JP2006328360A - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- JP2006328360A JP2006328360A JP2006092732A JP2006092732A JP2006328360A JP 2006328360 A JP2006328360 A JP 2006328360A JP 2006092732 A JP2006092732 A JP 2006092732A JP 2006092732 A JP2006092732 A JP 2006092732A JP 2006328360 A JP2006328360 A JP 2006328360A
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000004065 semiconductor Substances 0.000 title claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002253 acid Substances 0.000 claims abstract description 36
- 150000002148 esters Chemical class 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 150000005691 triesters Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 9
- 238000005476 soldering Methods 0.000 abstract description 7
- 229920003986 novolac Polymers 0.000 abstract description 6
- 238000007789 sealing Methods 0.000 abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001568 phenolic resin Polymers 0.000 abstract description 3
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 229910000679 solder Inorganic materials 0.000 description 25
- -1 terpene modified phenol Chemical class 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000035882 stress Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 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 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 239000011342 resin composition Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CWJVVYLURLZFDN-UHFFFAOYSA-N 2,3-di(octacosanoyloxy)propyl octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCC CWJVVYLURLZFDN-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical class OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-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
- RMXQRHVIUMSGLJ-UHFFFAOYSA-N O.[Bi]=O Chemical compound O.[Bi]=O RMXQRHVIUMSGLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 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 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 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
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 235000007586 terpenes Nutrition 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
- 150000003918 triazines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、エポキシ樹脂組成物及びそれを用いた半導体装置に関するものであり、特に流動性、離型性、連続成形性に優れた特性を有するエポキシ樹脂組成物及びそれを用いた耐半田性に優れた半導体装置に関するものである。 The present invention relates to an epoxy resin composition and a semiconductor device using the same, and particularly to an epoxy resin composition having excellent characteristics of fluidity, releasability, and continuous moldability, and solder resistance using the same. The present invention relates to an excellent semiconductor device.
近年、電子機器の高度化、軽薄短小化が求められる中、半導体素子の高集積化、表面実装化が進んでいる。これに伴い、半導体封止用エポキシ樹脂組成物への要求は益々厳しくなっているのが現状である。特に半導体装置の薄型化に際しては、封止成形時における金型とエポキシ樹脂組成物の硬化物との間の離型不足に伴う応力の発生により、半導体装置内部の半導体素子自体にクラックを生じたり、硬化物と半導体素子との界面における密着性が低下したりするといった問題が生じている。また、環境問題に端を発した有鉛半田から無鉛半田への移行に伴い、半田処理時の温度が高くなり、半導体装置中に含まれる水分の気化によって発生する爆発的な応力による耐半田性が、従来以上に大きな問題となってきている。 In recent years, as electronic devices have become more sophisticated and lighter, thinner and smaller, semiconductor devices have been highly integrated and surface-mounted. As a result, the demand for epoxy resin compositions for semiconductor encapsulation is becoming increasingly severe. In particular, when thinning a semiconductor device, a crack is caused in the semiconductor element itself in the semiconductor device due to generation of stress due to insufficient demolding between the mold and the cured epoxy resin composition at the time of sealing molding. There is a problem that the adhesion at the interface between the cured product and the semiconductor element is lowered. In addition, with the shift from leaded solder to lead-free solder, which originated from environmental problems, the temperature during the soldering process increased, and the solder resistance due to explosive stress generated by the evaporation of moisture contained in the semiconductor device However, it has become a bigger problem than before.
このため耐半田性を向上させるための種々の提案がされている。例えば、無機充填材の高充填化が可能な低粘度型エポキシ樹脂であるビフェニル型エポキシ樹脂を含むエポキシ樹脂組成物が提案されているが（特許文献１、２参照。）、無機充填材の高充填化により、流動性の低下が懸念される。そこで流動性、離型性、連続成形性に優れた特性を有するエポキシ樹脂組成物及びそれを用いた耐半田性に優れた半導体装置の開発が求められている。 For this reason, various proposals for improving solder resistance have been made. For example, an epoxy resin composition containing a biphenyl type epoxy resin, which is a low-viscosity type epoxy resin capable of highly filling an inorganic filler, has been proposed (see Patent Documents 1 and 2). Due to the filling, there is a concern about a decrease in fluidity. Therefore, development of an epoxy resin composition having excellent properties such as fluidity, releasability, and continuous moldability, and a semiconductor device excellent in solder resistance using the same is required.
本発明は、上記事情に鑑みてなされたものであり、その目的は、流動性、離型性、連続成形性に優れた特性を有するエポキシ樹脂組成物及びそれを用いた耐半田性に優れた半導体装置を提供するものである。 The present invention has been made in view of the above circumstances, and the object thereof is an epoxy resin composition having characteristics excellent in fluidity, releasability, and continuous moldability, and excellent solder resistance using the same. A semiconductor device is provided.
