JP2005350488A - Liquid state epoxy resin composition and semiconductor device - Google Patents

Liquid state epoxy resin composition and semiconductor device Download PDF

Info

Publication number
JP2005350488A
JP2005350488A JP2004169353A JP2004169353A JP2005350488A JP 2005350488 A JP2005350488 A JP 2005350488A JP 2004169353 A JP2004169353 A JP 2004169353A JP 2004169353 A JP2004169353 A JP 2004169353A JP 2005350488 A JP2005350488 A JP 2005350488A
Authority
JP
Japan
Prior art keywords
epoxy resin
liquid epoxy
group
resin composition
curing agent
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
Application number
JP2004169353A
Other languages
Japanese (ja)
Inventor
Hiroyuki Takenaka
博之 竹中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to JP2004169353A priority Critical patent/JP2005350488A/en
Publication of JP2005350488A publication Critical patent/JP2005350488A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/83909—Post-treatment of the layer connector or bonding area
    • H01L2224/83951—Forming additional members, e.g. for reinforcing, fillet sealant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01015—Phosphorus [P]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01027—Cobalt [Co]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01051—Antimony [Sb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01077—Iridium [Ir]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01082—Lead [Pb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01087—Francium [Fr]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]

Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid state epoxy resin composition giving a cured material excellent in void characteristics, close adhesion and toughness, and capable of becoming a sealing material of a semiconductor device, and a semiconductor device sealed by the cured material of the composition. <P>SOLUTION: This liquid state epoxy resin composition containing (A) a liquid state epoxy resin, (B) an aromatic amine-based curing agent, (C) an inorganic filler and (D) perfluoroalkyl group-containing silicone oil expressed by formula (1) [wherein, R<SP>1</SP>is a monovalent hydrocarbon group; (n) is 3-9 integer: and (p), (q) are each 50-500 integer] is provided by containing &ge;1 kind of compounds expressed by formulae (2) to (4) [wherein, R<SP>2</SP>to R<SP>5</SP>are each H or a monovalent hydrocarbon group] as the component (B) by &ge;5 mass %, having 0.7-1.2 equivalent ratio of the components (A) to (B) [(A) the epoxy equivalent/(B) amine equivalent] and &ge;3.5 K<SB>1c</SB>toughness value of the composition. The semiconductor device is sealed by the cured material of the composition. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

本発明は、半導体封止用として好適で、塗布時又は真空脱泡工程時の消泡性が高く、ボイド特性に優れ、かつシリコンチップの素子表面（特に感光性ポリイミド、窒化膜、酸化膜）との密着性に影響を与えない液状エポキシ樹脂組成物、及びこの組成物にて封止された半導体装置に関する。   The present invention is suitable for semiconductor sealing, has high defoaming properties at the time of coating or vacuum defoaming, has excellent void characteristics, and has a silicon chip element surface (especially photosensitive polyimide, nitride film, oxide film). The present invention relates to a liquid epoxy resin composition that does not affect the adhesion to the semiconductor device and a semiconductor device sealed with this composition.

電気機器の小型化、軽量化、高機能化に伴い、半導体の実装方法もピン挿入タイプから表面実装が主流になっている。また、半導体素子の高集積化に伴い、ダイサイズの一辺が１０ｍｍを超えるものもあり、ダイサイズの大型化が進んできている。このような大型ダイを用いた半導体装置では、半田リフロー時にダイと封止材にかかる応力が増大し、封止材とダイ及び基板の界面で剥離が生じたり、基板実装時にパッケージにクラックが入るといった問題がクローズアップされてきている。   Along with the downsizing, weight reduction, and higher functionality of electrical equipment, semiconductor mounting methods have become mainstream from pin insertion type to surface mounting. In addition, along with the high integration of semiconductor elements, there are cases in which one side of the die size exceeds 10 mm, and the die size is increasing. In a semiconductor device using such a large die, the stress applied to the die and the sealing material increases during solder reflow, and peeling occurs at the interface between the sealing material and the die and the substrate, or the package cracks when mounted on the substrate. These issues have been highlighted.

更に、近い将来に鉛含有半田が使用できなくなることから、鉛代替半田が多数開発されている。この種の半田は、溶融温度が鉛含有の半田より高くなることから、リフローの温度も２６０〜２７０℃で検討されており、従来の液状エポキシ樹脂組成物の封止材では、より一層の不良が予想される。このようにリフローの温度が高くなると、従来においては何ら問題のなかったフリップチップ型のパッケージもリフロー時にクラックが発生したり、チップ界面、基板界面との剥離が発生するという重大な問題が起こるようになった。   Furthermore, since lead-containing solder cannot be used in the near future, a number of lead substitute solders have been developed. Since this type of solder has a melting temperature higher than that of lead-containing solder, the reflow temperature has been studied at 260 to 270 ° C., and the conventional liquid epoxy resin composition sealing material is even more defective. Is expected. Thus, when the reflow temperature becomes high, the flip chip type package, which has not had any problems in the past, may cause a serious problem that cracks occur during reflow and peeling from the chip interface and the substrate interface occurs. Became.

また、液状エポキシ樹脂組成物のボイド特性として、液状エポキシ樹脂組成物のスクリーン印刷又はディスペンサー装置による塗布時又は真空脱泡工程時の消泡性も求められている。   In addition, as a void characteristic of the liquid epoxy resin composition, defoaming properties at the time of application of the liquid epoxy resin composition by screen printing or a dispenser device or a vacuum defoaming process are also required.

なお、本発明に関連する公知文献としては、下記のものがある。
特許第３２３８３４０号公報 特開平１０−１５８３６６号公報 In addition, as a well-known document relevant to this invention, there exist the following.
Japanese Patent No. 3238340 JP-A-10-158366

本発明は、上記事情に鑑みなされたもので、作業性、塗布時の消泡性が高く、ボイド特性に優れ、またシリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に影響を及ぼさず、かつ強靭性に優れた硬化物を与え、更にリフローの温度が従来温度２４０℃付近から２６０〜２７０℃に上昇しても不良が発生せず、ＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、−６５℃／１５０℃の温度サイクルにおいて数百サイクルを超えても剥離、クラックが発生しない半導体装置の封止材となり得る液状エポキシ樹脂組成物、及びこの組成物の硬化物で封止された半導体装置を提供することを目的とする。   The present invention has been made in view of the above circumstances, has high workability, high defoaming property at the time of application, excellent void characteristics, and affects the adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film. PCT (120 ° C./2.1 atm) does not occur even if the reflow temperature is increased from about 240 ° C. to 260 ° C. to 270 ° C. A liquid epoxy resin composition that does not deteriorate even under high-temperature and high-humidity conditions such as, and that can be a sealing material for a semiconductor device that does not peel or crack even if it exceeds several hundred cycles in a temperature cycle of −65 ° C./150° C., and An object is to provide a semiconductor device sealed with a cured product of this composition.

