JP2006008854A - Epoxy resin composition, semiconductor device and its manufacturing method - Google Patents
Epoxy resin composition, semiconductor device and its manufacturing method Download PDFInfo
- Publication number
- JP2006008854A JP2006008854A JP2004188179A JP2004188179A JP2006008854A JP 2006008854 A JP2006008854 A JP 2006008854A JP 2004188179 A JP2004188179 A JP 2004188179A JP 2004188179 A JP2004188179 A JP 2004188179A JP 2006008854 A JP2006008854 A JP 2006008854A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- semiconductor device
- epoxy
- composition according
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 127
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000004065 semiconductor Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 12
- 238000007259 addition reaction Methods 0.000 claims description 11
- 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 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- 238000003466 welding Methods 0.000 abstract description 17
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 49
- 238000000034 method Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene 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
- 238000011156 evaluation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- -1 oxygen anion Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 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
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RHTRCNTWBQACED-UHFFFAOYSA-N O=C(C1CC2OC2CC1)OCC1CC(C2)OC2C1 Chemical compound O=C(C1CC2OC2CC1)OCC1CC(C2)OC2C1 RHTRCNTWBQACED-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 239000011324 bead Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 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
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Wire Bonding (AREA)
Abstract
Description
本発明は、半導体封止材料として好適に使用することができるエポキシ樹脂組成物、並びにこのエポキシ樹脂組成物を用いて製造される半導体装置及びその製造方法に関するものである。 The present invention relates to an epoxy resin composition that can be suitably used as a semiconductor sealing material, a semiconductor device manufactured using the epoxy resin composition, and a manufacturing method thereof.
近年、電子機器のさらなる小型化及び高機能化を図るため、プリント配線板等の回路基板上にＩＣチップ等の電子部品を高密度で実装することが要求されている。実装密度を高める有力な手段の一つとして、フリップチップ実装が広く知られている。フリップチップ実装においては、バンプと呼ばれる突起を介してＩＣチップ上の複数の電極とプリント配線板上の所定の電極とを位置合わせした後、これらの電極間の電気接続が一括して形成される。次いで、電気絶縁性を有する封止用樹脂（アンダーフィル材）がＩＣチップとプリント配線板の間に注入されて加熱硬化される。封止用樹脂としては、エポキシ樹脂を配合した液状エポキシ樹脂組成物が汎用されている（例えば、特許文献１参照。）。
しかしながら、上記のフリップチップ実装では、電極接続工程と封止用樹脂の硬化工程を個別に行っていたため製造効率が悪いという問題があった。 However, the flip chip mounting described above has a problem in that the manufacturing efficiency is low because the electrode connecting step and the sealing resin curing step are separately performed.
そこで、金属バンプを介しての電極接続と同時に封止用樹脂の硬化を行うリフロー同時硬化法や、回路基板の表面に液状エポキシ樹脂を塗布した後に、ＩＣチップをエポキシ樹脂の塗布層上に配置してＩＣチップの背面から加圧加熱して電極接続と封止用樹脂の硬化を一段階で行う圧接法が提案されている。 Therefore, the reflow simultaneous curing method that cures the sealing resin at the same time as the electrode connection through the metal bump, or after applying the liquid epoxy resin to the surface of the circuit board, the IC chip is placed on the epoxy resin coating layer There has been proposed a pressure welding method in which electrode connection and curing of the sealing resin are performed in one step by applying pressure and heating from the back surface of the IC chip.
このうち、圧接法においては、圧接に要する時間がフリップチップ実装効率を決定する律速因子となるため、硬化時間が短く、かつ硬化した樹脂組成物内に気泡（ボイド）が発生しない封止用樹脂組成物の開発が待たれている。 Among these, in the pressure welding method, the time required for pressure welding is a rate-determining factor for determining flip chip mounting efficiency, so that the curing time is short and the sealing resin does not generate bubbles in the cured resin composition. The development of the composition is awaited.
本発明は上記の点に鑑みてなされたものであり、フリップチップ実装による半導体装置の製造効率を改善するため、圧接工程において短時間で硬化し、ボイドレスの優れた接着性を備えた硬化樹脂層を形成できるエポキシ樹脂組成物、並びにこのエポキシ樹脂組成物を用いて製造される半導体装置及びその製造方法を提供することを目的とするものである。 The present invention has been made in view of the above points, and in order to improve the manufacturing efficiency of a semiconductor device by flip chip mounting, a cured resin layer that is cured in a short time in the press-contacting process and has excellent adhesiveness of the voidless It is an object of the present invention to provide an epoxy resin composition capable of forming a semiconductor device, a semiconductor device manufactured using the epoxy resin composition, and a manufacturing method thereof.
本発明の請求項１に係るエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤を含有すると共に室温で液状であるエポキシ樹脂組成物において、硬化剤として、２−メチルイミダゾールと下記化学式（１）で示される脂環式エポキシとの付加反応物を用いて成ることを特徴とするものである。 The epoxy resin composition according to claim 1 of the present invention includes an epoxy resin and a curing agent, and is an epoxy resin composition that is liquid at room temperature, and is represented by 2-methylimidazole and the following chemical formula (1) as a curing agent. It is characterized by using an addition reaction product with alicyclic epoxy.
請求項２の発明は、請求項１において、エポキシ樹脂として、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、これらの水素添加型のエポキシ樹脂、脂環式エポキシ樹脂から選択される少なくとも１種のものを用いて成ることを特徴とするものである。 The invention of claim 2 is the epoxy resin according to claim 1, wherein the epoxy resin is selected from bisphenol F type epoxy resin, bisphenol A type epoxy resin, naphthalene ring-containing epoxy resin, these hydrogenated epoxy resins, and alicyclic epoxy resins. It is characterized by comprising using at least one of the above.
請求項３の発明は、請求項１又は２において、下記化学式（２）で示されるナフタレン環含有４官能型エポキシ樹脂をエポキシ当量比で全エポキシ樹脂の５〜４０％含有して成ることを特徴とするものである。 The invention of claim 3 comprises the naphthalene ring-containing tetrafunctional epoxy resin represented by the following chemical formula (2) according to claim 1 or 2, containing 5 to 40% of the total epoxy resin in an epoxy equivalent ratio. It is what.
請求項４の発明は、請求項１乃至３のいずれかにおいて、導電粒子を含有して成ることを特徴とするものである。 According to a fourth aspect of the present invention, in any one of the first to third aspects, the conductive particle is contained.
請求項５の発明は、請求項１乃至４のいずれかにおいて、ゲル化時間が１５０℃において６〜５０秒であることを特徴とするものである。 The invention of claim 5 is characterized in that in any one of claims 1 to 4, the gelation time is 6 to 50 seconds at 150 ° C.
請求項６の発明は、請求項１乃至５のいずれかにおいて、充填材として最大粒径が０．１〜１０μｍである球状非晶質シリカを含有して成ることを特徴とするものである。 A sixth aspect of the invention is characterized in that in any one of the first to fifth aspects, spherical amorphous silica having a maximum particle size of 0.1 to 10 μm is contained as a filler.
本発明の請求項７に係る半導体装置は、請求項１乃至６のいずれかに記載のエポキシ樹脂組成物で半導体チップを封止して成ることを特徴とするものである。 A semiconductor device according to a seventh aspect of the present invention is characterized in that a semiconductor chip is sealed with the epoxy resin composition according to any one of the first to sixth aspects.
