JP4561220B2 - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- JP4561220B2 JP4561220B2 JP2004221781A JP2004221781A JP4561220B2 JP 4561220 B2 JP4561220 B2 JP 4561220B2 JP 2004221781 A JP2004221781 A JP 2004221781A JP 2004221781 A JP2004221781 A JP 2004221781A JP 4561220 B2 JP4561220 B2 JP 4561220B2
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- 229920000647 polyepoxide Polymers 0.000 title claims description 88
- 239000003822 epoxy resin Substances 0.000 title claims description 87
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000004065 semiconductor Substances 0.000 title claims description 27
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 39
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 9
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 32
- 229910000679 solder Inorganic materials 0.000 description 17
- 239000001993 wax Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 230000035882 stress Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 238000011109 contamination Methods 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
- 229920003986 novolac Polymers 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 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
- 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
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 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
- 239000000654 additive Substances 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
- 229930003836 cresol Natural products 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000012546 transfer 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 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
- 150000001735 carboxylic acids Chemical class 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
- 230000000052 comparative effect Effects 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
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 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
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process 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
- 239000006082 mold release agent Substances 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000001721 transfer moulding Methods 0.000 description 1
- 230000007704 transition Effects 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
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
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、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 the semiconductor device is thinned, a stress is generated due to insufficient release between the mold and the cured product of the epoxy resin composition, thereby causing a crack in the semiconductor element itself in the semiconductor device or the cured product and the semiconductor. There is a problem that the adhesion at the interface with the element is lowered. In addition, with the transition from leaded solder to lead-free solder, which started with environmental problems, the temperature during soldering processing increased, and solder resistance due to explosive stress generated by vaporization of moisture contained in semiconductor devices 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 has been demanded.
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、低吸湿、低応力の樹脂成分、特定の離型剤及び特定の化合物を用いた流動性、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 its purpose is low moisture absorption, low stress resin components, specific mold release agents, and fluidity, mold release, and continuous moldability using specific compounds. The present invention provides an epoxy resin composition having excellent characteristics and a semiconductor device excellent in solder resistance using the same.
本発明は、
［１］ （Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂、（Ｃ）硬化促進剤、（Ｄ）無機質充填材、（Ｅ）酸化ポリエチレンワックス、（Ｆ）シランカップリング剤及び（Ｇ）芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物を必須成分とし、（Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂のうちの少なくとも片方が、一般式（１）で示される樹脂であり、（Ｅ）成分を全エポキシ樹脂組成物中に０．０１〜１重量％含み、かつ（Ｇ）成分を全エポキシ樹脂組成物中に０．０１〜１重量％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] (A) epoxy resin, (B) phenol resin, (C) curing accelerator, (D) inorganic filler, (E) oxidized polyethylene wax, (F) silane coupling agent and (G) aromatic ring A compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an essential component is used, and at least one of (A) an epoxy resin and (B) a phenol resin is a resin represented by the general formula (1). And (E) component is contained in the total epoxy resin composition in an amount of 0.01 to 1% by weight, and (G) component is included in the total epoxy resin composition in an amount of 0.01 to 1% by weight. Epoxy resin composition for sealing,
［２］ 前記（Ｅ）酸化ポリエチレンワックスの滴点が１００〜１４０℃である第［１］項記載のエポキシ樹脂組成物、
［３］ 前記（Ｅ）酸化ポリエチレンワックスの平均粒径が２０〜７０μｍであり、全酸化ポリエチレンワックス中における粒径１０６μｍ以上の粒子の含有比率が０．１重量％以下である第［１］又は［２］項記載のエポキシ樹脂組成物、
［４］ 前記（Ｅ）酸化ポリエチレンワックスの酸価が１０〜５０ｍｇ／ＫＯＨである第［１］、［２］又は［３］項のいずれかに記載のエポキシ樹脂組成物、
［５］ 前記（Ｅ）酸化ポリエチレンワックスの数平均分子量が５００〜５０００である第［１］ないし［４］項のいずれかに記載のエポキシ樹脂組成物、
［６］ 前記（Ｅ）酸化ポリエチレンワックスの密度が０．９４〜１．０３ｇ／ｃｍ3である第［１］ないし［５］項のいずれかに記載のエポキシ樹脂組成物、
［７］ 前記（Ｅ）酸化ポリエチレンワックスが低圧重合法によって製造されたポリエチレンワックスの酸化物、高圧重合法によって製造されたポリエチレンワックスの酸化物、及び高密度ポリエチレンポリマーの酸化物から選ばれる少なくとも一つである第［１］ないし［６］項のいずれかに記載のエポキシ樹脂組成物、
［８］ 第［１］ないし［７］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 epoxy resin composition according to [1], wherein the dropping point of the (E) oxidized polyethylene wax is 100 to 140 ° C.