本発明者は、上記目的を達成するために鋭意検討を重ねた結果、（Ａ）液状エポキシ樹脂、（Ｂ）芳香族アミン系硬化剤、（Ｃ）無機質充填剤、及び（Ｄ）下記一般式（１）

Figure 2005350488
［式中、Ｒ1は独立に炭素数１〜６の一価炭化水素基を示し、ｎは３〜９の整数、ｐ及びｑは各々５０〜５００の整数である。］
で表されるパーフロロアルキル基含有シリコーンオイルを含有する液状エポキシ樹脂組成物において、（Ｂ）芳香族アミン系硬化剤が、下記一般式（２）〜（４）で表される少なくとも１種類の純度が９９％以上の芳香族アミン化合物を硬化剤全体の５質量％以上含有し、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比［（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量］が０．７以上１．２以下の範囲であり、この組成物の靭性値Ｋ1cが３．５以上となるように配合することにより、塗布時又は真空脱泡工程時の消泡性が高く、ボイド特性に優れ、かつシリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に影響を与えず、かつ強靭性に優れた硬化物を与え、更にリフローの温度が従来温度２４０℃付近から２６０〜２７０℃に上昇しても不良が発生せず、ＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、熱衝撃に対して優れており、特に大型ダイサイズの半導体装置の封止材として有効であることを知見した。 As a result of intensive studies to achieve the above object, the present inventor has (A) a liquid epoxy resin, (B) an aromatic amine-based curing agent, (C) an inorganic filler, and (D) the following general formula. (1)
Figure 2005350488
 [Wherein, R 1 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer of 3 to 9, and p and q are each an integer of 50 to 500. ]
In the liquid epoxy resin composition containing a perfluoroalkyl group-containing silicone oil represented by the formula (B), the aromatic amine-based curing agent is at least one of the following general formulas (2) to (4): An aromatic amine compound having a purity of 99% or more is contained in an amount of 5% by mass or more of the entire curing agent, and an equivalent ratio of (A) liquid epoxy resin and (B) aromatic amine curing agent [(A) liquid epoxy resin The epoxy equivalent / (B) the amine equivalent of the aromatic amine curing agent] is in the range of 0.7 to 1.2, and the toughness value K 1c of this composition is 3.5 or more. High defoaming properties at the time of coating or vacuum defoaming, excellent void characteristics, and does not affect the adhesion to the surface of the silicon chip, especially photosensitive polyimide resin and nitride film, and toughness Gives an excellent cured product, Even if the low temperature rises from around 240 ° C to 260-270 ° C, no defects will occur and it will not deteriorate even under high temperature and high humidity conditions such as PCT (120 ° C / 2.1 atm). It has been found that it is particularly effective as a sealing material for a semiconductor device having a large die size.

Figure 2005350488
（式中、Ｒ2〜Ｒ5は水素原子又は炭素数１〜６の一価炭化水素基である。）
Figure 2005350488
 (Wherein, R 2 to R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

本発明は、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比［（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量］を０．７以上１．２以下の範囲で用いることによって、塗布時又は真空脱泡工程時の消泡性が高くボイド特性に優れ、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れ、かつ熱衝撃性が著しく向上し、高温多湿下でも優れた特性を得ることが可能となることを見出した。また、上記エポキシ樹脂とアミン系硬化剤の系では、シランカップリング剤を必須成分にしており、フリップチップ半導体装置の製造において、注入時又は樹脂の硬化時にボイドが発生するが、本発明では、これを改善するためにシランカップリング剤を配合しなくても信頼性に優れ、特に大型ダイサイズの半導体装置の封止材として有効となり得ることを見出し、本発明をなすに至ったものである。   In the present invention, the equivalent ratio of (A) liquid epoxy resin to (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B) amine equivalent of aromatic amine curing agent] is 0. When used in the range of 0.7 to 1.2, it has a high defoaming property at the time of coating or vacuum defoaming process and has excellent void characteristics, and adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or nitride film. In addition, the present inventors have found that the thermal shock resistance is remarkably improved and excellent characteristics can be obtained even under high temperature and high humidity. In the epoxy resin and amine curing agent system, a silane coupling agent is an essential component, and in the production of a flip chip semiconductor device, a void is generated at the time of injection or resin curing. In order to improve this, the present inventors have found that it is excellent in reliability without adding a silane coupling agent, and can be effective as a sealing material for a semiconductor device having a large die size, and has led to the present invention. .

従って、本発明は、
（Ａ）液状エポキシ樹脂
（Ｂ）芳香族アミン系硬化剤
（Ｃ）無機質充填剤
（Ｄ）下記一般式（１）

Figure 2005350488
［式中、Ｒ1は独立に炭素数１〜６の一価炭化水素基を示し、ｎは３〜９の整数、ｐ及びｑは各々５０〜５００の整数である。］
で表されるパーフロロアルキル基含有シリコーンオイル
を含有する液状エポキシ樹脂組成物において、上記（Ｂ）芳香族アミン系硬化剤として、上記一般式（２）〜（４）で表される少なくとも１種類の芳香族アミン化合物を硬化剤全体の５質量％以上含有し、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比［（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量］が０．７以上１．２以下であり、この組成物の靭性値Ｋ1cが３．５以上であることを特徴とする液状エポキシ樹脂組成物、及びこの液状エポキシ樹脂組成物の硬化物で封止された半導体装置を提供する。更に、上記液状エポキシ樹脂組成物の硬化物をアンダーフィル材として封止したフリップチップ型半導体装置を提供する。 Therefore, the present invention
(A) Liquid epoxy resin (B) Aromatic amine curing agent (C) Inorganic filler (D) The following general formula (1)
Figure 2005350488
 [Wherein, R 1 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer of 3 to 9, and p and q are each an integer of 50 to 500. ]
In the liquid epoxy resin composition containing the perfluoroalkyl group-containing silicone oil represented by the formula (2), at least one kind represented by the general formulas (2) to (4) as the aromatic amine curing agent (B). The aromatic amine compound is contained in an amount of 5% by mass or more of the entire curing agent, and the equivalent ratio of (A) liquid epoxy resin to (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B ) Amine equivalent of aromatic amine curing agent] is 0.7 or more and 1.2 or less, and a toughness value K 1c of the composition is 3.5 or more, and a liquid epoxy resin composition, Provided is a semiconductor device sealed with a cured product of this liquid epoxy resin composition. Furthermore, a flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition is sealed as an underfill material is provided.

本発明の液状エポキシ樹脂組成物は、塗布時又は真空脱泡時の消泡性に優れ、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れた硬化物を与え、吸湿後のリフローの温度が従来温度２４０℃付近から２６０〜２７０℃に上昇しても不良が発生せず、更にＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、−６５℃／１５０℃の温度サイクルにおいて数百サイクルを超えても剥離、クラックが起こらない半導体装置を提供することができる。   The liquid epoxy resin composition of the present invention is excellent in defoaming property at the time of coating or vacuum defoaming, gives a cured product having excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and absorbs moisture. Even if the temperature of the later reflow is increased from about 240 ° C. to about 260 to 270 ° C., no defect occurs, and it does not deteriorate even under high temperature and high humidity conditions such as PCT (120 ° C./2.1 atm). A semiconductor device in which peeling and cracking do not occur even when the temperature cycle of 65 ° C./150° C. exceeds several hundred cycles can be provided.