本発明の請求項８に係る半導体装置の製造方法は、請求項１乃至７のいずれかに記載のエポキシ樹脂組成物を用いて回路基板と半導体チップとを熱圧接により接着することを特徴とするものである。 A method of manufacturing a semiconductor device according to an eighth aspect of the present invention is characterized in that the circuit board and the semiconductor chip are bonded together by heat pressure welding using the epoxy resin composition according to any one of the first to seventh aspects. Is.
本発明の請求項１に係るエポキシ樹脂組成物によれば、２−メチルイミダゾールと上記化学式（１）で示される脂環式エポキシとの付加反応物を硬化剤として用いることによって、エポキシ樹脂組成物の硬化速度を飛躍的に高めることができ、圧接工程を含む半導体装置の製造方法において製造効率を改善することができると共に、ボイドレスの優れた接着性を備えた硬化樹脂層を半導体チップと回路基板との間に形成することができるものである。また、脂環式エポキシとの付加反応にすることにより硬化物のガラス転移温度(Ｔｇ)が上昇することにより加圧圧接後にボンディングツールをＩＣチップの背面から離す際においてチップ浮きを低減することができるものである。同時に脂環式エポキシはその製法上、塩素のようなハロゲン化合物を含まないため、耐湿絶縁性に悪影響を及ぼすようなイオン性不純物を低減することができるものである。さらには低粘度液体である脂環式エポキシを用いた付加反応物をエポキシ樹脂組成物に使用することで、エポキシ樹脂組成物の低粘度化を実現することができるものである。 According to the epoxy resin composition of claim 1 of the present invention, an epoxy resin composition is obtained by using an addition reaction product of 2-methylimidazole and the alicyclic epoxy represented by the above chemical formula (1) as a curing agent. The curing rate of the semiconductor device can be dramatically increased, the manufacturing efficiency can be improved in the manufacturing method of the semiconductor device including the press-contacting process, and the cured resin layer having excellent adhesiveness of the voidless is formed on the semiconductor chip and the circuit board. Can be formed between the two. In addition, the glass transition temperature (Tg) of the cured product is increased by the addition reaction with the alicyclic epoxy, thereby reducing chip floating when the bonding tool is separated from the back surface of the IC chip after pressure welding. It can be done. At the same time, the alicyclic epoxy does not contain a halogen compound such as chlorine because of its production method, and therefore can reduce ionic impurities that adversely affect moisture resistance insulation. Furthermore, by using an addition reaction product using an alicyclic epoxy that is a low-viscosity liquid for the epoxy resin composition, the viscosity of the epoxy resin composition can be reduced.
請求項２の発明によれば、立体障害の異なるエポキシ樹脂を適宜組み合わせることによって、所望の硬化速度を実現することができるものである。 According to the invention of claim 2, a desired curing rate can be realized by appropriately combining epoxy resins having different steric hindrances.
請求項３の発明によれば、より短時間でボイドレスを実現することができると共に、硬化物のガラス転移温度(Ｔｇ)が上昇することにより加圧圧接後にボンディングツールをＩＣチップの背面から離す際においてチップ浮きを低減することができるものである。 According to the invention of claim 3, it is possible to realize the void dress in a shorter time, and when the bonding tool is separated from the back surface of the IC chip after pressurizing and pressing by increasing the glass transition temperature (Tg) of the cured product. The chip floating can be reduced.
請求項４の発明によれば、導電粒子を含むエポキシ樹脂組成物は、絶縁性の高い接着剤中に導電粒子が均一に分散した材料であり、電子部品の相対する電極間の電気接続と、隣接電極間の絶縁性、及び固定の目的に使用することができるものである。 According to the invention of claim 4, the epoxy resin composition containing conductive particles is a material in which conductive particles are uniformly dispersed in an adhesive having high insulating properties, and electrical connection between opposing electrodes of an electronic component; It can be used for the purpose of insulating and fixing between adjacent electrodes.
請求項５の発明によれば、回路基板と半導体チップとを熱圧接により接着する場合において両者が電気的に接続される前に樹脂が硬化するようなことを防止することができると共に、圧接工程に要する時間が短時間となり、製造効率の向上を十分に達成することができるものである。 According to the invention of claim 5, in the case where the circuit board and the semiconductor chip are bonded by hot pressing, it is possible to prevent the resin from being cured before both are electrically connected, and the pressing process. The time required for the process is shortened, and the production efficiency can be sufficiently improved.
請求項６の発明によれば、粘度増加の抑制、低熱膨張率化、金属バンプと基板電極間の高い接続信頼性を実現することができるものである。 According to the invention of claim 6, it is possible to realize suppression of increase in viscosity, reduction in thermal expansion coefficient, and high connection reliability between the metal bump and the substrate electrode.
本発明の請求項７に係る半導体装置によれば、上記のような半導体装置の製造方法であれば、ボイドレスの優れた接着性を備えた硬化樹脂層を半導体チップと回路基板との間に形成することができるものである。 According to the semiconductor device according to claim 7 of the present invention, in the semiconductor device manufacturing method as described above, the cured resin layer having excellent voidless adhesiveness is formed between the semiconductor chip and the circuit board. Is something that can be done.
本発明の請求項８に係る半導体装置の製造方法によれば、フリップチップ実装による半導体装置の製造効率を改善することができ、圧接工程においてエポキシ樹脂組成物を短時間で硬化させることができるものである。 According to the method for manufacturing a semiconductor device according to claim 8 of the present invention, the manufacturing efficiency of the semiconductor device by flip chip mounting can be improved, and the epoxy resin composition can be cured in a short time in the pressure welding process. It is.
以下、本発明の実施の形態を説明する。 Embodiments of the present invention will be described below.
本発明に係るエポキシ樹脂組成物は、室温で液状であって、エポキシ樹脂及び硬化剤を含有するものである。硬化剤としては、２−メチルイミダゾールと上記化学式（１）で示される脂環式エポキシとの付加反応物（イミダゾール誘導体）を用いる。これらの付加反応物を得るにあたっては、米国特許第４０６６６２５号明細書に記載の方法を使用することができる。そして、上記のようなエポキシ樹脂組成物は、例えば、フリップチップ実装工程においてＩＣチップ等の電子部品とプリント配線板等の回路基板との間の隙間を封止するための半導体封止用材料として好適に用いることができるものであり、上記のエポキシ樹脂組成物を用いてフリップチップ実装を行えば、動作信頼性の高い半導体装置を効率よく製造することができると共に、ボイドレスの優れた接着性を備えた硬化樹脂層を半導体チップと回路基板との間に形成することができるものである。すなわち、上記の硬化剤を用いることによって、エポキシ樹脂組成物の硬化速度を飛躍的に高めることができ、後述するような圧接工程を含む半導体装置の製造方法において製造効率を改善することができるものである。なお、上記の硬化剤は、２−メチルイミダゾールと上記化学式（１）で示される脂環式エポキシとを繰り返し付加することによって得られる化合物を含む。 The epoxy resin composition according to the present invention is liquid at room temperature and contains an epoxy resin and a curing agent. As a curing agent, an addition reaction product (imidazole derivative) of 2-methylimidazole and an alicyclic epoxy represented by the above chemical formula (1) is used. In obtaining these addition reactants, the method described in US Pat. No. 4,066,625 can be used. The epoxy resin composition as described above is used, for example, as a semiconductor sealing material for sealing a gap between an electronic component such as an IC chip and a circuit board such as a printed wiring board in a flip chip mounting process. When flip-chip mounting is performed using the above epoxy resin composition, a semiconductor device with high operation reliability can be efficiently manufactured, and the excellent adhesiveness of the voidless can be obtained. The provided cured resin layer can be formed between the semiconductor chip and the circuit board. That is, by using the curing agent described above, the curing rate of the epoxy resin composition can be dramatically increased, and the manufacturing efficiency can be improved in the method of manufacturing a semiconductor device including a pressing process as described later. It is. In addition, said hardening | curing agent contains the compound obtained by adding 2-methylimidazole and the alicyclic epoxy shown by said Chemical formula (1) repeatedly.
