, solder resistance, and high-temperature storage characteristics.
[0007]
[Problems to be solved by the invention]
The present invention provides an epoxy resin composition for semiconductor encapsulation having excellent flame retardancy without containing a halogen-based flame retardant and an antimony compound, and having excellent moldability, solder resistance, and high-temperature storage characteristics, and the use thereof. To provide a semiconductor device in which a semiconductor element is sealed.
[0008]
[Means for Solving the Problems]
The present invention
[1] (A) an epoxy resin selected from the general formulas (1) to (3), (B) a phenol resin selected from the general formulas (4) to (6), (C) a curing accelerator, It contains (D) an inorganic filler and (E) a phosphoric ester compound represented by the general formula (7), and the phosphoric ester compound accounts for 0.05 to 5% by weight of the entire epoxy resin composition. Epoxy resin composition for semiconductor encapsulation,
[0009]
Embedded image
(R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. A is 0 or 1 to 3. n is an average value and is a positive number of 1 to 10.)
[0011]
Embedded image
(R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. A is 0 or 1 to 3. n is an average value and is a positive number of 1 to 10.)
[0013]
Embedded image
(R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other. B is 1 or 2. n is an average number and a positive number of 1 to 10.)
[0015]
Embedded image
(R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. A is 0 or 1 to 3. n is an average value and is a positive number of 1 to 10.)
[0017]
Embedded image
(R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. A is 0 or 1 to 3. n is an average value and is a positive number of 1 to 10.)
[0019]
Embedded image
(R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. .B is 1 or 2. n is an average value and a positive number of 1 to 10.)
[0021]
Embedded image
(R represents an organic group and may be the same or different from each other)
[2] The epoxy resin composition for semiconductor encapsulation according to [1], wherein R of the phosphate compound represented by the general formula (7) is a substituted or unsubstituted aryl group.
[3] A semiconductor device obtained by sealing a semiconductor element with the epoxy resin composition according to the item [1] or [2],
It is.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
Since the epoxy resins represented by the general formulas (1) to (3) used in the present invention have a hydrophobic resin skeleton, a cured product of the epoxy resin composition using the epoxy resin has low hygroscopicity. And the distance between the cross-linking points of the cured product becomes longer, so that the elastic modulus at the soldering temperature is lowered. Therefore, the generated stress is small and the adhesiveness is excellent, so that the solder resistance is good. The epoxy resins represented by the general formulas (1) to (3) have a high aromatic ring content in the resin, so that the resin itself has the property of flame resistance, and the amount of the flame retardant compounded. Can be kept low.
Other epoxy resins may be used in combination as long as the properties of the epoxy resins represented by the general formulas (1) to (3) are not impaired. The epoxy resin used in combination includes all monomers, oligomers and polymers having two or more epoxy groups in one molecule, such as biphenyl epoxy resin, bisphenol epoxy resin, stilbene epoxy resin, phenol novolak epoxy resin, and cresol. Novolak-type epoxy resin, triphenolmethane-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol-type epoxy resin, and the like. No problem.
[0024]
Since the phenolic resins represented by the general formulas (4) to (6) used in the present invention have a hydrophobic resin skeleton, a cured product of the epoxy resin composition using the phenolic resin has low hygroscopicity. And the distance between the cross-linking points of the cured product becomes longer, so that the elastic modulus at the soldering temperature is lowered. Therefore, the generated stress is small and the adhesiveness is excellent, so that the solder resistance is good. Further, the epoxy resins represented by the general formulas (4) to (6) have a high aromatic ring content in the resin, so that the resin itself has the property of flame resistance, and the amount of the flame retardant compounded. Can be kept low.
Other phenol resins may be used in combination as long as the properties of the phenol resins represented by the general formulas (4) to (6) are not impaired. The phenol resin used in combination includes all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule, such as phenol novolak resin, cresol novolak resin, dicyclopentadiene-modified phenol resin, terpene-modified phenol resin, Phenol methane type resin resins and the like may be mentioned, and these may be used alone or as a mixture.
The epoxy resins represented by the general formulas (1) to (3) and the phenolic resins represented by the general formulas (4) to (6) have excellent characteristics as described above. Moldability such as curability and mold release properties tend to be slightly inferior, and it is necessary to minimize the amount of additives that inhibit moldability.
The ratio of the number of epoxy groups of all epoxy resins to the number of phenolic hydroxyl groups of all phenolic resins is preferably in the range of 0.8 to 1.3. If it is less than 0.8, the curability and the heat resistance of the cured product decrease, and the moisture absorption rate increases. If it exceeds 1.3, the heat resistance and the flame resistance of the cured product tend to decrease.
[0025]
As the curing accelerator used in the present invention, any one can be used as long as it promotes the curing reaction between the epoxy group and the phenolic hydroxyl group, and those generally used for a sealing material can be used. For example, 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, 2-methylimidazole, tetraphenylphosphonium / tetraphenylborate and the like can be mentioned, and these may be used alone or in combination. .
