JP4399902B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same - Google Patents

Description

（ただし、式中、R1、R2、R3及びR4は、それぞれ独立に、水素、アルキル基（炭素数１〜５のものが好ましい）、アルコキシアルキル基（炭素数２〜５のものが好ましい）またはジアルキルアミノアルキル基（炭素数３〜６のものが好ましい）を示す）
【化２】

（ただし、式中、R1、R2、R3及びR4は、それぞれ独立に水素、アルキル基（炭素数１〜５のものが好ましい）、アルコキシアルキル基（炭素数２〜５のものが好ましい）またはジアルキルアミノアルキル基（炭素数３〜６のものが好ましい）を示す）
【化３】

(ただし、式中、R1、R2、R3及びR4は、それぞれ独立に水素、アルキル基（炭素数１〜５のものが好ましい）、アルコキシアルキル基（炭素数２〜５のものが好ましい）またはジアルキルアミノアルキル基（炭素数３〜６のものが好ましい）を示す）
などが挙げられる。
【００１０】
硬化剤は特に限定はないが、たとえば、電子部品封止用エポキシ樹脂成形材料で一般に使用されているもので、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド等のアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂、フェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等があり、単独又は併用して用いることができる。中でも、耐リフロー性向上の観点から好適なものとして、フェノール・アラルキル樹脂が挙げられる。
硬化剤は、エポキシ樹脂のエポキシ基１当量に対して、エポキシ基との反応基、例えば、上記ノボラック樹脂のフェノール性水酸基、が０．５〜１．５当量になうように配合されることが好ましく、特に、０．７〜１．２当量配合することが好ましい。
【００１１】
硬化促進剤としては、特に制限はなく、例えば、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、１，５−ジアザ−ビシクロ（４，３，０）ノネン、５、６−ヂブチルアミノ−１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の３級アミン類及びこれらの誘導体、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール等のイミダゾール類及びこれらの誘導体、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン類及びこれらのホスフィン類に無水マレイン酸、ベンゾキノン、ジアゾフェニルメタン等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物、テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、２−エチル−４−メチルイミダゾールテトラフェニルボレート、Ｎ−メチルモテトラフェニルホスホニウム−テトラフェニルボレート、トリフェニルホスフィン、トリフェニルホスフィンとベンゾキノンの付加物、トリパラトリルフォスフィンとベンゾキノンの付加物、１，８−ジアザービシクロ（５，４，０）−ウンデセン−７，２−フェニル−４メチル−イミダゾール、トリフェニルホスホニウム−トリフェニルボラン等があり、単独又は併用して用いることができる。
硬化促進剤は、エポキシ樹脂と硬化剤の合計量に対して、０．１〜８重量％使用することが好ましい。
【００１２】
また、充填材としては、吸湿性低減及び強度向上の観点から無機充填材を用いることが必要である。無機充填材としては、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化珪素、窒化ホウ素、ベリリア、ジルコニア等の粉体、又はこれらを球形化したビーズ、チタン酸カリウム、炭化珪素、窒化珪素、アルミナ等の単結晶繊維、ガラス繊維等を１種類以上配合することができる。さらに、難燃効果のある無機充填材としては水酸化アルミニウム、硼酸亜鉛等が挙げられ、これらを単独または併用することができる。
無機充填材の配合量としては、吸湿性、線膨張係数の低減、強度向上及び半田耐熱性の観点から、本発明おける半導体封止用エポキシ樹脂組成物全体に対して７５〜９７重量％の範囲内であることが好ましく、特に、８０〜９５重量％の範囲内であることが好ましい。
上記の無機充填材の中で、線膨張係数低減の観点からは溶融シリカが、高熱伝導性の観点からはアルミナが好ましく、充填材形状は成形時の流動性及び金型摩耗性の点から球形が好ましい。
【００１３】
必須成分（Ｄ）成分のフタロシアニン系化合物は、代表構造として一般式（４）で表される
【化４】