本発明は、
［１］ （Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂系硬化剤、（Ｃ）硬化促進剤、（Ｄ）無機質充填材を主成分とするエポキシ樹脂組成物において、前記（Ａ）エポキシ樹脂、前記（Ｂ）フェノール樹脂系硬化剤のうちの少なくとも一方が、一般式（１）で示される樹脂を含み、更に（Ｅ）グリセリントリ脂肪酸エステルを全エポキシ樹脂組成物中に０．０１重量％以上１重量％以下の割合で含み、かつ（Ｆ）一般式（２）で示されるシランカップリング剤を全エポキシ樹脂組成物中に０．０５重量％以上０．５重量％以下の割合で含むことを特徴とする半導体封止用エポキシ樹脂組成物、
The present invention
[1] In the epoxy resin composition comprising (A) an epoxy resin, (B) a phenol resin-based curing agent, (C) a curing accelerator, and (D) an inorganic filler, the (A) epoxy resin, (B) At least one of the phenol resin-based curing agents contains a resin represented by the general formula (1), and (E) glycerin trifatty acid ester is added in an amount of 0.01% by weight or more to the total epoxy resin composition. And (F) containing a silane coupling agent represented by the general formula (2) in a ratio of 0.05% by weight or more and 0.5% by weight or less in the total epoxy resin composition. An epoxy resin composition for semiconductor encapsulation,
［２］ 前記（Ｅ）グリセリントリ脂肪酸エステルの平均粒径が２０μｍ以上７０μｍ以下であり、全グリセリントリ脂肪酸エステル中における粒径１０６μｍ以上の粒子の含有比率が０．１重量％以下である第［１］項記載のエポキシ樹脂組成物、
［３］ 前記（Ｅ）グリセリントリ脂肪酸エステルがグリセリンと炭素数２４以上３６以下の飽和脂肪酸とのトリエステルである第［１］又は［２］項記載のエポキシ樹脂組成物、
［４］ 第［１］ないし［３］項のいずれかに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。
[2] The (E) glycerin trifatty acid ester has an average particle size of 20 μm or more and 70 μm or less, and the content ratio of particles having a particle size of 106 μm or more in all glycerin trifatty acid esters is 0.1% by weight or less. 1] The epoxy resin composition according to item
[3] The epoxy resin composition according to item [1] or [2], wherein (E) the glycerin trifatty acid ester is a triester of glycerin and a saturated fatty acid having 24 to 36 carbon atoms.
[4] A semiconductor device comprising a semiconductor element sealed with the epoxy resin composition according to any one of [1] to [3],
It is.
本発明に従うと、成形封止する時の流動性、離型性、連続成形性に優れ、かつ低吸湿、低応力性、金属系部材との密着力に優れた特性を有するエポキシ樹脂組成物、並びに耐半田性に優れた半導体装置を得ることができる。 According to the present invention, an epoxy resin composition having excellent fluidity, releasability, and continuous moldability when molded and sealed, and low moisture absorption, low stress, and excellent adhesion to metal-based members, In addition, a semiconductor device excellent in solder resistance can be obtained.
本発明は、（Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂系硬化剤、（Ｃ）硬化促進剤、（Ｄ）無機質充填材を主成分とするエポキシ樹脂組成物において、前記（Ａ）エポキシ樹脂、前記（Ｂ）フェノール樹脂系硬化剤のうちの少なくとも一方が、主鎖にビフェニレン骨格を有するノボラック構造の樹脂を含み、更に（Ｅ）グリセリントリ脂肪酸エステル及び（Ｆ）特定構造のシランカップリング剤を特定量含むことにより、成形封止する時の流動性、離型性、連続成形性に優れ、かつ低吸湿、低応力性、金属系部材との密着力に優れた特性を有するエポキシ樹脂組成物、並びに耐半田性に優れた半導体装置が得られるものである。
以下、本発明について詳細に説明する。
The present invention relates to (A) an epoxy resin, (B) a phenol resin-based curing agent, (C) a curing accelerator, and (D) an epoxy resin composition mainly composed of an inorganic filler. At least one of the (B) phenol resin-based curing agent includes a novolak resin having a biphenylene skeleton in the main chain, and further includes (E) a glycerin trifatty acid ester and (F) a silane coupling agent having a specific structure. By including a specific amount, an epoxy resin composition having excellent fluidity, releasability, and continuous moldability during molding and sealing, as well as low moisture absorption, low stress, and excellent adhesion to metal members. In addition, a semiconductor device having excellent solder resistance can be obtained.
Hereinafter, the present invention will be described in detail.
本発明でエポキシ樹脂（Ａ）として用いられる一般式（１）で示されるエポキシ樹脂（Ｘはグリシジルエーテル基）は、樹脂骨格中に疎水性の構造を多く含むことから、これを用いたエポキシ樹脂組成物の硬化物は吸湿率が低く、また架橋密度が低いため、ガラス転移温度以上の高温域での弾性率が小さいといった特徴を有している。これを用いたエポキシ樹脂組成物の樹脂硬化物は低い吸湿性を有し、半田処理時における水分の気化による爆発的な応力を低減できる。また熱時に低弾性率であることから半田処理時に発生する熱応力が小さくなり、結果として耐半田性に優れる。 The epoxy resin represented by the general formula (1) used as the epoxy resin (A) in the present invention (X is a glycidyl ether group) contains a lot of hydrophobic structures in the resin skeleton. Since the cured product of the composition has a low moisture absorption rate and a low crosslink density, it has a characteristic that its elastic modulus is small in a high temperature region above the glass transition temperature. The cured resin of the epoxy resin composition using this has low hygroscopicity, and can reduce explosive stress due to vaporization of water during soldering. In addition, since it has a low elastic modulus when heated, the thermal stress generated during the soldering process is reduced, resulting in excellent solder resistance.