[0026]
As the inorganic filler used in the present invention, those generally used for a sealing material can be used. For example, fused silica, crystalline silica, talc, alumina, silicon nitride and the like can be mentioned, and these may be used alone or in combination. The blending amount of the inorganic filler is preferably 60 to 95% by weight in the total epoxy resin composition from the balance between moldability and solder resistance. If the amount is less than 60% by weight, the soldering resistance decreases with an increase in the moisture absorption. If the amount exceeds 95% by weight, problems such as wire sweep and pad shift are caused, which is not preferable.
[0027]
The phosphoric ester compound represented by the general formula (7) used in the present invention promotes carbonization by phosphorus, that is, forms a non-combustible carbonized layer on the surface of the cured product of the epoxy resin composition, whereby the surface of the cured product is It is presumed that protection and blocking of oxygen provide high flame retardancy. R in the formulas represent the same or different organic groups, but a substituted or unsubstituted aryl group is preferable from the viewpoint of heat resistance and moisture resistance. Specific examples of the phosphate compound represented by the general formula (7) include triphenyl phosphate, trixylenyl phosphate, tricredinyl, credinyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, -Ethylhexyl diphenyl phosphate and the like.
The phosphate compound represented by the general formula (7) used in the present invention has a plurality of phosphate ester compounds represented by the general formula (8) bonded thereto via a divalent organic group (R 1 ). Also included are compounds of the structure. As the divalent organic group that bonds the phosphoric ester compounds, a residue obtained by removing two hydrogen atoms from a hydroxyl group of a bifunctional phenol compound such as hydroquinone, 4,4'-bisphenol, and bisphenol A is preferable. The phosphate compound bound may be the same or different.
[0028]
Embedded image
The phosphate compound in the present invention may be used alone or in combination. The amount of the phosphate compound is preferably 0.05 to 5% by weight, more preferably 0.3 to 3% by weight, based on the total epoxy resin composition. If the value is less than the lower limit, the effect of improving the flame retardancy cannot be obtained, and if the value exceeds the upper limit, the moldability decreases due to a decrease in strength, a decrease in solder heat resistance due to an increase in water absorption, and a deterioration in curability. . Within this range, an epoxy resin composition excellent in moldability and solder resistance can be obtained even with a combination of the epoxy resin and the phenol resin used in the present invention.
[0030]
The epoxy resin composition of the present invention comprises, in addition to the components (A) to (E), if necessary, other flame retardants, inorganic ion exchangers such as bismuth oxide hydrate, colorants such as carbon black and red iron oxide, Various additives such as a low stress agent such as silicone oil and silicone rubber, a release agent such as natural wax and synthetic wax, higher fatty acid and its metal salts or paraffin, and an antioxidant can be blended.
[0031]
The epoxy resin composition of the present invention is obtained by mixing the components (A) to (E) and other additives using a mixer, and then melt-kneading with a kneader such as a hot roll, a heating kneader, an extruder, and cooling. It is obtained by subsequent grinding.
In order to manufacture a semiconductor device by encapsulating an electronic component such as a semiconductor element using the epoxy resin composition of the present invention, it is sufficient to cure and mold by a molding method such as a transfer mold, a compression mold, and an injection mold.
[0032]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. The mixing ratio is by weight.
Example 1
6.3 parts by weight of an epoxy resin of the formula (9) (softening point: 60 ° C., epoxy equivalent: 270 g / eq.)
Embedded image
4.7 parts by weight of a phenol resin of the formula (10) (softening point 73 ° C., hydroxyl equivalent 199 g / eq.)
Embedded image
86.0 parts by weight of fused spherical silica (average particle size: 20 μm) 2.0 parts by weight of phosphoric ester compound of formula (11)
Embedded image
Triphenylphosphine 0.2 part by weight Epoxysilane (γ-glycidoxypropyltrimethoxysilane) 0.2 part by weight Carbon black 0.3 part by weight Carnauba wax 0.3 part by weight after mixing at room temperature using a mixer The mixture was kneaded using two rolls having a surface temperature of 90 ° C. and 45 ° C., cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following method. Table 1 shows the results.
[0039]
Evaluation method Spiral flow: Measurement was performed using a mold for spiral flow measurement according to EMMI-1-66 at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The unit is cm.
Curability: Molding was performed using a low-pressure transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds. Ten seconds after the mold was opened, the surface hardness of the runner was measured with a Bacol hardness meter # 935. Bacol hardness is an index of curability, and the larger the value, the better the curability.
Moisture absorption: Using a low-pressure transfer molding machine, mold a mold with a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, a curing time of 120 seconds, a diameter of 50 mm and a thickness of 3 mm, and post-curing at 175 ° C for 8 hours. It was left for 168 hours in an environment of 85 ° C. and a relative humidity of 85%, and a change in weight was measured to determine a moisture absorption rate. The unit is% by weight.
Flexural strength at heating: Flexural strength at 240 ° C. was measured according to JIS K 6911. The unit is MPa.