イミダゾールをエポキシ樹脂の硬化剤として用いる場合、イミダゾールの１位活性水素がエポキシ基に付加反応した後に、３級窒素の電子対が別のエポキシ樹脂を攻撃する。この際、生じた酸素アニオンがさらに反応に寄与することで３次元架橋した硬化物が得られる。このうち、最初の（１位）活性水素の付加反応がこれら一連の反応速度を律速する。本発明は、立体障害の比較的少ない２−メチルイミダゾールと上記化学式（１）で示される脂環式エポキシとの付加反応物を硬化剤として用いると飛躍的に反応性が高まることを見出したことにより、完成に至ったものである。 When imidazole is used as a curing agent for an epoxy resin, a tertiary nitrogen electron pair attacks another epoxy resin after the 1st-position active hydrogen of imidazole undergoes an addition reaction with an epoxy group. At this time, the generated oxygen anion further contributes to the reaction, whereby a three-dimensionally cross-linked cured product is obtained. Of these, the first (first-position) active hydrogen addition reaction determines the rate of these series of reactions. The present invention has found that when an addition reaction product of 2-methylimidazole having relatively little steric hindrance and an alicyclic epoxy represented by the above chemical formula (1) is used as a curing agent, the reactivity is dramatically increased. As a result, it was completed.
ここで、硬化剤である上記の付加反応物は、例えば、エポキシ樹脂組成物を圧接工法に使用する場合において、エポキシ樹脂１００質量部に対して０．２〜２０質量部配合することが好ましい。０．２質量部より少ない場合は、十分な硬化速度が得られず、ゲル化に長時間を要するおそれがあり、逆に２０質量部より多い場合は、十分な硬化速度は得られるものの、高温で急速に加熱したとき、それ自体が反応に寄与する前に揮発するため、気泡（ボイド）が硬化物中に残存し、製造される半導体装置の信頼性を低下させるおそれがあるとともに電極接続に至る前に封止樹脂が硬化してしまい電気的な導通が得られないおそれがある。 Here, for example, when the epoxy resin composition is used in the pressure welding method, the addition reaction product as a curing agent is preferably blended in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin. When the amount is less than 0.2 parts by mass, a sufficient curing rate may not be obtained, and it may take a long time for gelation. Conversely, when the amount is more than 20 parts by mass, a sufficient curing rate can be obtained, but the temperature is high. When it is heated rapidly, it volatilizes itself before contributing to the reaction, so that voids remain in the cured product, which may reduce the reliability of the manufactured semiconductor device and connect the electrodes. There is a possibility that the sealing resin is hardened before reaching the electrical conduction.
本発明においてエポキシ樹脂としては、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、これらの水素添加型のエポキシ樹脂、脂環式エポキシ樹脂（例えば、上記化学式（１）で示される脂環式エポキシ）の中から選択される少なくとも１種のものを用いることが好ましい。エポキシ樹脂の硬化速度に最も影響するのはエポキシ基近傍の立体障害であり、エポキシ基に嵩高い置換基が付いていたり、分子構造の平面性が損なわれていたりする場合は、硬化剤の求核攻撃が阻害され、硬化速度は遅くなる。逆にエポキシ基に大きな置換基がなく、分子構造の平面性が保たれている場合は、硬化剤がエポキシ基にアタックしやすいため硬化反応は速くなる。よって、上記のように、立体障害の異なるエポキシ樹脂を適宜組み合わせることで、所望の硬化速度を実現することができるものである。 As the epoxy resin in the present invention, bisphenol F type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene ring-containing epoxy resin, these hydrogenated epoxy resins, alicyclic epoxy resins (for example, the above chemical formula It is preferable to use at least one selected from (alicyclic epoxy represented by (1)). The steric hindrance in the vicinity of the epoxy group has the most influence on the curing rate of the epoxy resin. If the epoxy group has a bulky substituent or the planarity of the molecular structure is impaired, the need for a curing agent is obtained. Nuclear attack is hindered and cure speed is slowed down. On the contrary, when the epoxy group has no large substituent and the planarity of the molecular structure is maintained, the curing reaction is accelerated because the curing agent easily attacks the epoxy group. Therefore, as described above, a desired curing rate can be realized by appropriately combining epoxy resins having different steric hindrances.
また、上記化学式（２）で示されるナフタレン環含有４官能型エポキシ樹脂をエポキシ当量比で全エポキシ樹脂の５〜４０％含有することが好ましい。このナフタレン環含有４官能型エポキシ樹脂は、分子の平面性が極めて高く、さらに反応点となるエポキシ基を４個有していることから、適当量含有することによって、ボイドレスで、より短時間で硬化可能なエポキシ樹脂組成物を容易に調製することができるとと共に、硬化物のガラス転移温度（Ｔｇ）を高めることができるものである。さらに、硬化物のガラス転移温度(Ｔｇ)が上昇することにより、加圧圧接後にボンディングツールをＩＣチップの背面から離す際においてチップ浮きを低減することができるものである。なお、上記化学式（２）で示されるナフタレン環含有４官能型エポキシ樹脂は、室温で固体状態であり、気化しにくい性質を有する。このナフタレン環含有４官能型エポキシ樹脂がエポキシ当量比で４０％を超える場合は、エポキシ樹脂組成物の粘度が上昇することにより流動性が低下して作業性が低下するおそれがあり、逆にエポキシ当量比で５％未満の場合は、硬化速度及びガラス転移温度（Ｔｇ）を高める効果を十分に得ることができないおそれがある。 Moreover, it is preferable to contain the naphthalene ring containing tetrafunctional epoxy resin shown by the said Chemical formula (2) by 5-40% of all the epoxy resins by an epoxy equivalent ratio. This naphthalene ring-containing tetrafunctional epoxy resin has extremely high molecular planarity and further has four epoxy groups that are reactive sites. A curable epoxy resin composition can be easily prepared and the glass transition temperature (Tg) of the cured product can be increased. Furthermore, since the glass transition temperature (Tg) of the cured product is increased, chip lifting can be reduced when the bonding tool is separated from the back surface of the IC chip after pressure welding. Note that the naphthalene ring-containing tetrafunctional epoxy resin represented by the chemical formula (2) is in a solid state at room temperature and has a property of being hardly vaporized. When this naphthalene ring-containing tetrafunctional epoxy resin exceeds 40% in terms of the epoxy equivalent ratio, the viscosity of the epoxy resin composition increases, so that the fluidity may decrease and workability may decrease. If the equivalent ratio is less than 5%, the effect of increasing the curing rate and glass transition temperature (Tg) may not be sufficiently obtained.