４分子のイソインドールの１、３位が４個のアザ基（−Ｎ＝）で結合し、大環状を形成する構造である。中心金属Ｍには、Ｆｅ、Ｎｉ、Ｖ、ＶＯ、Ｃｕ、Ｃｏ等が挙げられ、中でもレーザーマーク性の観点からＶ、ＶＯが好適である。Ｒ１、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、水素、塩化チオニル基、フェニル基、ナフチルアゾ基等の共役π電子系置換基、アルキル基（炭素数が１〜６のものが好ましい）、アルコキシ基（炭素数が１〜６のものが好ましい）、アルキルチオ基（炭素数が１〜６のものが好ましい）等の電子供与性置換基等が挙げられ、中でもレーザーマーク性の観点から、−ＳＯ2Ｃｌ、−ＣＨ3、−ＣＨ2ＣＨ2ＣＨ2ＣＨ3等が好適である。また、（Ｄ）のフタロシアニン系化合物は、８００ｎｍ〜１２００ｎｍ付近の波長を吸収できるものであり、特に１０００ｎｍ〜１１００ｎｍの波長を吸収する化合物ほどレーザーマーク性の観点から好適である。また、フタロシアニン系化合物の含有量は、（Ａ）エポキシ樹脂と（Ｂ）硬化剤の合計量に対して０．０５重量％未満では、捺印性が充分ではなく、１５重量％を超えると成形性が不十分となるため、０．０５〜１５重量％が好ましい。さらに好ましくは、３．５〜９重量％の範囲である。
【００１４】
本発明における半導体封止用エポキシ樹脂組成物には、カップリング剤を添加することができる。
カップリング剤については、特に制限はなく、シランカップリング剤以外に従来公知のカップリング剤を併用してもよい。たとえば、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−［ビス（β−ヒドロキシエチル）］アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−（β−アミノエチル）アミノプロピルジメトキシメチルシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、Ｎ−（ジメトキシメチルシリルイソプロピル）エチレンジアミン、メチルトリメトキシシラン、メチルトリエトキシシラン、、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラン、γ−アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等のシラン系カップリング剤、あるいはイソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリ（Ｎ−アミノエチル−アミノエチル）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート等のチタネート系カップリング剤を１種以上併用することができる。
カップリング剤は、本発明おける半導体封止用エポキシ樹脂組成物全体に対して３重量％以下で使用することが好ましく、その効果を発揮させるためには０．１重量％以上使用することが好ましい。
【００１５】
また、本発明における半導体封止用エポキシ樹脂組成物には、離型剤を添加することができる。
離型剤についても、特に制限はないが、高級脂肪酸例えばカルナバワックス等とポリエチレン系ワックスを単独又は併用して用いることができる。
離型剤は、エポキシ樹脂と硬化剤の合計量に対して、１０重量％以下で使用することが好ましく、その効果を発揮させるためには、０．５重量％以上が好ましい。
【００１６】
その他の添加剤として、着色剤（カーボンブラック等）、改質材（シリコーン、シリコーンゴム等）、イオントラッパー（ハイドロタルサイト、アンチモン−ビスマス系含水酸化物等）を用いることができる。着色剤としてカーボンブラック等の導電性粒子を併用する場合は、本発明の目的を達成するために、粒径１０μｍ以上の粒子が１重量％以下のものを用いることが好ましく、その添加量としては（Ａ）エポキシ樹脂と（Ｂ）硬化剤の合計量に対し３重量％以下が好ましい。
【００１７】
以上のような原材料を用いて成形材料を作製する一般的な方法としては、所定の配合量の原材料混合物をミキサー等によって充分混合した後、熱ロール、押出機等によって混練し、冷却、粉砕、することによって成形材料を得ることができる。
本発明で得られるエポキシ樹脂組成物を用いて電子部品を封止する方法としては、低圧トランスファー成形法が最も一般的であるが、インジェクション成形、圧縮成形、注型等の方法によっても可能である。
上記した手段を用いて製造したエポキシ樹脂組成物は、レーザーマーク性、電気特性に優れ、且つ成形性、信頼性に優れており、IC、LSI等の封止に好適に用いることができる。
【００１８】
【実施例】
以下に本発明の実施例について説明するが、本発明はこれに限定されるものではない。
実施例１〜５ 比較例１〜４
まず、表１および２に示す各種の素材を予備混合（ドライブレンド）した後、二軸ロール（ロール表面温度約８０℃）で１０分間混練し、冷却粉砕して製造した。
【００１９】
【表１】

【００２０】
【表２】

【００２１】
なお、表１および表２記載の材料は次の通りである。
ビフェニル型エポキシ樹脂：YX-4000H、油化シェルエポキシ(株)商品名
臭素化エポキシ樹脂：YDB-400、東都化成工業（株）商品名
アラルキル型フェノール樹脂：XL-225-3L、三井化学(株)商品名
エポキシシラン：A-187、日本ユニカ（株）商品名
カルバワックス：カルナウバＮｏ．１、野田化学（株）商品名
ポリエチレンワックス：ＰＥＤ−１９１、クラリアント・ジャパン（株）商品名
フタロシアニン系化合物（800〜1200nmの波長を吸収、一般式（４）において、Ｒ１、Ｒ２，Ｒ３及びＲ４はすべて水素、ＭはＶＯ）
カーボンビーズ：CB-3-500)、三井鉱山(株)商品名
金属錯体染料：Neo Super Black C-832R、中央合成(株)商品名
ジスアゾ系染料：Chuo Sudan Black 141、中央合成(株)商品名
アジン系染料：Spirit Black 920、住友化学工業(株)商品名
カーボンブラック(粒子径：18nm)：三菱化学(株)製
この封止材を用い、トランスファー成形機を用い、金型温度１８０℃、成形圧力７０kgf／cm²、硬化時間９０秒の条件で各試験を行なった。スパイラルフローは、ＥＭＭ１１−６６により測定した。熱時硬度は、シェア硬度計にて測定した。
また、この封止材を用いて、半導体素子をトランスファー成形機で同様の条件で成形しポストキュアー（１７５℃／６ｈ）後耐湿性、半田耐熱性、レーザーーマーク性及び電気特性（リーク電流）を評価した。
体積抵抗率は、円板金型をトランスファプレスにセットし、上記封止材を用い直径１００ｍｍ、厚さ３ｍｍの円板を成形し後硬化した後、体積抵抗計にて測定した。
耐湿性に用いた半導体装置はＳＯＰ−２８ピンであり、８５℃／８５ＲＨ％７２時間吸湿＋２１５℃／９０秒（ＶＰＳ）の前処理後、ＰＣＴ（１２１℃／２気圧）に放置してチップ上配線の断線の有無を評価した。
半田耐熱性に用いた半導体装置は、ＱＦＰ−８０ピンの樹脂封止型半導体装置（外形寸法２０ｘ１４ｘ２．０ｍｍ）であり、リードフレームは４２アロイ材（加工なし）で８ｘ１０ｍｍのチップサイズを有するものである。
この様にして得られた樹脂封止型半導体装置について、半田耐熱性を１２５℃／２４ｈベーキング後、８５℃／８５ＲＨ％で所定の時間吸湿した後、２４０℃／１０ｓｅｃの処理を行なった時の樹脂封止型半導体装置のクラック発生率により判定した。
レーザーマーク性に用いた半導体装置は、ＱＦＰ−５４ピンであり、パッケージ表面をＹＡＧレーザーマーキング装置で印字し、目視でマーク性を評価した。
【００２２】
上記のＹＡＧレーザーの条件を以下に示す。
ＹＡＧレーザー波長：１０６４ｎｍ
レーザーパワー：５Ｊ
【００２３】
電気特性に用いた半導体装置は、ＬＱＦＰ１６７ピンであり、リーク電流の有無を評価した。
上記の試験結果をまとめて表３に示す。
【００２４】
【表３】

【００２５】
【発明の効果】
エポキシ樹脂、硬化剤、硬化促進剤及び無機充填材を主成分とする半導体素子封止用エポキシ樹脂組成物において、中心金属にＶまたはＶＯを有するフタロシアニン系化合物を必須成分として配合することにより、レーザーマーク性、電気特性、成形性、信頼性に優れた封止材及びそれを用いた半導体装置を得ることができた。[0001]
[Technical field belonging to the invention]
The present invention relates to an epoxy resin composition for semiconductor encapsulation excellent in laser mark properties, electrical characteristics, moldability, and reliability, and a semiconductor device using the same.
[0002]
[Prior art]
The resin-sealed semiconductor devices (diodes, transistors, ICs, LSIs, etc.) are all marked with characteristics and model numbers. Conventionally, this marking has been performed by a method of printing using a thermosetting or ultraviolet curable ink. In recent years, laser systems that can streamline productivity from this printing system are becoming mainstream. The laser printing mechanism irradiates the surface of a resin-encapsulated semiconductor device with characters, symbols, etc. in a pattern, and the irradiated portion is locally burned or sublimated to roughen the surface, resulting in characters and symbols. Is printed. The required marking time by this laser method is several seconds or less, which is much shorter than the minute order of the ink printing method. This laser system is roughly classified into those using a carbon dioxide laser or a YAG laser. In order to obtain a clear contrast in marking with these lasers, the epoxy resin composition for sealing contains a combination of carbon black and an azo organic dye (Japanese Patent Laid-Open No. 11-60904) and a near infrared absorber as a colorant. However, there are problems such as a decrease in moisture resistance and moldability or color tone.
[0003]
In addition, the surface mounting method that enables high-density mounting in response to miniaturization and thinning of electronic devices has been rapidly spread instead of the pin insertion type. As a result, when the semiconductor device is attached to the substrate, the semiconductor device itself is exposed to a high-temperature atmosphere such as a solder bath or a reflow bath that becomes 200 ° C. or higher in a short time. At this time, moisture contained in the sealing material is vaporized, and the vapor pressure generated here acts as a peeling stress at the interface between the sealing material and the insert of the element, lead frame, etc., and between the sealing material and the insert. In particular, in the case of a thin semiconductor device, it becomes a problem due to blisters and cracks in the semiconductor device. This phenomenon is called a reflow crack and is the most important issue for surface-mount semiconductor devices.
[0004]
Further, semiconductor chips such as LSIs have been improved in chip integration, chip size reduction, semiconductor device miniaturization, thinning, and multi-pinning. As a result, distances between pitches such as between inner leads, pads, and wires are becoming narrower. At this time, if conductive material such as carbon black contained in the sealing material exists as large coarse particles, conductive carbon black is sandwiched between the inner leads, between the pads, and between the wires, leading to poor electrical characteristics. It is a problem.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above, and has excellent laser markability and electrical characteristics, and does not cause leakage or short-circuit failure due to a conductive substance even in a semiconductor device having a short distance between pads or wires. An object of the present invention is to provide a sealing material excellent in reliability, such as property and reflow resistance, and a semiconductor device using the same.
[0006]
[Means for Solving the Problems]
The present invention relates to the following.
(1) (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) phthalocyanine compound, and (E) an epoxy resin composition for semiconductor encapsulation, which contains an inorganic filler as essential components object.
(2) The epoxy resin composition for semiconductor encapsulation according to (1), wherein the phthalocyanine compound has V or VO as a central metal.
(3) The epoxy resin composition for semiconductor encapsulation according to (1) or (2), wherein the epoxy resin has a melt viscosity at 150 ° C. of 0.5 poise or less.
(4) The epoxy resin for semiconductor encapsulation according to any one of (1) to (3), wherein the content of the phthalocyanine compound is 0.05 to 15% by weight based on the total amount of the epoxy resin and the curing agent. Composition.
(5) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (4), which contains 75 to 97% by weight of an inorganic filler.
(6) A resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition for encapsulating a semiconductor according to any one of (1) to (5).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The (A) epoxy resin of this invention is not specifically limited, The epoxy resin generally used with the epoxy resin molding material for sealing can be used. For example, phenols such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β-naphthol. Epoxide of novolak resin obtained by condensation or cocondensation of naphthols such as dihydroxynaphthalene and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. under an acidic catalyst, bisphenol A, bisphenol AD Epoxidizing bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted or unsubstituted biphenol, and phenol-aralkyl resins Epoxidized adducts or polyadducts of phenols with dicyclopentadiene or terpenes, glycidyl ester type epoxy resins obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin, diamino Examples include glycidylamine type epoxy resins obtained by reaction of polyamines such as diphenylmethane and isocyanuric acid with epichlorohydrin, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins. Any number of these can be used in combination.
[0008]
The purity of the epoxy resin of component (A), especially the amount of hydrolyzable chlorine, is better because it relates to corrosion of aluminum wiring on the IC and other elements. In order to obtain it, it is preferable that it is 500 ppm or less. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of an epoxy resin of a sample in 30 ml of dioxane, adding 5 ml of a 1N-KOH methanol solution and refluxing for 30 minutes, and then obtaining by potentiometric titration. is there.
[0009]
Among them, those suitable as the epoxy resin (A) of the present invention are preferably those capable of high filling of the filler from the viewpoint of improving solder heat resistance, and those having a 150 ° C melt viscosity of 0.5 poise or less are preferably used. it can. Moreover, a 150 degreeC melt viscosity of 0.1 poise or more is preferable. For example,

(However, in the formula, R1, R2, R3 and R4 are each independently hydrogen, an alkyl group (preferably having 1 to 5 carbon atoms), an alkoxyalkyl group (preferably having 2 to 5 carbon atoms) or A dialkylaminoalkyl group (preferably having 3 to 6 carbon atoms)
[Chemical formula 2]

(In the formula, R1, R2, R3 and R4 are each independently hydrogen, an alkyl group (preferably having 1 to 5 carbon atoms), an alkoxyalkyl group (preferably having 2 to 5 carbon atoms) or dialkyl. An aminoalkyl group (preferably having 3 to 6 carbon atoms)
[Chemical 3]

(Wherein R1, R2, R3 and R4 are each independently hydrogen, an alkyl group (preferably having 1 to 5 carbon atoms), an alkoxyalkyl group (preferably having 2 to 5 carbon atoms) or dialkyl. An aminoalkyl group (preferably having 3 to 6 carbon atoms)
Etc.
[0010]
The curing agent is not particularly limited. For example, the curing agent is generally used in an epoxy resin molding material for electronic component sealing, and phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, or α-naphthol. , Β-naphthol, dihydroxynaphthalene and other naphthols and formaldehyde and other aldehydes can be condensed or co-condensed in the presence of an acidic catalyst, such as novolak resin, phenol / aralkyl resin, naphthol / aralkyl resin, etc. Can be used. Among them, a phenol / aralkyl resin is preferable from the viewpoint of improving reflow resistance.
The curing agent is blended so that the reactive group with the epoxy group, for example, the phenolic hydroxyl group of the novolak resin, is 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. In particular, it is preferable to add 0.7 to 1.2 equivalents.
[0011]
The curing accelerator is not particularly limited, and for example, 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5-diaza-bicyclo (4,3,0) nonene, 5,6 -Tertiary amines such as dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and their derivatives, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; Anhydrous malein , Benzoquinone, diazophenylmethane and the like, phosphorus compounds having intramolecular polarization, tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenyl Borate, N-methylmotetraphenylphosphonium-tetraphenylborate, triphenylphosphine, adduct of triphenylphosphine and benzoquinone, adduct of triparatolyphosphine and benzoquinone, 1,8-diazabicyclo (5,4,0 ) -Undecene-7,2-phenyl-4methyl-imidazole, triphenylphosphonium-triphenylborane and the like, which can be used alone or in combination.
The curing accelerator is preferably used in an amount of 0.1 to 8% by weight based on the total amount of the epoxy resin and the curing agent.
[0012]
Moreover, as a filler, it is necessary to use an inorganic filler from a viewpoint of hygroscopic reduction and strength improvement. Examples of inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, boron nitride, beryllia, zirconia, or spherical beads of these, potassium titanate, silicon carbide One or more kinds of single crystal fibers such as silicon nitride and alumina, glass fibers, and the like can be blended. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate, and these can be used alone or in combination.
The blending amount of the inorganic filler is in the range of 75 to 97% by weight based on the entire epoxy resin composition for semiconductor encapsulation in the present invention, from the viewpoint of hygroscopicity, reduction of linear expansion coefficient, strength improvement and solder heat resistance. It is preferably within the range, and particularly preferably within the range of 80 to 95% by weight.
Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is spherical from the viewpoint of fluidity and mold wear during molding. Is preferred.
[0013]
The phthalocyanine compound as the essential component (D) is represented by the general formula (4) as a representative structure:

This is a structure in which 1 and 3 positions of 4 molecules of isoindole are bonded by 4 aza groups (—N═) to form a macrocycle. Examples of the central metal M include Fe, Ni, V, VO, Cu, Co, and the like. Among these, V and VO are preferable from the viewpoint of laser mark property. R1, R2, R3 and R4 are each independently hydrogen, thionyl chloride group, phenyl group, conjugated π-electron substituent such as naphthylazo group, alkyl group (preferably having 1 to 6 carbon atoms), alkoxy group (Preferably those having 1 to 6 carbon atoms), electron-donating substituents such as alkylthio groups (preferably having 1 to 6 carbon atoms) and the like. Among them, from the viewpoint of laser mark property, -SO2Cl, -CH3, -CH2CH2CH2CH3, etc. are preferred. The (D) phthalocyanine compound is capable of absorbing wavelengths in the vicinity of 800 nm to 1200 nm, and in particular, a compound that absorbs wavelengths of 1000 nm to 1100 nm is more preferable from the viewpoint of laser mark properties. Further, if the content of the phthalocyanine compound is less than 0.05% by weight based on the total amount of (A) the epoxy resin and (B) the curing agent, the sealability is not sufficient, and if it exceeds 15% by weight, the moldability is increased. Is insufficient, so 0.05 to 15% by weight is preferable. More preferably, it is in the range of 3.5 to 9% by weight.
[0014]
A coupling agent can be added to the epoxy resin composition for semiconductor encapsulation in the present invention.
There is no restriction | limiting in particular about a coupling agent, You may use a conventionally well-known coupling agent together with a silane coupling agent. For example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, Tiltrimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyltri Silane coupling agents such as methoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, or isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) Titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (di (Cutylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) One or more titanate coupling agents such as titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate can be used in combination.
The coupling agent is preferably used in an amount of 3% by weight or less based on the entire epoxy resin composition for encapsulating a semiconductor in the present invention, and is preferably used in an amount of 0.1% by weight or more in order to exert its effect. .
[0015]
Moreover, a mold release agent can be added to the epoxy resin composition for semiconductor sealing in this invention.
The release agent is not particularly limited, and higher fatty acids such as carnauba wax and polyethylene wax can be used alone or in combination.
The release agent is preferably used at 10% by weight or less based on the total amount of the epoxy resin and the curing agent, and 0.5% by weight or more is preferable in order to exert the effect.
[0016]
As other additives, a colorant (carbon black or the like), a modifier (silicone, silicone rubber or the like), or an ion trapper (hydrotalcite, antimony-bismuth hydrous oxide or the like) can be used. When conductive particles such as carbon black are used in combination as a colorant, in order to achieve the object of the present invention, it is preferable to use particles having a particle size of 10 μm or more and 1% by weight or less. (A) 3 weight% or less is preferable with respect to the total amount of an epoxy resin and (B) hardening | curing agent.
[0017]
As a general method for producing a molding material using the raw materials as described above, a raw material mixture of a predetermined blending amount is sufficiently mixed by a mixer or the like, then kneaded by a hot roll, an extruder, etc., cooled, pulverized, By doing so, a molding material can be obtained.
As a method for sealing an electronic component using the epoxy resin composition obtained in the present invention, a low-pressure transfer molding method is the most common, but it can also be performed by a method such as injection molding, compression molding, or casting. .
The epoxy resin composition produced by using the above-mentioned means is excellent in laser mark property and electrical characteristics, and excellent in moldability and reliability, and can be suitably used for sealing ICs, LSIs and the like.
[0018]
【Example】
Examples of the present invention will be described below, but the present invention is not limited thereto.
Examples 1-5 Comparative Examples 1-4
First, various materials shown in Tables 1 and 2 were premixed (dry blended), then kneaded with a biaxial roll (roll surface temperature of about 80 ° C.) for 10 minutes, cooled and pulverized.
[0019]
[Table 1]

[0020]
[Table 2]

[0021]
The materials listed in Tables 1 and 2 are as follows.
Biphenyl type epoxy resin: YX-4000H, Yuka Shell Epoxy Co., Ltd. trade name Brominated epoxy resin: YDB-400, Toto Kasei Kogyo Co., Ltd. trade name Aralkyl type phenolic resin: XL-225-3L, Mitsui Chemicals, Inc. ) Trade name: Epoxy silane: A-187, Nippon Unica Co., Ltd. 1, Noda Chemical Co., Ltd. trade name polyethylene wax: PED-191, Clariant Japan Co., Ltd. trade name, phthalocyanine compound (absorbs wavelength of 800-1200 nm, in general formula (4), R1, R2, R3 and R4 Are all hydrogen, M is VO)
Carbon beads: CB-3-500), Mitsui Mining Co., Ltd. Trade name Metal complex dye: Neo Super Black C-832R, Chuo Gosei Co., Ltd. Trade name Disazo dye: Chuo Sudan Black 141, Chuo Gosei Co., Ltd. Name azine dye: Spirit Black 920, Sumitomo Chemical Co., Ltd., trade name Carbon black (particle size: 18 nm): Mitsubishi Chemical Co., Ltd. Using this sealing material, using a transfer molding machine, mold temperature 180 ° C Each test was performed under the conditions of a molding pressure of 70 kgf / cm ² and a curing time of 90 seconds. Spiral flow was measured by EMM11-66. The hot hardness was measured with a shear hardness meter.
Also, using this encapsulant, a semiconductor element is molded under the same conditions with a transfer molding machine, post-curing (175 ° C./6 h), moisture resistance, solder heat resistance, laser mark property, and electrical characteristics (leakage current). Evaluated.
The volume resistivity was measured with a volume resistance meter after setting a disk mold on a transfer press, molding a disk having a diameter of 100 mm and a thickness of 3 mm using the above-mentioned sealing material, and curing it.
The semiconductor device used for moisture resistance is an SOP-28 pin. After pretreatment of 85 ° C./85 RH% 72 hours moisture absorption + 215 ° C./90 seconds (VPS), it is left on PCT (121 ° C./2 atm) on the chip. The presence or absence of wire breakage was evaluated.
The semiconductor device used for solder heat resistance is a QFP-80 pin resin-encapsulated semiconductor device (outer dimension 20 × 14 × 2.0 mm), and the lead frame is 42 alloy material (no processing) and has a chip size of 8 × 10 mm. is there.
With respect to the resin-encapsulated semiconductor device thus obtained, the solder heat resistance was 125 ° C./24 h after baking, and after moisture absorption at 85 ° C./85 RH% for a predetermined time, 240 ° C./10 sec. The determination was made based on the crack occurrence rate of the resin-encapsulated semiconductor device.
The semiconductor device used for the laser mark property was a QFP-54 pin, the package surface was printed with a YAG laser marking device, and the mark property was evaluated visually.
[0022]
The conditions of the above YAG laser are shown below.
YAG laser wavelength: 1064 nm
Laser power: 5J
[0023]
The semiconductor device used for the electrical characteristics is the LQFP167 pin, and the presence or absence of leakage current was evaluated.
The test results are summarized in Table 3.
[0024]
[Table 3]

[0025]
【The invention's effect】
In an epoxy resin composition for encapsulating a semiconductor element mainly composed of an epoxy resin, a curing agent, a curing accelerator and an inorganic filler, a phthalocyanine-based compound having V or VO as a central metal is blended as an essential component, thereby forming a laser. A sealing material excellent in mark property, electrical property, moldability, and reliability and a semiconductor device using the same were obtained.

Claims (4)

(A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, a semiconductor which comprises as an essential component phthalocyanine compound and (E) an inorganic filler represented by (D) the following general formula (4) An epoxy resin composition for sealing .

(In the formula, M is V and VO, and R1, R2, R3, and R4 are each independently hydrogen, thionyl chloride group, phenyl group, naphthylazo group, alkyl group, alkoxy group, and alkylthio group.) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the content of the phthalocyanine compound is 0.05 to 15% by weight based on the total amount of the epoxy resin and the curing agent.   3. The epoxy resin composition for semiconductor encapsulation according to claim 1, comprising 75 to 97 wt% of an inorganic filler.   A resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition for encapsulating a semiconductor according to claim 1.