Flame retardancy: Specimen (127 mm × 12.7 mm, 1.0 mm, 1.6 mm, 3.2 mm thick) with mold temperature of 175 ° C., injection pressure of 9.8 MPa, curing time of 120 seconds using low pressure transfer molding machine After molding at 175 ° C. for 8 hours, ΔF and Fmax were measured according to the UL-94 vertical method, and the flame retardancy was determined.
[0040]
Moisture resistance reliability: Using a low-pressure transfer molding machine, mold at 175 ° C, injection pressure of 9.8MPa, curing time of 120 seconds, mold 16pSOP (using TEG3 of simulated element, wiring width 20μm), and form at 175 ° C, 8 hours After the post-curing, the moisture resistance reliability was evaluated (processed by applying an applied voltage of 10 V at 140 ° C./85% relative humidity), and an open defect between wirings was confirmed. For 20 packages, the number of defective packages after 500 hours and 1000 hours of processing is shown as a percentage of defectives as a percentage. Units%.
Solder resistance: Using a low-pressure transfer molding machine, 80pQFP (2 mm thick, chip size 9.0 mm × 9.0 mm) was molded at a mold temperature of 175 ° C., an injection pressure of 8.3 MPa, and a curing time of 120 seconds. After hardening for 8 hours, the substrate was left for 168 hours at 85 ° C. and a relative humidity of 85%, and then immersed in a solder bath at 240 ° C. for 10 seconds. Observation with a microscope was performed to determine the crack occurrence rate [(crack occurrence rate) = {(number of external crack occurrence packages) / (total number of packages)} × 100]. Units%. The peeling area at the interface between the semiconductor element and the cured product of the epoxy resin composition was measured using an ultrasonic flaw detector, and the peeling rate [(peeling rate) = {(peeling area) / (semiconductor element area)} × 100 ]. Units%.
High temperature storage characteristics: 16pDIP (chip size 3.0mm x 3.5mm) was molded using a low pressure transfer molding machine at a mold temperature of 175 ° C, an injection pressure of 9.8MPa, and a curing time of 120 seconds, and at 175 ° C for 8 hours. After post-curing, a high-temperature storage test (185 ° C., 1000 hours) was performed, and a package in which the electric resistance between wirings increased by 20% from the initial value was determined to be defective. The percentage of defective packages out of the 15 packages (defective rate) is shown in percentage. Units%.
Torque value of curast meter: Measured using a curast meter V type (manufactured by Orientec Co., Ltd.) at a 35φ die, an amplitude angle of 1 °, and a temperature of 175 ° C. The torque value after 90 seconds was measured, and the curability was evaluated. It is called “curast torque”. The unit is Nm.
[0041]
Examples 2 to 7, Comparative Examples 1 to 4
According to the formulation in Table 1, an epoxy resin composition was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
[0042]
Epoxy resin of the formula (12) (softening point 62 ° C., epoxy equivalent 227 g / eq.)
[0043]
Embedded image
Epoxy resin of formula (13) (softening point 73 ° C., epoxy equivalent 269 g / eq.)
[0045]
Embedded image
Epoxy resin of the formula (14) (softening point: 81 ° C., epoxy equivalent: 265 g / eq.)
[0047]
Embedded image
Phenolic resin of formula (15) (softening point 77 ° C., hydroxyl equivalent 174 g / eq.)
[0049]
Embedded image
Phenolic resin of formula (16) (softening point 87 ° C., hydroxyl equivalent 210 g / eq.)
[0051]
Embedded image
Phosphate ester compound of formula (17)
Embedded image
Phosphate compound of formula (18)
Embedded image
The brominated bisphenol A type epoxy resin used in Comparative Example 4 had an epoxy equivalent of 365 g / eq. And a bromine atom content of 48% by weight.
[0057]
[Table 1]
[Table 2]
【The invention's effect】
According to the present invention, a semiconductor encapsulation having excellent flame retardancy without containing a halogen-based flame retardant and an antimony compound, and having excellent moldability such as curability and mold release, solder resistance, and high-temperature storage characteristics. Epoxy resin composition is obtained.
Claims (3)
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| JP2005344081A (en) * | 2004-06-07 | 2005-12-15 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product |
| JP2006034042A (en) * | 2004-07-20 | 2006-02-02 | Yaskawa Electric Corp | Thermosetting resin composite for vacuum and its production |
| WO2006049156A1 (en) * | 2004-11-02 | 2006-05-11 | Sumitomo Bakelite Company, Ltd. | Epoxy resin composition and semiconductor device |
| JP2006131655A (en) * | 2004-11-02 | 2006-05-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2006182803A (en) * | 2004-12-24 | 2006-07-13 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2006206748A (en) * | 2005-01-28 | 2006-08-10 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2006274185A (en) * | 2005-03-30 | 2006-10-12 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| JP2008007692A (en) * | 2006-06-30 | 2008-01-17 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing and electronic part device |
| JP2011246545A (en) * | 2010-05-25 | 2011-12-08 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing and electronic part device |
| CN111051374A (en) * | 2017-09-11 | 2020-04-21 | 明和化成株式会社 | Phenolic resin composition for photoresist and photoresist composition |
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