また、本発明に係るエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤に加えて、さらに導電粒子を含有することもできる。導電粒子としては、例えば、ポリスチレン系の高分子粒子の核の表面をＡｕめっきしたもの（粒子径５μｍ程度）等を用いることができる。このような導電粒子を含むエポキシ樹脂組成物は、絶縁性の高いエポキシ樹脂及び硬化剤からなる接着剤中に導電粒子が均一に分散した材料であり、電子部品（半導体チップや回路基板など）の相対する電極間の電気接続、隣接電極間の絶縁性の確保、電子部品の固定の目的に使用することができるものである。そして、導電粒子を介して半導体チップの金属バンプと回路基板の基板電極間の電気接続を行うことにより、金属バンプと基板電極の高さのばらつきやチップ搭載時の平行度が緩和されることとなり、より高い接続信頼性を実現することができるものである。 Moreover, the epoxy resin composition according to the present invention can further contain conductive particles in addition to the epoxy resin and the curing agent. As the conductive particles, for example, those obtained by plating the surface of the core of polystyrene polymer particles with Au (particle diameter of about 5 μm) can be used. An epoxy resin composition containing such conductive particles is a material in which conductive particles are uniformly dispersed in an adhesive composed of a highly insulating epoxy resin and a curing agent, and is used for electronic components (semiconductor chips, circuit boards, etc.). It can be used for the purpose of electrical connection between opposing electrodes, ensuring insulation between adjacent electrodes, and fixing electronic components. And, by making electrical connection between the metal bumps of the semiconductor chip and the substrate electrodes of the circuit board via the conductive particles, the variation in the heights of the metal bumps and the substrate electrodes and the parallelism when mounting the chip are alleviated. Therefore, higher connection reliability can be realized.
なお、エポキシ樹脂組成物が、特開２０００−１１７６０号公報や特開２０００−２１２３６号公報などに示される導電粒子を含む異方導電性ペースト（ＡＣＰ）の場合においても、上述の硬化剤を併用すれば、エポキシ樹脂組成物内に気泡（ボイド）を発生させることなく、エポキシ樹脂組成物を短時間で硬化させることができるものである。 In addition, even when the epoxy resin composition is an anisotropic conductive paste (ACP) containing conductive particles as disclosed in JP 2000-11760 A or JP 2000-21236 A, the above curing agent is used in combination. In this case, the epoxy resin composition can be cured in a short time without generating bubbles in the epoxy resin composition.
また、本発明に係るエポキシ樹脂組成物は、１５０℃におけるゲル化時間が６〜５０秒であることが好ましい。これにより、回路基板と半導体チップとを熱圧接により接着する場合において両者が電気的に接続される前に樹脂が硬化するようなことを防止することができると共に、圧接工程に要する時間が短時間となり、製造効率の向上を十分に達成することができるものである。ただし、ゲル化時間が６秒よりも短い場合は、半導体チップを搭載する熱圧接の工程において金属バンプが回路基板の基板電極に接触して電気的な接続が取れる前に樹脂が硬化してしまうおそれがあり、逆にゲル化時間が５０秒よりも長い場合は、圧接工程に長時間を要して製造効率の向上を十分に達成できないおそれがある。 The epoxy resin composition according to the present invention preferably has a gelation time at 150 ° C. of 6 to 50 seconds. As a result, when the circuit board and the semiconductor chip are bonded by thermal pressure welding, it is possible to prevent the resin from being cured before both are electrically connected, and the time required for the pressure welding process is short. Thus, the manufacturing efficiency can be sufficiently improved. However, when the gelation time is shorter than 6 seconds, the resin is cured before the metal bumps contact the substrate electrodes of the circuit board and the electrical connection can be made in the process of heat-pressure welding for mounting the semiconductor chip. On the contrary, if the gelation time is longer than 50 seconds, it may take a long time for the pressure contact process, and the production efficiency may not be sufficiently improved.
また、本発明に係るエポキシ樹脂組成物は、さらに充填材を含有することもできる。この充填材としては、シリカ、アルミナ、窒化アルミニウム、ボロンナイトライド、窒化珪素、炭化珪素、炭酸カルシウム等の無機フィラーを用いることができる。このような充填材の中でも、特に球状非晶質シリカを用いるのが好ましい。このように粒子形状が球状であると、破砕されたままの不均一な形状であるよりも、充填材の含有量を高めた際のエポキシ樹脂組成物の粘度増加を抑えることができる。また、非晶質シリカは、アモルファスシリカとも呼ばれるが、単一金属元素からなる酸化物、窒化物あるいは炭化物の中では、最も熱膨張係数が小さい点でも好ましい。 Moreover, the epoxy resin composition according to the present invention can further contain a filler. As this filler, inorganic fillers such as silica, alumina, aluminum nitride, boron nitride, silicon nitride, silicon carbide, calcium carbonate, and the like can be used. Among such fillers, it is particularly preferable to use spherical amorphous silica. Thus, when the particle shape is spherical, it is possible to suppress an increase in the viscosity of the epoxy resin composition when the content of the filler is increased, rather than a non-uniform shape as crushed. Amorphous silica is also referred to as amorphous silica, but is preferable because it has the smallest thermal expansion coefficient among oxides, nitrides, and carbides composed of a single metal element.
さらに、上記の球状非晶質シリカの最大粒径が０．１〜１０μｍであることが好ましい。これにより、粘度増加の抑制、低熱膨張率化、金属バンプと基板電極間の高い接続信頼性を実現することができるものである。最大粒径が０．１μｍより小さいと、比表面積が極めて大きくなり、粘度が増加して作業性が低下するおそれがあり、逆に最大粒径が１０μｍより大きいと、圧接時に金属バンプと基板電極との間に挟み込まれて接続信頼性を低下させるおそれがある。 Furthermore, the maximum particle size of the spherical amorphous silica is preferably 0.1 to 10 μm. Thereby, suppression of increase in viscosity, reduction in thermal expansion coefficient, and high connection reliability between the metal bump and the substrate electrode can be realized. If the maximum particle size is smaller than 0.1 μm, the specific surface area becomes extremely large, the viscosity may increase, and the workability may be reduced. Conversely, if the maximum particle size is larger than 10 μm, the metal bump and the substrate electrode during pressure welding There is a risk that the connection reliability will be reduced.
充填材の添加量はエポキシ樹脂組成物全量に対して６５質量％以下であることが好ましい。添加量が６５質量％を超える場合は、エポキシ樹脂組成物の粘度が高くなりすぎて作業性を悪化させたり、圧接時に金属バンプと基板電極との間に挟み込まれる確率が高くなり、接続信頼性を低下させたりするおそれがある。 The addition amount of the filler is preferably 65% by mass or less with respect to the total amount of the epoxy resin composition. When the added amount exceeds 65% by mass, the viscosity of the epoxy resin composition becomes too high, and the workability is deteriorated, or the probability of being sandwiched between the metal bump and the substrate electrode at the time of pressure welding increases, and the connection reliability is increased. May be reduced.
なお、本発明に係るエポキシ樹脂組成物には、本発明の目的を損なわない限り、必要に応じて、難燃剤、低弾性化剤、密着性付与剤、着色剤、希釈剤、カップリング剤等の他の物質を配合してもよい。 In addition, the epoxy resin composition according to the present invention includes a flame retardant, a low elastic agent, an adhesion imparting agent, a colorant, a diluent, a coupling agent, etc., as necessary, as long as the purpose of the present invention is not impaired. You may mix | blend other substances.
本発明に係るエポキシ樹脂組成物を調製するにあたっては、上記の各成分を撹拌型の分散機で混合したり、ビーズミルで分散混合したり、３本ロールで分散混合したりすることによって、行うことができる。なお、これら以外の混合方法を採用してもよい。 In preparing the epoxy resin composition according to the present invention, the above components are mixed by a stirrer-type disperser, dispersed and mixed by a bead mill, or dispersed and mixed by a three roll. Can do. In addition, you may employ | adopt mixing methods other than these.