本発明の半導体封止材（液状エポキシ樹脂組成物）において、液状エポキシ樹脂（Ａ）は、１分子内に２官能基以下のエポキシ基を含有する常温で液状であるエポキシ樹脂なら、いかなるものでも使用可能であるが、ＢＨ型回転粘度計により測定した２５℃における粘度が２００Ｐａ・ｓ以下、特に５０Ｐａ・ｓ以下のものが好ましく、特に、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニルグリシジルエーテルなどが挙げられ、この中でも室温で液状のエポキシ樹脂が望ましい。これらのエポキシ樹脂には、下記構造で示されるエポキシ樹脂を浸入性に影響を及ぼさない範囲で添加しても何ら問題はない。   In the semiconductor sealing material (liquid epoxy resin composition) of the present invention, the liquid epoxy resin (A) may be any epoxy resin that is liquid at room temperature and contains two or less functional groups in one molecule. Although usable, those having a viscosity at 25 ° C. of 200 Pa · s or less, particularly 50 Pa · s or less as measured by a BH type rotational viscometer are preferred, and in particular, bisphenols such as bisphenol A type epoxy resin and bisphenol F type epoxy resin Type epoxy resin, naphthalene type epoxy resin, phenyl glycidyl ether and the like. Among these, a liquid epoxy resin at room temperature is preferable. To these epoxy resins, there is no problem even if an epoxy resin represented by the following structure is added within a range that does not affect the penetration property.

Figure 2005350488
Figure 2005350488

上記液状エポキシ樹脂中の全塩素含有量は、１，５００ｐｐｍ以下、望ましくは１，０００ｐｐｍ以下であることが好ましい。また、１００℃で５０％エポキシ樹脂濃度における２０時間での抽出水塩素が１０ｐｐｍ以下であることが好ましい。全塩素含有量が１，５００ｐｐｍを超え、又は抽出水塩素が１０ｐｐｍを超えると半導体素子の信頼性、特に耐湿性に悪影響を与えるおそれがある。   The total chlorine content in the liquid epoxy resin is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. Moreover, it is preferable that the extraction water chlorine in 20 hours in the 50% epoxy resin density | concentration at 100 degreeC is 10 ppm or less. If the total chlorine content exceeds 1,500 ppm or the extracted water chlorine exceeds 10 ppm, the reliability of the semiconductor element, particularly the moisture resistance, may be adversely affected.

次に、本発明に使用する芳香族アミン系硬化剤（Ｂ）は、下記一般式（２）〜（４）で表される少なくとも１種類の純度が９９％以上の芳香族アミン化合物を硬化剤全体の５質量％以上、好ましくは１０〜１００質量％、より好ましくは２０〜１００質量％含有する。一般式（２）〜（４）で表される芳香族アミン化合物が、硬化剤全体の５質量％未満であると、接着力が低下したり、クラックが発生したりする。また純度が９９％未満であると、匂いが強いため生産作業性に劣る。なお、ここでいう純度とは、モノマーの純度である。   Next, the aromatic amine curing agent (B) used in the present invention is an aromatic amine compound having a purity of at least 99% represented by the following general formulas (2) to (4). The total content is 5% by mass or more, preferably 10 to 100% by mass, and more preferably 20 to 100% by mass. When the aromatic amine compound represented by the general formulas (2) to (4) is less than 5% by mass of the entire curing agent, the adhesive force is reduced or cracks are generated. On the other hand, if the purity is less than 99%, the production operability is inferior because the smell is strong. In addition, purity here is the purity of a monomer.

Figure 2005350488
（式中、Ｒ2〜Ｒ5は水素原子又は炭素数１〜６の一価炭化水素基である。）
Figure 2005350488
 (Wherein, R 2 to R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

ここで、Ｒ2〜Ｒ5の一価炭化水素基としては、炭素数１〜６、特に１〜３のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ヘキシル基等のアルキル基、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、フェニル基などや、これらの炭化水素基の水素原子の一部又は全部を塩素、フッ素、臭素等のハロゲン原子で置換したフロロメチル基、ブロモエチル基、トリフルオロプロピル基等のハロゲン置換一価炭化水素基を挙げることができる。 Here, the monovalent hydrocarbon group of R 2 to R 5 is preferably a group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, Alkyl groups such as tert-butyl group and hexyl group, vinyl groups, allyl groups, propenyl groups, butenyl groups, alkenyl groups such as hexenyl groups, phenyl groups, etc., and some or all of hydrogen atoms of these hydrocarbon groups Mention may be made of halogen-substituted monovalent hydrocarbon groups such as a fluoromethyl group, a bromoethyl group and a trifluoropropyl group substituted with halogen atoms such as chlorine, fluorine and bromine.

また、上記芳香族アミン系硬化剤以外の硬化剤としては、２，４−ジアミノトルエン、１，４−ジアミノベンゼン、１，３−ジアミノベンゼン等の低分子芳香族アミンであることが好ましい。   The curing agent other than the aromatic amine curing agent is preferably a low molecular aromatic amine such as 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene.

上記芳香族アミン系硬化剤は、通常、常温で固体であり、そのまま配合すると樹脂粘度が上昇し、作業性が著しく悪くなるため、あらかじめエポキシ樹脂と溶融混合することが好ましく、後述する指定の配合量で、７０〜１５０℃の温度範囲で１時間〜２時間溶融混合することが望ましい。混合温度が７０℃未満であると芳香族アミン系硬化剤が相溶しにくくなるおそれがあり、１５０℃を超える温度であるとエポキシ樹脂と反応して粘度上昇するおそれがある。また、混合時間が１時間未満であると芳香族アミン系硬化剤が十分に相溶せず、粘度上昇を招くおそれがあり、２時間を超えるとエポキシ樹脂と反応し、粘度上昇するおそれがある。   The aromatic amine-based curing agent is usually solid at room temperature, and when blended as it is, the resin viscosity increases and workability becomes significantly worse. It is desirable to melt and mix in the temperature range of 70 to 150 ° C. for 1 to 2 hours. If the mixing temperature is less than 70 ° C, the aromatic amine curing agent may not be compatible, and if the mixing temperature is higher than 150 ° C, it may react with the epoxy resin and increase the viscosity. Also, if the mixing time is less than 1 hour, the aromatic amine curing agent is not sufficiently compatible and may increase the viscosity, and if it exceeds 2 hours, it may react with the epoxy resin and increase the viscosity. .

なお、本発明に用いられる芳香族アミン系硬化剤の総配合量は、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比［（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量］を０．７以上１．２以下、好ましくは０．７以上１．１以下、更に好ましくは０．８５以上１．０５以下の範囲にすることが必要である。当量比が０．７未満では未反応のアミノ基が残存し、ガラス転移温度の低下となり、また密着性が低下する。逆に１．２を超えるとＫ1c値が下がり、硬化物が硬く脆くなり、リフロー時にクラックが発生する。 The total amount of the aromatic amine curing agent used in the present invention is the equivalent ratio of (A) liquid epoxy resin and (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B) Amine equivalent of aromatic amine-based curing agent] is 0.7 to 1.2, preferably 0.7 to 1.1, and more preferably 0.85 to 1.05. is required. If the equivalent ratio is less than 0.7, unreacted amino groups remain, resulting in a decrease in the glass transition temperature and a decrease in adhesion. Conversely, if it exceeds 1.2, the K 1c value decreases, the cured product becomes hard and brittle, and cracks occur during reflow.

一方、本発明に用いられる無機質充填剤（Ｃ）は、膨張係数を小さくする目的から、従来より知られている各種の無機質充填剤を添加することができる。無機質充填剤として、具体的には、溶融シリカ、結晶シリカ、アルミナ、ボロンナイトライド、チッカアルミニウム、チッカ珪素、マグネシア、マグネシウムシリケート、アルミニウムなどが挙げられる。中でも真球状の溶融シリカが低粘度化のため望ましい。なお、これらの無機質充填剤は、シランカップリング剤等で表面処理されたものであってもよいが、表面処理なしでも使用できる。   On the other hand, various inorganic fillers conventionally known can be added to the inorganic filler (C) used in the present invention for the purpose of reducing the expansion coefficient. Specific examples of the inorganic filler include fused silica, crystalline silica, alumina, boron nitride, ticker aluminum, ticker silicon, magnesia, magnesium silicate, aluminum and the like. Among them, spherical fused silica is desirable for reducing the viscosity. These inorganic fillers may be surface-treated with a silane coupling agent or the like, but can be used without surface treatment.

本発明の組成物をポッティング材として使用する場合、平均粒径が２〜２０μｍで、最大粒径が７５μｍ以下、特に５０μｍ以下のものが望ましい。平均粒径が２μｍ未満では粘度が高くなり、多量に充填できない場合があり、一方２０μｍを超えると粗い粒子が多くなり、リード線につまり、ボイドとなるおそれがある。なお、本発明において、平均粒径及び最大粒径は、例えばレーザー光回折法による粒度分布測定により得ることができ、平均粒子径は、重量平均値（又はメジアン径）等として求めることができる。   When the composition of the present invention is used as a potting material, an average particle size of 2 to 20 μm and a maximum particle size of 75 μm or less, particularly 50 μm or less are desirable. If the average particle size is less than 2 μm, the viscosity is high and a large amount may not be filled. On the other hand, if the average particle size is more than 20 μm, coarse particles increase, which may lead to a lead wire, that is, a void. In the present invention, the average particle diameter and the maximum particle diameter can be obtained by, for example, particle size distribution measurement by a laser light diffraction method, and the average particle diameter can be obtained as a weight average value (or median diameter) or the like.

この場合、無機質充填剤の充填量は、エポキシ樹脂１００質量部に対して１００〜６００質量部の範囲が好ましい。１００質量部未満では、膨張係数が大きく、冷熱試験においてクラックの発生を誘発させるおそれがある。６００質量部を超えると、粘度が高くなり、流動性の低下をもたらすおそれがある。   In this case, the filling amount of the inorganic filler is preferably in the range of 100 to 600 parts by mass with respect to 100 parts by mass of the epoxy resin. If it is less than 100 parts by mass, the expansion coefficient is large, and there is a risk of inducing cracks in the cold test. If it exceeds 600 parts by mass, the viscosity will increase and the fluidity may be lowered.

なお、アンダーフィル材として使用する場合には、侵入性の向上と低線膨張化の両立を図るため、フリップチップギャップ幅（基板と半導体チップとの隙間）に対して平均粒径が約１／１０以下、最大粒径が１／２以下のものが好ましい。   When used as an underfill material, in order to achieve both improved penetration and low linear expansion, the average particle size is about 1 / fifth with respect to the flip chip gap width (gap between the substrate and the semiconductor chip). Those having a maximum particle size of 10 or less and a maximum particle size of 1/2 or less are preferred.

この場合の無機質充填剤の配合量としては、エポキシ樹脂１００質量部に対して５０〜４００質量部で配合することが好ましく、より好ましくは１００〜２５０質量部の範囲で配合する。５０質量部未満では、膨張係数が大きく、冷熱試験においてクラックの発生を誘発させるおそれがある。４００質量部を超えると、粘度が高くなり、薄膜侵入性の低下をもたらすおそれがある。   As a compounding quantity of the inorganic filler in this case, it is preferable to mix | blend by 50-400 mass parts with respect to 100 mass parts of epoxy resins, More preferably, it mix | blends in the range of 100-250 mass parts. If it is less than 50 parts by mass, the expansion coefficient is large, and there is a risk of inducing cracks in the cold test. If it exceeds 400 parts by mass, the viscosity will increase and the thin film penetration may be reduced.

本発明で使用する（Ｄ）成分のパーフロロアルキル基含有シリコーンオイルは、下記一般式（１）で示されるものであり、本発明の液状エポキシ樹脂組成物の塗布時又は真空脱泡工程時の消泡性を付与するために配合され、本発明を特徴づける重要な成分である。   The perfluoroalkyl group-containing silicone oil (D) used in the present invention is represented by the following general formula (1), and is applied at the time of coating the liquid epoxy resin composition of the present invention or during the vacuum defoaming step. It is an important component formulated to impart antifoaming properties and characterizes the present invention.

Figure 2005350488
［式中、Ｒ1は独立に炭素数１〜６の一価炭化水素基を示し、ｎは３〜９の整数、ｐ及びｑは各々５０〜５００の整数である。］
Figure 2005350488
 [Wherein, R 1 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer of 3 to 9, and p and q are each an integer of 50 to 500. ]

上記Ｒ1の炭素数１〜６、好ましくは１〜３の一価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基等のアリール基；ビニル基、アリル基等のアルケニル基などが挙げられ、これらの中でもメチル基が好ましい。上記Ｒ1はそれぞれ同一であっても異なっていてもよい。 Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms of R 1 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group. An alkyl group such as a group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group; an alkenyl group such as a vinyl group and an allyl group. Among these, a methyl group is preferable. R 1 may be the same or different.

パーフルオロアルキル基の鎖長に係るｎは３〜９、好ましくは４〜８の整数であり、ｎが２以下では樹脂組成物への溶解性が高すぎるので（Ｄ）成分が泡膜に付着し難いために消泡効果が認められず、また、１０以上では樹脂組成物への溶解性が悪くなり均一に分散させることができなくなる。   N related to the chain length of the perfluoroalkyl group is an integer of 3 to 9, preferably 4 to 8. If n is 2 or less, the solubility in the resin composition is too high, so component (D) adheres to the foam film. Therefore, the defoaming effect is not recognized, and if it is 10 or more, the solubility in the resin composition becomes poor and it cannot be uniformly dispersed.

上記ｐ及びｑは各々５０〜５００、好ましくはｐは１００〜４００、ｑは５０〜２００の整数である。ｐが５０未満、又はｑが５００を超えると（Ｄ）成分のシリコーンオイルの樹脂組成物中への溶解性、分散性及び泡膜への拡張性が悪くなるので消泡効果が十分に発揮されない。一方、ｐが５００を超え、又はｑが５０未満であると（Ｄ）成分の表面張力の低下が不十分となり、樹脂組成物への溶解性が高すぎるものとなるので消泡効果が十分に発揮されない。上記ｐ及びｑの値から、（Ｄ）成分のシリコーンオイル中の好適なパーフロロアルキル基含有量（パーフロロアルキル基質量／重量平均分子量）を質量％で表すと９〜９１質量％となる。   P and q are each 50 to 500, preferably p is 100 to 400, and q is an integer of 50 to 200. If p is less than 50 or q is more than 500, the solubility, dispersibility, and expandability of the component (D) silicone oil in the resin composition are deteriorated, so that the defoaming effect is not sufficiently exhibited. . On the other hand, if p exceeds 500 or q is less than 50, the surface tension of the component (D) is not sufficiently lowered, and the solubility in the resin composition becomes too high, so that the defoaming effect is sufficient. It is not demonstrated. From the values of p and q, the preferred perfluoroalkyl group content (perfluoroalkyl group mass / weight average molecular weight) in the silicone oil of component (D) is 9 to 91% by mass.

この（Ｄ）成分のパーフロロアルキル基含有シリコーンオイルの具体例としては、下記式（６）及び下記式（７）で示されるものが挙げられるが、これらに限定されるものではない。なお、式中「Ｍｅ」はメチル基を意味する。   Specific examples of this (D) component perfluoroalkyl group-containing silicone oil include, but are not limited to, those represented by the following formula (6) and the following formula (7). In the formula, “Me” means a methyl group.

Figure 2005350488
なお、（Ｄ）成分は、１種単独でも２種以上組み合わせても使用することができる。
Figure 2005350488
 In addition, (D) component can be used even if single 1 type also combines 2 or more types.

（Ｄ）成分の配合量は、上記（Ａ）、（Ｂ）成分の合計量１００質量部に対して、通常、０．０１〜２０質量部、好ましくは０．５〜５質量部の範囲とするのがよい。（Ｄ）成分の配合量が多すぎるとＫ1c値が下がり、硬化物が硬く脆くなり、リフロー時にクラックが発生するおそれがあり、逆に少なすぎると十分な消泡効果が得られない場合がある。 (D) The compounding quantity of a component is 0.01-20 mass parts normally with respect to 100 mass parts of total amounts of the said (A) and (B) component, Preferably it is the range of 0.5-5 mass parts, It is good to do. If the amount of component (D) is too large, the K 1c value decreases, the cured product becomes hard and brittle, and cracks may occur during reflow. Conversely, if the amount is too small, sufficient defoaming effect may not be obtained. is there.

本発明の液状エポキシ樹脂組成物には、応力を低下させる目的でシリコーンゴム、シリコーンオイルや液状のポリブタジエンゴム、メタクリル酸メチル−ブタジエン−スチレンよりなる熱可塑性樹脂などを配合してもよい。好ましくは、アルケニル基含有エポキシ樹脂又はフェノール樹脂のアルケニル基と、下記平均組成式（５）で示される１分子中の珪素原子の数が２０〜４００であり、かつ珪素原子に直接結合した水素原子（ＳｉＨ基）の数が１〜５であるオルガノポリシロキサンのＳｉＨ基との付加反応により得られる共重合体からなるシリコーン変性樹脂を配合することが好ましい。   The liquid epoxy resin composition of the present invention may be blended with silicone rubber, silicone oil, liquid polybutadiene rubber, thermoplastic resin made of methyl methacrylate-butadiene-styrene, or the like for the purpose of reducing stress. Preferably, the alkenyl group of the alkenyl group-containing epoxy resin or phenol resin and the number of silicon atoms in one molecule represented by the following average composition formula (5) are 20 to 400, and hydrogen atoms bonded directly to the silicon atoms It is preferable to blend a silicone-modified resin made of a copolymer obtained by an addition reaction with an SiH group of an organopolysiloxane having 1 to 5 (SiH groups).

ＨaＲ6 bＳｉＯ(4-a-b)/2 （５）
（式中、Ｒ6は脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基、ａは０．０１〜０．１、ｂは１．８〜２．２、１．８１≦ａ＋ｂ≦２．３である。） H a R 6 b SiO (4-ab) / 2 (5)
(In the formula, R 6 is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, a is 0.01 to 0.1, b is 1.8 to 2.2, 1.81 ≦ a + b ≦ 2.3.)

なお、Ｒ6の置換又は非置換の一価炭化水素基としては、炭素数１〜１０、特に１〜８のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ヘキシル基、オクチル基、デシル基等のアルキル基、フェニル基、キシリル基、トリル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基などや、これらの炭化水素基の水素原子の一部又は全部を塩素、フッ素、臭素等のハロゲン原子で置換したフロロメチル基、ブロモエチル基、トリフルオロプロピル基等のハロゲン置換一価炭化水素基を挙げることができる。
上記共重合体としては、中でも下記構造のものが望ましい。 The substituted or unsubstituted monovalent hydrocarbon group for R 6 is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. Alkyl groups such as tert-butyl group, hexyl group, octyl group and decyl group, aryl groups such as phenyl group, xylyl group and tolyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, etc. And halogen-substituted monovalent hydrocarbon groups such as a fluoromethyl group, a bromoethyl group, and a trifluoropropyl group, in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with halogen atoms such as chlorine, fluorine, and bromine.
Among the above copolymers, those having the following structures are desirable.

Figure 2005350488
Figure 2005350488

上記式中、Ｒ7は上記と同じであり、Ｒ8は水素原子又は炭素数１〜４のアルキル基であり、Ｒ9は−ＣＨ2ＣＨ2ＣＨ2−、−ＯＣＨ2−ＣＨ（ＯＨ）−ＣＨ2−Ｏ−ＣＨ2ＣＨ2ＣＨ2−又は−Ｏ−ＣＨ2ＣＨ2ＣＨ2−である。ｎは４〜１９９、好ましくは１９〜１０９の整数、ｐは１〜１０の整数、ｑは１〜１０の整数である。 In the above formula, R 7 is the same as above, R 8 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 9 is —CH 2 CH 2 CH 2 —, —OCH 2 —CH (OH). -CH 2 -O-CH 2 CH 2 CH 2 - or -O-CH 2 CH 2 CH 2 - is. n is an integer of 4 to 199, preferably 19 to 109, p is an integer of 1 to 10, and q is an integer of 1 to 10.

上記共重合体をジオルガノポリシロキサン単位が（Ａ）液状エポキシ樹脂１００質量部に対して０〜２０質量部、特には２〜１５質量部含まれるように配合することで応力をより一層低下させることができる。   The stress is further reduced by blending the above copolymer so that the diorganopolysiloxane unit is contained in an amount of 0 to 20 parts by mass, particularly 2 to 15 parts by mass with respect to 100 parts by mass of the liquid epoxy resin (A). be able to.

本発明の液状エポキシ樹脂組成物には、更に必要に応じ、接着向上用炭素官能性シラン、カーボンブラックなどの顔料、染料、酸化防止剤、その他の添加剤を本発明の目的を損なわない範囲で配合することができる。   In the liquid epoxy resin composition of the present invention, if necessary, a carbon functional silane for improving adhesion, a pigment such as carbon black, a dye, an antioxidant, and other additives within a range not impairing the object of the present invention. Can be blended.

本発明の液状エポキシ樹脂組成物は、例えば、液状エポキシ樹脂、芳香族アミン系硬化剤、無機質充填剤及びその他の添加剤等を同時に又は別々に、必要により加熱処理を加えながら、撹拌、溶解、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。またこれら装置を適宜組み合わせて使用してもよい。   The liquid epoxy resin composition of the present invention is, for example, a liquid epoxy resin, an aromatic amine-based curing agent, an inorganic filler, and other additives, simultaneously or separately, with heat treatment as necessary, stirring, dissolving, It can be obtained by mixing and dispersing. There are no particular limitations on the apparatus for mixing, stirring, dispersing, etc., and a raikai machine equipped with a stirring and heating apparatus, a three-roll, a ball mill, a planetary mixer, and the like can be used. Moreover, you may use combining these apparatuses suitably.

なお、本発明において、封止材として用いる液状エポキシ樹脂組成物は、ＢＨ型回転粘度計により測定した２５℃における粘度が１，０００Ｐａ・ｓ以下のものが好ましい。また、この組成物の成形方法、成形条件は、常法とすることができるが、好ましくは、先に１００〜１２０℃、０．５時間以上、その後１３０〜１８０℃、０．５時間以上の条件で熱オーブンキュアを行う。１００〜１２０℃での加熱が０．５時間未満では、硬化後にボイドが発生する場合がある。また１３０〜１８０℃での加熱が０．５時間未満では、十分な硬化物特性が得られない場合がある。   In the present invention, the liquid epoxy resin composition used as a sealing material preferably has a viscosity at 25 ° C. of 1,000 Pa · s or less as measured with a BH rotational viscometer. The molding method and molding conditions for this composition can be conventional methods, but preferably 100 to 120 ° C. for 0.5 hour or longer, and then 130 to 180 ° C. for 0.5 hour or longer. Heat oven cure under conditions. When heating at 100 to 120 ° C. is less than 0.5 hour, voids may occur after curing. Further, if the heating at 130 to 180 ° C. is less than 0.5 hours, sufficient cured product characteristics may not be obtained.

また、本発明の液状エポキシ樹脂組成物の靭性値Ｋ1cは３．５以上であり、好ましくは４．０以上である。靭性値Ｋ1cが３．５未満であると熱衝撃性、温度サイクル性が低下する。なお、靭性値Ｋ1cはＡＳＴＭ＃Ｄ５０４５に基づき求めることができる。 The toughness value K 1c of the liquid epoxy resin composition of the present invention is 3.5 or more, preferably 4.0 or more. When the toughness value K 1c is less than 3.5, the thermal shock resistance and the temperature cycle performance are deteriorated. The toughness value K 1c can be obtained based on ASTM # D5045.

ここで、本発明に用いるフリップチップ型半導体装置としては、例えば図１に示したように、通常、有機基板１の配線パターン面に複数個のバンプ２を介して半導体チップ３が搭載されているものであり、上記有機基板１と半導体チップ３との隙間（バンプ２間の隙間）にアンダーフィル材４が充填され、その側部がフィレット材５で封止されたものとすることができるが、本発明の封止材は、特にアンダーフィル材として使用する場合に有効である。   Here, as a flip chip type semiconductor device used in the present invention, for example, as shown in FIG. 1, for example, a semiconductor chip 3 is usually mounted on a wiring pattern surface of an organic substrate 1 via a plurality of bumps 2. The gap between the organic substrate 1 and the semiconductor chip 3 (the gap between the bumps 2) is filled with the underfill material 4 and the side portion thereof is sealed with the fillet material 5. The sealing material of the present invention is particularly effective when used as an underfill material.

本発明の液状エポキシ樹脂組成物をアンダーフィル材として用いる場合、その硬化物のガラス転移温度以下の膨張係数が２０〜４０ｐｐｍ／℃であることが好ましい。なお、この場合、フィレット材用の封止材は公知のものでよく、特に上述したアンダーフィル材と同様の液状エポキシ樹脂組成物を用いることができるが、この場合はその硬化物のガラス転移温度以下の膨張係数が１０〜２０ｐｐｍ／℃であるものが好ましい。   When using the liquid epoxy resin composition of this invention as an underfill material, it is preferable that the expansion coefficient below the glass transition temperature of the hardened | cured material is 20-40 ppm / degreeC. In this case, the sealing material for the fillet material may be a known material, and in particular, a liquid epoxy resin composition similar to the above-described underfill material can be used. In this case, the glass transition temperature of the cured product is used. The following expansion coefficient is preferably 10 to 20 ppm / ° C.

以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記式において、Ｍｅはメチル基を示す。   EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In the following formulae, Me represents a methyl group.

［実施例１〜５、比較例１〜４］
表１で示す成分を３本ロールで均一に混練することにより、樹脂組成物を得た。これらの樹脂組成物を用いて、以下に示す試験を行った。その結果を表１に併記する。 [Examples 1 to 5, Comparative Examples 1 to 4]
A resin composition was obtained by uniformly kneading the components shown in Table 1 with three rolls. The test shown below was done using these resin compositions. The results are also shown in Table 1.

［粘度］
ＢＨ型回転粘度計を用いて４ｒｐｍの回転数で２５℃における粘度を測定した。 [viscosity]
The viscosity at 25 ° C. was measured at a rotation speed of 4 rpm using a BH type rotational viscometer.

［ボイドテスト］
ポリイミドコートした１０ｍｍ×１０ｍｍのシリコンチップを３０ｍｍ×３０ｍｍのＦＲ−４基板に約１００μｍのスペーサを用いて設置し、生じた隙間に組成物を侵入させて１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させ、ボイドの有無をＣ−ＳＡＭ（ＳＯＮＩＸ社製）で確認した。 [Void test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It hardened | cured on condition of time, and the presence or absence of the void was confirmed by C-SAM (made by SONIX).

［靭性値Ｋ1c］
ＡＳＴＭ＃Ｄ５０４５に基づき、常温の強靭性値Ｋ1cを測定した。 [Toughness value K 1c ]
Based on ASTM # D5045, the normal temperature toughness value K 1c was measured.

［Ｔｇ（ガラス転移温度）、ＣＴＥ１（膨張係数）、ＣＴＥ２（膨張係数）］
樹脂組成物を１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させた５ｍｍ×５ｍｍ×１５ｍｍの硬化物試験片を用いて、ＴＭＡ（熱機械分析装置）により毎分５℃の速さで昇温した時のＴｇを測定した。また、以下の温度範囲の膨張係数を測定した。
ＣＴＥ１の温度範囲は５０〜８０℃、ＣＴＥ２の温度範囲は２００〜２３０℃である。 [Tg (glass transition temperature), CTE1 (expansion coefficient), CTE2 (expansion coefficient)]
Using a 5 mm × 5 mm × 15 mm cured product specimen obtained by curing the resin composition at 120 ° C./0.5 hours + 165 ° C./3 hours, a TMA (thermomechanical analyzer) was used at a rate of 5 ° C. per minute. The Tg when the temperature was raised was measured. Moreover, the expansion coefficient in the following temperature range was measured.
The temperature range of CTE1 is 50 to 80 ° C, and the temperature range of CTE2 is 200 to 230 ° C.

［接着力テスト］
感光性ポリイミドをコートしたシリコンチップ上に上面の直径２ｍｍ、下面の直径５ｍｍ、高さ３ｍｍの円錐台形状の試験片を載せ、１２０℃で０．５時間、次いで１６５℃で３時間硬化させた。硬化後、得られた試験片の剪断接着力を測定し、初期値とした。更に、硬化させた試験片をＰＣＴ（１２１℃／２．１ａｔｍ）で３３６時間吸湿させた後、接着力を測定した。いずれの場合も試験片の個数は５個で行い、その平均値を接着力として表記した。 [Adhesion test]
A test piece in the shape of a truncated cone having a top diameter of 2 mm, a bottom diameter of 5 mm, and a height of 3 mm was placed on a silicon chip coated with photosensitive polyimide, and cured at 120 ° C. for 0.5 hour and then at 165 ° C. for 3 hours. . After curing, the shear strength of the obtained specimen was measured and used as the initial value. Further, the cured test piece was absorbed with PCT (121 ° C./2.1 atm) for 336 hours, and then the adhesive strength was measured. In any case, the number of test pieces was five, and the average value was expressed as adhesive strength.

［ＰＣＴ剥離テスト］
ポリイミドコートした１０ｍｍ×１０ｍｍのシリコンチップを３０ｍｍ×３０ｍｍのＦＲ−４基板に約１００μｍのスペーサを用いて設置し、生じた隙間に組成物を侵入させて１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させ、３０℃／６５％ＲＨ／１９２時間後に最高温度２６５℃に設定したＩＲリフローにて５回処理した後の剥離、更にＰＣＴ（１２１℃／２．１ａｔｍ）の環境下に置き、３３６時間後の剥離をＣ−ＳＡＭ（ＳＯＮＩＸ社製）で確認した。 [PCT peel test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, peeled after being treated 5 times by IR reflow set at a maximum temperature of 265 ° C. after 30 ° C./65% RH / 192 hours, and further in an environment of PCT (121 ° C./2.1 atm) The peeling after 336 hours was confirmed by C-SAM (manufactured by SONIX).

［熱衝撃テスト］
ポリイミドコートした１０ｍｍ×１０ｍｍのシリコンチップを３０ｍｍ×３０ｍｍのＦＲ−４基板に約１００μｍのスペーサを用いて設置し、生じた隙間に組成物を侵入させて１２０℃／０．５時間＋１６５℃／３時間の条件で硬化させ、３０℃／６５％ＲＨ／１９２時間後に最高温度２６５℃に設定したＩＲリフローにて５回処理した後、−６５℃／３０分、１５０℃／３０分を１サイクルとし、２５０，５００，７５０サイクル後の剥離、クラックを確認した。 [Thermal shock test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, and after 30 treatments with IR reflow set to a maximum temperature of 265 ° C after 30 ° C / 65% RH / 192 hours, -65 ° C / 30 minutes, 150 ° C / 30 minutes is one cycle. , 250, 500, 750 cycles after peeling and cracks were confirmed.

Figure 2005350488
Figure 2005350488

Ｃ−１００Ｓ：ジエチルジアミノフェニルメタン（日本化薬社製）
Ｃ−３００Ｓ：テトラエチルジアミノフェニルメタン（日本化薬社製）
セイカキュア−Ｓ：４，４’−ジアミノジフェニルスルホン（和歌山精化工業社製）
ＲＥ３０３Ｓ−Ｌ：ビスフェノールＦ型エポキシ樹脂（日本化薬社製）
ＭＨ７００：メチルテトラヒドロ無水フタル酸（新日本理化製）
ＹＨ３０７：３，４−ジメチル−６−（２−メチル−１−プロぺニル）−１，２，３，６−テトラハイドロフタル酸と、１−イソプロピル−４−メチル−バイサクロ［２．２．２］オクト−５−エン−２，３−ジカルボン酸の混合物（混合モル比率＝６：４）（油化シェルエポキシ製）
球状シリカ：最大粒径２４μｍ、平均粒径６μｍの球状シリカ
シリコーンオイルＡ：下記式で示される化合物 C-100S: Diethyldiaminophenylmethane (manufactured by Nippon Kayaku Co., Ltd.)
C-300S: Tetraethyldiaminophenylmethane (Nippon Kayaku Co., Ltd.)
Seikacure-S: 4,4′-diaminodiphenyl sulfone (Wakayama Seika Kogyo Co., Ltd.)
RE303S-L: Bisphenol F type epoxy resin (Nippon Kayaku Co., Ltd.)
MH700: Methyltetrahydrophthalic anhydride (manufactured by Nippon Nippon Chemical Co., Ltd.)
YH307: 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic acid and 1-isopropyl-4-methyl-bisacrole [2.2. 2] Mixture of oct-5-ene-2,3-dicarboxylic acid (mixing molar ratio = 6: 4) (made by oil-coated shell epoxy)
Spherical silica: Spherical silica silicone oil having a maximum particle size of 24 μm and an average particle size of 6 μm A: a compound represented by the following formula

Figure 2005350488
ＫＢＭ４０３：シランカップリング剤、γ−グリシドキシプロピルトリメトキシシラン（信越化学工業製）
Figure 2005350488
 KBM403: Silane coupling agent, γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

共重合体：

Figure 2005350488
２Ｅ４ＭＺ：２−エチル−４−メチルイミダゾール（四国化成製） Copolymer:
Figure 2005350488
 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals)

本発明の封止材を用いたフリップチップ型半導体装置の一例を示す断面図である。It is sectional drawing which shows an example of the flip chip type semiconductor device using the sealing material of this invention.

符号の説明Explanation of symbols

１ 有機基板
２ バンプ
３ 半導体チップ
４ アンダーフィル材
５ フィレット材
DESCRIPTION OF SYMBOLS 1 Organic substrate 2 Bump 3 Semiconductor chip 4 Underfill material 5 Fillet material

Claims (5)

（Ａ）液状エポキシ樹脂
（Ｂ）芳香族アミン系硬化剤
（Ｃ）無機質充填剤
（Ｄ）下記一般式（１）
Figure 2005350488
 ［式中、Ｒ1は独立に炭素数１〜６の一価炭化水素基を示し、ｎは３〜９の整数、ｐ及びｑは各々５０〜５００の整数である。］
で表されるパーフロロアルキル基含有シリコーンオイル
を含有する液状エポキシ樹脂組成物において、上記（Ｂ）芳香族アミン系硬化剤として、下記一般式（２）〜（４）で表される少なくとも１種類の芳香族アミン化合物を硬化剤全体の５質量％以上含有し、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比［（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量］が０．７以上１．２以下であり、この組成物の靭性値Ｋ1cが３．５以上であることを特徴とする液状エポキシ樹脂組成物。
Figure 2005350488
 （式中、Ｒ2〜Ｒ5は水素原子又は炭素数１〜６の一価炭化水素基である。） (A) Liquid epoxy resin (B) Aromatic amine curing agent (C) Inorganic filler (D) The following general formula (1)
Figure 2005350488
 [Wherein, R 1 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer of 3 to 9, and p and q are each an integer of 50 to 500. ]
In the liquid epoxy resin composition containing the perfluoroalkyl group-containing silicone oil represented by the formula (B), at least one kind represented by the following general formulas (2) to (4) is used as the aromatic amine-based curing agent. The aromatic amine compound is contained in an amount of 5% by mass or more of the entire curing agent, and the equivalent ratio of (A) liquid epoxy resin to (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B ) Amine equivalent of aromatic amine curing agent] is 0.7 or more and 1.2 or less, and a toughness value K 1c of the composition is 3.5 or more, a liquid epoxy resin composition.
Figure 2005350488
 (Wherein, R 2 to R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.) アルコキシ系シランカップリング剤を、無機質充填剤の表面処理に用いる以外に含まないことを特徴とする請求項１記載の液状エポキシ樹脂組成物。   2. The liquid epoxy resin composition according to claim 1, wherein an alkoxy-based silane coupling agent is not included except for the surface treatment of the inorganic filler. 更に、アルケニル基含有エポキシ樹脂又はアルケニル基含有フェノール樹脂のアルケニル基と、下記平均組成式（５）
ＨaＲ6 bＳｉＯ(4-a-b)/2 （５）
（式中、Ｒ6は脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基、ａは０．０１〜０．１、ｂは１．８〜２．２、１．８１≦ａ＋ｂ≦２．３である。）
で示される１分子中の珪素原子の数が２０〜４００であり、かつ珪素原子に直接結合した水素原子（ＳｉＨ基）の数が１〜５であるオルガノポリシロキサンのＳｉＨ基との付加反応により得られる共重合体からなるシリコーン変性樹脂を含有する請求項１又は２記載の液状エポキシ樹脂組成物。 Further, the alkenyl group of the alkenyl group-containing epoxy resin or alkenyl group-containing phenol resin, and the following average composition formula (5)
H a R 6 b SiO (4-ab) / 2 (5)
(In the formula, R 6 is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, a is 0.01 to 0.1, b is 1.8 to 2.2, 1.81 ≦ a + b ≦ 2.3.)
By the addition reaction with SiH groups of organopolysiloxane in which the number of silicon atoms in one molecule is 20 to 400 and the number of hydrogen atoms (SiH groups) directly bonded to silicon atoms is 1 to 5 The liquid epoxy resin composition of Claim 1 or 2 containing the silicone modified resin which consists of a copolymer obtained. 請求項１乃至３のいずれか１項記載の液状エポキシ樹脂組成物の硬化物で封止された半導体装置。   The semiconductor device sealed with the hardened | cured material of the liquid epoxy resin composition of any one of Claims 1 thru | or 3. 請求項１乃至３のいずれか１項記載の液状エポキシ樹脂組成物の硬化物をアンダーフィル材として封止したフリップチップ型半導体装置。
A flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition according to any one of claims 1 to 3 is sealed as an underfill material.
JP2004169353A 2004-06-08 2004-06-08 Liquid state epoxy resin composition and semiconductor device Pending JP2005350488A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004169353A JP2005350488A (en) 2004-06-08 2004-06-08 Liquid state epoxy resin composition and semiconductor device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004169353A JP2005350488A (en) 2004-06-08 2004-06-08 Liquid state epoxy resin composition and semiconductor device

Publications (1)

Publication Number Publication Date
JP2005350488A true JP2005350488A (en) 2005-12-22

Family

ID=35585234

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004169353A Pending JP2005350488A (en) 2004-06-08 2004-06-08 Liquid state epoxy resin composition and semiconductor device

Country Status (1)

Country Link
JP (1) JP2005350488A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239822A (en) * 2007-03-27 2008-10-09 Matsushita Electric Works Ltd Thermosetting resin composition and electronic device
JP2012025924A (en) * 2010-07-28 2012-02-09 Shin-Etsu Chemical Co Ltd Liquid epoxy resin composition, and semiconductor device sealed with cured product formed by curing the liquid epoxy resin composition
CN104312513A (en) * 2014-11-17 2015-01-28 南京艾布纳密封技术有限公司 Two-component epoxy electronic potting silica gel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239822A (en) * 2007-03-27 2008-10-09 Matsushita Electric Works Ltd Thermosetting resin composition and electronic device
JP2012025924A (en) * 2010-07-28 2012-02-09 Shin-Etsu Chemical Co Ltd Liquid epoxy resin composition, and semiconductor device sealed with cured product formed by curing the liquid epoxy resin composition
CN104312513A (en) * 2014-11-17 2015-01-28 南京艾布纳密封技术有限公司 Two-component epoxy electronic potting silica gel
CN104312513B (en) * 2014-11-17 2016-08-24 南京艾布纳密封技术股份有限公司 A kind of bi-component epoxy electronics embedding silica gel

Similar Documents

Publication Publication Date Title
JP5354753B2 (en) Underfill material and semiconductor device
JP5502268B2 (en) Resin composition set for system-in-package semiconductor devices
JP5277537B2 (en) Liquid resin composition for electronic components and electronic component device using the same
JP5116152B2 (en) Resin composition for manufacturing semiconductor devices
JP4066174B2 (en) Liquid epoxy resin composition, flip chip type semiconductor device and sealing method thereof
JP5692212B2 (en) Liquid resin composition for electronic components and electronic component device using the same
JP3952143B2 (en) Liquid epoxy resin composition and semiconductor device
JP3912515B2 (en) Liquid epoxy resin composition and semiconductor device
JP3997422B2 (en) Liquid epoxy resin composition and semiconductor device
JP2007162001A (en) Liquid epoxy resin composition
JP3773022B2 (en) Flip chip type semiconductor device
JP2009173744A (en) Underfill agent composition
JP2010111747A (en) Underfill agent composition
JP2010077234A (en) Liquid epoxy resin composition and semiconductor device
JP4697476B2 (en) Liquid epoxy resin composition and flip chip type semiconductor device
JP2001055487A (en) Encapsulant for flip chip type semiconductor device and flip chip type semiconductor device
JP4221585B2 (en) Liquid epoxy resin composition and semiconductor device
JP4557148B2 (en) Liquid epoxy resin composition and semiconductor device
JP5013536B2 (en) Underfill agent composition
JP2012082281A (en) Liquid epoxy resin composition and semiconductor device
JP3867784B2 (en) Liquid epoxy resin composition and semiconductor device
JP5354721B2 (en) Underfill agent composition
JP3871032B2 (en) Liquid epoxy resin composition and flip chip type semiconductor device
JP4009853B2 (en) Liquid epoxy resin composition and flip chip type semiconductor device
JP4678149B2 (en) Liquid epoxy resin composition for semiconductor encapsulation and flip chip type semiconductor device