JP2003192769A - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor deviceInfo
- Publication number
- JP2003192769A JP2003192769A JP2001397125A JP2001397125A JP2003192769A JP 2003192769 A JP2003192769 A JP 2003192769A JP 2001397125 A JP2001397125 A JP 2001397125A JP 2001397125 A JP2001397125 A JP 2001397125A JP 2003192769 A JP2003192769 A JP 2003192769A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- general formula
- represented
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 82
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 239000005011 phenolic resin Substances 0.000 claims abstract description 40
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910000679 solder Inorganic materials 0.000 abstract description 28
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 229920001568 phenolic resin Polymers 0.000 abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 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 4
- -1 dicyclopentadiene Modified phenol Chemical class 0.000 description 4
- 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 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RMXQRHVIUMSGLJ-UHFFFAOYSA-N O.[Bi]=O Chemical compound O.[Bi]=O RMXQRHVIUMSGLJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000013003 hot bending Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- 239000001993 wax Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- NBWCUDDSVCYILY-UHFFFAOYSA-M [O-]C(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.C(C=C1)=CC=C1[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [O-]C(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.C(C=C1)=CC=C1[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 NBWCUDDSVCYILY-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 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
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐半田クラック性
に優れた半導体封止用エポキシ樹脂組成物、及び半導体
装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor encapsulating epoxy resin composition having excellent solder crack resistance and a semiconductor device.
【０００２】[0002]
【従来の技術】従来からダイオード、トランジスタ、集
積回路等の電子部品は、主にエポキシ樹脂組成物を用い
て封止されている。特に集積回路では、エポキシ樹脂、
フェノール樹脂、及び溶融シリカ、結晶シリカ等の無機
充填材を配合した耐熱性、耐湿性に優れたエポキシ樹脂
組成物が用いられている。ところが近年、電子機器の小
型化、軽量化、高性能化の市場動向において、半導体素
子の高集積化が年々進み、又半導体装置の表面実装化が
促進されるなかで、半導体素子の封止に用いられている
エポキシ樹脂組成物への要求は益々厳しいものとなって
きている。特に半導体装置の表面実装化が一般的になっ
てきている現状では、吸湿した半導体装置が半田リフロ
ー処理時に高温にさらされ、半導体素子やリードフレー
ムとエポキシ樹脂組成物の硬化物との界面に剥離が発生
し、ひいては半導体装置にクラックを生じる等、半導体
装置の信頼性を大きく損なう不良が生じ、これらの不良
の防止、即ち耐半田クラック性の向上が大きな課題とな
っている。2. Description of the Related Art Conventionally, electronic parts such as diodes, transistors and integrated circuits have been sealed mainly with an epoxy resin composition. Especially in integrated circuits, epoxy resin,
An epoxy resin composition having excellent heat resistance and moisture resistance, which is a mixture of a phenol resin and an inorganic filler such as fused silica or crystalline silica, is used. However, in recent years, in the market trend of miniaturization, weight reduction, and high performance of electronic devices, semiconductor elements have been highly integrated year by year, and surface mounting of semiconductor devices has been promoted. The demands on the epoxy resin composition used are becoming increasingly severe. Particularly in the current situation where surface mounting of semiconductor devices is becoming common, the absorbed semiconductor device is exposed to high temperature during solder reflow processing, and peels off at the interface between the semiconductor element or lead frame and the cured product of the epoxy resin composition. Occurs, resulting in cracks in the semiconductor device, which greatly impair the reliability of the semiconductor device, and prevention of these defects, that is, improvement of solder crack resistance is a major issue.
【０００３】更に、環境負荷物質の撤廃の一環として、
鉛を含まない半田への代替が進められている。鉛を含ま
ない半田では、従来の半田に比べ融点が高いため表面実
装時のリフロー温度は、従来より２０℃程度高く、２６
０℃が必要とされる。鉛を含まない半田対応のための半
田リフロー温度の変更によって、エポキシ樹脂組成物の
硬化物とパッドとの界面での剥離、半導体素子と半導体
樹脂ペーストとの界面での剥離に起因する半導体装置の
クラックの問題が生じてきた。これら、半田クラックや
剥離は、半田リフロー処理前の半導体装置自身が吸湿
し、半田リフロー処理時の高温下でその水分が水蒸気爆
発を起こすことによって生じると考えられており、それ
を防ぐためにエポキシ樹脂組成物に低吸湿性を付与する
等の手法が用いられている。その低吸湿化の手法の一つ
として、例えば、低吸湿性の一般式（１）でＸ1、Ｘ2、
Ｙ1、Ｙ2が共にＨのエポキシ樹脂、及び低吸湿性の一般
式（２）で示されるＸ3、Ｘ4、Ｙ3、Ｙ4が共にＨのフェ
ノール樹脂を用いて、エポキシ樹脂組成物の硬化物の低
吸湿化を図る方法がある。しかしながら、この低吸湿性
の樹脂成分を使用したエポキシ樹脂組成物といえども、
鉛を含まない半田に対応のエポキシ樹脂組成物としては
不十分であった。このため、２６０℃表面実装時の耐半
田クラック性向上を目的とするにはエポキシ樹脂組成物
の硬化物の更なる低吸水化を含む改良が望まれている。Furthermore, as part of the elimination of environmentally hazardous substances,
Replacement of lead-free solder is underway. Since the solder containing no lead has a higher melting point than the conventional solder, the reflow temperature during surface mounting is about 20 ° C. higher than that of the conventional solder.
0 ° C is required. By changing the solder reflow temperature for soldering that does not contain lead, peeling at the interface between the cured product of the epoxy resin composition and the pad, and peeling at the interface between the semiconductor element and the semiconductor resin paste The problem of cracks has arisen. These solder cracks and peeling are considered to be caused by moisture absorption by the semiconductor device itself before the solder reflow treatment, and the moisture causing steam explosion at high temperature during the solder reflow treatment. Techniques such as imparting low hygroscopicity to the composition are used. As one of the methods for reducing the hygroscopicity, for example, in the general formula (1) of low hygroscopicity, X 1 , X 2 ,
An epoxy resin composition using an epoxy resin in which Y 1 and Y 2 are both H, and a phenol resin in which X 3 , X 4 , Y 3 , and Y 4 are both H, which are represented by the general formula (2) and have low hygroscopicity. There is a method for reducing the moisture absorption of the cured product. However, even with an epoxy resin composition using this low hygroscopic resin component,
It has been insufficient as an epoxy resin composition compatible with lead-free solder. Therefore, in order to improve the solder crack resistance during surface mounting at 260 ° C., improvements including further lowering of water absorption are desired for the cured product of the epoxy resin composition.