本発明に係る半導体装置は、上記のようにして得たエポキシ樹脂組成物で半導体チップを封止することによって、製造することができる。特に、本発明に係るエポキシ樹脂組成物は、半導体チップをフリップチップ実装する際に用いるのが好ましい。具体的には、まず、上記のようにして得たエポキシ樹脂組成物を回路基板の表面に塗布する。この回路基板としては、ＦＲ４やＦＲ５等の繊維基材を含む有機基板や、ポリイミドやポリエステル等の有機フィルムのほか、セラミックス等の無機基板等を用いることができる。次に、エポキシ樹脂組成物を塗布した回路基板の基板電極と、半導体チップの表面に形成されている金属バンプとの位置合わせを行った後に、半導体チップの背面（回路基板と対向していない側の面）からこの半導体チップを熱圧接し、回路基板と半導体チップとを接着することによって、半導体装置を製造することができる。熱圧接する際の圧接条件としては、回路基板の種類によって制約を受けるので特に限定されるものではないが、例えば、有機基板を用いる場合には、樹脂温度が１００〜２５０℃の条件で数秒〜数十秒間圧接すればよい。また、塗布した樹脂に流動性をもたせたり、回路基板との濡れ性を良くする目的で５０〜１００℃に加温してもよい。なお、エポキシ樹脂組成物の硬化をより完全にするため、１００〜１５０℃で０．５〜２時間の後硬化を行うことが好ましい。 The semiconductor device according to the present invention can be manufactured by sealing a semiconductor chip with the epoxy resin composition obtained as described above. In particular, the epoxy resin composition according to the present invention is preferably used when flip-chip mounting a semiconductor chip. Specifically, first, the epoxy resin composition obtained as described above is applied to the surface of a circuit board. As this circuit board, an organic substrate including a fiber base material such as FR4 or FR5, an organic film such as polyimide or polyester, an inorganic substrate such as ceramics, or the like can be used. Next, after aligning the substrate electrode of the circuit board coated with the epoxy resin composition and the metal bump formed on the surface of the semiconductor chip, the back surface of the semiconductor chip (the side not facing the circuit board) The semiconductor device can be manufactured by heat-welding the semiconductor chip from the surface and bonding the circuit board and the semiconductor chip. There are no particular limitations on the pressure contact conditions for the heat pressure contact because there are restrictions depending on the type of circuit board. For example, when an organic substrate is used, the resin temperature is 100 to 250 ° C. for several seconds to It is sufficient to press contact for several tens of seconds. Moreover, you may heat to 50-100 degreeC in order to give fluidity | liquidity to apply | coated resin and to improve wettability with a circuit board. In addition, in order to complete the curing of the epoxy resin composition, it is preferable to perform post-curing at 100 to 150 ° C. for 0.5 to 2 hours.
上記のような半導体装置の製造方法であれば、フリップチップ実装による半導体装置の製造効率を改善することができ、圧接工程においてエポキシ樹脂組成物を短時間で硬化させることができるものであり、また、このようにして得られた半導体装置にあっては、ボイドレスの優れた接着性を備えた硬化樹脂層を半導体チップと回路基板との間に形成することができるものである。 If it is the manufacturing method of the semiconductor device as described above, the manufacturing efficiency of the semiconductor device by flip chip mounting can be improved, and the epoxy resin composition can be cured in a short time in the press-contacting process. In the semiconductor device thus obtained, a cured resin layer having excellent voidless adhesiveness can be formed between the semiconductor chip and the circuit board.
以下、本発明を実施例によって具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples.
まず、実施例１〜６及び比較例１〜３のエポキシ樹脂組成物を調製するのに使用した材料について説明する。各材料の配合量（質量部）は表１に示す。 First, materials used for preparing the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 will be described. The blending amount (parts by mass) of each material is shown in Table 1.
（エポキシ樹脂）
樹脂Ａ：ビスフェノールＦ型エポキシ樹脂（東都化成株式会社製、品番「エポトートＹＤＦ−８１７０」、エポキシ当量１６０）
樹脂Ｂ：ビスフェノールＡ型エポキシ樹脂（東都化成株式会社製、品番「エポトートＹＤ−８１２５」、エポキシ当量１７２）
樹脂Ｃ：脂環式エポキシ（上記化学式（１）で示される脂環式エポキシ）（ダイセル化学工業株式会社製、品番「セロキサイド２０２１」、エポキシ当量１３４）
樹脂Ｄ：ナフタレン環含有エポキシ樹脂（大日本インキ化学工業株式会社製、品番「エピクロンＨＰ−４０３２」、エポキシ当量１４３）
樹脂Ｅ：上記化学式（２）で示されるナフタレン環含有４官能型エポキシ樹脂（大日本インキ化学工業株式会社製、品番「エピクロンＥＸＡ４７０１」、エポキシ当量１６５）
（硬化剤）
硬化剤Ａ：イミダゾール誘導体を作製した。すなわち、この硬化剤Ａは、２−メチルイミダゾール（四国化成株式会社製、品番「キュアゾール２ＭＺ-Ｐ」）２０ｇと、上記化学式（１）で示される脂環式エポキシ４０ｇとを用いて、米国特許第４０６６６２５号明細書に記載されているのと同様の方法によって作製した。
(Epoxy resin)
Resin A: Bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., product number “Epototo YDF-8170”, epoxy equivalent 160)
Resin B: Bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd., product number “Epototo YD-8125”, epoxy equivalent 172)
Resin C: Alicyclic epoxy (alicyclic epoxy represented by the above chemical formula (1)) (manufactured by Daicel Chemical Industries, Ltd., product number “Celoxide 2021”, epoxy equivalent 134)
Resin D: Naphthalene ring-containing epoxy resin (manufactured by Dainippon Ink and Chemicals, product number “Epicron HP-4032”, epoxy equivalent 143)
Resin E: Naphthalene ring-containing tetrafunctional epoxy resin represented by the above chemical formula (2) (manufactured by Dainippon Ink & Chemicals, Inc., product number “Epicron EXA4701”, epoxy equivalent 165)
(Curing agent)
Curing agent A: An imidazole derivative was prepared. That is, this curing agent A is a US patent using 20 g of 2-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product number “Curazole 2MZ-P”) and 40 g of alicyclic epoxy represented by the above chemical formula (1) It was produced by the same method as described in the specification of No. 4066625.
硬化剤Ｂ：イミダゾール誘導体を作製した。すなわち、この硬化剤Ｂは、２−メチルイミダゾール（四国化成株式会社製、品番「キュアゾール２ＭＺ-Ｐ」）２０ｇと、上記ビスフェノールＡ型エポキシ樹脂４８ｇとを用いて、米国特許第４０６６６２５号明細書に記載されているのと同様の方法によって作製した。 Curing agent B: An imidazole derivative was prepared. That is, this curing agent B is obtained by using 20 g of 2-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product number “Curazole 2MZ-P”) and 48 g of the bisphenol A type epoxy resin in US Pat. No. 4,066,625. It was made by the same method as described.