[3] The average particle diameter of the (E) oxidized polyethylene wax is 20 to 70 μm, and the content ratio of particles having a particle diameter of 106 μm or more in the total oxidized polyethylene wax is 0.1% by weight or less [1] or The epoxy resin composition according to item [2],
[4] The epoxy resin composition according to any one of [1], [2] or [3], wherein the acid value of the (E) oxidized polyethylene wax is 10 to 50 mg / KOH,
[5] The epoxy resin composition according to any one of [1] to [4], wherein the number average molecular weight of the (E) oxidized polyethylene wax is 500 to 5,000.
[6] The epoxy resin composition according to any one of [1] to [5], wherein the density of the (E) oxidized polyethylene wax is 0.94 to 1.03 g / cm 3 .
[7] The (E) oxidized polyethylene wax is at least one selected from an oxide of polyethylene wax produced by a low pressure polymerization method, an oxide of polyethylene wax produced by a high pressure polymerization method, and an oxide of a high density polyethylene polymer. The epoxy resin composition according to any one of items [1] to [6],
[8] A semiconductor device comprising a semiconductor element sealed with the epoxy resin composition according to any one of [1] to [7],
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、（Ｃ）硬化促進剤、（Ｄ）無機質充填材、（Ｅ）酸化ポリエチレンワックス、（Ｆ）シランカップリング剤及び（Ｇ）芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物を必須成分とし、（Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂のうちの少なくとも片方が、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であり、（Ｅ）成分及び（Ｇ）成分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 includes (A) an epoxy resin, (B) a phenol resin, (C) a curing accelerator, (D) an inorganic filler, (E) an oxidized polyethylene wax, (F) a silane coupling agent, and (G) an aromatic ring. And a novolac structure in which at least one of (A) an epoxy resin and (B) a phenol resin has a biphenylene skeleton in the main chain. By containing a specific amount of the component (E) and the component (G), the resin has excellent fluidity, mold release and continuous moldability when molded and sealed, and has low moisture absorption, low stress, and metal system. An epoxy resin composition having excellent adhesion to the member and a semiconductor device excellent in solder resistance can be obtained.
Hereinafter, the present invention will be described in detail.
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）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。 Since the epoxy resin represented by the general formula (1) used in the present invention (X is a glycidyl ether group) contains a lot of hydrophobic structures in the resin skeleton, the cured product of the epoxy resin composition using the epoxy resin is Since the moisture absorption rate is low and the crosslink density is low, the elastic modulus is low 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（２）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 (2), it is not limited to these.