【０００４】又、エポキシ樹脂組成物中には、難燃性を
付与するために臭素含有化合物等のハロゲン系難燃剤、
及びアンチモン化合物が配合されている。近年、地球環
境に配慮した企業活動の重視によって有害性のおそれの
ある物質の削減・撤廃の動きがあり、ハロゲン系難燃
剤、アンチモン化合物を使用しないで、難燃性に優れた
エポキシ樹脂組成物の開発が要求されている。これらに
代わる環境対応の難燃剤としては、水酸化アルミニウ
ム、水酸化マグネシウム等の金属水酸化物やリン系難燃
剤等があるが、前者を多量に含むエポキシ樹脂組成物は
成形性、硬化性共、十分に満足できるものでないという
問題があり、また後者を少量でも含むエポキシ樹脂組成
物を用いた半導体装置は高温多湿下での電気特性の安定
性の低下、即ち、半導体装置の抵抗値が時間と共に増大
して半導体素子の導通不良が発生するという問題があ
り、全ての要求に対応することができなかった。In addition, in the epoxy resin composition, a halogen-based flame retardant such as a bromine-containing compound for imparting flame retardancy,
And an antimony compound. In recent years, there has been a movement to reduce or eliminate substances that may be harmful due to the importance of corporate activities that consider the global environment. Epoxy resin compositions with excellent flame retardancy without using halogen-based flame retardants or antimony compounds. Development is required. Examples of environment-friendly flame retardants that can replace these include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and phosphorus-based flame retardants.However, epoxy resin compositions containing a large amount of the former have both moldability and curability. However, there is a problem that it is not sufficiently satisfactory, and a semiconductor device using an epoxy resin composition containing the latter even in a small amount deteriorates the stability of electric characteristics under high temperature and high humidity, that is, the resistance value of the semiconductor device is less than time. However, there is a problem that the semiconductor element increases in number with the occurrence of defective conduction, and it is not possible to meet all requirements.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来の難燃
剤を多量に用いなくとも難燃性に優れ、かつ成形性に優
れた半導体封止用エポキシ樹脂組成物、及び耐半田クラ
ック性に優れた半導体装置を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides an epoxy resin composition for semiconductor encapsulation, which has excellent flame retardancy and moldability without using a large amount of conventional flame retardant, and solder crack resistance. An excellent semiconductor device is provided.
【０００６】[0006]
【課題を解決するための手段】本発明は、（Ａ）一般式
（１）で示されるエポキシ樹脂、（Ｂ）一般式（２）で
示されるフェノール樹脂、及び一般式（３）で示される
フェノール樹脂の群から選択される１種以上のフェノー
ル樹脂、（Ｃ）硬化促進剤、及び（Ｄ）無機充填材をが
必須成分であることを特徴とする半導体封止用エポキシ
樹脂組成物である。MEANS FOR SOLVING THE PROBLEMS The present invention is represented by (A) an epoxy resin represented by the general formula (1), (B) a phenol resin represented by the general formula (2), and a general formula (3). An epoxy resin composition for semiconductor encapsulation, wherein one or more phenol resins selected from the group of phenol resins, (C) a curing accelerator, and (D) an inorganic filler are essential components. .
【０００７】[0007]
【化４】
（式中のＸ1、Ｘ2、Ｙ1、Ｙ2は、Ｈ、ＣＨ3、Ｃ2Ｈ5、
Ｃ3Ｈ7、ｔ−Ｂｕから選択される基であり、互いに同一
であっても、異なっていても良いが、少なくとも１つ以
上はＨ以外のものを含む。ｎは平均値で１〜５の正
数。）[Chemical 4] (In the formula, X 1 , X 2 , Y 1 and Y 2 are H, CH 3 , C 2 H 5 ,
It is a group selected from C 3 H 7 and t-Bu, which may be the same or different from each other, but at least one or more of them include those other than H. n is an average value and is a positive number of 1 to 5. )
【０００８】[0008]
【化５】
（式中のＸ3、Ｘ4、Ｙ3、Ｙ4は、Ｈ、ＣＨ3、Ｃ2Ｈ5、
Ｃ3Ｈ7、ｔ−Ｂｕから選択される基であり、互いに同一
であっても、異なっていても良い。ｎは平均値で１〜５
の正数。）[Chemical 5] (In the formula, X 3 , X 4 , Y 3 , and Y 4 are H, CH 3 , C 2 H 5 ,
It is a group selected from C 3 H 7 and t-Bu, and may be the same as or different from each other. n is an average value of 1 to 5
Positive number. )
【０００９】[0009]
【化６】
（式中のＺ1は、ＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、ｔ−Ｂｕから
選択される基であり、互いに同一であっても、異なって
いても良い。ｍ、ｎは平均値で１〜５の正数。）[Chemical 6] (Z 1 in the formula is a group selected from CH 3 , C 2 H 5 , C 3 H 7 , and t-Bu, and may be the same or different. M and n are average. Value is a positive number from 1 to 5.)
【００１０】また、前記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半導体装置である。A semiconductor device is obtained by encapsulating a semiconductor element using the epoxy resin composition.
【００１１】[0011]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で用いられる一般式（１）で示されるエポキシ樹
脂は、１分子中にエポキシ基を２個以上有し、各エポキ
シ基間に疎水性構造を有するとともに、Ｘ1、Ｘ2、
Ｙ1、Ｙ2の少なくとも１つはＨ以外であることを特徴と
する。一般式（１）で示されるエポキシ樹脂を用いたエ
ポキシ樹脂組成物の硬化物は、エポキシ基間の疎水性構
造により架橋点間距離が長いためガラス転移温度を越え
た高温域での弾性率が低く、又一般式（１）でＸ1、
Ｘ2、Ｙ1、Ｙ2が共にＨであるエポキシ樹脂を用いたエ
ポキシ樹脂組成物の硬化物と比較しても疎水性の構造を
多く含むことから吸湿率がより低いという特徴があり、
このことにより２６０℃での表面実装の半田付け時にお
ける熱応力にも耐え得るという特徴を発現できるもので
ある。また、エポキシ基間の疎水性構造により架橋点間
距離が長いことで、エポキシ樹脂組成物の硬化物は燃焼
時の温度では非常に軟らかくなっているため、燃焼時に
硬化物の内部で発生する熱分解ガスが、硬化物の層をゴ
ムのように膨張させて発泡層を形成し、この発泡層によ
る未燃焼部への酸素の遮断と断熱作用によって、難燃性
が非常に高いという特徴を有している。この場合、燃焼
時の温度域での弾性率が重要であり、硬化物の層が硬す
ぎると硬化物の内部で発生する熱分解ガスにより発泡層
が形成されずに硬化物中に亀裂が発生してしまい、逆に
硬化物の層が軟らかすぎると発泡層は形成されるものの
発泡層が容易に壊れてしまうため、難燃性が低下するも
のと考えられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The epoxy resin represented by the general formula (1) used in the present invention has two or more epoxy groups in one molecule, has a hydrophobic structure between each epoxy group, and has X 1 , X 2 ,
At least one of Y 1 and Y 2 is other than H. A cured product of an epoxy resin composition using an epoxy resin represented by the general formula (1) has a long distance between cross-linking points due to a hydrophobic structure between epoxy groups, and therefore has a modulus of elasticity in a high temperature range exceeding a glass transition temperature. Low, X 1 in the general formula (1),
Compared with a cured product of an epoxy resin composition using an epoxy resin in which X 2 , Y 1 and Y 2 are both H, it has a feature that the moisture absorption rate is lower because it contains many hydrophobic structures.
As a result, it is possible to develop the feature of being able to withstand the thermal stress at the time of surface mounting soldering at 260 ° C. In addition, since the distance between the cross-linking points is long due to the hydrophobic structure between the epoxy groups, the cured product of the epoxy resin composition becomes very soft at the temperature during combustion, so the heat generated inside the cured product during combustion is The decomposed gas expands the cured product layer like rubber to form a foamed layer, and the foamed layer blocks oxygen to the unburned part and has an adiabatic effect, which is extremely flame retardant. is doing. In this case, the elastic modulus in the temperature range during combustion is important, and if the layer of the cured product is too hard, the pyrolysis gas generated inside the cured product does not form a foam layer and cracks occur in the cured product. On the contrary, if the layer of the cured product is too soft, the foamed layer is formed but the foamed layer is easily broken, so that the flame retardancy is considered to be lowered.
【００１２】又本発明では、一般式（１）で示されるエ
ポキシ樹脂の特徴を損なわない範囲で、他のエポキシ樹
脂を併用してもよい。併用できるエポキシ樹脂として
は、分子内にエポキシ基を有するモノマー、オリゴマ
ー、及びポリマー全般を言う。例えば、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
フェノールノボラック型エポキシ樹脂、オルソクレゾー
ルノボラック型エポキシ樹脂、ナフトールノボラック型
エポキシ樹脂、フェノールアラルキル型エポキシ樹脂
（ジフェニレン骨格を有する）、ナフトールアラルキル
型エポキシ樹脂（フェニレン骨格、ジフェニレン骨格等
を有する）、ジシクロペンタジエン変性フェノール型エ
ポキシ樹脂、ビフェニル型エポキシ樹脂、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、
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等が挙げられ、これらは１
種類を単独で用いても２種類以上を併用してもよい。一
般式（１）で示されるエポキシ樹脂の使用量しては、全
エポキシ樹脂中に７０重量％以上が好ましい。７０重量
％未満だと、燃焼しやすくなったり、吸湿率が高くなっ
たり、高弾性化による耐半田クラック性の低下が起こる
可能性がある。Further, in the present invention, other epoxy resins may be used in combination as long as the characteristics of the epoxy resin represented by the general formula (1) are not impaired. Epoxy resins that can be used in combination include all monomers, oligomers, and polymers having an epoxy group in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin (having diphenylene skeleton), naphthol aralkyl type epoxy resin (having phenylene skeleton, diphenylene skeleton, etc.), dicyclopentadiene Modified phenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenol methane type epoxy resin,
Examples include alkyl-modified triphenol methane type epoxy resins, triazine nucleus-containing epoxy resins, etc.
One type may be used alone, or two or more types may be used in combination. The amount of the epoxy resin represented by the general formula (1) used is preferably 70% by weight or more based on the total epoxy resin. If it is less than 70% by weight, there is a possibility that combustion is likely to occur, the moisture absorption rate is high, and solder crack resistance is deteriorated due to high elasticity.
【００１３】本発明で用いられる一般式（２）で示され
るフェノール樹脂は、１分子中にフェノール性水酸基を
２個以上有し、各フェノール性水酸基間に疎水性構造を
有することを特徴とする。一般式（２）で示されるフェ
ノール樹脂を用いたエポキシ樹脂組成物の硬化物は、疎
水性の構造を多く含むことから吸湿率が低く、又架橋密
度が低いためガラス転移温度を越えた高温域での弾性率
が低いという特徴があり、表面実装の半田付け時におけ
る熱応力を低減し、耐半田クラック性、半田処理後の基
材との密着性に優れるという特徴を有している。また、
フェノール性水酸基間の疎水性構造により架橋点間距離
が長いことで、エポキシ樹脂組成物の硬化物は燃焼時の
温度では非常に軟らかくなっているため、燃焼時に硬化
物の内部で発生する熱分解ガスが、硬化物の層をゴムの
ように膨張させて発泡層を形成し、この発泡層による未
燃焼部への酸素の遮断と断熱作用によって、難燃性が非
常に高いという特徴を有している。The phenol resin represented by the general formula (2) used in the present invention is characterized by having two or more phenolic hydroxyl groups in one molecule and having a hydrophobic structure between each phenolic hydroxyl group. . A cured product of an epoxy resin composition using a phenol resin represented by the general formula (2) has a low moisture absorption rate because it contains many hydrophobic structures, and also has a low crosslink density, so that it is in a high temperature range exceeding the glass transition temperature. Has a low elastic modulus, reduces thermal stress at the time of surface mounting soldering, and has excellent solder crack resistance and adhesion to a base material after soldering. Also,
Due to the long distance between the cross-linking points due to the hydrophobic structure between the phenolic hydroxyl groups, the cured product of the epoxy resin composition becomes extremely soft at the temperature during combustion, so thermal decomposition that occurs inside the cured product during combustion The gas expands the layer of the cured material like rubber to form a foamed layer, and the foamed layer blocks oxygen to the unburned part and has an adiabatic effect. ing.