硬化剤Ｃ：アミンアダクト（株式会社味の素製、品番「アミキュアＰＮ２３」）
硬化剤Ｄ：メチルヘキサヒドロ無水フタル酸（ＭＨＨＰＡ、大日本インキ化学工業株式会社製、品番「エピクロンＢ−６５０」、硬化剤当量１６８）
硬化剤Ｅ：四塩基酸無水物（大日本インキ化学工業株式会社製、品番「エピクロンＢ−４４００」、硬化剤当量１３２）
硬化剤Ｆ：イミダゾール類を核とするマイクロカプセル（旭化成工業株式会社製、品番「ノバキュアＨＸ３７２２」）
硬化剤Ｇ：カチオン重合開始剤（三新化学工業株式会社、品番「サンエイドＳＩ−６０Ｌ」）
なお、硬化剤当量とは、エポキシ樹脂に対する硬化剤との化学量論上の反応基のモル比で硬化剤の分子量を除した量である。
Curing agent C: Amine adduct (Ajinomoto Co., Inc., product number “Amicure PN23”)
Curing agent D: Methylhexahydrophthalic anhydride (MHHPA, manufactured by Dainippon Ink and Chemicals, product number “Epiclon B-650”, curing agent equivalent 168)
Curing agent E: tetrabasic acid anhydride (manufactured by Dainippon Ink and Chemicals, product number “Epiclon B-4400”, curing agent equivalent 132)
Curing agent F: Microcapsule with imidazole as the core (manufactured by Asahi Kasei Corporation, product number “Novacure HX3722”)
Curing agent G: Cationic polymerization initiator (Sanshin Chemical Co., Ltd., product number “Sun-Aid SI-60L”)
The curing agent equivalent is an amount obtained by dividing the molecular weight of the curing agent by the molar ratio of the stoichiometric reactive group to the curing agent with respect to the epoxy resin.
（無機充填材）
充填材Ａ：球状非晶質シリカ（三菱レイヨン株式会社製、品番「シリカエースＱＳ−０７」、最大粒径３μｍ、真比重２．２）
充填材Ｂ：球状非晶質シリカ（株式会社アドマテックス製、品番「アドマファインＳＥ１０５０」、最大粒径０．６μｍ、真比重２．２）
（導電粒子）
ポリスチレン系の高分子粒子の核の表面をＡｕめっきしたもの（積水ファインケミカル株式会社製、品番「ミクロパールＡＵ−２０５」、粒子径５μｍ）
（添加剤）
シランカップリング剤
(Inorganic filler)
Filler A: Spherical amorphous silica (manufactured by Mitsubishi Rayon Co., Ltd., product number “Silica Ace QS-07”, maximum particle size 3 μm, true specific gravity 2.2)
Filler B: Spherical amorphous silica (manufactured by Admatechs Co., Ltd., product number “Admafine SE1050”, maximum particle size 0.6 μm, true specific gravity 2.2)
(Conductive particles)
Surface of core of polystyrene polymer particles plated with Au (Sekisui Fine Chemical Co., Ltd., product number “Micropearl AU-205”, particle size 5 μm)
(Additive)
Silane coupling agent
そして、上記の材料を用いて下記の製造方法Ａ〜Ｃによりエポキシ樹脂組成物を調製した。 And the epoxy resin composition was prepared with the following manufacturing method AC using said material.
（製造方法Ａ）
エポキシ樹脂組成物の構成成分であるエポキシ樹脂、硬化剤、導電粒子を表１に示す配合量で配合し、これをホモディスパー（特殊機化工業製）にて３００〜５００ｒｐｍの条件で分散・混合することによって、エポキシ樹脂組成物を調製した。
(Production method A)
The epoxy resin, the curing agent, and the conductive particles, which are the constituent components of the epoxy resin composition, are blended in the blending amounts shown in Table 1, and this is dispersed and mixed with a homodisper (made by Tokushu Kika Kogyo Co., Ltd.) at 300 to 500 rpm. Thus, an epoxy resin composition was prepared.
（製造方法Ｂ）
エポキシ樹脂組成物の構成成分であるエポキシ樹脂、硬化剤、無機充填材及びその他の成分を表１に示す配合量で配合し、これをプラネタリーミキサーで混合し、さらに３本ロールにて分散することによって、エポキシ樹脂組成物を調製した。
(Production method B)
The epoxy resin, which is a component of the epoxy resin composition, a curing agent, an inorganic filler, and other components are blended in the blending amounts shown in Table 1, mixed with a planetary mixer, and further dispersed with three rolls. Thus, an epoxy resin composition was prepared.
（製造方法Ｃ）
エポキシ樹脂組成物の構成成分であるエポキシ樹脂、硬化剤及び無機充填材を表１に示す配合量で配合し、これをビューラー社製ビーズミルにて分散・混合した後、さらにホモディスパー（特殊機化工業製）にて３００〜５００ｒｐｍの条件で分散・混合することによって、エポキシ樹脂組成物を調製した。
(Manufacturing method C)
The epoxy resin, which is a component of the epoxy resin composition, a curing agent and an inorganic filler are blended in the blending amounts shown in Table 1 and dispersed and mixed in a beer mill manufactured by Buehler. An epoxy resin composition was prepared by dispersing and mixing under the conditions of 300 to 500 rpm.
なお、表１においてフィラー質量％とは、エポキシ樹脂組成物中における充填材の質量％を示す。 In Table 1, the filler mass% means the mass% of the filler in the epoxy resin composition.
また、実施例６では、樹脂Ｅ（化学式（２））を全エポキシ樹脂中にエポキシ当量比で２０％配合した（請求項３）。 In Example 6, resin E (chemical formula (2)) was blended in an epoxy equivalent ratio of 20% in all epoxy resins (claim 3).
そして、上記のようにして得た実施例１〜６及び比較例１〜４のエポキシ樹脂組成物の特性を下記の方法により評価した。 And the characteristic of the epoxy resin composition of Examples 1-6 and Comparative Examples 1-4 obtained as mentioned above was evaluated by the following method.
（１）ゲル化時間
ホットプレートの温度を１５０±２℃に設定し、このホットプレート上に約１ｇのエポキシ樹脂組成物を置き、これを１秒間隔で撹拌して撹拌不能になるまでの時間を測定した。結果を表２に示す。
(1) Gelation time The time until the temperature of the hot plate is set to 150 ± 2 ° C., about 1 g of the epoxy resin composition is placed on the hot plate, and the mixture is stirred at intervals of 1 second to make stirring impossible. Was measured. The results are shown in Table 2.
（２）密着性
接触面積が０．７ｃｍ角の剪断引っ張り試験で密着性を評価した。具体的には、１．６ｍｍ厚のＦＲ４の銅張り両面板に金メッキを施し、これを０．７ｃｍ幅×７ｃｍ長に切り出し、端部から１ｃｍの部分をアセトンで十分に脱脂した。このようにして得られた２枚の板の脱脂した端部同士をエポキシ樹脂組成物により接着して引っ張り試験片を得た。エポキシ樹脂組成物の硬化条件は１５０℃、１時間である。そして剪断引っ張り試験機を用いて上記の試験片について密着力を測定した。結果を表２に示す。
(2) Adhesiveness Adhesiveness was evaluated by a shear tensile test with a contact area of 0.7 cm square. Specifically, a 1.6 mm thick FR4 copper-clad double-sided plate was plated with gold, cut into 0.7 cm width × 7 cm length, and 1 cm from the end was sufficiently degreased with acetone. The degreased ends of the two plates thus obtained were bonded with an epoxy resin composition to obtain a tensile test piece. The curing conditions for the epoxy resin composition are 150 ° C. and 1 hour. And the adhesive force was measured about said test piece using the shear tensile tester. The results are shown in Table 2.
