JP2008195875A - Epoxy resin composition and semiconductor device - Google Patents

Epoxy resin composition and semiconductor device Download PDF

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JP2008195875A
JP2008195875A JP2007034153A JP2007034153A JP2008195875A JP 2008195875 A JP2008195875 A JP 2008195875A JP 2007034153 A JP2007034153 A JP 2007034153A JP 2007034153 A JP2007034153 A JP 2007034153A JP 2008195875 A JP2008195875 A JP 2008195875A
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epoxy resin
organopolysiloxane
group
resin composition
general formula
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JP4952283B2 (en
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Yasuhiro Mizuno
恭宏 水野
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Sumitomo Bakelite Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means 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
    • H01L2224/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321Disposition
    • H01L2224/32151Disposition 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
    • H01L2224/32221Disposition 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
    • H01L2224/32245Disposition 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 metallic
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means 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
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/44Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001Core members of the connector
    • H01L2224/45099Material
    • H01L2224/451Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144Gold (Au) as principal constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means 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
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means 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
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting 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
    • H01L2224/48221Connecting 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
    • H01L2224/48245Connecting 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 metallic
    • H01L2224/48247Connecting 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 metallic connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means 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
    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
    • H01L2224/73265Layer and wire connectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10Details of semiconductor or other solid state devices to be connected
    • H01L2924/11Device type
    • H01L2924/13Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301Thyristor

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition excellent in solder heat resistance and excellent in balance between mold release properties in molding, continuous moldability, surface appearance of a cured resin article, contamination of mold, etc., and to provide a semiconductor device. <P>SOLUTION: The epoxy resin composition comprises (A) an epoxy resin, (B) a phenolic resin-based handener, (C) an organopolysiloxane (c1) having a polycaprolactone group, and/or a reaction product (c2) of the organopolysiloxane having a polycaprolactone group (c1) with an epoxy resin, and (D) an organopolysiloxane represented by general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、エポキシ樹脂組成物及び半導体装置に関するものである。   The present invention relates to an epoxy resin composition and a semiconductor device.

近年、電子機器の小型化、軽量化、高性能化の市場動向において、半導体の高集積化が年々進み、またパッケージの表面実装化が促進されてきている。更に地球環境へ配慮した企業活動が重要視され、有害物質である鉛を特定用途以外で全廃することが求められている。しかしながら、鉛フリー半田の融点は従来の鉛/スズ半田に比べて高いため、赤外線リフロー、半田浸漬等の半田実装時の温度も従来の220〜240℃から、240℃〜260℃へと高くなる。このような実装温度の上昇により、実装時に樹脂部にクラックが入り易くなり、信頼性を保証することが困難になってきているという問題が生じている。更にリードフレームについても、外装半田メッキも脱鉛する必要があるとの観点から、外装半田メッキの代わりに事前にニッケル・パラジウムメッキを施したリードフレームの適用が進められている。このニッケル・パラジウムメッキは一般的な封止材料との密着性が低く、実装時に界面において剥離が生じ易く、樹脂部にクラックも入り易い。   In recent years, in the market trend of downsizing, weight reduction, and high performance of electronic devices, higher integration of semiconductors has progressed year by year, and surface mounting of packages has been promoted. Furthermore, corporate activities that take the global environment into account are regarded as important, and lead, which is a hazardous substance, must be completely abolished except for specific purposes. However, since the melting point of lead-free solder is higher than that of conventional lead / tin solder, the temperature at the time of solder mounting such as infrared reflow and solder immersion is increased from 220 to 240 ° C. to 240 to 260 ° C. . Due to such an increase in mounting temperature, there is a problem that cracks are likely to occur in the resin part during mounting, and it has become difficult to guarantee reliability. Further, with respect to the lead frame, from the viewpoint that it is necessary to remove lead from the external solder plating, the use of a lead frame that has been subjected to nickel / palladium plating in advance instead of the external solder plating is being promoted. This nickel / palladium plating has low adhesion to a general sealing material, and is likely to be peeled off at the interface during mounting, and cracks are likely to occur in the resin part.

このような課題に対し、半田耐熱性の向上に対して低吸水性のエポキシ樹脂や硬化剤を適用することにより(例えば、特許文献1、2、3参照。)、実装温度の上昇に対して対応が取れるようになってきた。その半面、このような低吸水・低弾性率を示すエポキシ樹脂組成物は架橋密度が低く、硬化直後の成形物は軟らかく、連続生産では金型への樹脂トラレ等の成形性での不具合が生じ、生産性を低下させる問題があった。
また、連続成形性向上への取り組みとしては、離型効果の高い離型剤の適用が提案されている(例えば、特許文献4参照。)が、離型効果の高い離型剤は必然的に樹脂硬化物の表面に浮き出しやすく、連続生産すると樹脂硬化物表面の外観及び金型表面を著しく汚してしまう欠点があった。樹脂硬化物表面の外観に優れるエポキシ樹脂組成物として、特定の構造を有するシリコーン化合物を添加する手法等が提案されている(例えば、特許文献5、6参照。)が、離型性は不充分で連続成形においてエアベント部分で樹脂が付着してエアベントを塞ぐことにより、未充填等の成形不具合を生じさせる等、連続成形性の低下を引き起こす問題があった。以上より、半田耐熱性、離型性、連続成形性、樹脂硬化物表面の外観、金型汚れ全ての課題に対応したエポキシ樹脂組成物が求められている。
For such a problem, by applying a low water-absorbing epoxy resin or a curing agent to improve solder heat resistance (for example, refer to Patent Documents 1, 2, and 3), the mounting temperature rises. The correspondence has come to come. On the other hand, the epoxy resin composition exhibiting such low water absorption and low elastic modulus has a low crosslinking density, and the molded product immediately after curing is soft, and in continuous production, there is a problem in moldability such as resin tray on the mold. There was a problem of lowering productivity.
In addition, as an effort to improve continuous moldability, application of a release agent having a high release effect has been proposed (see, for example, Patent Document 4), but a release agent having a high release effect is inevitably required. There is a drawback that the surface of the cured resin is easily raised and the appearance of the surface of the cured resin and the surface of the mold are significantly stained when continuously produced. As an epoxy resin composition having an excellent appearance on the surface of a cured resin product, a method of adding a silicone compound having a specific structure has been proposed (see, for example, Patent Documents 5 and 6), but the releasability is insufficient. In continuous molding, there is a problem that the continuous moldability is deteriorated, for example, the resin adheres at the air vent portion and the air vent is blocked to cause molding defects such as unfilling. In view of the above, there is a need for an epoxy resin composition that addresses all of the problems of solder heat resistance, mold release, continuous moldability, appearance of the cured resin surface, and mold contamination.

特開平9−3161号公報Japanese Patent Laid-Open No. 9-3161 特開平9−235353号公報JP 9-235353 A 特開平11−140277号公報JP-A-11-140277 特開2002−80695号公報JP 2002-80695 A 特開2002−97344号公報JP 2002-97344 A 特開2001−310930号公報JP 2001-310930 A

本発明は、半田耐熱性が良好で、成形時における離型性、連続成形性、樹脂硬化物表面の外観、又は金型汚れ性等とのバランスに優れるエポキシ樹脂組成物及び半導体装置を提供するものである。   The present invention provides an epoxy resin composition and a semiconductor device that have good solder heat resistance and are excellent in balance with mold release properties, continuous moldability, appearance of the surface of a cured resin, or mold contamination. Is.

本発明は、
[1] (A)エポキシ樹脂、(B)フェノール樹脂系硬化剤、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)、並びに(D)下記一般式(1)で表されるオルガノポリシロキサンを含むことを特徴とするエポキシ樹脂組成物、

Figure 2008195875
(ただし、上記一般式(1)において、R1は水素、メチル基、フェニル基、及びR2から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるアルキル基を有する有機基である。n1の平均値は1以上、50以下の正数である。上記R2において、aの平均値は1以上、20以下の正数である。) The present invention
[1] (A) Epoxy resin, (B) Phenolic resin-based curing agent, (C) Organopolysiloxane (c1) having a polycaprolactone group, and / or Organopolysiloxane (c1) having a polycaprolactone group and an epoxy An epoxy resin composition comprising a reaction product (c2) with a resin, and (D) an organopolysiloxane represented by the following general formula (1):
Figure 2008195875
(However, in the general formula (1), R1 is a group selected from hydrogen, a methyl group, a phenyl group, and R2, and may be the same or different from each other, but at least one of them is R2. (It is an organic group having an alkyl group. The average value of n1 is a positive number of 1 or more and 50 or less. In R2, the average value of a is a positive number of 1 or more and 20 or less.)

[2] 前記ポリカプロラクトン基を有するオルガノポリシロキサン(c1)が下記一般式(2)で表されるオルガノポリシロキサンである第[1]項に記載のエポキシ樹脂組成物、

Figure 2008195875
(ただし、上記一般式(2)において、R3は水素、メチル基、フェニル基、及びR4から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるポリカプロラクトン基を有する有機基である。n2の平均値は1以上、50以下の正数である。上記R4において、bの平均値は1以上、20以下の正数であり、R5は炭素数1〜30の有機基である。) [2] The epoxy resin composition according to item [1], wherein the organopolysiloxane (c1) having a polycaprolactone group is an organopolysiloxane represented by the following general formula (2):
Figure 2008195875
(However, in the general formula (2), R3 is a group selected from hydrogen, a methyl group, a phenyl group, and R4, which may be the same or different from each other, but at least one of them is R2. The average value of n2 is a positive number of 1 to 50. In R4, the average value of b is a positive number of 1 to 20, and R5 is an organic group having a polycaprolactone group. Is an organic group having 1 to 30 carbon atoms.)

[3] 前記(A)エポキシ樹脂がビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂を含む第[1]項又は第[2]項に記載のエポキシ樹脂組成物、   [3] The epoxy resin composition according to [1] or [2], wherein the (A) epoxy resin includes a phenol aralkyl type epoxy resin having a biphenylene skeleton,

[4] 前記(A)エポキシ樹脂が下記一般式(3)で表されるエポキシ樹脂(a1)を含む第[1]項又は第[2]項に記載のエポキシ樹脂組成物、

Figure 2008195875
(ただし、上記一般式(3)において、n3の平均値は1以上、10以下の正数である。) [4] The epoxy resin composition according to [1] or [2], wherein the (A) epoxy resin includes an epoxy resin (a1) represented by the following general formula (3):
Figure 2008195875
(However, in the general formula (3), the average value of n3 is a positive number of 1 or more and 10 or less.)

[5] 前記(B)フェノール樹脂系硬化剤がビフェニレン骨格を有するフェノールアラルキル樹脂を含む第[1]項ないし第[4]項のいずれかに記載のエポキシ樹脂組成物、   [5] The epoxy resin composition according to any one of [1] to [4], wherein the (B) phenol resin-based curing agent includes a phenol aralkyl resin having a biphenylene skeleton.

[6] 前記(B)フェノール樹脂系硬化剤が下記一般式(4)で表されるフェノール樹脂(b1)を含む第[1]項ないし第[4]項のいずれかに記載のエポキシ樹脂組成物、

Figure 2008195875
(ただし、上記一般式(4)において、n4の平均値は1以上、10以下の正数である。) [6] The epoxy resin composition according to any one of [1] to [4], wherein the (B) phenol resin-based curing agent includes a phenol resin (b1) represented by the following general formula (4): object,
Figure 2008195875
(However, in the general formula (4), the average value of n4 is a positive number of 1 or more and 10 or less.)

[7] 半導体封止用である第[1]項ないし第[6]項のいずれかに記載半導体封止用エポキシ樹脂組成物、
[8] 第[7]項に記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を封止してなることを特徴とする半導体装置、
である。
[7] The epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [6], which is for semiconductor encapsulation.
[8] A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to item [7],
It is.

本発明に従うと、半導体装置実装時において優れた半田耐熱性を示すとともに、半導体素子の封止成形時における離型性、連続成形性、樹脂硬化物表面の外観、金型汚れ性等のバランスに優れるエポキシ樹脂組成物が得られるものである。   According to the present invention, it exhibits excellent solder heat resistance when mounted on a semiconductor device, and in balance of mold release properties, continuous moldability, appearance of a cured resin surface, mold dirtiness, etc., when sealing a semiconductor element. An excellent epoxy resin composition can be obtained.

本発明は、ポリカプロラクトン基を有するオルガノポリシロキサン及び一般式(1)で表されるオルガノポリシロキサンを配合することにより、半導体素子の封止成形時において離型性、連続成形性、樹脂硬化物表面の外観が良好で金型汚れも発生し難いという優れた成形性を示すとともに、半導体装置実装時の半田耐熱性に優れたエポキシ樹脂組成物が得られるものである。
以下、本発明について詳細に説明する。
In the present invention, by incorporating an organopolysiloxane having a polycaprolactone group and an organopolysiloxane represented by the general formula (1), a mold release property, a continuous moldability, and a resin cured product at the time of sealing molding of a semiconductor element. It is possible to obtain an epoxy resin composition having an excellent surface appearance and excellent moldability such that mold contamination is less likely to occur and excellent solder heat resistance when mounted on a semiconductor device.
Hereinafter, the present invention will be described in detail.

本発明で用いられる(A)エポキシ樹脂とは、1分子内にエポキシ基を2個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造を特に限定するものではないが、例えば、ビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェニレン骨格、ビフェニレン骨格等を有するフェノールアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェニレン骨格、ビフェニレン骨格等を有するナフトールアラルキル型エポキシ樹脂等が挙げられ、これらは1種類を単独で用いても、2種類以上を併用してもよい。耐半田性の向上という観点からは、ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂が好ましく、下記一般式(3)で表されるエポキシ樹脂(a1)がより好ましい。粘度上昇を抑える観点から、下記一般式(3)において、n3の平均値は1以上、10以下の正数であることが好ましく、1以上、6以下の正数であることがより好ましく、1以上、4以下の正数であることが特に好ましい。

Figure 2008195875
(ただし、上記一般式(3)において、n3の平均値は1以上、10以下の正数である。) The (A) epoxy resin used in the present invention is a monomer, oligomer or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclo Pentadiene-modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene skeleton, biphenylene skeleton, naphthalene type epoxy resin, naphthol novolac type epoxy resin, phenylene skeleton, biphenylene bone Naphthol aralkyl type epoxy resins. Having a like, which may be used one kind alone or in combination of two or more. From the viewpoint of improving solder resistance, a phenol aralkyl type epoxy resin having a biphenylene skeleton is preferable, and an epoxy resin (a1) represented by the following general formula (3) is more preferable. From the viewpoint of suppressing an increase in viscosity, in the following general formula (3), the average value of n3 is preferably a positive number of 1 or more and 10 or less, more preferably a positive number of 1 or more and 6 or less. As described above, a positive number of 4 or less is particularly preferable.
Figure 2008195875
(However, in the general formula (3), the average value of n3 is a positive number of 1 or more and 10 or less.)

本発明で用いられるエポキシ樹脂(A)全体の配合割合の下限値については、特に限定されないが、全エポキシ樹脂組成物中に、3重量%以上であることが好ましく、5重量%以上であることがより好ましい。配合割合の下限値が上記範囲内であると、流動性の低下等を引き起こす恐れが少ない。また、エポキシ樹脂(A)全体の配合割合の上限値については、特に限定されないが、全エポキシ樹脂組成物中に、12重量%以下であることが好ましく、10重量%以下であることがより好ましい。配合割合の上限値が上記範囲内であると、耐半田性の低下等を引き起こす恐れが少ない。   Although it does not specifically limit about the lower limit of the compounding ratio of the whole epoxy resin (A) used by this invention, It is preferable that it is 3 weight% or more in all the epoxy resin compositions, and it is 5 weight% or more. Is more preferable. When the lower limit of the blending ratio is within the above range, there is little possibility of causing a decrease in fluidity. Further, the upper limit of the blending ratio of the entire epoxy resin (A) is not particularly limited, but is preferably 12% by weight or less, more preferably 10% by weight or less in the total epoxy resin composition. . When the upper limit of the blending ratio is within the above range, there is little possibility of causing a decrease in solder resistance.

本発明で用いられる(B)フェノール樹脂系硬化剤とは、1分子内にフェノール性水酸基を2個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造を特に限定するものではないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂、フェニレン骨格、ビフェニレン骨格等を有するフェノールアラルキル樹脂、ナフトールノボラック樹脂、フェニレン骨格、ビフェニレン骨格等を有するナフトールアラルキル樹脂等が挙げられ、これらは1種類を単独で用いても、2種類以上を併用してもよい。耐半田性の向上という観点からは、ビフェニレン骨格を有するフェノールアラルキル樹脂が好ましく、下記一般式(4)で表されるフェノール樹脂(b1)がより好ましい。粘度上昇を抑える観点から、下記一般式(4)において、n4の平均値は1以上、10以下の正数であることが好ましく、1以上、6以下の正数であることがより好ましく、1以上、4以下の正数であることが特に好ましい。

Figure 2008195875
(ただし、上記一般式(4)において、n4の平均値は1以上、10以下の正数である。) The (B) phenolic resin-based curing agent used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, dicyclopentadiene modified phenol resin, terpene modified phenol resin, triphenolmethane type resin, phenol aralkyl resin having phenylene skeleton, biphenylene skeleton, naphthol novolak resin, phenylene skeleton, biphenylene skeleton Naphthol aralkyl resins and the like, which may be used alone, may be used alone or in combination of two or more. From the viewpoint of improving solder resistance, a phenol aralkyl resin having a biphenylene skeleton is preferable, and a phenol resin (b1) represented by the following general formula (4) is more preferable. From the viewpoint of suppressing an increase in viscosity, in the following general formula (4), the average value of n4 is preferably a positive number of 1 or more and 10 or less, more preferably a positive number of 1 or more and 6 or less. As described above, a positive number of 4 or less is particularly preferable.
Figure 2008195875
(However, in the general formula (4), the average value of n4 is a positive number of 1 or more and 10 or less.)

本発明で用いられるフェノール樹脂系硬化剤(B)の配合割合の下限値については、特に限定されないが、全エポキシ樹脂組成物中に、2重量%以上であることが好ましく、4重量%以上であることがより好ましい。配合割合の下限値が上記範囲内であると、流動性の低下等を引き起こす恐れが少ない。また、フェノール樹脂系硬化剤(B)の配合割合の上限値については、10重量%以下であることが好ましく、8重量%以下であることがより好ましい。配合割合の上限値が上記範囲内であると、耐半田性の低下等を引き起こす恐れが少ない。   Although it does not specifically limit about the lower limit of the mixture ratio of the phenol resin type hardening | curing agent (B) used by this invention, It is preferable that it is 2 weight% or more in all the epoxy resin compositions, and is 4 weight% or more. More preferably. When the lower limit of the blending ratio is within the above range, there is little possibility of causing a decrease in fluidity. Moreover, about the upper limit of the mixture ratio of a phenol resin type hardening | curing agent (B), it is preferable that it is 10 weight% or less, and it is more preferable that it is 8 weight% or less. When the upper limit of the blending ratio is within the above range, there is little possibility of causing a decrease in solder resistance.

また、(A)エポキシ樹脂及び(B)フェノール樹脂系硬化剤の配合比率としては、全エポキシ樹脂のエポキシ基数(EP)と全フェノール樹脂系硬化剤のフェノール性水酸基数(OH)との比(EP)/(OH)が0.8以上、1.3以下であることが好ましい。当量比がこの範囲であると、エポキシ樹脂組成物の硬化性の低下、又は樹脂硬化物の物性の低下等を引き起こす恐れが少ない。   The blending ratio of (A) epoxy resin and (B) phenol resin curing agent is the ratio of the number of epoxy groups (EP) of all epoxy resins to the number of phenolic hydroxyl groups (OH) of all phenol resin curing agents ( EP) / (OH) is preferably 0.8 or more and 1.3 or less. When the equivalent ratio is within this range, there is little possibility of causing a decrease in the curability of the epoxy resin composition or a decrease in the physical properties of the resin cured product.

本発明では、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)と、(D)一般式(1)で表されるオルガノポリシロキサンと、を併用することが好ましい。これにより、エポキシ樹脂マトリックスと(D)一般式(1)で表されるオルガノポリシロキサンとを適正な状態に相溶化させることができるため、これらを併用したエポキシ樹脂組成物は、その成形時において、樹脂硬化物表面の外観と離型性とを両立させることができ、連続成形性が良好になる。   In the present invention, (C) an organopolysiloxane (c1) having a polycaprolactone group and / or a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin, and (D) It is preferable to use together with the organopolysiloxane represented by the general formula (1). Thereby, since the epoxy resin matrix and the organopolysiloxane represented by the general formula (1) can be compatibilized in an appropriate state, the epoxy resin composition using these in combination is formed at the time of molding. In addition, the appearance of the cured resin surface and the releasability can be made compatible, and the continuous moldability becomes good.

一方、(D)一般式(1)で表されるオルガノポリシロキサンを使用せずに、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)のみを使用した場合では、離型性が不充分となり、連続成形性が低下する。また、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)を使用せずに、(D)一般式(1)で表されるオルガノポリシロキサンのみを使用した場合では、エポキシ樹脂マトリックス中における(D)一般式(1)で表されるオルガノポリシロキサンの相溶化が不充分となり、樹脂硬化物表面の外観が悪化する。   On the other hand, (D) without using the organopolysiloxane represented by the general formula (1), (C) an organopolysiloxane having a polycaprolactone group (c1) and / or an organopolysiloxane having a polycaprolactone group When only the reaction product (c2) of (c1) and the epoxy resin is used, the releasability becomes insufficient and the continuous moldability is lowered. Also, (C) an organopolysiloxane (c1) having a polycaprolactone group and / or a reaction product (c2) of an epoxy resin with an organopolysiloxane (c1) having a polycaprolactone group, D) When only the organopolysiloxane represented by the general formula (1) is used, the compatibilization of the organopolysiloxane represented by the general formula (1) in the epoxy resin matrix becomes insufficient, and the resin The appearance of the cured product surface deteriorates.

本発明で用いられるポリカプロラクトン基を有するオルガノポリシロキサン(c1)は、ポリカプロラクトンとオルガノポリシロキサンを混合し、白金触媒下50〜100℃で反応させることで得られる。ポリカプロラクトン基を有するオルガノポリシロキサン(c1)としては、特に限定するものではないが、下記一般式(2)で表されるオルガノポリシロキサンが好ましい。

Figure 2008195875
(ただし、上記一般式(2)において、R3は水素、メチル基、フェニル基、及びR4から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるポリカプロラクトン基を有する有機基である。n2の平均値は1以上、50以下の正数である。上記R4において、bの平均値は1以上、20以下の正数であり、R5は炭素数1〜30の有機基である。) The organopolysiloxane (c1) having a polycaprolactone group used in the present invention is obtained by mixing polycaprolactone and organopolysiloxane and reacting them at 50 to 100 ° C. under a platinum catalyst. Although it does not specifically limit as organopolysiloxane (c1) which has a polycaprolactone group, The organopolysiloxane represented by following General formula (2) is preferable.
Figure 2008195875
(However, in the general formula (2), R3 is a group selected from hydrogen, a methyl group, a phenyl group, and R4, which may be the same or different from each other, but at least one of them is R2. The average value of n2 is a positive number of 1 to 50. In R4, the average value of b is a positive number of 1 to 20, and R5 is an organic group having a polycaprolactone group. Is an organic group having 1 to 30 carbon atoms.)

一般式(2)において、R3は水素、メチル基、フェニル基及びR4から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるポリカプロラクトン基を有する有機基である。R4において、bの平均値は1以上、20以下の正数であり、R3は炭素数1〜30の有機基である。ポリカプロラクトン基を有する有機基の炭素数が上記範囲内であると、エポキシ樹脂マトリックスとの相溶性が適正な状態となり、樹脂硬化物表面の外観悪化を抑えることができる。また、一般式(2)において、n2の平均値は1以上、50以下の正数である。n2の平均値が上記範囲内であると、オルガノポリシロキサン自体の粘度が適正な範囲となるため、流動性の悪化を引き起こす恐れが少ない。   In the general formula (2), R3 is a group selected from hydrogen, a methyl group, a phenyl group and R4, which may be the same or different from each other, but at least one is a polycaprolactone represented by R2. An organic group having a group. In R4, the average value of b is a positive number of 1 or more and 20 or less, and R3 is an organic group having 1 to 30 carbon atoms. When the carbon number of the organic group having a polycaprolactone group is within the above range, the compatibility with the epoxy resin matrix becomes appropriate, and deterioration of the appearance of the cured resin surface can be suppressed. In the general formula (2), the average value of n2 is a positive number of 1 or more and 50 or less. When the average value of n2 is within the above range, the viscosity of the organopolysiloxane itself is in an appropriate range, and therefore there is little possibility of causing deterioration of fluidity.

(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)を使用すると、流動性の低下を引き起こさず、(D)一般式(1)で表されるオルガノポリシロキサンとの相溶性が特に悪いエポキシ樹脂マトリックスを用いた場合においても、樹脂硬化物表面の外観を良好にすることができる。   When the reaction product (c2) of (C) an organopolysiloxane (c1) having a polycaprolactone group and / or an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin is used, the fluidity is reduced. (D) Even when an epoxy resin matrix having a particularly poor compatibility with the organopolysiloxane represented by the general formula (1) is used, the appearance of the resin cured product surface can be improved.

ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)の製法については、特に限定するものではないが、例えば、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)をエポキシ樹脂と硬化促進剤により溶融・反応させることで得ることができる。ここで言う硬化促進剤とは、オルガノポリシロキサン(c1)のポリカプロラクトン基とエポキシ化合物のエポキシ基との硬化反応を促進させるものであればよく、後述するエポキシ樹脂(A)のエポキシ基とフェノール樹脂系硬化剤(B)のフェノール性水酸基との硬化反応を促進させる硬化促進剤と同じものを用いることができる。また、ここで言うエポキシ化合物とは、1分子内にフェノール性水酸基を2個以上有するモノマー、オリゴマー、ポリマー全般であり、前述したエポキシ樹脂(A)と同じものを用いることができる。ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)を使用すると、更に、連続成形後の型汚れが発生し難く、連続成形性が極めて良好になる。   The method for producing a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin is not particularly limited. For example, an organopolysiloxane (c1) having a polycaprolactone group is epoxy-modified. It can be obtained by melting and reacting with a resin and a curing accelerator. The curing accelerator referred to here may be anything that accelerates the curing reaction between the polycaprolactone group of the organopolysiloxane (c1) and the epoxy group of the epoxy compound, and the epoxy group and phenol of the epoxy resin (A) described later. The same thing as the hardening accelerator which accelerates | stimulates hardening reaction with the phenolic hydroxyl group of a resin type hardening | curing agent (B) can be used. Moreover, the epoxy compound said here is the monomer, oligomer, and polymer in general which have two or more phenolic hydroxyl groups in 1 molecule, and the same thing as the epoxy resin (A) mentioned above can be used. When a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin is used, mold stains after continuous molding hardly occur and the continuous moldability becomes extremely good.

(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)の配合量は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)での配合量として、全エポキシ樹脂組成物中0.01重量%以上、3重量%以下であることが好ましい。配合量が上記範囲内であると、(D)一般式(1)で表されるオルガノポリシロキサンによる樹脂硬化物表面の外観汚れを抑えることができる。また、配合量が上記範囲内であると、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)自体による樹脂硬化物表面の外観悪化を抑えることができる。
また、本発明に用いられる(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)を添加する効果を損なわない範囲で、他のオルガノポリシロキサンを併用することができる。
(C) The compounding amount of the reaction product (c2) of the organopolysiloxane (c1) having a polycaprolactone group and / or the organopolysiloxane (c1) having a polycaprolactone group and the epoxy resin is such that the polycaprolactone group The amount of the organopolysiloxane (c1) to be contained is preferably 0.01% by weight or more and 3% by weight or less in the total epoxy resin composition. When the blending amount is within the above range, (D) appearance stains on the surface of the cured resin due to the organopolysiloxane represented by the general formula (1) can be suppressed. Moreover, the deterioration of the external appearance of the resin cured material surface by organopolysiloxane (c1) itself which has a polycaprolactone group can be suppressed as a compounding quantity exists in the said range.
Further, (C) an organopolysiloxane (c1) having a polycaprolactone group and / or a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin used in the present invention is added. Other organopolysiloxanes can be used in combination within a range that does not impair the effect.

本発明に用いられる(D)一般式(1)で表されるオルガノポリシロキサンは、単独で使用した場合、成形品の外観を低下させる場合があるが、(D)一般式(1)で表されるオルガノポリシロキサンと(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)とを併用することにより、成形品の外観と離型性を両立でき、成形品の外観が良好になる。また、本発明において一般式(1)で表されるオルガノポリシロキサンは、一般式(1)で表されるものであれば特に限定されるものではなく、他のオルガノポリシロキサンを併用してもよい。

Figure 2008195875
(ただし、上記一般式(1)において、R1は水素、メチル基、フェニル基、及びR2から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるアルキル基を有する有機基である。n1の平均値は1以上、50以下の正数である。上記R2において、aの平均値は1以上、20以下の正数である。) The organopolysiloxane represented by (D) general formula (1) used in the present invention may deteriorate the appearance of a molded product when used alone, but is represented by (D) general formula (1). And (C) organopolysiloxane (c1) having a polycaprolactone group and / or a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin By doing so, both the appearance of the molded product and the releasability can be achieved, and the appearance of the molded product becomes good. In the present invention, the organopolysiloxane represented by the general formula (1) is not particularly limited as long as it is represented by the general formula (1), and other organopolysiloxanes may be used in combination. Good.
Figure 2008195875
(However, in the general formula (1), R1 is a group selected from hydrogen, a methyl group, a phenyl group, and R2, and may be the same or different from each other, but at least one of them is R2. (It is an organic group having an alkyl group. The average value of n1 is a positive number of 1 or more and 50 or less. In R2, the average value of a is a positive number of 1 or more and 20 or less.)

本発明で用いられる(D)成分の配合量は、全エポキシ樹脂組成物中0.01重量%以上、3重量%以下が好ましい。配合量を上記範囲にすることで、離型剤や過剰のオルガノポリシロキサンによる成形品の外観汚れを抑え、良好な連続成形性を得ることができる。   The blending amount of the component (D) used in the present invention is preferably 0.01% by weight or more and 3% by weight or less in the total epoxy resin composition. By setting the blending amount within the above range, it is possible to suppress appearance stains on the molded product due to the release agent and excess organopolysiloxane, and to obtain good continuous moldability.

本発明のエポキシ樹脂組成物は、(A)エポキシ樹脂、(B)フェノール樹脂系硬化剤、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)、並びに(D)一般式(1)で表されるオルガノポリシロキサンを含むものであるが、更に(E)硬化促進剤、(F)無機充填材等を配合することができる。   The epoxy resin composition of the present invention comprises (A) an epoxy resin, (B) a phenol resin-based curing agent, (C) an organopolysiloxane having a polycaprolactone group (c1), and / or an organopoly having a polycaprolactone group. It contains a reaction product (c2) of siloxane (c1) and an epoxy resin, and (D) an organopolysiloxane represented by the general formula (1), but further comprises (E) a curing accelerator and (F) an inorganic filler. A material etc. can be mix | blended.

本発明に用いることができる(E)硬化促進剤としては、(A)エポキシ樹脂のエポキシ基と(B)フェノール樹脂系硬化剤のフェノール性水酸基との硬化反応を促進させるものであればよく、一般にエポキシ樹脂組成物に使用するものを用いることができる。例えば、1,8−ジアザビシクロ(5,4,0)ウンデセン−7等のジアザビシクロアルケン及びその誘導体;トリフェニルホスフィン、メチルジフェニルホスフィン等の有機ホスフィン類;2−メチルイミダゾール等のイミダゾール化合物;テトラフェニルホスホニウム・テトラフェニルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート等が挙げられ、これらは1種類を単独で用いても、2種類以上を併用しても差し支えない。   As the (E) curing accelerator that can be used in the present invention, any curing accelerator may be used as long as it promotes the curing reaction between the epoxy group of (A) the epoxy resin and the phenolic hydroxyl group of the (B) phenol resin curing agent, What is generally used for an epoxy resin composition can be used. For example, diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; imidazole compounds such as 2-methylimidazole; tetra Examples thereof include tetra-substituted phosphonium and tetra-substituted borates such as phenylphosphonium and tetraphenylborate, and these may be used alone or in combination of two or more.

本発明に用いることができる(E)硬化促進剤の配合割合の下限値については、特に限定されないが、全エポキシ樹脂組成物中0.05重量%以上であることが好ましく、0.1重量%以上であることがより好ましい。配合割合の下限値が上記範囲内であると、硬化性の低下等を引き起こす恐れが少ない。また、(E)硬化促進剤の配合割合の上限値については、特に限定されないが、全エポキシ樹脂組成物中1重量%以下であることが好ましく、0.5重量%以下であることがより好ましい。配合割合の上限値が上記範囲内であると、流動性の低下等を引き起こす恐れが少ない。   The lower limit of the blending ratio of the (E) curing accelerator that can be used in the present invention is not particularly limited, but is preferably 0.05% by weight or more, and 0.1% by weight in the total epoxy resin composition. More preferably. When the lower limit of the blending ratio is within the above range, there is little risk of causing a decrease in curability. Further, the upper limit of the blending ratio of the (E) curing accelerator is not particularly limited, but is preferably 1% by weight or less, more preferably 0.5% by weight or less in the total epoxy resin composition. . When the upper limit of the blending ratio is within the above range, there is little possibility of causing a decrease in fluidity.

本発明に用いることができる(F)無機充填材としては、一般にエポキシ樹脂組成物に使用されているものを用いることができる。例えば、溶融シリカ、結晶シリカ、タルク、アルミナ、窒化珪素等が挙げられ、最も好適に使用されるものは、球状の溶融シリカである。これらの(F)無機充填材は、1種類を単独で用いても、2種類以上を併用しても差し支えない。またこれらがカップリング剤により表面処理されていてもかまわない。(F)無機充填材の形状としては、流動性の観点から、できるだけ真球状であり、かつ粒度分布がブロードであることが好ましい。   As the inorganic filler (F) that can be used in the present invention, those generally used in epoxy resin compositions can be used. For example, fused silica, crystalline silica, talc, alumina, silicon nitride and the like can be mentioned, and the most preferably used is spherical fused silica. These (F) inorganic fillers may be used alone or in combination of two or more. These may be surface-treated with a coupling agent. (F) The shape of the inorganic filler is preferably as spherical as possible and has a broad particle size distribution from the viewpoint of fluidity.

本発明に用いることができる(F)無機充填材の含有量の下限値については、全エポキシ樹脂組成物中78重量%以上であることが好ましく、80重量%以上であることがより好ましい。含有量の下限値が上記範囲内であると、実装時における良好な耐半田性を得ることができる。また、(F)無機充填材の含有量の上限値については、全エポキシ樹脂組成物中93重量%以下であることが好ましく、91重量%以下であることがより好ましい。含有量の上限値が上記範囲内であると、成形時における充分な流動性を得ることができる。   About the lower limit of content of the (F) inorganic filler which can be used for this invention, it is preferable that it is 78 weight% or more in all the epoxy resin compositions, and it is more preferable that it is 80 weight% or more. When the lower limit value of the content is within the above range, good solder resistance during mounting can be obtained. Moreover, about the upper limit of content of (F) inorganic filler, it is preferable that it is 93 weight% or less in all the epoxy resin compositions, and it is more preferable that it is 91 weight% or less. When the upper limit of the content is within the above range, sufficient fluidity at the time of molding can be obtained.

本発明のエポキシ樹脂組成物は、上記(A)〜(F)成分以外に、更に必要に応じて、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシランカップリング剤や、チタネートカップリング剤、アルミニウムカップリング剤、アルミニウム/ジルコニウムカップリング剤等のカップリング剤;カーボンブラック等の着色剤;シリコーンオイル、ゴム等の低応力添加剤;臭素化エポキシ樹脂や三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛、モリブデン酸亜鉛、フォスファゼン等の難燃剤;カルナバワックス等の天然ワックス、ポリエチレンワックス等の合成ワックス、ステアリン酸やステアリン酸亜鉛等の高級脂肪酸及びその金属塩類若しくはパラフィン等の離型剤;酸化ビスマス水和物等の酸化防止剤等の添加剤を適宜配合しても差し支えない。   In addition to the above components (A) to (F), the epoxy resin composition of the present invention, if necessary, silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, Titanate coupling agents, aluminum coupling agents, coupling agents such as aluminum / zirconium coupling agents; colorants such as carbon black; low-stress additives such as silicone oil and rubber; brominated epoxy resins, antimony trioxide, water Flame retardants such as aluminum oxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene; natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate, and metal salts or paraffins thereof etc Release agents; no problem be appropriately blended additives such as antioxidants such as bismuth oxide hydrate.

また、本発明のエポキシ樹脂組成物は、上記(A)〜(F)成分、その他の添加剤等を、ミキサー等を用いて充分に均一に混合したもの、その後、更に熱ロール、ニーダー、押出機等の混練機で溶融混練し、冷却後粉砕したものなど、必要に応じて適宜分散度や流動性等を調整したものを用いることができる。   In addition, the epoxy resin composition of the present invention is a mixture in which the above components (A) to (F) and other additives are sufficiently uniformly mixed using a mixer or the like, and then further heated rolls, kneaders, extrusions. It is possible to use a material in which the degree of dispersion, fluidity, and the like are appropriately adjusted as necessary, such as those obtained by melt-kneading with a kneading machine such as a machine and pulverizing after cooling.

封止を行う半導体素子としては、例えば、集積回路、大規模集積回路、トランジスタ、サイリスタ、ダイオード、固体撮像素子等で特に限定されるものではなく、半導体装置の形態も特に限定されない。低圧トランスファー成形などの方法で封止された半導体装置は、そのまま、或いは80〜200℃の温度で15秒〜10時間かけて完全硬化させた後、電子機器等に搭載される。
本発明の半導体装置の形態としては、特に限定されないが、例えば、デュアル・インライン・パッケージ(DIP)、プラスチック・リード付きチップ・キャリヤ(PLCC)、クワッド・フラット・パッケージ(QFP)、スモール・アウトライン・パッケージ(SOP)、スモール・アウトライン・Jリード・パッケージ(SOJ)、薄型スモール・アウトライン・パッケージ(TSOP)、薄型クワッド・フラット・パッケージ(TQFP)、テープ・キャリア・パッケージ(TCP)、ボール・グリッド・アレイ(BGA)、チップ・サイズ・パッケージ(CSP)等が挙げられる。
The semiconductor element for sealing is not particularly limited to, for example, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a solid-state imaging element, and the like, and the form of the semiconductor device is not particularly limited. A semiconductor device sealed by a method such as low-pressure transfer molding is mounted on an electronic device or the like as it is or after being completely cured at a temperature of 80 to 200 ° C. for 15 seconds to 10 hours.
The form of the semiconductor device of the present invention is not particularly limited. For example, the dual in-line package (DIP), the plastic lead chip carrier (PLCC), the quad flat package (QFP), the small outline, and the like. Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Examples include an array (BGA), a chip size package (CSP), and the like.

図1は、本発明に係るエポキシ樹脂組成物を用いた半導体装置の一例について、断面構造を示した図である。ダイパッド3上に、ダイボンド材硬化体2を介して半導体素子1が固定されている。半導体素子1の電極パッドとリードフレーム5との間は金線4によって接続されている。半導体素子1は、エポキシ樹脂組成物の硬化体6によって封止されている。
本発明のエポキシ樹脂組成物を用いて、半導体素子を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の従来からの成形方法で硬化成形すればよい。
FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition according to the present invention. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of an epoxy resin composition.
In order to encapsulate a semiconductor element and manufacture a semiconductor device using the epoxy resin composition of the present invention, it may be cured by a conventional molding method such as transfer molding, compression molding, injection molding or the like.

以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。配合割合は重量部とする。
実施例1
エポキシ樹脂1:下記式(3)で表されるエポキシ樹脂(日本化薬(株)製、NC3000P。エポキシ当量274、軟化点58℃。下記式(3)において、n3の平均値3.8。) 8.01重量部

Figure 2008195875
Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
Example 1
Epoxy resin 1: Epoxy resin represented by the following formula (3) (manufactured by Nippon Kayaku Co., Ltd., NC3000P. Epoxy equivalent 274, softening point 58 ° C. In the following formula (3), the average value of n3 is 3.8. 8.01 parts by weight

Figure 2008195875

フェノール樹脂系硬化剤1:下記式(4)で表されるフェノール樹脂(明和化成(株)製、MEH−7851SS。水酸基当量203、軟化点107℃。下記式(4)において、n4の平均値は3.5。) 5.39重量部

Figure 2008195875
Phenol resin-based curing agent 1: phenol resin represented by the following formula (4) (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 203, softening point: 107 ° C. In the following formula (4), the average value of n4 3.5.) 5.39 parts by weight
Figure 2008195875

オルガノポリシロキサン1:下記式(5)で表されるオルガノポリシロキサン(ポリカプロラクトンと両末端にクロルを有するオルガノポリシロキサンを混合し、白金触媒下80℃で反応させることで得た。下記式(5)においてn5の平均値は18.0。)
0.20重量部

Figure 2008195875
Organopolysiloxane 1: An organopolysiloxane represented by the following formula (5) (obtained by mixing polycaprolactone and an organopolysiloxane having chloro at both ends and reacting at 80 ° C. under a platinum catalyst. In 5), the average value of n5 is 18.0.)
0.20 parts by weight
Figure 2008195875

オルガノポリシロキサン3:下記式(6)で表されるオルガノポリシロキサン(GE東芝シリコーン(株)製、SILSOFT034。) 0.20重量部

Figure 2008195875
Organopolysiloxane 3: Organopolysiloxane represented by the following formula (6) (GE Toshiba Silicone Co., Ltd., SILSOFT 034) 0.20 parts by weight
Figure 2008195875

1,8−ジアザビシクロ(5,4,0)ウンデセン−7(以下、DBUという)
0.20重量部
溶融球状シリカ(平均粒径21μm) 85.00重量部
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) 0.40重量部
カーボンブラック 0.40重量部
カルナバワックス 0.20重量部
を混合し、熱ロールを用いて、95℃で8分間溶融混練して冷却後粉砕し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表1に示す。
1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU)
0.20 parts by weight Fused spherical silica (average particle size 21 μm) 85.00 parts by weight Coupling agent (γ-glycidoxypropyltrimethoxysilane) 0.40 parts by weight Carbon black 0.40 parts by weight Carnauba wax 0.20 Part by weight was mixed, melted and kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.

評価方法
スパイラルフロー:低圧トランスファー成形機(コータキ精機株式会社製、KTS−15)を用いて、EMMI−1−66に準じたスパイラルフロー測定用金型に、金型温度175℃、注入圧力6.9MPa、保圧時間120秒の条件でエポキシ樹脂組成物を注入し、流動長を測定した。単位はcm。判定基準は70cm未満を不合格、70cm以上を合格とした。
Evaluation method: Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement according to EMMI-1-66, a mold temperature of 175 ° C. and an injection pressure of 6. The epoxy resin composition was injected under the conditions of 9 MPa and pressure holding time of 120 seconds, and the flow length was measured. The unit is cm. The criteria for the evaluation were less than 70 cm, and 70 cm or more.

連続成形性:低圧トランスファー自動成形機(第一精巧製、GP−ELF)を用いて、金型温度175℃、注入圧力9.8MPa、硬化時間70秒の条件で、エポキシ樹脂組成物によりシリコンチップ等を封止して80ピン・クワッド・フラット・パッケージ(80pQFP;Cu製リードフレーム、パッケージ外寸:14mm×20mm×2mm厚、パッドサイズ:6.5mm×6.5mm、チップサイズ6.0mm×6.0mm×0.35mm厚)を得る成形を、連続で700ショットまで行なった。判定基準は未充填等全く問題なく700ショットまで連続成形できたものを◎、未充填等全く問題なく500ショットまで連続成形できたものを○、それ以外を×とした。   Continuous moldability: Silicon chip using epoxy resin composition under conditions of mold temperature of 175 ° C, injection pressure of 9.8 MPa, curing time of 70 seconds using low pressure transfer automatic molding machine (Daiichi Seisaku, GP-ELF) 80-pin quad flat package (80pQFP; Cu lead frame, package outer dimensions: 14mm x 20mm x 2mm thickness, pad size: 6.5mm x 6.5mm, chip size 6.0mm x 6.0 mm × 0.35 mm thickness) was continuously performed up to 700 shots. Judgment criteria were ◎ for those that could be continuously molded up to 700 shots without any problems such as unfilled, ◯ for those that could be continuously molded up to 500 shots without any problems such as unfilled, and x otherwise.

パッケージ外観及び金型汚れ性:上記連続成形性の評価において、300、500及び700ショット成形後のパッケージ表面及び金型表面について、目視で汚れを評価した。パッケージ外観判断及び金型汚れ基準は、700ショットまで汚れていないものを◎で、500ショットまで汚れていないものを○で、300ショットまで汚れていないものを△で、汚れているものを×で表す。また、上記連続成形性において、300ショットまで連続成形できなかったものについては、連続成形を断念した時点でのパッケージ外観及び金型汚れ状況で判断し、汚れていないものを△で、汚れているものを×とした。   Package appearance and mold stain resistance: In the evaluation of the continuous moldability, the package surface and mold surface after 300, 500 and 700 shot molding were visually evaluated for stain. The package appearance judgment and mold contamination criteria are ◎ for those that are not dirty up to 700 shots, ◯ for those that are not dirty up to 500 shots, △ that are not dirty up to 300 shots, and × that are dirty. To express. In addition, in the above-described continuous formability, those that could not be continuously formed up to 300 shots were judged by the package appearance and the mold contamination status at the time when continuous molding was abandoned. The thing was made into x.

耐半田性:上記連続成形性の評価において成形したパッケージを、175℃、8時間加熱処理を行って後硬化し、次いで85℃、相対湿度60%で168時間加湿処理後、260℃の半田槽にパッケージを10秒間浸漬した。半田に浸漬させたパッケージ20個の半導体素子とエポキシ樹脂組成物の硬化物との界面の密着状態を、超音波探傷装置(日立建機ファインテック社製 mi−scope 10)により観察し、剥離発生率[(剥離発生パッケージ数)/(全パッケージ数)×100]を算出した。耐半田性の判断基準は、剥離が発生しなかったものは◎、剥離発生率が5%以上、10%未満のものは○、10%以上、20%未満のものは△、20%以上のものは×とした。   Solder resistance: A package molded in the above-described evaluation of continuous formability is subjected to post-curing by heat treatment at 175 ° C. for 8 hours, and then humidified for 168 hours at 85 ° C. and 60% relative humidity, and then a solder bath at 260 ° C. The package was immersed for 10 seconds. The adhesion state of the interface between the 20 semiconductor elements immersed in the solder and the cured epoxy resin composition is observed with an ultrasonic flaw detector (mi-scope 10 manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), and peeling occurs. The rate [(number of peeled packages) / (total number of packages) × 100] was calculated. The judgment criteria for solder resistance are ◎ for those where no peeling occurred, ◯ for peeling occurrence rates of 5% or more and less than 10%, ◯ for 10% or more, less than 20%, △, or 20% or more. The thing was set as x.

実施例2〜9、比較例1〜5
表1及び2の配合に従い、実施例1と同様にしてエポキシ樹脂組成物を得て、実施例1と同様にして評価した。結果を表1及び2に示す。
実施例1以外で用いた原材料を以下に示す。
エポキシ樹脂2:ビフェニル型エポキシ樹脂(ジャパンエポキシレジン(株)製、YX−4000。エポキシ当量190g/eq、融点105℃。)
エポキシ樹脂3:オルソクレゾールノボラック型エポキシ樹脂(日本化薬(株)製、EOCN−1020 62。エポキシ当量200g/eq、軟化点62℃。)
フェノール樹脂系硬化剤2:パラキシリレン変性ノボラック型フェノール樹脂(三井化学(株)製、XLC−4L。水酸基当量168g/eq、軟化点62℃。)
Examples 2-9, Comparative Examples 1-5
According to the composition of Tables 1 and 2, an epoxy resin composition was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: biphenyl type epoxy resin (YX-4000, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 190 g / eq, melting point 105 ° C.)
Epoxy resin 3: Orthocresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020 62. Epoxy equivalent 200 g / eq, softening point 62 ° C.)
Phenol resin-based curing agent 2: paraxylylene-modified novolak-type phenol resin (manufactured by Mitsui Chemicals, Inc., XLC-4L. Hydroxyl equivalent 168 g / eq, softening point 62 ° C.)

オルガノポリシロキサン2:下記式(7)で表されるオルガノポリシロキサン(ポリカプロラクトンと片末端にクロルを有するオルガノポリシロキサンを混合し、白金触媒下80℃で反応させることで得た。下記式(7)においてn7の平均値は18.0。)

Figure 2008195875
Organopolysiloxane 2: An organopolysiloxane represented by the following formula (7) (obtained by mixing polycaprolactone and an organopolysiloxane having chloro at one end and reacting at 80 ° C. under a platinum catalyst. 7) The average value of n7 is 18.0.)
Figure 2008195875

反応生成物A:ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン製、YL−6810、エポキシ当量170g/eq、融点47℃)66.1重量部を140℃で加温溶融し、オルガノポリシロキサン1(式(5)で表されるオルガノポリシロキサン)33.1重量部及びトリフェニルホスフィン0.8重量部を添加して、30分間溶融混合して反応生成物Aを得た。   Reaction product A: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, YL-6810, epoxy equivalent 170 g / eq, melting point 47 ° C.) 66.1 parts by weight was heated and melted at 140 ° C. to obtain organopolysiloxane 1 (formula The organopolysiloxane represented by (5)) 33.1 parts by weight and 0.8 parts by weight of triphenylphosphine were added and melt-mixed for 30 minutes to obtain a reaction product A.

オルガノポリシロキサン4:下記式(8)で表されるオルガノポリシロキサン(エチレン系炭化水素とオルガノポリシロキサンを混合し、白金触媒下80℃で反応させることで得た。)

Figure 2008195875
Organopolysiloxane 4: Organopolysiloxane represented by the following formula (8) (obtained by mixing ethylene hydrocarbon and organopolysiloxane and reacting at 80 ° C. under a platinum catalyst)
Figure 2008195875

オルガノポリシロキサン5:下記式(9)で表されるオルガノポリシロキサン(東レダウコーニング製、L−45。下記式(9)においてn9の平均値は18.0。)

Figure 2008195875
Organopolysiloxane 5: Organopolysiloxane represented by the following formula (9) (Toray Dow Corning, L-45. In the following formula (9), the average value of n9 is 18.0.)
Figure 2008195875

Figure 2008195875
Figure 2008195875

Figure 2008195875
Figure 2008195875

実施例1〜9は、(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)、並びに(D)一般式(1)で表されるオルガノポリシロキサンをともに含むものであり、(C)成分の配合量や種類を変えたもの、(D)成分の配合量や種類を変えたもの、或いは、樹脂の種類や無機充填材の配合量を変えたものを含むものであるが、いずれにおいても、流動性(スパイラルフロー)、連続成形性、パッケージ外観、金型汚れ性、耐半田性の全てに亘って、良好な結果が得られた。   Examples 1 to 9 include (C) an organopolysiloxane (c1) having a polycaprolactone group, and / or a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin, and (D) It contains both organopolysiloxanes represented by general formula (1), (C) the amount and type of component (C) are changed, (D) the amount and type of component are changed, Or, it includes those with different types of resins and blended amounts of inorganic fillers, but in all cases, all of fluidity (spiral flow), continuous formability, package appearance, mold contamination, and solder resistance. Over time, good results were obtained.

一方、比較例1、3は(D)一般式(1)で表されるオルガノポリシロキサンを用いていないものであるが、離型性が不充分なため、連続成形性が低下する結果となった。
また、比較例2、4は(C)成分を用いていないものであるが、(D)一般式(1)で表されるオルガノポリシロキサンの分散が不充分となり、パッケージ表面の外観が悪化し、金型キャビティが汚れる結果となった。
また、比較例5は(C)成分、(D)成分をともに用いていないものであるが、離型性が不充分なため、連続成形性が劣る結果となった。
On the other hand, Comparative Examples 1 and 3 do not use (D) the organopolysiloxane represented by the general formula (1), but due to insufficient releasability, continuous moldability is reduced. It was.
In Comparative Examples 2 and 4, the component (C) is not used, but (D) the organopolysiloxane represented by the general formula (1) is not sufficiently dispersed, and the appearance of the package surface is deteriorated. As a result, the mold cavity became dirty.
Moreover, although the comparative example 5 does not use both (C) component and (D) component, since the releasability was insufficient, it resulted in inferior continuous moldability.

本発明に従うと、半導体装置実装時において優れた半田耐熱性を示すとともに、半導体素子の封止成形時における離型性、連続成形性、樹脂硬化物表面の外観、金型汚れ性等とのバランスに優れるエポキシ樹脂組成物が得られるため、工業的な樹脂封止型半導体装置、特に表面実装用の樹脂封止型半導体装置の製造に好適に用いることができる。   According to the present invention, it exhibits excellent solder heat resistance when mounted on a semiconductor device, and is balanced with mold release properties, continuous moldability, appearance of a cured resin surface, mold contamination, etc., when sealing a semiconductor element. Therefore, it can be suitably used for producing an industrial resin-sealed semiconductor device, particularly a resin-sealed semiconductor device for surface mounting.

本発明に係るエポキシ樹脂組成物を用いた半導体装置の一例について、断面構造を示した図である。It is the figure which showed the cross-section about an example of the semiconductor device using the epoxy resin composition which concerns on this invention.

符号の説明Explanation of symbols

1 半導体素子
2 ダイボンド材硬化体
3 ダイパッド
4 金線
5 リードフレーム
6 エポキシ樹脂組成物の硬化体
DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Curing body of epoxy resin composition

Claims (8)

(A)エポキシ樹脂、
(B)フェノール樹脂系硬化剤、
(C)ポリカプロラクトン基を有するオルガノポリシロキサン(c1)、及び/又は、ポリカプロラクトン基を有するオルガノポリシロキサン(c1)とエポキシ樹脂との反応生成物(c2)、
並びに
(D)下記一般式(1)で表されるオルガノポリシロキサン
を含むことを特徴とするエポキシ樹脂組成物。
Figure 2008195875
(ただし、上記一般式(1)において、R1は水素、メチル基、フェニル基、及びR2から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるアルキル基を有する有機基である。n1の平均値は1以上、50以下の正数である。上記R2において、aの平均値は1以上、20以下の正数である。)
(A) epoxy resin,
(B) a phenolic resin-based curing agent,
(C) an organopolysiloxane (c1) having a polycaprolactone group and / or a reaction product (c2) of an organopolysiloxane (c1) having a polycaprolactone group and an epoxy resin,
(D) An epoxy resin composition comprising an organopolysiloxane represented by the following general formula (1).
Figure 2008195875
(However, in the general formula (1), R1 is a group selected from hydrogen, a methyl group, a phenyl group, and R2, and may be the same or different from each other, but at least one of them is R2. (It is an organic group having an alkyl group. The average value of n1 is a positive number of 1 or more and 50 or less. In R2, the average value of a is a positive number of 1 or more and 20 or less.)
前記ポリカプロラクトン基を有するオルガノポリシロキサン(c1)が下記一般式(2)で表されるオルガノポリシロキサンである請求項1に記載のエポキシ樹脂組成物。
Figure 2008195875
(ただし、上記一般式(2)において、R3は水素、メチル基、フェニル基、及びR4から選ばれる基であり、互いに同一であっても異なっていてもよいが、少なくとも1つ以上がR2で表されるポリカプロラクトン基を有する有機基である。n2の平均値は1以上、50以下の正数である。上記R4において、bの平均値は1以上、20以下の正数であり、R5は炭素数1〜30の有機基である。)
The epoxy resin composition according to claim 1, wherein the organopolysiloxane (c1) having a polycaprolactone group is an organopolysiloxane represented by the following general formula (2).
Figure 2008195875
(However, in the general formula (2), R3 is a group selected from hydrogen, a methyl group, a phenyl group, and R4, which may be the same or different from each other, but at least one of them is R2. The average value of n2 is a positive number of 1 to 50. In R4, the average value of b is a positive number of 1 to 20, and R5 is an organic group having a polycaprolactone group. Is an organic group having 1 to 30 carbon atoms.)
前記(A)エポキシ樹脂がビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂を含む請求項1又は請求項2に記載のエポキシ樹脂組成物。   The epoxy resin composition according to claim 1, wherein the (A) epoxy resin contains a phenol aralkyl type epoxy resin having a biphenylene skeleton. 前記(A)エポキシ樹脂が下記一般式(3)で表されるエポキシ樹脂(a1)を含む請求項1又は請求項2に記載のエポキシ樹脂組成物。
Figure 2008195875
(ただし、上記一般式(3)において、n3の平均値は1以上、10以下の正数である。)
The epoxy resin composition according to claim 1 or 2, wherein the (A) epoxy resin contains an epoxy resin (a1) represented by the following general formula (3).
Figure 2008195875
(However, in the general formula (3), the average value of n3 is a positive number of 1 or more and 10 or less.)
前記(B)フェノール樹脂系硬化剤がビフェニレン骨格を有するフェノールアラルキル樹脂を含む請求項1ないし請求項4のいずれかに記載のエポキシ樹脂組成物。   The epoxy resin composition according to any one of claims 1 to 4, wherein the (B) phenol resin-based curing agent includes a phenol aralkyl resin having a biphenylene skeleton. 前記(B)フェノール樹脂系硬化剤が下記一般式(4)で表されるフェノール樹脂(b1)を含む請求項1ないし請求項4のいずれかに記載のエポキシ樹脂組成物。
Figure 2008195875
(ただし、上記一般式(4)において、n4の平均値は1以上、10以下の正数である。)
The epoxy resin composition according to any one of claims 1 to 4, wherein the (B) phenol resin-based curing agent includes a phenol resin (b1) represented by the following general formula (4).
Figure 2008195875
(However, in the general formula (4), the average value of n4 is a positive number of 1 or more and 10 or less.)
半導体封止用である請求項1ないし請求項6のいずれかに記載の半導体封止用エポキシ樹脂組成物。   The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 6, wherein the epoxy resin composition is for semiconductor encapsulation. 請求項7に記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を封止してなることを特徴とする半導体装置。   A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to claim 7.
JP2007034153A 2007-02-14 2007-02-14 Epoxy resin composition and semiconductor device Expired - Fee Related JP4952283B2 (en)

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