【００１４】また、本発明で用いる一般式（３）のフェ
ノール樹脂は、フェノール樹脂の良好な硬化性とアルキ
ルフェノール樹脂の低吸湿性を兼ね備えた特性を発現す
る。一般式（３）中のｍとｎとのモル比（ｍ／ｎ）は、
０．１〜１０が好ましく、より好ましくは０．２〜５の
範囲である。これはフェノールの比率が高くなると硬化
性や強度は向上するものの、耐吸湿性が低下し、アルキ
ルフェノールの比率が高くなると耐吸湿性は向上するも
のの、硬化性や強度が低下するためである。用いるアル
キルフェノールとしては、オルソ、パラ、及びメタの３
種の異性体があり、２種以上を併用しても良い。例え
ば、Ｚ1がＣＨ3の場合は、工業製品としての入手の容易
さからオルソ、もしくは３種の混合物を使用することが
好ましい。また、その場合、合成に用いるアルデヒド源
としては特に限定しないが、ホルムアルデヒドあるいは
パラホルムアルデヒドが工業的に大量生産され安価であ
る点で好ましい。Further, the phenol resin of the general formula (3) used in the present invention exhibits the characteristics of both good curability of the phenol resin and low hygroscopicity of the alkylphenol resin. The molar ratio (m / n) between m and n in the general formula (3) is
It is preferably 0.1 to 10, more preferably 0.2 to 5. This is because when the proportion of phenol is high, the curability and strength are improved, but the moisture absorption resistance is lowered, and when the proportion of alkylphenol is high, the moisture absorption resistance is improved, but the curability and strength are lowered. Alkylphenols used are ortho, para, and meta.
There are two types of isomers, and two or more types may be used in combination. For example, when Z 1 is CH 3 , it is preferable to use an ortho or a mixture of three kinds because it is easily available as an industrial product. Further, in that case, the aldehyde source used for the synthesis is not particularly limited, but formaldehyde or paraformaldehyde is preferable because it is industrially mass-produced and inexpensive.
【００１５】本発明では、一般式（２）で示されるフェ
ノール樹脂、及び一般式（３）で示されるフェノール樹
脂の群から選択させる１種以上のフェノール樹脂を使用
するが、近年の鉛を含まない半田への対応材では、一般
式（２）及び一般式（３）の両者のフェノール樹脂を用
いた方がより好ましい。一般式（２）に一般式（３）で
示されるフェノール樹脂を併用することにより、一般式
（２）で示されるフェノール樹脂のみを使用したエポキ
シ樹脂組成物よりも更に加熱時の溶融粘度が低いエポキ
シ樹脂組成物となるため、一般式（２）のもつ低弾性、
低吸湿の特徴をある程度保ちながら、エポキシ樹脂組成
物の流動性が良くなり、無機充填材を更に高充填化する
ことができ、ひいては更に高い強度を得ることができ
る。半田リフロー処理時に生じる半導体装置のクラック
は、エポキシ樹脂組成物の硬化物とリードフレームとの
界面での剥離又はエポキシ樹脂組成物の硬化物と半導体
素子との界面での剥離に起因しているため、低吸湿、高
強度のエポキシ樹脂組成物を得ることにより、これらの
剥離が低減し、半導体装置の耐半田クラック性を著しく
向上させることができる。一般式（２）で示されるフェ
ノール樹脂と、一般式（３）で示されるフェノール樹脂
との重量比［（２）／（３）］としては、０．１〜１０
が好ましい。０．１未満だとエポキシ樹脂組成物の硬化
物の低吸湿化、低弾性化が十分でなく、又硬化物の難燃
性が低下し、一方、１０を越えると無機充填材の高充填
化ができず、硬化物の高強度化が十分に図れない場合が
ある。In the present invention, one or more phenolic resins selected from the group consisting of the phenolic resin represented by the general formula (2) and the phenolic resin represented by the general formula (3) are used. It is more preferable to use the phenol resin of both the general formula (2) and the general formula (3) as a material compatible with no solder. By using the phenol resin represented by the general formula (3) in combination with the general formula (2), the melt viscosity upon heating is further lower than that of the epoxy resin composition using only the phenol resin represented by the general formula (2). Since it is an epoxy resin composition, the low elasticity of the general formula (2),
While maintaining the characteristic of low moisture absorption to some extent, the fluidity of the epoxy resin composition is improved, the inorganic filler can be further highly filled, and even higher strength can be obtained. The crack of the semiconductor device generated during the solder reflow treatment is caused by peeling at the interface between the cured product of the epoxy resin composition and the lead frame or peeling at the interface between the cured product of the epoxy resin composition and the semiconductor element. By obtaining an epoxy resin composition having low moisture absorption and high strength, peeling of these can be reduced, and the solder crack resistance of the semiconductor device can be significantly improved. The weight ratio [(2) / (3)] of the phenol resin represented by the general formula (2) and the phenol resin represented by the general formula (3) is 0.1 to 10
Is preferred. If it is less than 0.1, the moisture absorption and elasticity of the cured product of the epoxy resin composition are not sufficient, and the flame retardancy of the cured product is reduced, while if it exceeds 10, the inorganic filler is highly filled. In some cases, the cured product cannot be sufficiently strengthened.
【００１６】本発明では、一般式（２）で示されるフェ
ノール樹脂、及び一般式（３）で示されるフェノール樹
脂の群から選択させる１種以上のフェノール樹脂を使用
するが、これらの特徴を損なわない範囲で、他のフェノ
ール樹脂を併用してもよい。併用できるフェノール樹脂
としては、分子内にフェノール性水酸基を有するモノマ
ー、オリゴマー、及びポリマー全般を言う。例えば、フ
ェノールノボラック樹脂、フェノールアラルキル樹脂
（ジフェニレン骨格等を有する）、ナフトールアラルキ
ル樹脂（フェニレン、ジフェニレン骨格等を有する）、
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、ビスフェノールＡ、トリフェノール
メタン型樹脂等が挙げられ、これらは１種類を単独で用
いても２種類以上を併用してもよい。一般式（２）で示
されるフェノール樹脂、一般式（３）で示されるフェノ
ール樹脂との合計量としては、全フェノール樹脂中に７
０重量％以上が好ましい。下限値を下回ると、流動性、
硬化性の低下や十分な強度を得ることが出来ず、耐半田
クラック性の低下が起こる可能性がある。In the present invention, one or more phenol resins selected from the group consisting of the phenol resin represented by the general formula (2) and the phenol resin represented by the general formula (3) are used, but these characteristics are impaired. Other phenolic resins may be used in combination as long as they are not present. Examples of the phenol resin that can be used in combination include monomers, oligomers and polymers having a phenolic hydroxyl group in the molecule. For example, phenol novolac resin, phenol aralkyl resin (having a diphenylene skeleton, etc.), naphthol aralkyl resin (having a phenylene, diphenylene skeleton, etc.),
Examples thereof include terpene-modified phenol resin, dicyclopentadiene-modified phenol resin, bisphenol A, and triphenolmethane type resin. These may be used alone or in combination of two or more. The total amount of the phenol resin represented by the general formula (2) and the phenol resin represented by the general formula (3) is 7 in all phenol resins.
It is preferably 0% by weight or more. Below the lower limit, liquidity,
There is a possibility that the hardenability may not be reduced or sufficient strength may not be obtained and the solder crack resistance may be reduced.
【００１７】更に本発明の様に、一般式（１）で示され
るエポキシ樹脂と、一般式（２）で示されるエポキシ樹
脂及び一般式（３）で示されるフェノール樹脂の群から
選択させる１種以上のフェノール樹脂とを組み合わせて
用いると、吸湿後の半田処理での耐半田クラック性、難
燃性等の点で最も高い効果が得られる。全エポキシ樹脂
中のエポキシ基数と全フェノール樹脂中のフェノール性
水酸基数の比（当量比）としては、（エポキシ基数）／
（フェノール性水酸基数）＝０．７〜１．５が好まし
く、この範囲を外れると、エポキシ樹脂組成物の硬化性
の低下、或いは硬化物のガラス転移温度の低下、耐湿信
頼性の低下等が生じる可能性があり好ましくない。Further, as in the present invention, one selected from the group consisting of the epoxy resin represented by the general formula (1), the epoxy resin represented by the general formula (2) and the phenol resin represented by the general formula (3). When used in combination with the above-mentioned phenol resin, the highest effect is obtained in terms of solder crack resistance, flame retardancy, etc. in the solder treatment after moisture absorption. The ratio (equivalent ratio) of the number of epoxy groups in the total epoxy resin to the number of phenolic hydroxyl groups in the total phenolic resin is (the number of epoxy groups) /
(Number of phenolic hydroxyl groups) = 0.7 to 1.5 is preferable, and when it is out of this range, the curability of the epoxy resin composition is lowered, or the glass transition temperature of the cured product is lowered, the moisture resistance reliability is lowered, and the like. It may occur and is not preferable.
【００１８】本発明で用いられる硬化促進剤としては、
エポキシ基とフェノール性水酸基との硬化反応を促進さ
せるものであればよく、一般に封止材料に使用されてい
るものを広く使用することができる。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等のジアザビシクロアルケン及びその誘導
体、トリブチルアミン、ベンジルジメチルアミン等のア
ミン系化合物、テトラフェニルホスホニウム・テトラナ
フトイックアシッドボレート、トリフェニルホスフィン
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。これらの硬化促進剤は１種類を単独で
用いても２種類以上を併用してもよい。これらの内で
は、特に１，８−ジアザビシクロ（５，４，０）ウンデ
セン−７が、各種基材に対する密着性の向上のために有
効であり、更にテトラフェニルホスホニウム・テトラナ
フトイックアシッドボレートは、エポキシ樹脂組成物の
常温保管特性を大幅に向上させる効果がある。The curing accelerator used in the present invention includes:
Any material that accelerates the curing reaction between the epoxy group and the phenolic hydroxyl group may be used, and those generally used for sealing materials may be widely used. For example, tributylamine, 1,8-diazabicyclo (5,4,0) undecene-7 and other diazabicycloalkenes and derivatives thereof, amine compounds such as tributylamine and benzyldimethylamine, tetraphenylphosphonium tetranaphthoic acid Examples thereof include, but are not limited to, organic phosphorus compounds such as borate and triphenylphosphine, imidazole compounds such as 2-methylimidazole, and the like. These curing accelerators may be used alone or in combination of two or more. Of these, 1,8-diazabicyclo (5,4,0) undecene-7 is particularly effective for improving the adhesion to various substrates, and tetraphenylphosphonium / tetranaphthoic acid borate is It has the effect of significantly improving the room temperature storage characteristics of the epoxy resin composition.
【００１９】本発明で用いられる無機充填材としては、
一般に封止材料に使用されているものを広く使用するこ
とができ、例えば、溶融シリカ、球状シリカ、結晶シリ
カ、２次凝集シリカ、多孔質シリカ、２次凝集シリカ又
は多孔質シリカを粉砕したシリカ、アルミナ、窒化珪素
等が挙げられるが、これらに限定されるものではない。
これらは１種類を単独で用いても２種類以上を併用して
もよい。特に、溶融シリカ、結晶シリカが好ましい。又
無機充填材の形状としては、破砕状でも球状でもかまわ
ないが、耐半田クラック性を向上させるために高充填す
る点や、流動性、機械強度及び熱的特性のバランスの点
から球状溶融シリカが好ましい。最大粒径としては７５
μｍ以下が好ましく、平均粒径としては５〜２５μｍが
好ましい。粒度分布としては広いものが、成形時のエポ
キシ樹脂組成物の溶融粘度を低減するために有効であ
る。更にシランカップリング剤等で予め表面処理をした
ものを用いてもよい。As the inorganic filler used in the present invention,
A wide range of materials generally used as sealing materials can be used, for example, fused silica, spherical silica, crystalline silica, secondary agglomerated silica, porous silica, secondary agglomerated silica or silica obtained by pulverizing porous silica. , Alumina, silicon nitride and the like, but are not limited thereto.
These may be used alone or in combination of two or more. In particular, fused silica and crystalline silica are preferable. The shape of the inorganic filler may be crushed or spherical, but spherical fused silica is used from the viewpoint of high filling to improve solder crack resistance and the balance of fluidity, mechanical strength and thermal properties. Is preferred. 75 as the maximum particle size
The average particle size is preferably 5 to 25 μm. A broad particle size distribution is effective for reducing the melt viscosity of the epoxy resin composition during molding. Further, a surface-treated material such as a silane coupling agent may be used.
【００２０】無機充填材の配合量としては、全エポキシ
樹脂組成物中に６５〜９５重量％が好ましい。下限値を
下回ると、エポキシ樹脂組成物の硬化物の吸湿量が増大
し、しかも半田処理温度での強度が低下してしまうた
め、半田処理時に半導体装置にクラックが生じやすくな
り、一方、上限値を越えると、エポキシ樹脂組成物の成
形時の流動性が低下し、未充填や半導体素子のパッドシ
フトが発生し易くなる可能性がある。無機充填材はなる
べく多く配合した方が、エポキシ樹脂組成物の硬化物の
吸湿率が減少し、耐半田クラック性が向上するので、成
形時の流動性が許容される範囲内でなるべく多く配合し
た方が好ましい。The content of the inorganic filler is preferably 65 to 95% by weight based on the total epoxy resin composition. If the lower limit is exceeded, the moisture absorption of the cured product of the epoxy resin composition will increase, and since the strength at the solder processing temperature will decrease, cracks will easily occur in the semiconductor device during solder processing, while the upper limit If it exceeds, the fluidity of the epoxy resin composition at the time of molding may be lowered, and unfilling or pad shift of a semiconductor element may easily occur. If the inorganic filler is blended as much as possible, the moisture absorption rate of the cured product of the epoxy resin composition will be decreased and the solder crack resistance will be improved, so the blending amount was as much as possible within the range in which the fluidity during molding is allowed. Is preferred.
【００２１】本発明のエポキシ樹脂組成物は、（Ａ）〜
（Ｄ）成分の他、環境負荷物質であるハロゲン含有難燃
剤、アンチモン化合物、及び、少量添加でも電気的耐湿
信頼性に問題のあるリン系難燃剤以外の難燃剤を添加す
ることは差し支えないが、完全に含まれない方が好まし
い。例えば、水酸化アルミニウム、水酸化マグネシウム
等の金属水酸化物等の難燃剤であれば、硬化性の低下が
激しく成形性で十分満足を得ることができなくならない
よう、全エポキシ樹脂組成物中に５重量％以下の使用に
留めることが好ましい。The epoxy resin composition of the present invention comprises (A)-
In addition to component (D), halogen-containing flame retardants that are environmentally hazardous substances, antimony compounds, and flame retardants other than phosphorus-based flame retardants that have a problem in electrical humidity resistance reliability even if added in small amounts may be added. , Preferably not completely contained. For example, in the case of flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, the curability is drastically deteriorated, and moldability is not sufficiently satisfied. It is preferable to use only 5% by weight or less.
【００２２】本発明のエポキシ樹脂組成物は、（Ａ）〜
（Ｄ）成分の他、必要に応じて酸化ビスマス水和物等の
無機イオン交換体、γ-グリシドキシプロピルトリメト
キシシラン等のカップリング剤、カーボンブラック、ベ
ンガラ等の着色剤、シリコーンオイル、シリコーンゴム
等の低応力化成分、天然ワックス、合成ワックス、高級
脂肪酸及びその金属塩類もしくはパラフィン等の離型
剤、酸化防止剤等の各種添加剤を配合することができ
る。本発明のエポキシ樹脂組成物は、（Ａ）〜（Ｄ）成
分、及びその他の添加剤等、ミキサー等を用いて常温混
合し、ロール、ニーダー、押出機等の混練機で加熱混
練、冷却後粉砕して得られる。本発明のエポキシ樹脂組
成物は、電気部品或いは電子部品であるトランジスタ、
集積回路等の被覆・絶縁・封止等に適用することができ
る。本発明のエポキシ樹脂組成物を用いて、半導体素子
等の電子部品を封止し、半導体装置を製造するには、ト
ランスファーモールド、コンプレッションモールド、イ
ンジェクションモールド等の成形方法で成形硬化すれば
よい。The epoxy resin composition of the present invention comprises (A)-
In addition to the component (D), if necessary, an inorganic ion exchanger such as bismuth oxide hydrate, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black and red iron oxide, a silicone oil, It is possible to add various additives such as a stress reducing component such as silicone rubber, a natural wax, a synthetic wax, a releasing agent such as higher fatty acids and their metal salts or paraffin, and an antioxidant. The epoxy resin composition of the present invention is mixed at room temperature using components such as components (A) to (D), other additives, and the like, and is kneaded by heating with a kneader such as a roll, kneader, or extruder, and after cooling. Obtained by crushing. The epoxy resin composition of the present invention is a transistor that is an electric component or an electronic component,
It can be applied to covering, insulating, sealing, etc. of integrated circuits. In order to manufacture a semiconductor device by sealing an electronic component such as a semiconductor element using the epoxy resin composition of the present invention, molding and curing may be performed by a molding method such as a transfer mold, a compression mold or an injection mold.
【００２３】[0023]
【実施例】以下に、本発明の実施例を挙げて詳細に説明
するが、本発明はこれらに限定されるものではない。各
成分の配合割合は重量％とする。
＜実施例１＞
式（４）で示されるエポキシ樹脂ａ（融点７５℃、１５０℃でのＩＣＩ溶融粘
度２．５×１０2ｍＰａ・ｓ、エポキシ当量２５０） ７．９７重量％The present invention will be described in detail below with reference to examples of the present invention, but the present invention is not limited thereto. The mixing ratio of each component is% by weight. Example 1 Epoxy resin a represented by the formula (4) (melting point 75 ° C., ICI melt viscosity at 150 ° C. 2.5 × 10 2 mPa · s, epoxy equivalent 250) 7.97% by weight
【００２４】[0024]
【化７】 [Chemical 7]
【００２５】 式（５）で示されるフェノール樹脂ｄ（軟化点６５℃、１５０℃でのＩＣＩ溶 融粘度０．９×１０2ｍＰａ・ｓ、水酸基当量１６８） ４．１３重量％Phenol resin d represented by the formula (5) (softening point 65 ° C., ICI melt viscosity at 150 ° C. 0.9 × 10 2 mPa · s, hydroxyl group equivalent 168) 4.13% by weight
【００２６】[0026]
【化８】 [Chemical 8]
【００２７】 式（６）で示されるフェノール樹脂ｆ（軟化点５０℃、１５０℃でのＩＣＩ溶 融粘度０．５×１０2ｍＰａ・ｓ、水酸基当量１１２） ０．５０重量％Phenol resin f represented by the formula (6) (softening point 50 ° C., ICI melt viscosity at 150 ° C. 0.5 × 10 2 mPa · s, hydroxyl group equivalent 112) 0.50% by weight
【００２８】[0028]
【化９】 [Chemical 9]
【００２９】
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％
球状溶融シリカ（最大粒径７５μｍ、平均粒径２２μｍ） ８６．００重量％
カーボンブラック ０．３０重量％
カルナバワックス ０．３０重量％
酸化ビスマス水和物 ０．３０重量％
γ−グリシドキシプロピルトリメトキシシラン ０．３０重量％
をミキサーを用いて常温で混合し、７０〜１１０℃でロ
ールを用いて混練し、冷却後粉砕し、タブレット化して
エポキシ樹脂組成物を得た。このエポキシ樹脂組成物を
以下の方法で評価した。結果を表１に示す。1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU) 0.20% by weight Spherical fused silica (maximum particle size 75 μm, average particle size 22 μm) 86.00% by weight carbon black 0.30% by weight Carnauba wax 0.30% by weight Bismuth oxide hydrate 0.30% by weight γ-glycidoxypropyltrimethoxysilane 0.30% by weight is mixed at room temperature using a mixer, and 70 to 110 ° C. Was kneaded by using a roll, cooled, pulverized, and tableted to obtain an epoxy resin composition. This epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.
【００３０】評価方法
・スパイラルフロー：ＥＭＭＩ−１−６６に準じたスパ
イラルフロー測定用の金型を用いて、金型温度１７５
℃、注入圧力６．９ＭＰａ、硬化時間１２０ｓで測定し
た。単位はｃｍ。
・熱時曲げ強度・熱時曲げ弾性率：低圧トランスファー
成形機を用いて、金型温度１７５℃、注入圧力９．８Ｍ
Ｐａ、硬化時間１２０ｓで試験片を成形し、ポストキュ
アとして１７５℃で８時間処理した後、熱時曲げ強度、
又は熱時曲げ弾性率をＪＩＳ Ｋ ６９１１に準じて
（２６０℃で）測定した。単位はいずれもＮ／ｍｍ2。
・吸湿率：低圧トランスファー成形機を用いて金型温度
１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０ｓで
直径５０ｍｍ、厚さ３ｍｍの円盤状試験片を成形し、ポ
ストキュアとして１７５℃で８時間処理した。試験片の
吸湿処理前と、８５℃、相対湿度８５％の環境下で１６
８時間吸湿処理した後の重量変化を測定し、試験片の吸
湿率を百分率で示した。単位は％。Evaluation method Spiral flow: A mold temperature of 175 was used by using a mold for spiral flow measurement according to EMMI-1-66.
C., injection pressure 6.9 MPa, curing time 120 s. The unit is cm. -Hot bending strength-Hot bending elastic modulus: Using a low-pressure transfer molding machine, mold temperature 175 ° C, injection pressure 9.8M
The test piece was molded with Pa and a curing time of 120 s, and after being post-cured at 175 ° C. for 8 hours, the bending strength under heat,
Alternatively, the bending elastic modulus at the time of heating was measured according to JIS K 6911 (at 260 ° C.). The unit is N / mm 2 . Moisture absorption rate: A low temperature transfer molding machine is used to mold a disc-shaped test piece having a diameter of 50 mm and a thickness of 3 mm at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa and a curing time of 120 s, and post-cured at 175 ° C. for 8 hours. Processed. 16 before the moisture absorption treatment of the test piece and under the environment of 85 ° C and relative humidity of 85%
The weight change after moisture absorption treatment for 8 hours was measured, and the moisture absorption rate of the test piece was shown in percentage. Units%.
【００３１】・耐半田クラック性：低圧トランスファー
成形機を用いて金型温度１７５℃、注入圧力９．３ＭＰ
ａ、硬化時間１２０ｓで１６０ｐＬＱＦＰ（厚さ１．４
ｍｍ、チップサイズ７ｍｍ×７ｍｍ）を成形した。ポス
トキュアとして１７５℃で８時間処理したパッケージ５
個を、８５℃、相対湿度６０％の環境下で１６８時間処
理した後、ＩＲリフロー処理（２６０℃）を行った。処
理後の内部の剥離又はクラックの有無を超音波探傷装置
で観察し、不良パッケージの個数を数えた。不良パッケ
ージの個数がｎ個であるとき、ｎ／５と表示する。
・難燃性：低圧トランスファー成形機を用いて、試験片
（長さ５ｉｎｃｈ×幅１／２ｉｎｃｈ×厚さ１／８ｉｎ
ｃｈ）を金型温度１７５℃、注入圧力９．８ＭＰａ、硬
化時間１２０ｓで成形し、ポストキュアとして１７５℃
で８時間処理した後、ＵＬ−９４垂直試験を行い、難燃
性を判定した。Solder crack resistance: Mold temperature is 175 ° C., injection pressure is 9.3MP using a low pressure transfer molding machine.
a, curing time 120 s, 160 pLQFP (thickness 1.4
mm, chip size 7 mm × 7 mm). Package 5 treated as post cure for 8 hours at 175 ℃
Each piece was treated under an environment of 85 ° C. and a relative humidity of 60% for 168 hours, and then IR reflow treatment (260 ° C.) was performed. The presence or absence of internal peeling or cracks after the treatment was observed with an ultrasonic flaw detector to count the number of defective packages. When the number of defective packages is n, it is displayed as n / 5.・ Flame resistance: Using a low pressure transfer molding machine, test pieces (length 5 inch x width 1/2 inch x thickness 1/8 inch
ch) is molded at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa and a curing time of 120 s, and post-cured at 175 ° C.
After being treated for 8 hours, the UL-94 vertical test was performed to determine the flame retardancy.
【００３２】＜実施例２〜５、比較例１〜４＞表１の処
方に従い、実施例１と同様にしてエポキシ樹脂組成物を
得て、実施例１と同様にして評価した。結果を表１に示
す。以下に実施例１以外で用いた材料を示す。<Examples 2 to 5, Comparative Examples 1 to 4> According to the formulations in Table 1, epoxy resin compositions were obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1. The materials used in other than Example 1 are shown below.
【００３３】式（７）で示されるエポキシ樹脂ｂ（融点
７５℃、１５０℃でのＩＣＩ溶融粘度２．５×１０2ｍ
Ｐａ・ｓ、エポキシ当量２３５）Epoxy resin b represented by the formula (7) (melting point 75 ° C., ICI melt viscosity at 150 ° C. 2.5 × 10 2 m
Pa · s, epoxy equivalent 235)
【００３４】[0034]
【化１０】 [Chemical 10]
【００３５】式（８）で示されるエポキシ樹脂ｃ（融点
１０５℃、１５０℃でのＩＣＩ溶融粘度０．２×１０2
ｍＰａ・ｓ、エポキシ当量１８５）The epoxy resin c represented by the formula (8) (melting point 105 ° C., ICI melt viscosity at 150 ° C. 0.2 × 10 2
mPa · s, epoxy equivalent 185)
【００３６】[0036]
【化１１】 [Chemical 11]
【００３７】式（９）で示されるフェノール樹脂ｅ（軟
化点６５℃、１５０℃でのＩＣＩ溶融粘度１．０×１０
2ｍＰａ・ｓ、水酸基当量１７２）Phenolic resin e represented by the formula (9) (ICI melt viscosity at a softening point of 65 ° C. and 150 ° C. 1.0 × 10
2 mPa · s, hydroxyl equivalent 172)
【００３８】[0038]
【化１２】 [Chemical 12]
【００３９】式（１０）で示されるフェノール樹脂ｇ
（軟化点６０℃、１５０℃でのＩＣＩ溶融粘度０．６×
１０2ｍＰａ・ｓ、水酸基当量１１６）Phenolic resin g represented by the formula (10)
(Softening point 60 ° C, ICI melt viscosity at 150 ° C 0.6 ×
10 2 mPa · s, hydroxyl group equivalent 116)
【００４０】[0040]
【化１３】 [Chemical 13]
【００４１】式（１１）で示されるフェノール樹脂ｈ
（軟化点８０℃、１５０℃でのＩＣＩ溶融粘度１．９×
１０2ｍＰａ・ｓ、水酸基当量１０５）Phenolic resin h represented by the formula (11)
(Softening point 80 ° C, ICI melt viscosity at 150 ° C 1.9x
10 2 mPa · s, hydroxyl group equivalent 105)
【００４２】[0042]
【化１４】 [Chemical 14]
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】本発明に従うと、従来の難燃剤を多量に
用いなくとも難燃性に優れ、かつ成形性に優れた半導体
封止用エポキシ樹脂組成物が得られ、これを用いると耐
半田クラック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 for semiconductor encapsulation which is excellent in flame retardancy and moldability can be obtained without using a large amount of conventional flame retardant. It is possible to obtain a semiconductor device having excellent crackability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 23/31 Ｆターム(参考） 4J002 CC022 CD061 CD071 DA037 DJ007 DJ017 EN036 EU116 FA087 FD020 FD130 FD142 FD156 GQ05 4J036 AC01 AC02 AC03 DA04 DA05 DC05 DC41 DC46 DD07 FA02 FA05 FA13 FB20 GA04 HA12 JA07 KA05 4M109 EA03 EA20 EB03 EB04 EB09 EB12 EC03 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01L 23/31 F term (reference) 4J002 CC022 CD061 CD071 DA037 DJ007 DJ017 EN036 EU116 FA087 FD020 FD130 FD142 FD156 GQ05 4J036 AC01 AC02 AC03 DA04 DA05 DC05 DC41 DC46 DD07 FA02 FA05 FA13 FB20 GA04 HA12 JA07 KA05 4M109 EA03 EA20 EB03 EB04 EB09 EB12 EC03
Claims (2)
樹脂、（Ｂ）一般式（２）で示されるフェノール樹脂、
及び一般式（３）で示されるフェノール樹脂の群から選
択される１種以上のフェノール樹脂、（Ｃ）硬化促進
剤、及び（Ｄ）無機充填材が必須成分であることを特徴
とする半導体封止用エポキシ樹脂組成物。 【化１】 （式中のＸ1、Ｘ2、Ｙ1、Ｙ2は、Ｈ、ＣＨ3、Ｃ2Ｈ5、
Ｃ3Ｈ7、ｔ−Ｂｕから選択される基であり、互いに同一
であっても、異なっていても良いが、少なくとも１つ以
上はＨ以外のものを含む。ｎは平均値で１〜５の正
数。） 【化２】 （式中のＸ3、Ｘ4、Ｙ3、Ｙ4は、Ｈ、ＣＨ3、Ｃ2Ｈ5、
Ｃ3Ｈ7、ｔ−Ｂｕから選択される基であり、互いに同一
であっても、異なっていても良い。ｎは平均値で１〜５
の正数。） 【化３】 （式中のＺ1は、ＣＨ3、Ｃ2Ｈ5、Ｃ3Ｈ7、ｔ−Ｂｕから
選択される基であり、互いに同一であっても、異なって
いても良い。ｍ、ｎは平均値で１〜５の正数。）1. An epoxy resin represented by the general formula (1) (A), a phenol resin represented by the general formula (2) (B),
And at least one phenol resin selected from the group of phenol resins represented by the general formula (3), (C) a curing accelerator, and (D) an inorganic filler are essential components. Stopping epoxy resin composition. [Chemical 1] (In the formula, X 1 , X 2 , Y 1 and Y 2 are H, CH 3 , C 2 H 5 ,
It is a group selected from C 3 H 7 and t-Bu, which may be the same or different from each other, but at least one or more of them include those other than H. n is an average value and is a positive number of 1 to 5. ) [Chemical 2] (In the formula, X 3 , X 4 , Y 3 , and Y 4 are H, CH 3 , C 2 H 5 ,
It is a group selected from C 3 H 7 and t-Bu, and may be the same as or different from each other. n is an average value of 1 to 5
Positive number. ) [Chemical 3] (Z 1 in the formula is a group selected from CH 3 , C 2 H 5 , C 3 H 7 , and t-Bu, and may be the same or different. M and n are average. Value is a positive number from 1 to 5.)
いて半導体素子を封止してなる半導体装置。2. A semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2001397125A JP2003192769A (en) | 2001-12-27 | 2001-12-27 | Epoxy resin composition and semiconductor device |
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|---|---|---|---|
| JP2001397125A JP2003192769A (en) | 2001-12-27 | 2001-12-27 | Epoxy resin composition and semiconductor device |
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| JP2003192769A true JP2003192769A (en) | 2003-07-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101437141B1 (en) | 2010-12-31 | 2014-09-02 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor |
| JP2020536752A (en) * | 2017-10-04 | 2020-12-17 | サンーゴバン アブレイシブズ，インコーポレイティド | Polishing article and its forming method |
| US12226876B2 (en) | 2019-04-03 | 2025-02-18 | Saint-Gobain Abrasives, Inc. | Abrasive article, abrasive system and method for using and forming same |
-
2001
- 2001-12-27 JP JP2001397125A patent/JP2003192769A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101437141B1 (en) | 2010-12-31 | 2014-09-02 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor |
| JP2020536752A (en) * | 2017-10-04 | 2020-12-17 | サンーゴバン アブレイシブズ，インコーポレイティド | Polishing article and its forming method |
| JP7186770B2 (en) | 2017-10-04 | 2022-12-09 | サンーゴバン アブレイシブズ，インコーポレイティド | Abrasive article and method of forming same |
| US11712784B2 (en) | 2017-10-04 | 2023-08-01 | Saint-Gobain Abrasives, Inc. | Abrasive article and method for forming same |
| US12226876B2 (en) | 2019-04-03 | 2025-02-18 | Saint-Gobain Abrasives, Inc. | Abrasive article, abrasive system and method for using and forming same |
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