本発明で用いられる一般式（１）で示されるエポキシ樹脂（Ｘはグリシジルエーテル基）を用いることによる効果が損なわれない範囲で、他のエポキシ樹脂と併用することができる。併用する場合の他のエポキシ樹脂としては、例えば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、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、トリフェノールメタン型エポキシ樹脂、フェノールアラルキル（フェニレン骨格を含む）型エポキシ樹脂、ナフトール型エポキシ樹脂、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あり、これらは単独でも混合して用いてもよい。一般式（１）で示されるエポキシ樹脂（Ｘはグリシジルエーテル基）の具体例を式（３）に示すが、これらに限定されるものではない。 In the range which does not impair the effect by using the epoxy resin (X is a glycidyl ether group) shown by General formula (1) used by this invention, it can use together with another epoxy resin. Other epoxy resins used in combination include, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, phenol aralkyl (phenylene) (Including skeleton) type epoxy resin, naphthol type epoxy resin, alkyl-modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol type epoxy resin, etc. These may be used alone or in combination. Good. Although the specific example of the epoxy resin (X is a glycidyl ether group) shown by General formula (1) is shown in Formula (3), it is not limited to these.
本発明でフェノール樹脂系硬化剤（Ｂ）として用いられる一般式（１）で示されるフェノール樹脂（Ｘは水酸基）は、樹脂骨格中に疎水性の構造を多く含むことから、これを用いたエポキシ樹脂組成物の硬化物は吸湿率が低く、また架橋密度が低いため、ガラス転移温度以上の高温域での弾性率が小さいといった特徴を有している。これを用いたエポキシ樹脂組成物の樹脂硬化物は低吸湿率を示し、半田処理時における水分の気化による爆発的な応力を低減できる。また熱時に低弾性率であることから半田処理時に発生する熱応力が小さくなり、結果として耐半田性に優れる。 The phenol resin represented by the general formula (1) used as the phenol resin-based curing agent (B) in the present invention (X is a hydroxyl group) contains a lot of hydrophobic structures in the resin skeleton. Since the cured product of the resin composition has a low moisture absorption rate and a low crosslinking density, it has a characteristic that the elastic modulus in a high temperature region above the glass transition temperature is small. The resin cured product of the epoxy resin composition using this exhibits a low moisture absorption rate, and can reduce explosive stress due to vaporization of moisture during soldering. In addition, since it has a low elastic modulus when heated, the thermal stress generated during the soldering process is reduced, resulting in excellent solder resistance.
本発明で用いられる一般式（１）で示されるフェノール樹脂（Ｘは水酸基）を用いることによる効果が損なわれない範囲で、他のフェノール樹脂系硬化剤と併用することができる。併用する場合の他のフェノール樹脂系硬化剤としては、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、トリフェノールメタン樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、フェノールアラルキル樹脂（フェニレン骨格を含む）、ナフトールアラルキル樹脂等があり、これらは単独でも混合して用いてもよい。一般式（１）を基本骨格とするフェノール樹脂（Ｘは水酸基）の具体例を式（４）に示すが、これらに限定されるものではない。 In the range which does not impair the effect by using the phenol resin (X is a hydroxyl group) shown by General formula (1) used by this invention, it can use together with another phenol resin hardening | curing agent. Examples of other phenol resin curing agents used in combination include, for example, phenol novolac resin, cresol novolac resin, triphenolmethane resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin (including phenylene skeleton), There are naphthol aralkyl resins and the like, and these may be used alone or in combination. Although the specific example of the phenol resin (X is a hydroxyl group) which uses General formula (1) as a basic skeleton is shown in Formula (4), it is not limited to these.
本発明に用いられる全エポキシ樹脂のエポキシ基と全フェノール樹脂系硬化剤のフェノール性水酸基の当量比としては、好ましくは０．５以上、２以下であり、特に好ましくは０．７以上、１．５以下である。上記範囲内であると、耐湿性、硬化性等の低下を抑えることができる。 The equivalent ratio of the epoxy groups of all epoxy resins and the phenolic hydroxyl groups of all phenolic resin-based curing agents used in the present invention is preferably 0.5 or more and 2 or less, particularly preferably 0.7 or more. 5 or less. When it is within the above range, it is possible to suppress a decrease in moisture resistance, curability and the like.
本発明で用いられる硬化促進剤（Ｃ）としては、エポキシ樹脂とフェノール樹脂系硬化剤との架橋反応の触媒となり得るものを指し、例えばトリブチルアミン、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等のアミン系化合物、トリフェニルホスフィン、テトラフェニルホスホニウム・テトラフェニルボレート塩等の有機リン系化合物、２−メチルイミダゾール等のイミダゾール化合物等が挙げられるが、これらに限定されるものではない。またこれらの硬化促進剤は単独でも混合して用いてもよい。 The curing accelerator (C) used in the present invention refers to one that can be a catalyst for a crosslinking reaction between an epoxy resin and a phenol resin-based curing agent. For example, tributylamine, 1,8-diazabicyclo (5,4,0) Examples include, but are not limited to, amine compounds such as undecene-7, organic phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium / tetraphenylborate salts, and imidazole compounds such as 2-methylimidazole. . These curing accelerators may be used alone or in combination.
本発明で用いられる無機質充填材（Ｄ）としては、例えば溶融シリカ、結晶シリカ、アルミナ、窒化珪素、窒化アルミ等が挙げられる。無機質充填材の配合量を特に多くする場合は、溶融シリカを用いるのが一般的である。溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、かつエポキシ樹脂組成物の溶融粘度の上昇を抑えるためには、球状のものを主に用いる方が好ましい。更に球状シリカの配合量を高めるためには、球状シリカの粒度分布がより広くなるように調整することが望ましい。 Examples of the inorganic filler (D) used in the present invention include fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. When the amount of the inorganic filler is particularly large, it is common to use fused silica. Fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of fused silica and to suppress the increase in the melt viscosity of the epoxy resin composition, it is preferable to mainly use a spherical one. . In order to further increase the blending amount of the spherical silica, it is desirable to adjust so that the particle size distribution of the spherical silica becomes wider.
本発明に用いるグリセリントリ脂肪酸エステル（Ｅ）は、グリセリンと飽和脂肪酸より得られるトリエステルであり、離型性が非常に優れている。モノエステル、ジエステルでは残存する水酸基の影響によりエポキシ樹脂の硬化物の耐湿性が低下し、その結果として半田耐熱性に悪影響を及ぼすので好ましくない。本発明に用いるグリセリントリ脂肪酸エステルとしては、具体的にはグリセリントリカプロン酸エステル、グリセリントリカプリル酸エステル、グリセリントリカプリン酸エステル、グリセリントリラウリン酸エステル、グリセリントリミリスチン酸エステル、グリセリントリパルミチン酸エステル、グリセリントリステアリン酸エステル、グリセリントリアラキン酸エステル、グリセリントリベヘン酸エステル、グリセリントリリグノセリン酸エステル、グリセリントリセロチン酸エステル、グリセリントリモンタン酸エステル、グリセリントリメリシン酸エステル等が挙げられる。中でも炭素数２４以上３６以下の飽和脂肪酸とのグリセリントリ脂肪酸エステルが、離型性と成形品外観の観点から、好ましい。尚、本発明中の飽和脂肪酸の炭素数とは飽和脂肪酸中のアルキル基とカルボキシル基の炭素数を合計したものを指す。 The glycerin trifatty acid ester (E) used in the present invention is a triester obtained from glycerin and a saturated fatty acid, and has excellent release properties. Monoesters and diesters are not preferable because the moisture resistance of the cured epoxy resin is lowered by the influence of the remaining hydroxyl groups, and as a result, the solder heat resistance is adversely affected. Specific examples of the glycerin trifatty acid ester used in the present invention include glycerin tricaproic acid ester, glycerin tricaprylic acid ester, glycerin tricapric acid ester, glycerin trilauric acid ester, glycerin trimyristic acid ester, glycerin tripalmitic acid ester. Glycerin tristearic acid ester, glycerin triaraquinic acid ester, glycerin tribehenic acid ester, glycerin trilignoceric acid ester, glycerin tricelloic acid ester, glycerin trimontanic acid ester, glycerin trimellitic acid ester and the like. Among these, glycerin trifatty acid esters with saturated fatty acids having 24 to 36 carbon atoms are preferred from the viewpoint of mold release and appearance of molded products. In addition, the carbon number of the saturated fatty acid in the present invention refers to the sum of the carbon number of the alkyl group and the carboxyl group in the saturated fatty acid.
本発明で用いられるグリセリントリ脂肪酸エステルの滴点は、７０℃以上、１２０℃以下が好ましく、より好ましくは８０℃以上、１１０℃以下である。下限値未満だと熱安定性が十分でないため、連続成形時にグリセリントリ脂肪酸エステルの焼き付きが発生し、離型性が悪化し、連続成形性を損なう恐れがある。上限値を越えるとエポキシ樹脂組成物の硬化の際、グリセリントリ脂肪酸エステルが十分に溶融しないことにより、グリセリントリ脂肪酸エステルの分散性が低下し、グリセリントリ脂肪酸エステルの硬化物表面への偏析による金型汚れや樹脂硬化物外観の悪化を引き起こす恐れがある。酸価は１０ｍｇＫＯＨ／ｇ以上、５０ｍｇＫＯＨ／ｇ以下が好ましく、より好ましくは１５ｍｇＫＯＨ／ｇ以上、４０ｍｇＫＯＨ／ｇ以下である。酸価は樹脂硬化物との相溶性に影響し、下限値未満だとグリセリントリ脂肪酸エステルはエポキシ樹脂マトリックスと相分離を起こし、金型汚れや樹脂硬化物外観の悪化を引き起こす恐れがある。上限値を越えるとエポキシ樹脂マトリックスとの相溶性がよすぎるため、硬化物表面に染み出すことが出来ず、十分な離型性を確保することができない恐れがある。平均粒径は２０μｍ以上、７０μｍ以下が好ましく、より好ましくは３０μｍ以上、６０μｍ以下である。下限値未満だとグリセリントリ脂肪酸エステルがエポキシ樹脂マトリックスとの相溶性がよすぎるため、硬化物表面に染み出すことが出来ず、十分な離型付与効果が得られない恐れがある。上限値を越えるとグリセリントリ脂肪酸エステルが偏析し、金型汚れや樹脂硬化物外観の悪化を引き起こす恐れがある。また、エポキシ樹脂組成物の硬化の際、グリセリントリ脂肪酸エステルが十分に溶融しないことにより、流動性を阻害する恐れがある。また、全グリセリントリ脂肪酸エステル中における粒径１０６μｍ以上の粒子の含有比率は０．１重量％以下であることが好ましい。上限値を越えるとグリセリントリ脂肪酸エステルが偏析し、金型汚れや樹脂硬化物外観の悪化を引き起こす恐れがある。また、エポキシ樹脂組成物の硬化の際、グリセリントリ脂肪酸エステルが十分に溶融しないことにより、流動性を阻害する恐れがある。グリセリントリ脂肪酸エステルの含有量はエポキシ樹脂組成物中に、０．０１重量％以上１重量％以下であり、好ましくは０．０３重量％以上０．５重量％以下である。下限値未満だと離型性不足となり、上限値を越えるとリードフレーム部材との密着性が損なわれ、半田処理時に部材との剥離が発生する恐れがある。また、金型汚れや樹脂硬化物外観の悪化を引き起こす恐れがある。 The dropping point of the glycerin trifatty acid ester used in the present invention is preferably 70 ° C. or higher and 120 ° C. or lower, more preferably 80 ° C. or higher and 110 ° C. or lower. If it is less than the lower limit, the thermal stability is not sufficient, and seizure of glycerin trifatty acid ester occurs during continuous molding, which may deteriorate mold release properties and impair continuous moldability. If the upper limit is exceeded, the epoxy resin composition will not cure sufficiently when the glycerin trifatty acid ester is melted, resulting in a decrease in dispersibility of the glycerin trifatty acid ester and gold segregation on the cured product surface of the glycerin trifatty acid ester. There is a possibility of causing mold stains and deterioration of the appearance of the cured resin. The acid value is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value affects the compatibility with the cured resin, and if it is less than the lower limit, the glycerin trifatty acid ester may cause phase separation with the epoxy resin matrix, which may cause mold contamination and deterioration of the appearance of the cured resin. If the upper limit is exceeded, the compatibility with the epoxy resin matrix is too good, so that it cannot ooze out on the surface of the cured product and there is a possibility that sufficient releasability cannot be ensured. The average particle size is preferably 20 μm or more and 70 μm or less, more preferably 30 μm or more and 60 μm or less. If it is less than the lower limit, the glycerin trifatty acid ester is too compatible with the epoxy resin matrix, so that it cannot ooze out on the surface of the cured product and there is a possibility that a sufficient release imparting effect cannot be obtained. When the upper limit is exceeded, glycerin trifatty acid ester is segregated, which may cause mold stains and deterioration of the appearance of the cured resin. Moreover, when hardening an epoxy resin composition, there exists a possibility that fluidity | liquidity may be inhibited because glycerol tri fatty acid ester does not fully fuse | melt. Moreover, it is preferable that the content ratio of the particle | grains with a particle size of 106 micrometers or more in all the glycerol tri fatty acid ester is 0.1 weight% or less. When the upper limit is exceeded, glycerin trifatty acid ester is segregated, which may cause mold stains and deterioration of the appearance of the cured resin. Moreover, when hardening an epoxy resin composition, there exists a possibility that fluidity | liquidity may be inhibited because glycerol tri fatty acid ester does not fully fuse | melt. The content of glycerin trifatty acid ester is 0.01% by weight or more and 1% by weight or less, preferably 0.03% by weight or more and 0.5% by weight or less in the epoxy resin composition. If it is less than the lower limit value, the releasability becomes insufficient, and if it exceeds the upper limit value, the adhesion with the lead frame member is impaired, and there is a possibility that peeling from the member occurs during the soldering process. Moreover, there exists a possibility of causing deterioration of a mold | die stain | pollution | contamination and resin hardened | cured material external appearance.
本発明で用いられるグリセリントリ脂肪酸エステルは市販のものを入手し、粒度調整して使用することができる。
本発明で用いられるグリセリントリ脂肪酸エステルを用いることによる効果を損なわない範囲で他の離型剤を併用することもできる。併用できる離型剤としては、例えばカルナバワックス等の天然ワックス、ステアリン酸亜鉛等の高級脂肪酸の金属塩類等が挙げられる。
The glycerin trifatty acid ester used in the present invention is commercially available, and can be used after adjusting the particle size.
Other release agents can be used in combination as long as the effects of using the glycerin trifatty acid ester used in the present invention are not impaired. Examples of release agents that can be used in combination include natural waxes such as carnauba wax, and metal salts of higher fatty acids such as zinc stearate.
本発明に用いられる一般式（２）で示されるシランカップリング剤（Ｆ）を使用すると、従来のシランカップリング剤よりもエポキシ樹脂組成物の低粘度化が可能となるため、無機充填材をより多く充填させ易くなり、その結果半導体装置の反り及び耐半田性を向上させることができる。本発明に用いられる一般式（２）で示されるシランカップリング剤は、好ましくはＲ１がフェニル基であり、Ｒ２が炭素数１〜３のアルキル基、かつＲ３、Ｒ４はメチル基もしくはエチル基であることが好ましい。しかしこれらに限定されるものではなく、また単独で用いても併用してもよい。本発明に用いるシランカップリング剤の配合量は、全エポキシ樹脂組成物中に０．０５重量％以上０．５重量％以下が好ましく、下限値未満だと目的とする粘度特性および流動特性が得られない可能性がある。上限値を越えるとエポキシ樹脂組成物の硬化が阻害され、また硬化物の物性が劣り、半導体封止樹脂としての性能が悪化する可能性がある。また、一般式（２）で示されるシランカップリング剤を用いることによる効果を損なわない範囲であれば、その他のカップリング剤を併用しても差し支えない。併用できるカップリング剤としては、例えば、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシランカップリング剤や、チタネートカップリング剤、アルミニウムカップリング剤、アルミニウム／ジルコニウムカップリング剤等が挙げられる。 When the silane coupling agent (F) represented by the general formula (2) used in the present invention is used, the viscosity of the epoxy resin composition can be lowered as compared with the conventional silane coupling agent. It becomes easy to fill more, and as a result, warpage and solder resistance of the semiconductor device can be improved. In the silane coupling agent represented by the general formula (2) used in the present invention, preferably R1 is a phenyl group, R2 is an alkyl group having 1 to 3 carbon atoms, and R3 and R4 are a methyl group or an ethyl group. Preferably there is. However, it is not limited to these, and may be used alone or in combination. The compounding amount of the silane coupling agent used in the present invention is preferably 0.05% by weight or more and 0.5% by weight or less in the total epoxy resin composition, and if it is less than the lower limit value, desired viscosity characteristics and flow characteristics are obtained. It may not be possible. When the upper limit is exceeded, the curing of the epoxy resin composition is hindered, the physical properties of the cured product are inferior, and the performance as a semiconductor sealing resin may be deteriorated. Moreover, as long as the effect by using the silane coupling agent shown by General formula (2) is not impaired, another coupling agent may be used together. Examples of coupling agents that can be used in combination include silane coupling agents such as epoxy silane, mercaptosilane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanate coupling agents, aluminum coupling agents, aluminum / zirconium coupling agents, and the like. Is mentioned.
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｆ）成分を必須成分とするが、これ以外に必要に応じて臭素化エポキシ樹脂、三酸化アンチモン、リン化合物、金属水酸化物等の難燃剤、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、合成ゴム等の低応力剤、酸化ビスマス水和物等の酸化防止剤等の各種添加剤を適宜配合してもよい。
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｆ）成分及びその他の添加剤等をミキサー等を用いて混合後、加熱ニーダ、熱ロール、押し出し機等を用いて加熱混練し、続いて冷却、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従来からの成形方法で硬化成形すればよい。
The epoxy resin composition of the present invention comprises the components (A) to (F) as essential components, but it is difficult to use brominated epoxy resins, antimony trioxide, phosphorus compounds, metal hydroxides, etc. as necessary. Various additives such as a flame retardant, a colorant such as carbon black and bengara, a low stress agent such as silicone oil, silicone rubber, and synthetic rubber, and an antioxidant such as bismuth oxide hydrate may be appropriately blended.
The epoxy resin composition of the present invention is obtained by mixing the components (A) to (F) and other additives using a mixer and the like, followed by heating and kneading using a heating kneader, a hot roll, an extruder, etc. Obtained by cooling and grinding.
In order to seal an electronic component such as a semiconductor element by using the epoxy resin composition of the present invention and manufacture a semiconductor device, it may be cured by a conventional molding method such as transfer molding, compression molding, injection molding, or the like. .
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
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. The blending ratio is parts by weight.
Example 1
式（３）のエポキシ樹脂（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂）［日本化薬製、ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３］
７．４５重量部
7.45 parts by weight
式（５）のフェノール樹脂（フェニレン骨格を有するフェノールアラルキル樹脂［三井化学（株）製、ＸＬＣ−４Ｌ、軟化点６５℃、水酸基当量１７４］
４．７５重量部
4.75 parts by weight
１，８−ジアザビシクロ（５，４，０）ウンデセン−７（以下、「ＤＢＵ」という）
０．２０重量部
球状溶融シリカ（平均粒径３０．０μｍ） ８７．００重量部
グリセリントリモンタン酸エステル（クラリアントジャパン（株）製、リコルブＷＥ４、滴点８２℃、酸価２５ｍｇＫＯＨ／ｇ、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％） ０．１０重量部
1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as “DBU”)
0.20 parts by weight Spherical fused silica (average particle size 30.0 μm) 87.00 parts by weight Glycerin trimontanate (manufactured by Clariant Japan Co., Ltd., Recolve WE4, dropping point 82 ° C., acid value 25 mg KOH / g, average particle 0.10 parts by weight of particles having a diameter of 45 μm and a particle size of 106 μm or more 0.0% by weight)
式（６）で示されるシランカップリング剤［信越化学製、ＫＢＭ−５７３］
０．２０重量部
0.20 parts by weight
カーボンブラック ０．３０重量部
をミキサーを用いて混合した後、表面温度が９５℃と２５℃の２軸ロールを用いて２０回混練し、得られた混練物シートを冷却後粉砕して、エポキシ樹脂組成物とした。得られたエポキシ樹脂組成物の特性を以下の方法で評価した。
After mixing 0.30 parts by weight of carbon black using a mixer, the mixture was kneaded 20 times using a biaxial roll having surface temperatures of 95 ° C. and 25 ° C., and the resulting kneaded material sheet was cooled and pulverized to obtain an epoxy. A resin composition was obtained. The characteristics of the obtained epoxy resin composition were evaluated by the following methods.
評価方法
スパイラルフロー：低圧トランスファー成形機を用いて、ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型に、金型温度１７５℃、注入圧力６．９ＭＰa、硬化時間１２０秒の条件でエポキシ樹脂組成物を注入し、流動長を測定した。単位はｃｍ。
Evaluation method Spiral flow: Using a low-pressure transfer molding machine, a spiral flow measurement mold conforming to EMMI-1-66, epoxy resin under conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds The composition was injected and the flow length was measured. The unit is cm.
金線変形率：低圧トランスファー自動成形機を用いて、金型温度１７５℃、注入圧力９．６ＭＰａ、硬化時間７０秒で、１６０ｐＬＱＦＰ（ＣｕＬ／Ｆ、パッケージ外寸：２４ｍｍ×２４ｍｍ×１．４ｍｍ厚、パッドサイズ：８．５ｍｍ×８．５ｍｍ、チップサイズ７．４ｍｍ×７．４ｍｍ）を成形した。成形した１６０ｐＬＱＦＰパッケージを軟Ｘ線透視装置で観察し、金線の変形率を（流れ量）／（金線長）の比率で表した。判定基準は５％未満を○、５％以上を×とした。 Metal wire deformation rate: 160 pLQFP (CuL / F, package outer dimensions: 24 mm × 24 mm × 1.4 mm thickness) with a mold temperature of 175 ° C., injection pressure of 9.6 MPa, curing time of 70 seconds using a low-pressure transfer automatic molding machine , Pad size: 8.5 mm × 8.5 mm, chip size 7.4 mm × 7.4 mm). The molded 160 pLQFP package was observed with a soft X-ray fluoroscope, and the deformation rate of the gold wire was expressed as a ratio of (flow rate) / (gold wire length). The criterion was ○ for less than 5% and x for 5% or more.
連続成形性：低圧トランスファー自動成形機を用いて、金型温度１７５℃、注入圧力９．６ＭＰａ、硬化時間７０秒で、８０ｐＱＦＰ（ＣｕＬ／Ｆ、パッケージ外寸：１４ｍｍ×２０ｍｍ×２ｍｍ厚、パッドサイズ：６．５ｍｍ×６．５ｍｍ、チップサイズ６．０ｍｍ×６．０ｍｍ）を連続で５００ショットまで成形した。判定基準は未充填等の問題が全く発生せずに５００ショットまで連続成形できたものを○、それ以外を×とした。 Continuous formability: 80pQFP (CuL / F, package external dimensions: 14mm x 20mm x 2mm thickness, pad size, with a mold temperature of 175 ° C, injection pressure of 9.6MPa, curing time of 70 seconds, using a low-pressure transfer automatic molding machine : 6.5 mm × 6.5 mm, chip size 6.0 mm × 6.0 mm) was continuously molded up to 500 shots. As the judgment criteria, a case where continuous molding was performed up to 500 shots without any problems such as unfilling occurred was marked with ◯, and other cases were marked with x.
成形品外観及び金型汚れ：上記連続成形性の評価において５００ショット経過後のパッケージ及び金型について、目視で汚れを評価した。パッケージ外観判断及び金型汚れ基準は、汚れているものを×、５００ショットまで汚れていないものを○で表す。 Molded product appearance and mold stain: In the evaluation of the continuous moldability, the package and mold after 500 shots were visually evaluated for stain. The package appearance judgment and the mold contamination standard are indicated by “x” when dirty and by “◯” when not dirty up to 500 shots.
耐半田性：上記連続成形性の評価において成形したパッケージを１７５℃、８時間で後硬化し、得られたパッケージを８５℃、相対湿度８５％で１６８時間加湿処理後、２６０℃の半田槽にパッケージを１０秒間浸漬した。顕微鏡でパッケージを観察し、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］を算出した。単位は％。評価したパッケージの数は２０個。また、半導体素子とエポキシ樹脂組成物界面の密着状態を超音波探傷装置により観察した。評価したパッケージの数は２０個。耐半田性判断基準は、クラック発生率が０％で、かつ剥離なし：○、クラックもしくは剥離が発生したものは×とした。 Solder resistance: The package molded in the evaluation of the above-mentioned continuous formability is post-cured at 175 ° C. for 8 hours, and the resulting package is humidified for 168 hours at 85 ° C. and 85% relative humidity and then placed in a solder bath at 260 ° C. The package was immersed for 10 seconds. The package was observed with a microscope, and the crack generation rate [(crack generation rate) = (number of external crack generation packages) / (total number of packages) × 100] was calculated. Units%. The number of packages evaluated was 20. Moreover, the adhesion state of the semiconductor element and the epoxy resin composition interface was observed with an ultrasonic flaw detector. The number of packages evaluated was 20. The criteria for determining solder resistance were a crack occurrence rate of 0% and no peeling: .largecircle.
実施例２〜１１、比較例１〜８
表１、表２、表３に示す割合で各成分を配合し、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、表３に示す。
実施例１以外で用いた成分について、以下に示す。
Examples 2-11, Comparative Examples 1-8
Each component was mix | blended in the ratio shown in Table 1, Table 2, and Table 3, the epoxy resin composition was obtained like Example 1, and it evaluated like Example 1. FIG. The results are shown in Table 1, Table 2, and Table 3.
The components used in other than Example 1 are shown below.
式（７）のエポキシ樹脂（ビフェニル型エポキシ樹脂）［ジャバンエポキシレジン（株）製、ＹＸ−４０００Ｈ、融点１０５℃、エポキシ当量１９１］
式（４）のフェノール樹脂（ビフェニレン骨格を有するフェノールアラルキル樹脂）［明和化成（株）製、ＭＥＨ７８５１ＳＳ、軟化点６７℃、水酸基当量２０３］
グリセリントリメリシン酸エステル（滴点９５℃、酸価３０ｍｇＫＯＨ／ｇ、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％）
グリセリントリベヘン酸エステル（滴点８０℃、酸価１５ｍｇＫＯＨ／ｇ、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％）
グリセリンモノステアリン酸エステル（理研ビタミン（株）製、リケマールＳ−１００、滴点６５℃、酸価２ｍｇＫＯＨ／ｇ、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％）
Glycerin trimellisin ester (drop point 95 ° C., acid value 30 mgKOH / g, average particle size 45 μm, particle size 106 μm or more 0.0% by weight)
Glycerin tribehenate (drop point 80 ° C., acid value 15 mg KOH / g, average particle diameter 45 μm, particle diameter 106 μm or more 0.0% by weight)
Glycerin monostearate (Riken Vitamin Co., Ltd., Riquemar S-100, dropping point 65 ° C., acid value 2 mgKOH / g, average particle size 45 μm, particle size 106 μm or more 0.0% by weight)
式（８）で示されるシランカップリング剤［信越化学製、Ｘ−１２−８０６］
γ−グリシジルプロピルトリメトキシシラン
γ−アミノプロピルトリエトキシシラン
γ-glycidylpropyltrimethoxysilane γ-aminopropyltriethoxysilane
実施例１〜１１は、いずれも良好な流動性、離型性、連続成形性及び耐半田性を有する結果となった。一般式（１）で示される樹脂を用いていない比較例１では、低吸湿化効果と高温時での低応力化効果が発揮されないことで、耐半田性が劣る結果となった。また、グリセリントリ脂肪酸エステル（Ｅ）を用いていない比較例２では、連続成形性や生産性が悪化し、成形品外観、金型汚れ、耐半田性も劣る結果となった。グリセリントリ脂肪酸エステル（Ｅ）の配合量が不足している比較例３では、離型性が低下することで、連続成形性と耐半田性が劣る結果となった。グリセリントリ脂肪酸エステル（Ｅ）の配合量が過剰である比較例４では、過剰成分が部材との界面及び硬化物表面にブリードすることにより、金型表面の汚れや樹脂硬化物の外観が悪化し、耐半田性も劣る結果となった。また、一般式（２）で示されるシランカップリング剤を用いていない比較例５、７及び８では、流動性が低下し、金線変形率が増加する結果となった。一般式（２）で示されるシランカップリング剤の配合量が過剰である比較例６では、樹脂組成物の硬化性が低下することにより、連続成形性や生産性が悪化し、成形品外観、金型汚れ、耐半田性も劣る結果となった。以上より、本発明のエポキシ樹脂組成物を使用することにより、流動性、離型性、連続成形性及び耐半田性のバランスの優れた半導体装置パッケージを提供することができることが判った。 Examples 1 to 11 all had good fluidity, releasability, continuous formability, and solder resistance. In Comparative Example 1 in which the resin represented by the general formula (1) was not used, the low moisture absorption effect and the low stress reduction effect at high temperature were not exhibited, resulting in poor solder resistance. In Comparative Example 2 in which glycerin trifatty acid ester (E) was not used, the continuous moldability and productivity deteriorated, and the appearance of the molded product, mold contamination, and solder resistance were inferior. In Comparative Example 3 in which the blending amount of glycerin trifatty acid ester (E) is insufficient, the releasability is lowered, resulting in poor continuous moldability and solder resistance. In Comparative Example 4 in which the amount of glycerin trifatty acid ester (E) is excessive, the excess component bleeds to the interface with the member and the surface of the cured product, so that the mold surface becomes dirty and the appearance of the cured resin product deteriorates. The solder resistance was also inferior. Moreover, in Comparative Examples 5, 7 and 8 in which the silane coupling agent represented by the general formula (2) was not used, the fluidity decreased and the gold wire deformation rate increased. In Comparative Example 6 in which the amount of the silane coupling agent represented by the general formula (2) is excessive, the curability of the resin composition is lowered, so that the continuous moldability and productivity deteriorate, and the appearance of the molded product, Mold stains and solder resistance were also poor. From the above, it has been found that by using the epoxy resin composition of the present invention, a semiconductor device package having an excellent balance of fluidity, releasability, continuous formability and solder resistance can be provided.
本発明のエポキシ樹脂組成物は、低吸湿、低応力性に優れた特性を有しており、これを用いて半導体素子を成形封止する時の流動性、離型性、連続成形性に優れ、且つリードフレーム等の金属系部材に対し密着力が高く、耐半田性に優れた半導体装置を得ることができるため、無鉛半田を用いて表面実装を行う半導体装置に好適に用いることができる。 The epoxy resin composition of the present invention has excellent properties such as low moisture absorption and low stress, and is excellent in fluidity, releasability and continuous moldability when molding and sealing a semiconductor element using the epoxy resin composition. In addition, since it is possible to obtain a semiconductor device having high adhesion to a metal member such as a lead frame and excellent solder resistance, it can be suitably used for a semiconductor device that is surface-mounted using lead-free solder.
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| US8900710B2 (en) | 2007-02-06 | 2014-12-02 | Nichia Corporation | Light-emitting device, method for manufacturing same, and molded part |
| US9808970B2 (en) | 2007-02-06 | 2017-11-07 | Nichia Corporation | Light-emitting device, method for manufacturing same, and molded part |
| JP2008280492A (en) * | 2007-05-14 | 2008-11-20 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| JP2008297530A (en) * | 2007-06-04 | 2008-12-11 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2011178923A (en) * | 2010-03-02 | 2011-09-15 | Sumitomo Bakelite Co Ltd | Resin composition for sealing semiconductor, and semiconductor device |
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