（３）初期接続性
この試験では、以下の回路基板と半導体チップを用いた。回路基板のチップ搭載部にエポキシ樹脂組成物をディスペンサーで約０．０１ｇ塗布し、回路基板の基板電極と半導体チップの金属バンプとの位置合わせを行った後、１バンプ当たり５０ｇとなるように荷重を加えて半導体チップを回路基板に押し付けることによって、半導体装置を得た。この際、樹脂部分が２６０℃で５秒間曝されるように加熱を行った。圧接後の半導体装置を室温まで冷却した後、プローブを回路基板の電極に当てて電気的動作確認を行い、初期接続性を評価した。各エポキシ樹脂組成物について２０個の初期接続性を評価した。結果を表２に示す。
(3) Initial connectivity In this test, the following circuit boards and semiconductor chips were used. About 0.01 g of epoxy resin composition is applied to the chip mounting portion of the circuit board with a dispenser, and the substrate electrode of the circuit board and the metal bump of the semiconductor chip are aligned, and then the load is 50 g per bump. The semiconductor device was obtained by pressing the semiconductor chip against the circuit board. At this time, heating was performed so that the resin portion was exposed at 260 ° C. for 5 seconds. After cooling the pressure-welded semiconductor device to room temperature, the probe was placed on the electrode of the circuit board to check the electrical operation, and the initial connectivity was evaluated. Twenty initial connectivity properties were evaluated for each epoxy resin composition. The results are shown in Table 2.
（４）フィレット性
（３）で用いたのと同じ半導体装置について、半導体チップの端部と回路基板との間に形成されるフィレットの形状、成分分離の有無を評価した。評価基準は、半導体チップの４辺に形成されたフィレットが成分分離せずにチップ側面全体を覆っており、チップ上面に這い上がっていない場合は「○」とし、チップ側面の一部しか保護していないかあるいは全部を覆っていてもフィレット先端部に成分分離が認められた場合は「△」とし、フィレットが形成されないかあるいは形成されてもチップ上面に這い上がっている場合は「×」として、フィレット性を判定した。結果を表２に示す。
(4) Fillet properties For the same semiconductor device used in (3), the shape of the fillet formed between the end of the semiconductor chip and the circuit board and the presence or absence of component separation were evaluated. The evaluation standard is “○” when the fillet formed on the four sides of the semiconductor chip covers the entire side of the chip without separating the components and does not crawl up to the upper surface of the chip, and only a part of the side of the chip is protected. If the separation of the components is recognized at the fillet tip even if it is not covered or if it is entirely covered, “△” is indicated. The fillet property was determined. The results are shown in Table 2.
（５）ボイド発生量
（３）で用いたのと同じ半導体装置について、半導体チップと回路基板との間の樹脂部分のボイド（気泡）発生の有無を複合材料用超音波検査装置で評価した。評価基準は、ボイドの大きさが３０μｍ未満で、全ボイドの面積の合計が半導体チップの面積に対して１％未満であれば「○」とし、それ以外であれば「×」として、ボイド発生量を判定した。結果を表２に示す。
(5) Void generation amount For the same semiconductor device used in (3), the presence or absence of voids (bubbles) in the resin portion between the semiconductor chip and the circuit board was evaluated with an ultrasonic inspection apparatus for composite materials. Evaluation criteria are “O” if the void size is less than 30 μm and the total area of all voids is less than 1% of the area of the semiconductor chip, otherwise “X” is generated. The amount was determined. The results are shown in Table 2.
（６）温度サイクル（ＴＣ）性
（３）で用いたのと同じ半導体装置について、半導体装置の電気的動作が良品であったものを１０個取り出し、これらを温度サイクル性を評価するためのサンプルとした。これらのサンプルに−２５℃で５分間、１２５℃で５分間を１サイクルとする気相の温度サイクルを与え、２０００サイクルまで１００サイクルごとに半導体装置の動作確認を行い、良否を判定した。１０個のサンプルのうち不良の数が５個に達したときのサイクル数を求めた。結果を表２に示す。
(6) Temperature cycle (TC) property For the same semiconductor device used in (3), 10 samples in which the electrical operation of the semiconductor device was good were taken out and samples for evaluating the temperature cycle property It was. These samples were given a gas phase temperature cycle in which one cycle was −25 ° C. for 5 minutes and 125 ° C. for 5 minutes, and the operation of the semiconductor device was checked every 100 cycles up to 2000 cycles to determine pass / fail. The number of cycles when the number of defects reached 5 out of 10 samples was determined. The results are shown in Table 2.
表２に示すように、実施例１〜６の結果と比較例１〜４の結果とを比較すると、実施例１〜６ではゲル化時間が６〜５０秒の範囲内であり、半導体チップを回路基板に搭載する際の熱圧接工程を短時間で実施することができ、電気的な初期接続性、温度サイクル性も良好であることが確認された。また、この熱圧接時にエアーの巻き込みや成分揮発によるボイド発生もなく、実用的な条件下でも問題なく使用できることが確認された。 As shown in Table 2, when the results of Examples 1 to 6 and the results of Comparative Examples 1 to 4 are compared, in Examples 1 to 6, the gel time is in the range of 6 to 50 seconds, and the semiconductor chip is It was confirmed that the heat-welding process for mounting on a circuit board can be carried out in a short time, and the electrical initial connectivity and temperature cycleability are also good. In addition, it was confirmed that there was no air entrainment or void generation due to component volatilization during this hot pressing, and it could be used without any problem even under practical conditions.
一方、比較例１では、ゲル化時間が長すぎて熱圧接条件では完全な硬化物が得られなかった。これが、実施例１〜６に比べてＴＣ性が著しく悪化した原因と考えられる。また、比較例２では、ボイド発生量が多く、ＴＣ性が実施例１〜６に比べて悪いことが確認された。また、比較例３では、エポキシ樹脂硬化物中にボイドは観察されなかったが、ゲル化時間が短すぎて基板電極と金属バンプとの間の電気的な接続が取れる前にエポキシ樹脂組成物が硬化した。その結果、比較例３においては初期接続性が全数不良であり、ＴＣ性の評価を行うことができなかった。比較例４では、ボイド発生量及び初期接続ともに良好であったが、ガラス転移温度が実施例１〜６に比べて低くＴＣ性においては実施例１〜６に及ばなかった。 On the other hand, in Comparative Example 1, the gelation time was too long, and a complete cured product could not be obtained under the hot press conditions. This is considered to be the cause that the TC property was significantly deteriorated as compared with Examples 1-6. Further, in Comparative Example 2, it was confirmed that the amount of void generation was large and the TC property was poor compared to Examples 1-6. Moreover, in Comparative Example 3, no void was observed in the cured epoxy resin, but the epoxy resin composition was removed before the electrical connection between the substrate electrode and the metal bump could be taken because the gelation time was too short. Cured. As a result, in Comparative Example 3, the initial connectivity was totally poor, and the TC property could not be evaluated. In Comparative Example 4, both the void generation amount and the initial connection were good, but the glass transition temperature was low as compared with Examples 1 to 6, and the TC property did not reach that of Examples 1 to 6.