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）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。 Since the phenol resin represented by the general formula (1) used in the present invention (X is a hydroxyl group) contains many hydrophobic structures in the resin skeleton, the cured product of the epoxy resin composition using the phenol resin has a moisture absorption rate. Is low and the crosslink density is low, the elastic modulus is low in the high temperature range above the glass transition temperature. 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ない範囲で、他のフェノール樹脂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（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 phenol resin (X is a hydroxyl group) shown by General formula (1) used by this invention, it can use together with another phenol resin. Other phenol resins used in combination include, for example, phenol novolak resin, cresol novolak resin, triphenolmethane resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin (including phenylene skeleton), and naphthol aralkyl resin. These may be used alone or in combination. Although the specific example of the phenol resin (X is a hydroxyl group) which has general formula (1) as a basic skeleton is shown in Formula (3), 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０．５〜２であり、特に好ましくは０．７〜１．５である。上記範囲を外れると耐湿性、硬化性等が低下する恐れがあるので好ましくない。 The equivalent ratio of epoxy groups of all epoxy resins and phenolic hydroxyl groups of all phenol resins used in the present invention is preferably 0.5 to 2, and particularly preferably 0.7 to 1.5. If it is out of the above range, the moisture resistance, curability and the like may be lowered, which is not preferable.
本発明で用いられる硬化促進剤としては、エポキシ樹脂とフェノール樹脂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 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. For example, amines such as tributylamine and 1,8-diazabicyclo (5,4,0) undecene-7 Examples thereof include, but are not limited to, organic 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 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.
本発明で用いられる酸化ポリエチレンワックスは、一般的にカルボン酸等からなる極性基と長い炭素鎖からなる非極性基を有しているため、成形時に極性基は樹脂硬化物側に配向し、逆に非極性基は金型側に配向することにより離型剤として作用する。本発明で用いられる酸化ポリエチレンワックスの滴点は、１００〜１４０℃であり、好ましくは１１０〜１３０℃である。下限値未満だと熱安定性が十分でないため、連続成形時に酸化ポリエチレンワックス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、酸化ポリエチレンワックスが十分に溶融しないことにより、酸化ポリエチレンワックスの分散性が低下し、酸化ポリエチレンワックス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１０〜５０ｍｇ／ＫＯＨであり、好ましくは１５〜４０ｍｇ／ＫＯＨである。酸価は樹脂硬化物との相溶性に影響し、下限値未満だと酸化ポリエチレンワックス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。数平均分子量は５００〜５０００であり、好ましくは１０００〜４０００である。数平均分子量が下限値未満だと酸化ポリエチレンワックスはエポキシ樹脂マトリックスとの親和性が高まり、十分な離型性を得ることができない恐れがある。上限値を越えると相分離を起こし、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。密度は０．９４〜１．０３ｇ／ｃｍ3であり、好ましくは０．９７〜０．９９ｇ／ｃｍ3である。下限値未満だと熱安定性が十分でないため、連続成形時に酸化ポリエチレンワックス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、酸化ポリエチレンワックスが十分に溶融しないことにより、酸化ポリエチレンワックスの分散性が低下し、酸化ポリエチレンワックス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。平均粒径は２０〜７０μｍ以下であり、好ましくは３０〜６０μｍである。下限値未満だと酸化ポリエチレンワックス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。上限値を越えると酸化ポリエチレンワックスが偏析し、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、酸化ポリエチレンワックス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、全酸化ポリエチレンワックス中における粒径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。上限値を越えると酸化ポリエチレンワックスが偏析し、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、酸化ポリエチレンワックス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。酸化ポリエチレンワックスの含有量はエポキシ樹脂組成物中に、０．０１〜１重量％であり、好ましくは０．０３〜０．５重量％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。 Since the oxidized polyethylene wax used in the present invention generally has a polar group composed of carboxylic acid and the like and a nonpolar group composed of a long carbon chain, the polar group is oriented to the resin cured product side during molding, In addition, the nonpolar group acts as a release agent by being oriented on the mold side. The dropping point of the oxidized polyethylene wax used in the present invention is 100 to 140 ° C, preferably 110 to 130 ° C. If it is less than the lower limit, thermal stability is not sufficient, and seizure of oxidized polyethylene wax occurs during continuous molding, which may deteriorate mold release properties and impair continuous moldability. When the upper limit is exceeded, when the epoxy resin composition is cured, the oxidized polyethylene wax is not sufficiently melted, so that the dispersibility of the oxidized polyethylene wax is reduced. There is a risk of deteriorating the appearance of the cured resin. An acid value is 10-50 mg / KOH, Preferably it is 15-40 mg / KOH. The acid value affects the compatibility with the cured resin. If the acid value is less than the lower limit, the oxidized polyethylene wax causes phase separation from 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 number average molecular weight is 500 to 5000, preferably 1000 to 4000. If the number average molecular weight is less than the lower limit, the oxidized polyethylene wax has an increased affinity with the epoxy resin matrix, and there is a possibility that sufficient releasability cannot be obtained. When the upper limit is exceeded, phase separation occurs, which may cause mold contamination and deterioration of the appearance of the cured resin. The density is 0.94 to 1.03 g / cm 3 , preferably 0.97 to 0.99 g / cm 3 . If it is less than the lower limit, thermal stability is not sufficient, and seizure of oxidized polyethylene wax occurs during continuous molding, which may deteriorate mold release properties and impair continuous moldability. When the upper limit is exceeded, when the epoxy resin composition is cured, the oxidized polyethylene wax is not sufficiently melted, so that the dispersibility of the oxidized polyethylene wax is reduced. There is a risk of deteriorating the appearance of the cured resin. An average particle diameter is 20-70 micrometers or less, Preferably it is 30-60 micrometers. If it is less than the lower limit value, the polyethylene oxide wax is too compatible with the epoxy resin matrix, so that it cannot be oozed 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, the oxidized polyethylene wax is segregated, which may cause mold stains and deterioration of the appearance of the cured resin. In addition, when the epoxy resin composition is cured, the polyethylene oxide wax is not sufficiently melted, which may hinder fluidity. The content ratio of particles having a particle size of 106 μm or more in the total oxidized polyethylene wax is preferably 0.1% by weight or less. When the upper limit is exceeded, the oxidized polyethylene wax is segregated, which may cause mold contamination and deterioration of the appearance of the cured resin. In addition, when the epoxy resin composition is cured, the polyethylene oxide wax is not sufficiently melted, which may hinder fluidity. The content of the oxidized polyethylene wax is 0.01 to 1% by weight, preferably 0.03 to 0.5% by weight, in the epoxy resin composition. If it is less than the lower limit value, the releasability is 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 mold | die stain | pollution | contamination and resin hardened | cured material external appearance.
本発明で用いられる酸化ポリエチレンワックスとしては、低圧重合法によって製造されたポリエチレンワックスの酸化物、高圧重合法によって製造されたポリエチレンワックスの酸化物、高密度ポリエチレンポリマーの酸化物が好ましい。
本発明で用いられる酸化ポリエチレンワックス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 polyethylene oxide wax used in the present invention is preferably an oxide of polyethylene wax produced by a low pressure polymerization method, an oxide of polyethylene wax produced by a high pressure polymerization method, or an oxide of a high density polyethylene polymer.
Other release agents may be used in combination as long as the effects of using the oxidized polyethylene wax 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.
本発明に用いるシランカップリング剤（Ｆ）は、エポキシシラン、アミノシラン、ウレイドシラン、メルカプトシラン等特に限定せず、エポキシ樹脂組成物と無機充填剤との間で反応し、エポキシ樹脂組成物と無機充填剤の界面強度を向上させるものであればよい。芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物（Ｇ）（以下化合物（Ｇ）と称する）はシランカップリング剤（Ｆ）との相乗効果により、粘度特性と流動特性を著しく改善させるため、シランカップリング剤（Ｆ）は化合物（Ｇ）の効果を充分に得るためには必須である。これらのシランカップリング剤（Ｆ）は単独でも併用してもよい。本発明に用いるシランカップリング剤（Ｆ）の配合量は、全エポキシ樹脂組成物中０．０１重量％以上１重量％以下、好ましくは０．０５重量％以上０．８以下、特に好ましくは０．１重量％以上０．６重量％以下であり、下限値未満だと化合物（Ｇ）の効果が充分に得られず、また半導体パッケージにおける耐半田クラック性が低下する恐れがある。また、上限値を越えるとエポキシ樹脂組成物の吸水性が大きくなり、やはり半導体パッケージにおける耐半田クラック性が低下する恐れがある。 The silane coupling agent (F) used in the present invention is not particularly limited, such as epoxy silane, amino silane, ureido silane, mercapto silane, etc., and reacts between the epoxy resin composition and the inorganic filler, and the epoxy resin composition and the inorganic silane coupling agent (F). What is necessary is just to improve the interface strength of a filler. A compound (G) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting an aromatic ring (hereinafter referred to as compound (G)) has a viscosity characteristic and fluidity due to a synergistic effect with the silane coupling agent (F). In order to remarkably improve the characteristics, the silane coupling agent (F) is essential for sufficiently obtaining the effect of the compound (G). These silane coupling agents (F) may be used alone or in combination. The amount of the silane coupling agent (F) used in the present invention is 0.01% by weight or more and 1% by weight or less, preferably 0.05% by weight or more and 0.8 or less, particularly preferably 0% in the total epoxy resin composition. If it is 1 wt% or more and 0.6 wt% or less and less than the lower limit, the effect of the compound (G) cannot be sufficiently obtained, and solder crack resistance in the semiconductor package may be lowered. On the other hand, if the upper limit is exceeded, the water absorption of the epoxy resin composition increases, and the solder crack resistance in the semiconductor package may also be lowered.
本発明に用いる芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物（Ｇ）（以下化合物（Ｇ）と称する）は、水酸基以外の置換基を有していてもよい。化合物（Ｇ）としては、式（４）又は式（５）で表される化合物が好ましく、例えば、カテコール、ピロガロール、１、２−ジヒドロキシナフタレン、２、３−ジヒドロキシナフタレンおよびこれらの誘導体が挙げられる。そのうち流動性と硬化性の制御のしやすさ、低揮発性の点から母核はナフタレン環である化合物（１、２−ジヒドロキシナフタレン、２、３−ジヒドロキシナフタレンおよびその誘導体）がより好ましい。これらの化合物（Ｇ）は２種以上併用してもよい。かかる化合物（Ｇ）の配合量は全エポキシ樹脂組成物中０．０１〜１重量％、好ましくは０．０３〜０．８重量％、特に好ましくは０．０５〜０．５重量％である。下限値未満だとシランカップリング剤（Ｆ）との相乗効果による期待するような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ので好ましくない。 The compound (G) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting the aromatic ring used in the present invention (hereinafter referred to as compound (G)) may have a substituent other than a hydroxyl group. . As the compound (G), a compound represented by the formula (4) or the formula (5) is preferable, and examples thereof include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. . Of these, compounds (1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof) in which the mother nucleus is a naphthalene ring are more preferable from the viewpoint of ease of control of fluidity and curability and low volatility. Two or more of these compounds (G) may be used in combination. The compounding quantity of this compound (G) is 0.01 to 1 weight% in all the epoxy resin compositions, Preferably it is 0.03 to 0.8 weight%, Most preferably, it is 0.05 to 0.5 weight%. If it is less than the lower limit, viscosity characteristics and flow characteristics as expected due to a synergistic effect with the silane coupling agent (F) may not be obtained. Exceeding the upper limit is not preferable because the curing of the epoxy resin composition is inhibited, the physical properties of the cured product are inferior, and the performance as a semiconductor sealing resin may be deteriorated.
（ただし、上記式（４）において、Ｒ１、Ｒ５はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素又は水酸基、Ｒ２、Ｒ３、Ｒ４は水素又は水酸基。）
(In the above formula (4), one of R1 and R5 is a hydroxyl group, and when one is a hydroxyl group, the other is hydrogen or a hydroxyl group, and R2, R3, and R4 are hydrogen or a hydroxyl group.)
本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｇ）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）〜（Ｇ）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 (G) as essential components, but in addition to these, difficulties such as brominated epoxy resins, antimony trioxide, phosphorus compounds, metal hydroxides, etc. 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.
In the epoxy resin composition of the present invention, the components (A) to (G) and other additives are mixed using a mixer and the like, then heated and kneaded 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
式（２）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］
７．３６重量部
Example 1
Epoxy resin of formula (2) (phenol aralkyl type epoxy resin having a biphenylene skeleton) [manufactured by Nippon Kayaku, NC3000P, softening point 58 ° C., epoxy equivalent 273]
7.36 parts by weight
式（６）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］
４．６９重量部
4.69 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
酸化ポリエチレンワックス１（滴点１２０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量２０００、密度０．９８ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物） ０．１０重量部
γ−グリシジルプロピルトリメトキシシラン ０．３０重量部
２，３−ジヒドロキシナフタレン（試薬） ０．０５重量部
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。
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 Oxidized polyethylene wax 1 (drop point 120 ° C., acid value 20 mg / KOH, number average molecular weight 2000, density 0.98 g / cm 3 , 0.10 parts by weight γ-glycidylpropyltrimethoxysilane 0.30 parts by weight 2,3-dihydroxynaphthalene (reagent) ) 0.05 part by weight Carbon black 0.30 part by weight was mixed using a mixer, then kneaded 20 times using biaxial rolls with surface temperatures of 95 ° C. and 25 ° C., and the resulting kneaded material sheet was cooled. After pulverization, an epoxy 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：ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、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。
Evaluation method Spiral flow: Using a spiral flow measurement mold according to EMMI-1-66, measurement was performed 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.
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 dimension: 24 mm × 24 mm × 1.4 mm thickness) with a mold temperature of 175 ° C., an injection pressure of 9.6 MPa, a 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全く問題なく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. The judgment criteria were “good” for continuous molding up to 500 shots without any problem such as unfilling, and “x” for the others.
成形品外観及び金型汚れ：上記連続成形において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 Dirt: Dirt was evaluated visually for the package and mold after 500 shots in the continuous molding. The package appearance judgment and the mold contamination standard are indicated by “x” when dirty and by “◯” when not dirty up to 500 shots.
半田耐熱性：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。耐半田クラック性判断基準は、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 heat resistance: The package molded in the evaluation of the above-described 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 the solder crack resistance were a crack occurrence rate of 0% and no peeling: ○, and a crack or peeling occurred as x.
実施例２〜９、１２〜２３、参考例１０、１１、比較例１〜９
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。
式（３）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］
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.
Phenol resin of formula (3) (phenol aralkyl resin having a biphenylene skeleton) [Maywa Kasei Co., Ltd., MEH7851SS, softening point 67 ° C., hydroxyl group equivalent 203]
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］
酸化ポリエチレンワックス２（滴点１０５℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量１１００、密度０．９７ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、低圧重合法によって製造されたポリエチレンワックスの酸化物）
酸化ポリエチレンワックス３（滴点１３５℃、酸価２５ｍｇ／ＫＯＨ、数平均分子量３０００、密度０．９９ｇ／ｃｍ3、平均粒径４０μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
酸化ポリエチレンワックス４（滴点１１０℃、酸価１２ｍｇ／ＫＯＨ、数平均分子量１２００、密度０．９７ｇ／ｃｍ3、平均粒径５０μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
酸化ポリエチレンワックス５（滴点１１０℃、酸価４５ｍｇ／ＫＯＨ、数平均分子量２０００、密度０．９７ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高圧重合法によって製造されたポリエチレンワックスの酸化物）
酸化ポリエチレンワックス６（滴点１１０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量７５０、密度０．９８ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
酸化ポリエチレンワックス７（滴点１３０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量４５００、密度０．９９ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高圧重合法によって製造されたポリエチレンワックスの酸化物）
酸化ポリエチレンワックス８（滴点１１０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量１１００、密度０．９５ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、低圧重合法によって製造されたポリエチレンワックスの酸化物）
酸化ポリエチレンワックス９（滴点１１０℃、酸価２５ｍｇ／ＫＯＨ、数平均分子量２０００、密度１．０２ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
酸化ポリエチレンワックス１０（滴点１２０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量２０００、密度０．９８ｇ／ｃｍ3、平均粒径３０μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
酸化ポリエチレンワックス１１（滴点１２０℃、酸価２０ｍｇ／ＫＯＨ、数平均分子量２０００、密度０．９８ｇ／ｃｍ3、平均粒径６０μｍ、粒径１０６μｍ以上の粒子０．０重量％、高密度ポリエチレンポリマーの酸化物）
Oxidized polyethylene wax 2 (drop point 105 ° C., acid value 20 mg / KOH, number average molecular weight 1100, density 0.97 g / cm 3 , average particle size 45 μm, particle size 106 μm or more, 0.0% by weight, by low pressure polymerization method) Manufactured polyethylene wax oxide)
Oxidized polyethylene wax 3 (drop point: 135 ° C., acid value: 25 mg / KOH, number average molecular weight: 3000, density: 0.99 g / cm 3 , average particle size: 40 μm, particle size: 106 μm or more, 0.0% by weight, high density polyethylene polymer Oxide)
Oxidized polyethylene wax 4 (drop point 110 ° C., acid value 12 mg / KOH, number average molecular weight 1200, density 0.97 g / cm 3 , average particle size 50 μm, particle size 106 μm or more, 0.0% by weight, high density polyethylene polymer Oxide)
Oxidized polyethylene wax 5 (drop point 110 ° C., acid value 45 mg / KOH, number average molecular weight 2000, density 0.97 g / cm 3 , average particle diameter 45 μm, particle diameter 106 μm or more, 0.0% by weight, by high pressure polymerization method Manufactured polyethylene wax oxide)
Oxidized polyethylene wax 6 (drop point 110 ° C., acid value 20 mg / KOH, number average molecular weight 750, density 0.98 g / cm 3 , average particle size 45 μm, particle size 106 μm or more, 0.0% by weight, high density polyethylene polymer Oxide)
Oxidized polyethylene wax 7 (drop point 130 ° C., acid value 20 mg / KOH, number average molecular weight 4500, density 0.99 g / cm 3 , average particle diameter 45 μm, particle diameter 106 μm or more, 0.0% by weight, by high pressure polymerization method) Manufactured polyethylene wax oxide)
Oxidized polyethylene wax 8 (drop point 110 ° C., acid value 20 mg / KOH, number average molecular weight 1100, density 0.95 g / cm 3 , average particle size 45 μm, particle size 106 μm or more, 0.0% by weight, by low pressure polymerization method) Manufactured polyethylene wax oxide)
Oxidized polyethylene wax 9 (drop point 110 ° C., acid value 25 mg / KOH, number average molecular weight 2000, density 1.02 g / cm 3 , average particle size 45 μm, particle size 106 μm or more, 0.0% by weight, high density polyethylene polymer Oxide)
Oxidized polyethylene wax 10 (drop point 120 ° C., acid value 20 mg / KOH, number average molecular weight 2000, density 0.98 g / cm 3 , average particle size 30 μm, particle size 0.06% by weight, high density polyethylene polymer Oxide)
Oxidized polyethylene wax 11 (drop point 120 ° C., acid value 20 mg / KOH, number average molecular weight 2000, density 0.98 g / cm 3 , average particle size 60 μm, particle size 106 μm or more, 0.0% by weight, high density polyethylene polymer Oxide)
ポリエチレンワックス１（滴点１３５℃、酸価０ｍｇ／ＫＯＨ、数平均分子量５５００、密度０．９３ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、低圧重合法によって製造されたポリエチレンワックス）
ポリエチレンワックス２（滴点１１５℃、酸価０ｍｇ／ＫＯＨ、数平均分子量１８００、密度０．９３ｇ／ｃｍ3、平均粒径４５μｍ、粒径１０６μｍ以上の粒子０．０重量％、高圧重合法によって製造されたポリエチレンワックス）
Polyethylene wax 1 (drop point 135 ° C., acid value 0 mg / KOH, number average molecular weight 5500, density 0.93 g / cm 3 , average particle size 45 μm, particle size 106 μm or more 0.0% by weight, manufactured by low pressure polymerization method) Polyethylene wax)
Polyethylene wax 2 (drop point 115 ° C., acid value 0 mg / KOH, number average molecular weight 1800, density 0.93 g / cm 3 , average particle size 45 μm, particle size 106 μm or more 0.0% by weight, manufactured by high pressure polymerization method Polyethylene wax)
１，２−ジヒドロキシナフタレン（試薬）
カテコール（試薬）
ピロガロール（試薬）
１，６−ジヒドロキシナフタレン（試薬）
レゾルシノール（試薬）
1,2-dihydroxynaphthalene (reagent)
Catechol (reagent)
Pyrogallol (reagent)
1,6-dihydroxynaphthalene (reagent)
Resorcinol (reagent)
本発明のエポキシ樹脂組成物は、離型性、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。 The epoxy resin composition of the present invention has excellent properties such as releasability, low moisture absorption, and low stress, and it can be used for releasability and continuous moldability when molding and sealing semiconductor elements using this. It is possible to obtain a semiconductor device that is excellent and has high adhesion to a metal member such as a lead frame and excellent solder resistance.
Claims (5)
（Ｇ）芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物が、一般式（５）で表される化合物である半導体封止用エポキシ樹脂組成物。
(G) An epoxy resin composition for semiconductor encapsulation, wherein the compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring is a compound represented by the general formula (5).
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| JP2004221781A JP4561220B2 (en) | 2004-07-29 | 2004-07-29 | Epoxy resin composition and semiconductor device |
| US11/343,268 US20070043166A1 (en) | 2004-07-29 | 2006-01-30 | Epoxy resin composition for encapsulating semiconductor chip and semiconductor device |
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| JP2004221781A JP4561220B2 (en) | 2004-07-29 | 2004-07-29 | Epoxy resin composition and semiconductor device |
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| JP4569260B2 (en) * | 2004-10-27 | 2010-10-27 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| JP5179701B2 (en) * | 2004-11-24 | 2013-04-10 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| JP5141124B2 (en) * | 2006-08-07 | 2013-02-13 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| JP5868573B2 (en) * | 2010-03-02 | 2016-02-24 | 住友ベークライト株式会社 | Semiconductor sealing resin composition and semiconductor device |
| JP6192523B2 (en) * | 2013-03-05 | 2017-09-06 | エア・ウォーター株式会社 | Epoxy resin curing agent, production method, and use thereof |
| JP2017082052A (en) * | 2015-10-26 | 2017-05-18 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247748A (en) * | 1999-12-28 | 2001-09-11 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing, and electronic part device |
| JP2002322347A (en) * | 2001-04-26 | 2002-11-08 | Toray Ind Inc | Epoxy resin composition for sealing semiconductor and semiconductor device |
| JP2004175842A (en) * | 2002-11-25 | 2004-06-24 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing and electronic part device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247748A (en) * | 1999-12-28 | 2001-09-11 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing, and electronic part device |
| JP2002322347A (en) * | 2001-04-26 | 2002-11-08 | Toray Ind Inc | Epoxy resin composition for sealing semiconductor and semiconductor device |
| JP2004175842A (en) * | 2002-11-25 | 2004-06-24 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing and electronic part device |
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