上記のように、本発明に係るエポキシ樹脂組成物は、硬化剤として、２−メチルイミダゾールと上記化学式（１）で示される脂環式エポキシとの付加反応物を用いるので、エポキシ樹脂組成物の硬化速度を飛躍的に高めることができ、圧接工程を含む半導体装置の製造方法において製造効率を改善することができるものである。また、上記化学式（２）で示されるナフタレン環含有４官能型エポキシ樹脂をエポキシ当量比で全エポキシ樹脂の１０〜４０％含有する場合は、より短時間でボイドレスなエポキシ樹脂組成物の硬化層を得ることができる。このように、本発明に係るエポキシ樹脂組成物によれば、フリップチップ実装工程によって動作信頼性の高い半導体装置を効率よく製造することができる。
As described above, the epoxy resin composition according to the present invention uses an addition reaction product of 2-methylimidazole and the alicyclic epoxy represented by the above chemical formula (1) as a curing agent. The curing speed can be dramatically increased, and the manufacturing efficiency can be improved in the method for manufacturing a semiconductor device including a pressure welding process. When the naphthalene ring-containing tetrafunctional epoxy resin represented by the chemical formula (2) is contained in an epoxy equivalent ratio of 10 to 40% of the total epoxy resin, a voided epoxy resin composition cured layer is formed in a shorter time. Obtainable. As described above, according to the epoxy resin composition of the present invention, a semiconductor device with high operation reliability can be efficiently manufactured by the flip chip mounting process.
Claims (8)
A method of manufacturing a semiconductor device, comprising: bonding a circuit board and a semiconductor chip by hot pressing using the epoxy resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004188179A JP4079125B2 (en) | 2004-06-25 | 2004-06-25 | Epoxy resin composition, semiconductor device and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004188179A JP4079125B2 (en) | 2004-06-25 | 2004-06-25 | Epoxy resin composition, semiconductor device and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006008854A true JP2006008854A (en) | 2006-01-12 |
| JP4079125B2 JP4079125B2 (en) | 2008-04-23 |
Family
ID=35776456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004188179A Expired - Fee Related JP4079125B2 (en) | 2004-06-25 | 2004-06-25 | Epoxy resin composition, semiconductor device and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4079125B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282824A (en) * | 2005-03-31 | 2006-10-19 | Somar Corp | Epoxy resin composition for protecting electronic component, and semiconductor device using the same |
| JP2008050544A (en) * | 2006-08-28 | 2008-03-06 | Matsushita Electric Works Ltd | Epoxy resin composition, semiconductor device and manufacturing process of semiconductor device |
| JP2010111711A (en) * | 2008-11-04 | 2010-05-20 | Shin-Etsu Chemical Co Ltd | Liquid epoxy resin composition for semiconductor encapsulation, and flip chip semiconductor device using cured product of the same as underfill material |
| JP2011195778A (en) * | 2010-03-23 | 2011-10-06 | Hitachi Chem Co Ltd | Polymer curing agent and method for producing the same, resin composition, adhesive for semiconductor, and semiconductor device |
| US8304469B2 (en) | 2008-06-03 | 2012-11-06 | Yokohama Rubber Co., Ltd. | Highly heat-conductive epoxy resin composition |
| JP2020200445A (en) * | 2019-05-07 | 2020-12-17 | 長春人造樹脂廠股▲ふん▼有限公司 | Resin composition and uses of the same |
| CN114773789A (en) * | 2021-08-20 | 2022-07-22 | 广东四会互感器厂有限公司 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
| US11702520B2 (en) | 2018-01-11 | 2023-07-18 | Lg Chem, Ltd. | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same |
-
2004
- 2004-06-25 JP JP2004188179A patent/JP4079125B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282824A (en) * | 2005-03-31 | 2006-10-19 | Somar Corp | Epoxy resin composition for protecting electronic component, and semiconductor device using the same |
| JP2008050544A (en) * | 2006-08-28 | 2008-03-06 | Matsushita Electric Works Ltd | Epoxy resin composition, semiconductor device and manufacturing process of semiconductor device |
| US8304469B2 (en) | 2008-06-03 | 2012-11-06 | Yokohama Rubber Co., Ltd. | Highly heat-conductive epoxy resin composition |
| JP2010111711A (en) * | 2008-11-04 | 2010-05-20 | Shin-Etsu Chemical Co Ltd | Liquid epoxy resin composition for semiconductor encapsulation, and flip chip semiconductor device using cured product of the same as underfill material |
| JP2011195778A (en) * | 2010-03-23 | 2011-10-06 | Hitachi Chem Co Ltd | Polymer curing agent and method for producing the same, resin composition, adhesive for semiconductor, and semiconductor device |
| US11702520B2 (en) | 2018-01-11 | 2023-07-18 | Lg Chem, Ltd. | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same |
| JP2020200445A (en) * | 2019-05-07 | 2020-12-17 | 長春人造樹脂廠股▲ふん▼有限公司 | Resin composition and uses of the same |
| JP7149309B2 (en) | 2019-05-07 | 2022-10-06 | 長春人造樹脂廠股▲ふん▼有限公司 | Resin composition and its use |
| CN114773789A (en) * | 2021-08-20 | 2022-07-22 | 广东四会互感器厂有限公司 | Epoxy resin for closed combined electrical appliance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4079125B2 (en) | 2008-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7915743B2 (en) | Adhesive for electronic components, method for manufacturing semiconductor chip laminate, and semiconductor device | |
| TWI593774B (en) | Anisotropic conductive film and semiconductor device bonded by the same | |
| JP4816333B2 (en) | Manufacturing method of semiconductor device | |
| US8563362B2 (en) | Method of producing semiconductor chip laminate comprising an adhesive that comprises a curing compound, curing agent and spacer particles | |
| JP4339927B2 (en) | Method for stacking semiconductor chips | |
| JP5346166B2 (en) | Adhesive for electronic parts | |
| JP4079125B2 (en) | Epoxy resin composition, semiconductor device and manufacturing method thereof | |
| JP6115929B2 (en) | Epoxy resin composition | |
| JP3928603B2 (en) | Epoxy resin composition, semiconductor device and manufacturing method thereof | |
| JP3446730B2 (en) | Epoxy resin composition and semiconductor device | |
| JP2003160644A (en) | Semiconductor sealing epoxy resin composition and semiconductor device | |
| JP4966221B2 (en) | Pre-coated underfill sealing method | |
| JP2009158712A (en) | Adhesive for electronic component | |
| JP2003160643A (en) | Semiconductor sealing epoxy resin composition and semiconductor device | |
| JP4940486B2 (en) | Epoxy resin composition, semiconductor device and manufacturing method thereof | |
| JPWO2004069894A1 (en) | Epoxy resin composition, semiconductor device having cured layer of same composition, and method of manufacturing same | |
| JP3906837B2 (en) | Epoxy resin composition, semiconductor device and manufacturing method thereof | |
| JP2008088279A (en) | Liquid resin composition for underfill and semiconductor device | |
| JP2016204645A (en) | Heat curable resin composition for encapsulation, manufacturing method of semiconductor device and semiconductor device | |
| JP2003160642A (en) | Semiconductor sealing epoxy resin composition and semiconductor device | |
| JP2008189760A (en) | Underfill agent, semiconductor device obtained by using the same and method for producing the semiconductor device | |
| JP5047632B2 (en) | Mounting method using hot-pressure adhesive for flip chip connection | |
| JP2012004224A (en) | Electronic component jointed body manufacturing method and electronic component jointed body | |
| JP5135287B2 (en) | Epoxy resin composition, method for manufacturing semiconductor device, and semiconductor device | |
| JP2009227939A (en) | Liquid resin composition for underfill, semiconductor device and method for manufacturing semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080104 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080115 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080128 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110215 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4079125 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110215 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110215 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120215 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130215 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130215 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140215 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |