JP2001220565A - Adhesive, adherend member, semiconductor-mounting printing. wiring board provided with adhrend member and semiconductor device using the same - Google Patents

Adhesive, adherend member, semiconductor-mounting printing. wiring board provided with adhrend member and semiconductor device using the same

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Publication number
JP2001220565A
JP2001220565A JP2000180777A JP2000180777A JP2001220565A JP 2001220565 A JP2001220565 A JP 2001220565A JP 2000180777 A JP2000180777 A JP 2000180777A JP 2000180777 A JP2000180777 A JP 2000180777A JP 2001220565 A JP2001220565 A JP 2001220565A
Authority
JP
Japan
Prior art keywords
adhesive
weight
film
curing accelerator
wiring board
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000180777A
Other languages
Japanese (ja)
Other versions
JP3617417B2 (en
Inventor
Hiroko Tanaka
裕子 田中
Teiichi Inada
禎一 稲田
Yasushi Shimada
靖 島田
Hiroyuki Kuritani
弘之 栗谷
Yasushi Kamishiro
恭 神代
Kazunori Yamamoto
和徳 山本
Keiji Sumiya
圭二 住谷
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.)
Showa Denko Materials Co Ltd
Original Assignee
Hitachi 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 Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2000180777A priority Critical patent/JP3617417B2/en
Publication of JP2001220565A publication Critical patent/JP2001220565A/en
Application granted granted Critical
Publication of JP3617417B2 publication Critical patent/JP3617417B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • 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
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/2612—Auxiliary members for layer connectors, e.g. spacers
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    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Wire Bonding (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive capable of securing the pot life at 25 deg.C of three months or longer without losing the low elasticity, heat resistance and moisture resistance that are necessary at the time of mounting a semiconductor chip on a printing wiring board has a larger difference in the thermal expansion coefficient from the tip and is called an interposer for a glass epoxy substrate or flexible substrate. SOLUTION: The adhesive contains 100 pts.wt. of (1) an epoxy resin and a curing agent; 75-300 pts.wt. of (2) an epoxy group-containing acrylic copolymer, which contains 0.5-6 wt.% of glycidyl(meth)acrylate and has a Tg (a glass transition temperature) of -10 deg.C or higher and a weight-average molecular weight of 800,000 or more; and 0.1-20 pts.wt. of (3) a latent curing accelerator.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、接着剤、接着部
材、接着部材を備えた半導体搭載用配線基板及びこの接
着部材を用いて半導体チップと配線基板とを接着させた
半導体装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive, a bonding member, a wiring board for mounting a semiconductor provided with the bonding member, and a semiconductor device in which a semiconductor chip and a wiring board are bonded using the bonding member.

【０００２】[0002]

【従来の技術】近年、電子機器の発達に伴い電子部品の
搭載密度が高くなり、チップスケールパッケージやチッ
プサイズパッケージ（以下ＣＳＰと呼ぶ）と呼ばれるよ
うな半導体チップサイズとほぼ同等なサイズを有する半
導体パッケージや半導体のベアチップ実装など新しい形
式の実装方法が採用され始めている。2. Description of the Related Art In recent years, the mounting density of electronic components has increased with the development of electronic devices, and semiconductors having a size substantially equal to the size of a semiconductor chip called a chip scale package or a chip size package (hereinafter referred to as a CSP). New types of mounting methods, such as package and semiconductor bare chip mounting, are beginning to be adopted.

【０００３】半導体素子をはじめとする各種電子部品を
搭載した実装基板として最も重要な特性の一つとして信
頼性がある。その中でも、熱疲労に対する接続信頼性は
実装基板を用いた機器の信頼性に直接関係するため非常
に重要な項目である。この接続信頼性を低下させる原因
として、熱膨張係数の異なる各種材料を用いていること
から生じる熱応力が挙げられる。これは、半導体チップ
の熱膨張係数が約４ｐｐｍ／℃と小さいのに対し、電子
部品を実装する配線板の熱膨張係数が１５ｐｐｍ／℃以
上と大きいことから熱衝撃に対して熱ひずみが発生し、
その熱ひずみによって熱応力が発生するものである。従
来のＱＦＰやＳＯＰ等のリードフレームを有する半導体
パッケージを実装した基板では、リードフレームの変形
により熱応力を吸収し信頼性を保っていた。しかし、ベ
アチップ実装では、はんだボールを用いて半導体チップ
の電極と配線板の配線パッドを接続する方式やバンプと
称する小突起を作製して導電ペーストで接続する方式を
とっており、熱応力がこの接続部に集中して接続信頼性
を低下させていた。この熱応力を分散させるためにアン
ダーフィルと呼ばれる樹脂をチップと配線板の間に注入
させることが有効であることがわかっているが、実装工
程を増やし、コストアップを招いていた。また、従来の
ワイヤボンディングを用いて半導体チップの電極と配線
板の配線パッドを接続する方式もあるが、ワイヤを保護
するために封止材樹脂を被覆せねばならずやはり実装工
程を増やしていた。One of the most important characteristics of a mounting board on which various electronic components such as semiconductor elements are mounted is reliability. Among them, the connection reliability against thermal fatigue is a very important item because it is directly related to the reliability of the device using the mounting board. As a cause of reducing the connection reliability, there is a thermal stress caused by using various materials having different thermal expansion coefficients. This is because the thermal expansion coefficient of a semiconductor chip is as small as about 4 ppm / ° C., whereas the thermal expansion coefficient of a wiring board on which electronic components are mounted is as large as 15 ppm / ° C. or more, so that thermal strain is generated due to thermal shock. ,
Thermal stress is generated by the thermal strain. In a substrate on which a semiconductor package having a lead frame such as a conventional QFP or SOP is mounted, thermal stress is absorbed by deformation of the lead frame to maintain reliability. However, bare chip mounting employs a method of connecting electrodes of a semiconductor chip and wiring pads of a wiring board using solder balls, or a method of forming small protrusions called bumps and connecting them with a conductive paste. The connection reliability was reduced by focusing on the connection part. It has been found that it is effective to inject a resin called an underfill between the chip and the wiring board in order to disperse the thermal stress, but the number of mounting steps has been increased, resulting in an increase in cost. There is also a method of connecting the electrodes of the semiconductor chip and the wiring pads of the wiring board using conventional wire bonding, but the sealing material resin had to be coated to protect the wires, which also increased the mounting process. .

【０００４】ＣＳＰは他の電子部品と一括して実装でき
るために、日刊工業新聞社発行表面実装技術１９９７−
３号記事「実用化に入ったＣＳＰ（ファインピッチＢＧ
Ａ）のゆくえ」中の５ページ表１に示されたような各種
構造が提案されている。その中でも、インターポーザと
呼ばれる配線基板にテープやキャリア基板を用いた方式
の実用化が進んでいる。これは、前述表の中で、テセラ
社やＴＩ社などが開発している方式を含むものである。
これらはインターポーザと呼ばれる配線基板を介するた
めに、信学技報ＣＰＭ９６−１２１，ＩＣＤ９６−１６
０（１９９６−１２）「テープＢＧＡタイプＣＳＰの開
発」やシャープ技報第６６号（１９９６−１２）「チッ
プサイズパッケージ（Ｃｈｉｐ Ｓｉｚｅ Ｐａｃｋａ
ｇｅ）開発」に発表されているように優れた接続信頼性
を示している。これらのＣＳＰの半導体チップとインタ
ーポーザと呼ばれる配線基板との間には、それぞれの熱
膨張率差から生じる熱応力を低減するような接着部材が
使われる。このような接着部材には耐湿性や高温耐久性
が要求され、さらに、製造工程管理のしやすさから、フ
ィルムタイプの接着部材が求められている。Since the CSP can be mounted together with other electronic components, the surface mounting technology published by Nikkan Kogyo Shimbun, 1997-
No. 3 article “CSP (Fine-pitch BG has entered practical use)
Various structures such as those shown in Table 1 on page 5 of "A)" have been proposed. Among them, a system using a tape or a carrier substrate for a wiring substrate called an interposer has been put into practical use. This includes the methods developed by Tessera and TI in the table above.
Since these pass through a wiring board called an interposer, IEICE Technical Report CPM 96-121, ICD 96-16
0 (1996-12) "Development of Tape BGA Type CSP" and Sharp Technical Report No. 66 (1996-12) "Chip Size Package (Chip Size Package)
Ge) Development ”, it shows excellent connection reliability. An adhesive member is used between the semiconductor chip of these CSPs and a wiring board called an interposer so as to reduce the thermal stress caused by the difference in the coefficient of thermal expansion. Such adhesive members are required to have moisture resistance and high-temperature durability, and further, a film-type adhesive member is required for ease of manufacturing process control.

【０００５】フィルムタイプの接着剤は、フレキシブル
プリント配線板等で用いられており、アクリロニトリル
ブタジエンゴムを主成分とする系が多く用いられてい
る。プリント配線板関連材料として耐湿性を向上させた
ものとしては、特開昭６０−２４３１８０号公報に示さ
れるアクリル系樹脂、エポキシ樹脂、ポリイソシアネー
ト及び無機フィラーを含む接着剤があり、また特開昭６
１−１３８６８０号公報に示されるアクリル系樹脂、エ
ポキシ樹脂、分子中にウレタン結合を有する両末端が第
１級アミン化合物及び無機フィラーを含む接着剤があ
る。[0005] Film-type adhesives are used for flexible printed wiring boards and the like, and many of them use acrylonitrile-butadiene rubber as a main component. As a printed wiring board-related material having improved moisture resistance, there is an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate and an inorganic filler described in JP-A-60-243180. 6
There is an acrylic resin, an epoxy resin, and an adhesive containing a primary amine compound having a urethane bond in each molecule at both ends and a primary amine compound and an inorganic filler described in 1-1138680.

【０００６】上記の接着部材には、熱応力の緩和の作
用、耐熱性や耐湿性を有することが必要である。それに
加え、製造プロセスの上からは、半導体チップに設けら
れた電気信号を出力するための電極部分に接着剤が流出
してこないことが必要であり、かつ、配線基板に設けら
れた回路との間に空隙を残してはならない。電極部分に
接着剤が流出すると電極の接続不良が発生し、回路と接
着剤との間に空隙があると耐熱性、耐湿性の低下が起こ
りやすい。このため、接着剤のフロー量をコントロール
することが重要である。また、熱硬化性樹脂を含むフィ
ルム状接着剤は、経時変化によるフロー量や接着強度の
低下が起こりやすい。そのため、接着部材には、その可
使期間を通したフロー量や接着強度のコントロールが必
要となっている。[0006] The above-mentioned adhesive member is required to have a function of relaxing thermal stress, heat resistance and moisture resistance. In addition, from the viewpoint of the manufacturing process, it is necessary that the adhesive does not flow out to the electrode portion for outputting an electric signal provided on the semiconductor chip, and that the adhesive with the circuit provided on the wiring board is required. No gaps should be left between them. If the adhesive flows out to the electrode portion, connection failure of the electrode occurs, and if there is a gap between the circuit and the adhesive, heat resistance and moisture resistance are likely to be reduced. For this reason, it is important to control the flow amount of the adhesive. Further, in the case of a film adhesive containing a thermosetting resin, the flow amount and the adhesive strength are liable to decrease due to aging. Therefore, it is necessary for the adhesive member to control the flow amount and the adhesive strength throughout the usable life.

【０００７】熱硬化性樹脂を含むフィルム状接着剤は、
保管中に少しずつ硬化が進行する。また、半導体チップ
をインターポーザと呼ばれる配線基板へ実装する行程及
びパッケージ組立て等、パッケージが完成するまでの数
々の行程を経るうちに接着剤の硬化が進行する。接着剤
の取扱い性の向上や半導体チップの接続信頼性を高める
ために、接着剤の可使期間はできるだけ長い方がよい。
すなわち、可使期間が長いということは経時変化による
フロー量や接着強度の低下が少ないということであり、
フロー量や接着強度のコントロールが容易になる。従来
のフィルム状接着剤では、接着剤組成中の硬化促進剤添
加量を低減すれば可使期間を長くできたが、その場合に
は接着剤硬化時の硬化速度が遅く発泡が生じるという問
題点があった。発泡することなく可使期間を長くでき、
かつ、低弾性、耐熱性、耐湿性等を満足することができ
る接着剤が求められていた。A film adhesive containing a thermosetting resin is:
Hardening progresses little by little during storage. In addition, the curing of the adhesive proceeds during a number of steps such as mounting a semiconductor chip on a wiring board called an interposer and assembling the package until the package is completed. In order to improve the handleability of the adhesive and the connection reliability of the semiconductor chip, the usable life of the adhesive is preferably as long as possible.
In other words, a longer pot life means that there is less decrease in the flow amount and adhesive strength due to aging.
Control of flow amount and adhesive strength becomes easy. In conventional film adhesives, the service life could be extended by reducing the amount of the curing accelerator added in the adhesive composition, but in that case, the curing speed at the time of curing the adhesive was slow and foaming occurred. was there. The pot life can be extended without foaming,
Further, an adhesive capable of satisfying low elasticity, heat resistance, moisture resistance and the like has been demanded.

【０００８】また、半導体パッケージや配線に使用する
接着剤には耐熱性を向上させるため、エポキシ樹脂など
の熱硬化性を有する高分子量成分を含んでいる場合が多
い。しかし熱硬化性を有する高分子量成分は硬化に高温
と長時間を要するという欠点を抱えていた。この欠点を
解消するために、従来から熱硬化性樹脂に加えて硬化促
進剤を配合する手法が用いられてきた。しかし、硬化促
進剤を配合することによって硬化性は大幅に改善される
が、室温においても反応が進行することから、室温で保
存した場合に接着剤の流動性が変化し、製品として使用
できなくなることがあるという新たな問題が生じてい
た。この新たな問題の対策として、室温で不活性な潜在
性硬化促進剤を用いることが検討された。例えば、特開
平９−３０２３１３号公報では接着剤組成物中のエポキ
シ樹脂の硬化促進剤として、潜在性の高いイミダゾール
を使用している。しかし、潜在性硬化剤によって保存安
定性は改善されるものの、接着フィルムの製造工程にお
いては、接着剤組成物を熱処理してＢステージまで硬化
させる工程があるため、反応が一部進行した潜在性硬化
剤が室温においても活性を有するため、反応が徐々に進
行して、保存安定性が低下していることがわかった。こ
のことから、さらなる保存安定性の向上が求められてい
た。[0008] In addition, adhesives used for semiconductor packages and wirings often contain thermosetting high molecular weight components such as epoxy resins in order to improve heat resistance. However, the high molecular weight component having thermosetting properties has a disadvantage that it requires a high temperature and a long time for curing. In order to solve this drawback, a method of blending a curing accelerator in addition to a thermosetting resin has been used. However, although the curability is greatly improved by adding a curing accelerator, the reaction proceeds even at room temperature, so that when stored at room temperature, the fluidity of the adhesive changes and it cannot be used as a product A new problem has arisen. As a countermeasure for this new problem, the use of a latent curing accelerator which is inert at room temperature has been studied. For example, in JP-A-9-302313, imidazole having high potential is used as a curing accelerator for an epoxy resin in an adhesive composition. However, although the storage stability is improved by the latent curing agent, in the process of manufacturing the adhesive film, since there is a step of heat-treating the adhesive composition to the B stage, the potential of the reaction partially progressing is increased. Since the curing agent had activity even at room temperature, it was found that the reaction gradually progressed and storage stability was lowered. For this reason, further improvement in storage stability has been demanded.

【０００９】[0009]

【発明が解決しようとする課題】本発明は、ガラスエポ
キシ基板やフレキシブル基板等のインターポーザと呼ば
れる配線基板に熱膨張係数の差が大きい半導体チップを
実装する場合に必要な低弾性、耐熱性、耐湿性を損なう
ことなく２５℃における可使期間３ヶ月以上を確保する
ことができる接着剤、接着部材、この接着部材を備えた
半導体搭載用配線基板、及びこの接着部材を用いて半導
体チップと配線基板を接着させた半導体装置の提供を目
的とした。SUMMARY OF THE INVENTION The present invention provides a low elasticity, heat resistance, and moisture resistance required for mounting a semiconductor chip having a large difference in thermal expansion coefficient on a wiring board called an interposer such as a glass epoxy board or a flexible board. Adhesive, Adhesive Member, Semiconductor Mounting Wiring Board Equipped With This Adhesive Member, and Semiconductor Chip And Wiring Board Using This Adhesive Member, Which Can Ensure A Potential Life Of 3 Months Or More At 25 ° C. Without Impairing Properties The purpose of the present invention is to provide a semiconductor device to which is adhered.

【００１０】接着フィルムの製造工程では、塗工乾燥炉
で高温で熱処理する工程において硬化促進剤の反応が一
部進行するため、室温で保管している際にも硬化促進剤
が分解するなどして活性を有しており、それが潜在性硬
化促進剤であっても同様である。特に、フィルム中の架
橋性高分子成分の反応性が高いため、それらが架橋し、
流動性が大きく変化し、保存安定性が低下することが解
った。本発明は、この問題を鑑み、保存安定性に優れた
接着フィルムの製造に用いる接着剤を提供するものであ
る。In the production process of the adhesive film, the reaction of the curing accelerator partially proceeds in the step of heat treatment at a high temperature in a coating and drying furnace, so that the curing accelerator is decomposed even when stored at room temperature. The same applies even if it is a latent curing accelerator. In particular, because of the high reactivity of the crosslinkable polymer components in the film, they crosslink,
It was found that the fluidity greatly changed and the storage stability decreased. The present invention has been made in view of the above problems, and provides an adhesive used for producing an adhesive film having excellent storage stability.

【００１１】[0011]

【課題を解決するための手段】本発明は、次のものに関
する。 １． （１）エポキシ樹脂及びその硬化剤１００重量
部、（２）グリシジル（メタ）アクリレート０．５〜６
重量％を含むＴｇ（ガラス転移温度）が−１０℃以上で
かつ重量平均分子量が１０万以上であるエポキシ基含有
アクリル共重合体７５〜３００重量部、（３）潜在性硬
化促進剤０．１〜２０重量部を含有する接着剤。 ２． （１）エポキシ樹脂及びその硬化剤１００重量
部、（２）エポキシ樹脂と相溶性がありかつ重量平均分
子量が３万以上の高分子量樹脂５〜４０重量部、（３）
グリシジル（メタ）アクリレート０．５〜６重量％を含
むＴｇ（ガラス転移温度）が−１０℃以上でかつ重量平
均分子量が１０万以上であるエポキシ基含有アクリル共
重合体７５〜３００重量部、（４）潜在性硬化促進剤
０．１〜２０重量部を含有する接着剤。 ３． 潜在性硬化促進剤がアダクト型である項１又は項
２のいずれかに記載の接着剤。 ４． 潜在性硬化促進剤がアミンアダクトである項３に
記載の接着剤。 ５． 潜在性硬化促進剤がアミン−エポキシアダクトで
ある項４に記載の接着剤。 ６． 無機フィラーを、接着剤樹脂分１００体積部に対
して１〜２０体積部含む項１乃至項５のいずれかに記載
の接着剤。 ７． 無機フィラーがアルミナ、シリカ、水酸化アル
ミ、アンチモン酸化物のいずれかである項６に記載の接
着剤。 ８． 接着剤を、ＤＳＣを用いて測定した場合の全硬化
発熱量の１０〜４０％の発熱を終えた状態にした項１乃
至項７のいずれかに記載の接着剤。 ９． 残存溶媒量が５重量％以下である項１乃至項８の
いずれかに記載の接着剤。 １０． 動的粘弾性測定装置を用いて測定した場合の接
着剤硬化物の貯蔵弾性率が２５℃で２０〜２０００ＭＰ
ａであり、２６０℃で３〜５０ＭＰａである項１乃至項
９のいずれかに記載の接着剤。 １１． Ｂステージ状態で相分離する２種類の樹脂及び
硬化剤、硬化促進剤を必須成分とする接着剤組成物であ
り、Ｂステージ状態において硬化促進剤が分散相に相溶
性を有し、連続相とは相分離することを特徴とする接着
剤。 １２． Ｂステージ状態で、分散相がエポキシ樹脂及び
硬化剤を主成分とする相となり、連続相が重量平均分子
量１０万以上の高分子量成分を主成分とする相となるこ
とを特徴とする項１１記載の接着剤。 １３． 重量平均分子量１０万以上の高分子量成分がグ
リシジルメタクリレート又はグリシジルアクリレート２
〜６重量％を含むアクリル系共重合体であることを特徴
とする項２記載の接着剤。 １４． 硬化促進剤がエポキシアミンアダクト化合物で
ある項１１乃至項１３いずれかに記載の接着剤。 １５． 項１乃至項１４のいずれかに記載の接着剤をキ
ャリアフィルム上に形成して得られるフィルム状の接着
部材。 １６． 項１乃至項１４のいずれかに記載の接着剤をコ
ア材の両面に形成して得られる接着部材。 １７． コア材が耐熱性熱可塑フィルムである項１６に
記載の接着部材。 １８． 耐熱性熱可塑フィルム材料の軟化点が２６０℃
以上である項１７に記載の接着部材。 １９． コア材または耐熱性熱可塑フィルムが多孔質フ
ィルムである項１７又は項１８のいずれかに記載の接着
部材。 ２０． 耐熱性熱可塑フィルムが液晶ポリマである項１
７乃至項１９のいずれかに記載の接着部材。 ２１． 耐熱性熱可塑フィルムがポリアミドイミド、ポ
リイミド、ポリエーテルイミドまたはポリエーテルスル
ホンのいずれかである項１７乃至項２０のいずれかに記
載の接着部材。 ２２． 耐熱性熱可塑フィルムがポリテトラフルオロエ
チレン、エチレンテトラフルオロエチレンコポリマー、
テトラフルオロエチレン−ヘキサフルオロプロピレンコ
ポリマー、テトラフルオロエチレン−パーフルオロアル
キルビニルエーテルコポリマーのいずれかである項１７
乃至項２０のいずれかに記載の接着部材。 ２３． 配線基板の半導体チップ搭載面に項１５乃至項
２２のいずれかに記載の接着部材を備えた半導体搭載用
配線基板。 ２４． 半導体チップと配線基板を項１５乃至項２２の
いずれかに記載の接着部材を用いて接着させた半導体装
置。 ２５． 半導体チップの面積が、配線基板の面積の７０
％以上である半導体チップと配線基板を項１５乃至項２
２のいずれかに記載の接着部材を用いて接着させた半導
体装置。The present invention relates to the following. 1. (1) 100 parts by weight of an epoxy resin and its curing agent, (2) glycidyl (meth) acrylate 0.5 to 6
75 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of −10 ° C. or more and a weight average molecular weight of 100,000 or more containing 3% by weight, (3) a latent curing accelerator 0.1 An adhesive containing up to 20 parts by weight. 2. (1) 100 parts by weight of an epoxy resin and its curing agent, (2) 5 to 40 parts by weight of a high molecular weight resin compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more, (3)
75 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 100,000 or more containing 0.5 to 6% by weight of glycidyl (meth) acrylate, 4) An adhesive containing 0.1 to 20 parts by weight of a latent curing accelerator. 3. Item 3. The adhesive according to Item 1 or 2, wherein the latent curing accelerator is an adduct type. 4. Item 4. The adhesive according to Item 3, wherein the latent curing accelerator is an amine adduct. 5. Item 5. The adhesive according to item 4, wherein the latent curing accelerator is an amine-epoxy adduct. 6. Item 6. The adhesive according to any one of Items 1 to 5, wherein the inorganic filler contains 1 to 20 parts by volume with respect to 100 parts by volume of the adhesive resin component. 7. Item 7. The adhesive according to item 6, wherein the inorganic filler is any of alumina, silica, aluminum hydroxide, and antimony oxide. 8. Item 8. The adhesive according to any one of Items 1 to 7, wherein the adhesive has been heated to 10 to 40% of the total curing calorific value when measured using DSC. 9. Item 9. The adhesive according to any one of Items 1 to 8, wherein the amount of the residual solvent is 5% by weight or less. 10. Storage elastic modulus of the cured adhesive when measured using a dynamic viscoelasticity measuring device is 20 to 2000MP at 25 ° C.
Item a. The adhesive according to any one of Items 1 to 9, which is 3 to 50 MPa at 260 ° C. 11. An adhesive composition comprising two kinds of resins and a curing agent, which are phase-separated in a B-stage state, and a curing accelerator as essential components. In the B-stage state, the curing accelerator has compatibility with a dispersed phase, and has a Is an adhesive characterized by phase separation. 12. Item 11. In the B-stage state, the dispersed phase becomes a phase mainly containing an epoxy resin and a curing agent, and the continuous phase becomes a phase mainly containing a high molecular weight component having a weight average molecular weight of 100,000 or more. Glue. 13. A high molecular weight component having a weight average molecular weight of 100,000 or more is glycidyl methacrylate or glycidyl acrylate 2
Item 3. The adhesive according to item 2, which is an acrylic copolymer containing from 6 to 6% by weight. 14． Item 14. The adhesive according to any one of Items 11 to 13, wherein the curing accelerator is an epoxyamine adduct compound. 15. Item 15. A film-like adhesive member obtained by forming the adhesive according to any one of Items 1 to 14 on a carrier film. 16. Item 15. An adhesive member obtained by forming the adhesive according to any one of Items 1 to 14 on both surfaces of a core material. 17． Item 17. The adhesive member according to Item 16, wherein the core material is a heat-resistant thermoplastic film. 18. The softening point of the heat-resistant thermoplastic film material is 260 ° C
Item 18. The adhesive member according to Item 17, which is as described above. 19. Item 19. The adhesive member according to Item 17 or 18, wherein the core material or the heat-resistant thermoplastic film is a porous film. 20. Item 1 wherein the heat-resistant thermoplastic film is a liquid crystal polymer
Item 20. The adhesive member according to any one of Items 7 to 19. 21. Item 21. The adhesive member according to any one of Items 17 to 20, wherein the heat-resistant thermoplastic film is any one of polyamideimide, polyimide, polyetherimide, and polyethersulfone. 22. Heat resistant thermoplastic film is polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer,
Item 17 which is either a tetrafluoroethylene-hexafluoropropylene copolymer or a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer
21. The adhesive member according to any one of items 20 to 20. 23. 23. A wiring board for mounting a semiconductor, comprising the adhesive member according to any one of items 15 to 22 on a semiconductor chip mounting surface of the wiring board. 24. A semiconductor device in which a semiconductor chip and a wiring board are bonded using the bonding member according to any one of Items 15 to 22. 25. The area of the semiconductor chip is 70 times the area of the wiring board.
% Or more of the semiconductor chip and the wiring substrate.
3. A semiconductor device bonded using the bonding member according to any one of 2.

【００１２】[0012]

【発明の実施の形態】本発明において使用するエポキシ
樹脂は、硬化して接着作用を呈するものであればよく、
二官能以上で、好ましくは分子量が５０００未満（例え
ば、３００以上５０００未満）、より好ましくは３００
０未満のエポキシ樹脂が使用できる。二官能エポキシ樹
脂としては、ビスフェノールＡ型またはビスフェノール
Ｆ型樹脂等が例示される。ビスフェノールＡ型またはビ
スフェノールＦ型液状樹脂は、油化シェルエポキシ株式
会社から、エピコート８０７、エピコート８２７、エピ
コート８２８という商品名で市販されている。また、ダ
ウケミカル日本株式会社からは、Ｄ．Ｅ．Ｒ．３３０、
Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．３６１という商品名
で市販されている。さらに、東都化成株式会社から、Ｙ
Ｄ８１２５、ＹＤＦ８１７０という商品名で市販されて
いる。BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin used in the present invention is only required to be cured and exhibit an adhesive action.
Bifunctional or more, preferably with a molecular weight of less than 5000 (for example, 300 or more and less than 5000), more preferably 300
Less than zero epoxy resin can be used. Examples of the bifunctional epoxy resin include a bisphenol A type or bisphenol F type resin. The bisphenol A type or bisphenol F type liquid resin is commercially available from Yuka Shell Epoxy Co., Ltd. under the trade names of Epikote 807, Epikote 827 and Epikote 828. In addition, Dow Chemical Japan Co., Ltd. E. FIG. R. 330,
D. E. FIG. R. 331; E. FIG. R. 361. Furthermore, from Toto Kasei Co., Ltd.,
It is commercially available under the trade names D8125 and YDF8170.

【００１３】エポキシ樹脂としては、高Ｔｇ化を目的に
多官能エポキシ樹脂を加えてもよく、多官能エポキシ樹
脂としては、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等が例示される。フ
ェノールノボラック型エポキシ樹脂は、日本化薬株式会
社から、ＥＰＰＮ−２０１という商品名で市販されてい
る。クレゾールノボラック型エポキシ樹脂は、住友化学
工業株式会社から、ＥＳＣＮ−１９０、ＥＳＣＮ−１９
５という商品名で市販されている。また、前記日本化薬
株式会社から、ＥＯＣＮ１０１２、ＥＯＣＮ１０２５、
ＥＯＣＮ１０２７という商品名で市販されている。さら
に、前記東都化成株式会社から、ＹＤＣＮ７０１、ＹＤ
ＣＮ７０２、ＹＤＣＮ７０３、ＹＤＣＮ７０４という商
品名で市販されている。As the epoxy resin, a polyfunctional epoxy resin may be added for the purpose of increasing Tg. Examples of the polyfunctional epoxy resin include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. The phenol novolak epoxy resin is commercially available from Nippon Kayaku Co., Ltd. under the trade name EPPN-201. Cresol novolak type epoxy resin was obtained from Sumitomo Chemical Co., Ltd., ESCN-190, ESCN-19.
It is commercially available under the trade name 5. Further, from the Nippon Kayaku Co., Ltd., EOCN1012, EOCN1025,
It is commercially available under the trade name EOCN1027. In addition, YDCN701, YDN
It is commercially available under the trade names CN702, YDCN703, and YDCN704.

【００１４】エポキシ樹脂の硬化剤は、エポキシ樹脂の
硬化剤として通常用いられているものを使用でき、アミ
ン、ポリアミド、酸無水物、ポリスルフィッド、三弗化
硼素及びフェノール性水酸基を１分子中に２個以上有す
る化合物であるビスフェノールＡ、ビスフェノールＦ、
ビスフェノールＳ等が挙げられる。特に吸湿時の耐電食
性に優れるためフェノール樹脂であるフェノールノボラ
ック樹脂、ビスフェノールノボラック樹脂、クレゾール
ノボラック樹脂等を用いるのが好ましい。 このような
好ましいとした硬化剤は、大日本インキ化学工業株式会
社から、フェノールノボラック樹脂は、バーカムＴＤ２
０９０，バーカムＴＤ２１３１、プライオーフェンＬＦ
２８８２という商品名で、ビスフェノールノボラック樹
脂はフェノライトＬＦ２８８２、フェノライトＬＦ２８
２２、フェノライトＴＤ−２０９０、フェノライトＴＤ
−２１４９、フェノライトＶＨ４１５０、フェノライト
ＶＨ４１７０という商品名で市販されている。フェノー
ルノボラック樹脂、ビスフェノールノボラック樹脂また
はクレゾールノボラック樹脂としては、例えば、重量平
均分子量が５００〜２０００のものが好ましく、特に７
００〜１４００のものが好ましく用いられる。硬化剤
は、エポキシ樹脂のエポキシ基１当量に対して、硬化剤
のエポキシ基との反応基が０．６〜１．４当量使用する
ことが好ましく、０．８〜１．２当量使用することが好
ましい。硬化剤が少なすぎたり多すぎると耐熱性が低下
する傾向がある。As the curing agent for the epoxy resin, those usually used as curing agents for the epoxy resin can be used, and amine, polyamide, acid anhydride, polysulfide, boron trifluoride and phenolic hydroxyl group can be used in one molecule. Bisphenol A, bisphenol F,
Bisphenol S etc. are mentioned. In particular, it is preferable to use a phenol resin such as a phenol novolak resin, a bisphenol novolak resin, a cresol novolak resin, etc. because of its excellent electric corrosion resistance during moisture absorption. Such preferred curing agents are available from Dainippon Ink and Chemicals, Inc., and phenol novolak resins are available from Barcam TD2.
090, Barcam TD2131, Plyofen LF
Under the trade name of 2882, bisphenol novolak resins are phenolite LF2882 and phenolite LF28
22, phenolite TD-2090, phenolite TD
-2149, phenolite VH4150 and phenolite VH4170. As the phenol novolak resin, bisphenol novolak resin or cresol novolak resin, for example, those having a weight average molecular weight of 500 to 2,000 are preferable, and
Those having a size of from 00 to 1400 are preferably used. As for the curing agent, it is preferable to use 0.6 to 1.4 equivalents of the reactive group with the epoxy group of the curing agent per 1 equivalent of the epoxy group of the epoxy resin, and to use 0.8 to 1.2 equivalents. Is preferred. If the amount of the curing agent is too small or too large, the heat resistance tends to decrease.

【００１５】エポキシ樹脂と相溶性がありかつ重量平均
分子量が３万以上の高分子量樹脂としては、フェノキシ
樹脂、高分子量エポキシ樹脂、超高分子量エポキシ樹
脂、極性の大きい官能基含有ゴム、極性の大きい官能基
含有反応性ゴムなどが挙げられる。Ｂステージにおける
接着剤のタック性の低減や硬化時の可撓性を向上させる
ため重量平均分子量が３万以上とされる。エポキシ樹脂
と相溶性がありかつ重量平均分子量が３万以上の高分子
量樹脂は、重量平均分子量が５０万以下が好ましく、３
万〜１０万であることがさらに好ましい。この樹脂の分
子量が大きすぎると樹脂流動性が低下する。前記極性の
大きい官能基含有反応性ゴムは、アクリルゴムにカルボ
キシル基のような極性が大きい官能基を付加したゴムが
挙げられる。ここで、エポキシ樹脂と相溶性があると
は、硬化後にエポキシ樹脂と分離して二つ以上の相に分
かれることなく、均質混和物を形成する性質を言う。エ
ポキシ樹脂と相溶性がありかつ重量平均分子量が３万以
上の高分子量樹脂の配合量は、エポキシ樹脂と硬化剤の
合計量１００重量部に対して、エポキシ樹脂を主成分と
する相（以下エポキシ樹脂相という）の可撓性の不足、
タック性の低減やクラック等による絶縁性の低下を防止
するため５重量部以上、エポキシ樹脂相のＴｇの低下を
防止するため４０重量部以下とされ、好ましくは１０〜
２０重量部とされる。フェノキシ樹脂は、東都化成株式
会社から、フェノトートＹＰ−４０、フェノトートＹＰ
−５０という商品名で市販されている。また、フェノキ
シアソシエート社から、ＰＫＨＣ、ＰＫＨＨ、ＰＫＨＪ
いう商品名で市販されている。高分子量エポキシ樹脂
は、分子量が３万〜８万の高分子量エポキシ樹脂、さら
には、分子量が８万を超える超高分子量エポキシ樹脂
（特公平７−５９６１７号、特公平７−５９６１８号、
特公平７−５９６１９号、特公平７−５９６２０号、特
公平７−６４９１１号、特公平７−６８３２７号公報参
照）があり、何れも日立化成工業株式会社で製造してい
る。極性の大きい官能基含有反応性ゴムとして、カルボ
キシル基含有アクリルゴムは、帝国化学産業株式会社か
ら、ＨＴＲ−８６０Ｐという商品名で市販されている。The high molecular weight resin compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more includes a phenoxy resin, a high molecular weight epoxy resin, an ultrahigh molecular weight epoxy resin, a highly polar functional group-containing rubber, and a highly polar resin. And functional group-containing reactive rubber. The weight average molecular weight is set to 30,000 or more in order to reduce the tackiness of the adhesive in the B stage and improve the flexibility at the time of curing. A high molecular weight resin having a weight average molecular weight of 30,000 or more, which is compatible with the epoxy resin, preferably has a weight average molecular weight of 500,000 or less.
More preferably, it is 10,000 to 100,000. If the molecular weight of this resin is too large, the resin fluidity will decrease. Examples of the highly polar functional group-containing reactive rubber include a rubber obtained by adding a highly polar functional group such as a carboxyl group to an acrylic rubber. Here, “compatible with the epoxy resin” refers to a property of forming a homogeneous mixture without being separated from the epoxy resin and being separated into two or more phases after curing. The compounding amount of the high molecular weight resin compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more is determined based on the total amount of the epoxy resin and the curing agent, 100 parts by weight, relative to the phase containing the epoxy resin as a main component Lack of flexibility)
It is at least 5 parts by weight in order to prevent a decrease in tackiness and insulation properties due to cracks, etc., and up to 40 parts by weight in order to prevent a decrease in Tg of the epoxy resin phase, and preferably 10 to 10 parts by weight.
20 parts by weight. Phenoxy resin is available from Toto Kasei Co., Ltd. as phenothoto YP-40, phenototo YP
It is marketed under the trade name -50. Phenoxy Associates also provided PKHC, PKHH, PKHJ
It is marketed under the trade name. The high molecular weight epoxy resin is a high molecular weight epoxy resin having a molecular weight of 30,000 to 80,000, and an ultrahigh molecular weight epoxy resin having a molecular weight exceeding 80,000 (Japanese Patent Publication No. 7-59617, Japanese Patent Publication No. 7-59618,
Japanese Patent Publication No. 7-59619, Japanese Patent Publication No. 7-59620, Japanese Patent Publication No. 7-64911 and Japanese Patent Publication No. 7-68327), all of which are manufactured by Hitachi Chemical Co., Ltd. As a highly polar functional group-containing reactive rubber, a carboxyl group-containing acrylic rubber is commercially available from Teikoku Chemical Industry Co., Ltd. under the trade name of HTR-860P.

【００１６】グリシジル（メタ）アクリレート０．５〜
６重量％を含むＴｇが−１０℃以上でかつ重量平均分子
量が１０万以上であるエポキシ基含有アクリル共重合体
は、帝国化学産業株式会社から市販されている商品名Ｈ
ＴＲ−８６０Ｐ−３を使用することができる。官能基モ
ノマーが、カルボン酸タイプのアクリル酸や、水酸基タ
イプのヒドロキシメチル（メタ）アクリレートを用いる
と、架橋反応が進行しやすく、ワニス状態でのゲル化、
Ｂステージ状態での硬化度の上昇による接着力の低下等
の問題があるため好ましくない。また、官能基モノマー
として用いるグリシジル（メタ）アクリレートの量は、
０．５〜６重量％の共重合体比とする。耐熱性を確保す
るため、０．５重量％以上とし、ゴム添加量を低減し、
ワニス固形分比を上げるために６重量％以下とされる。
６重量％を超えた場合には、接着剤硬化物の弾性率を低
減させるために多量のエポキシ基含有アクリル共重合体
が必要となる。エポキシ基含有アクリル共重合体は分子
量が高いため、重量比率が高くなると接着剤ワニスの粘
度が上昇する。このワニス粘度が高いと、フィルム化が
困難になるため、粘度低下を目的に適量の溶剤で希釈す
る。この場合、接着剤ワニスの固形分が低下し、接着剤
ワニス作製量が増大し、製造の効率が低下する問題が発
生する。グリシジル（メタ）アクリレート以外の残部
は、メチルアクリレート、メチルメタクリレートなどの
炭素数１〜８のアルキル基をもつアルキルアクリレート
又はアルキルメタクリレート、およびこれらとスチレン
やアクリロニトリルなどとの混合物を用いることができ
る。これらの混合比率は、共重合体のＴｇを考慮して決
定する。Ｔｇが−１０℃未満であるとＢステージ状態で
の接着フィルムのタック性が大きくなり取扱性が悪化す
るので、−１０℃以上とされる。このＴｇは４０℃以下
であることが好ましく、さらに、−１０℃〜２０℃が好
ましい。このＴｇが高すぎるとフィルムの取り扱い時室
温で破断しやすくなる。重合方法はパール重合、溶液重
合等が挙げられ、これらにより得ることができる。例え
ば、（ａ）アクリロニトリル１８〜４０重量％、（ｂ）
グリシジル（メタ）アクリレート０．５〜６重量％及び
（ｃ）エチルアクリレート、エチルメタクリレート、ブ
チルアクリレート又はブチルメタクリレート５４〜８０
重量％を共重合させて得られる共重合体が好適である。
エポキシ基含有アクリル共重合体の重量平均分子量は、
１０万以上とされ、特に８０万以上であることが好まし
い。この範囲では、シート状、フィルム状での強度や可
撓性の低下やタック性の増大が少ないからである。ま
た、分子量が大きくなるにつれフロー性が小さく配線の
回路充填性が低下してくるので、エポキシ基含有アクリ
ル共重合体の重量平均分子量は、２００万以下であるこ
とが好ましい。上記エポキシ基含有アクリル共重合体配
合量は、エポキシ樹脂と硬化剤の合計量１００重量部に
対して、弾性率低減や成形時のフロー性抑制のため７５
重量部以上とされ、エポキシ基含有アクリル共重合体の
配合量が増えると、ゴム成分の相が多くなり、エポキシ
樹脂相が少なくなるため、高温での取扱性の低下が起こ
るため、３００重量部以下とされることが好ましく、さ
らに、１００〜２５０重量部とされることが好ましい。Glycidyl (meth) acrylate 0.5 to
An epoxy group-containing acrylic copolymer having a Tg of not less than −10 ° C. and a weight average molecular weight of not less than 100,000 containing 6% by weight is a trade name H commercially available from Teikoku Chemical Industry Co., Ltd.
TR-860P-3 can be used. When the functional group monomer uses carboxylic acid type acrylic acid or hydroxyl group type hydroxymethyl (meth) acrylate, the crosslinking reaction proceeds easily, and gelation in a varnish state occurs.
It is not preferable because there is a problem such as a decrease in adhesive strength due to an increase in the degree of curing in the B-stage state. The amount of glycidyl (meth) acrylate used as the functional group monomer is
The copolymer ratio is 0.5 to 6% by weight. In order to ensure heat resistance, the content is set to 0.5% by weight or more, and the amount of rubber added is reduced.
In order to increase the varnish solid content ratio, the content is set to 6% by weight or less.
If it exceeds 6% by weight, a large amount of epoxy group-containing acrylic copolymer is required to reduce the elastic modulus of the cured adhesive. Since the epoxy group-containing acrylic copolymer has a high molecular weight, as the weight ratio increases, the viscosity of the adhesive varnish increases. If the varnish viscosity is high, it becomes difficult to form a film, and the varnish is diluted with an appropriate amount of a solvent for the purpose of decreasing the viscosity. In this case, the solid content of the adhesive varnish decreases, the amount of the adhesive varnish produced increases, and the production efficiency decreases. As the remainder other than glycidyl (meth) acrylate, alkyl acrylate or alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and methyl methacrylate, and a mixture thereof with styrene, acrylonitrile, or the like can be used. These mixing ratios are determined in consideration of the Tg of the copolymer. If the Tg is less than -10 ° C, the tackiness of the adhesive film in the B-stage state is increased and the handling property is deteriorated. This Tg is preferably 40 ° C or lower, and more preferably -10 ° C to 20 ° C. If the Tg is too high, the film tends to break at room temperature during handling. Examples of the polymerization method include pearl polymerization, solution polymerization, and the like, which can be obtained. For example, (a) 18 to 40% by weight of acrylonitrile, (b)
Glycidyl (meth) acrylate 0.5 to 6% by weight and (c) ethyl acrylate, ethyl methacrylate, butyl acrylate or butyl methacrylate 54 to 80
Copolymers obtained by copolymerizing weight% are preferred.
The weight average molecular weight of the epoxy group-containing acrylic copolymer,
It is 100,000 or more, and particularly preferably 800,000 or more. This is because in this range, the strength and flexibility of the sheet or film are not significantly reduced and the tackiness is not increased. Further, since the flowability decreases and the circuit filling property of the wiring decreases as the molecular weight increases, the weight average molecular weight of the epoxy group-containing acrylic copolymer is preferably 2,000,000 or less. The amount of the epoxy group-containing acrylic copolymer is 75 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the curing agent for the purpose of reducing the elastic modulus and suppressing the flowability during molding.
When the amount of the epoxy group-containing acrylic copolymer is increased, the rubber component phase increases and the epoxy resin phase decreases, which causes a decrease in handleability at high temperatures. The content is preferably as follows, and more preferably 100 to 250 parts by weight.

【００１７】潜在性硬化促進剤とは、接着剤の硬化温度
での反応速度を維持したまま室温における反応速度を極
めて低くできる硬化促進剤のことであり、室温ではエポ
キシ樹脂に不溶の固体の硬化促進剤で、加熱することで
可溶化し促進剤として機能するものである。本発明に用
いられる潜在性硬化促進剤としては、従来から提案され
ている潜在性硬化剤を用いることができ、その代表例と
してはジシアンジミド、アジピン酸ジヒドラジド等のジ
ヒドラジド化合物、グアナミン酸、メラミン酸、エポキ
シ化合物とイミダゾールの化合物との付加化合物、エポ
キシ化合物とジアルキルアミン類との付加化合物、アミ
ンと尿素、チオ尿素又はこれらの誘導体との付加化合物
（アミン−ウレイドアダクト系潜在性硬化促進剤）、ア
ミンとイソシアネートとの付加化合物（アミン−ウレタ
ンアダクト系潜在性硬化促進剤）が挙げられるが、これ
らに限定されるものではない。室温での活性を低減でき
る点でアダクト型の構造をとっているものが好ましい。
アダクト型の構造とは、触媒活性を有する化合物と種々
の化合物を反応させて得られる付加化合物のことであ
り、触媒活性を有する化合物がイミダゾール化合物や
１，２，３，級アミノ基を有する化合物などのアミン類
であればアミンアダクト型という。さらに、アダクトし
ている化合物の種類によりアミン−エポキシアダクト
系、アミン−ウレイドアダクト系、アミン−ウレタンア
ダクト系等がある。硬化時に発泡せず、かつ低弾性を有
し、耐熱性、耐湿性が良好な接着剤硬化物を得られる点
でアミン−エポキシアダクト系が最も好ましい。さらに
エポキシ化合物が長鎖であるものが潜在性がより高く優
れている。The latent curing accelerator is a curing accelerator capable of extremely lowering the reaction rate at room temperature while maintaining the reaction rate at the curing temperature of the adhesive. An accelerator which is solubilized by heating and functions as an accelerator. As the latent curing accelerator used in the present invention, a latent curing agent conventionally proposed can be used, and typical examples thereof include dicyandiimide, dihydrazide compounds such as adipic dihydrazide, guanamic acid, melamic acid, Addition compound of epoxy compound and imidazole compound, addition compound of epoxy compound and dialkylamines, addition compound of amine with urea, thiourea or derivatives thereof (amine-ureido adduct latent curing accelerator), amine And an isocyanate-added compound (amine-urethane adduct-based latent curing accelerator), but are not limited thereto. Those having an adduct-type structure are preferable in that the activity at room temperature can be reduced.
An adduct-type structure is an addition compound obtained by reacting a compound having catalytic activity with various compounds, and the compound having catalytic activity is an imidazole compound or a compound having a 1,2,3, -class amino group. Such amines are called amine adduct type. Further, there are an amine-epoxy adduct system, an amine-ureido adduct system, an amine-urethane adduct system, and the like, depending on the type of the adduct. The amine-epoxy adduct system is most preferable in that an adhesive cured product that does not foam during curing, has low elasticity, and has good heat resistance and moisture resistance can be obtained. Further, those having a long chain of the epoxy compound have higher potential and are superior.

【００１８】本発明に用いられるアミン−エポキシアダ
クト系潜在性硬化促進剤とは、室温ではエポキシ樹脂に
不溶性の固体で、加熱することで可溶化し促進剤として
機能する、アミン類とエポキシ化合物を反応させて得ら
れる付加物であり、これらの付加物の表面をイソシアネ
ート化合物や酸性化合物で処理したもの等も含まれる。The amine-epoxy adduct latent curing accelerator used in the present invention is a solid which is insoluble in an epoxy resin at room temperature, is solubilized by heating, and functions as an accelerator. These are adducts obtained by the reaction, and include those obtained by treating the surfaces of these adducts with isocyanate compounds or acidic compounds.

【００１９】アミン−エポキシアダクト系潜在性硬化促
進剤の製造原料として用いられるエポキシ化合物として
は、例えば、ビスフェノールＡ、ビスフェノールＦ、カ
テコール、レゾルシノール等の多価フェノール、または
グリセリンやポリエチレングリコール等の多価アルコー
ルとエピクロルヒドリンを反応させて得られるポリグリ
シジルエーテル、あるいはｐ−ヒドロキシ安息香酸、β
−ヒドロキシナフトエ酸等のヒドロキシカルボン酸とエ
ピクロルヒドリンを反応させて得られるグリシジルエー
テルエステル、あるいはフタル酸、テレフタル酸等のポ
リカルボン酸とエピクロルヒドリンを反応させて得られ
るポリグリシジルエステル、あるいは４，４'−ジアミ
ノジフェニルメタンやｍ−アミノフェノールなどとエピ
クロルヒドリンを反応させて得られるグリシジルアミン
化合物、さらにはエポキシ化フェノールノボラック樹
脂、エポキシ化クレゾールノボラック樹脂、エポキシ化
ポリオレフィン等の多官能性エポキシ化合物や、ブチル
グリシジルエーテル、フェニルグリシジルエーテル、グ
リシジルメタクリレート等の単官能性エポキシ化合物等
が挙げられるが、これらに限定されるものではない。Examples of the epoxy compound used as a raw material for producing the amine-epoxy adduct latent curing accelerator include polyphenols such as bisphenol A, bisphenol F, catechol and resorcinol, and polyhydric phenols such as glycerin and polyethylene glycol. Polyglycidyl ether obtained by reacting alcohol and epichlorohydrin, or p-hydroxybenzoic acid, β
A glycidyl ether ester obtained by reacting a hydroxycarboxylic acid such as hydroxynaphthoic acid with epichlorohydrin, or a polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin, or 4,4′- Glycidylamine compounds obtained by reacting epichlorohydrin with diaminodiphenylmethane or m-aminophenol, furthermore, epoxidized phenol novolak resins, epoxidized cresol novolak resins, polyfunctional epoxy compounds such as epoxidized polyolefins, butyl glycidyl ether, Examples include, but are not limited to, monofunctional epoxy compounds such as phenylglycidyl ether and glycidyl methacrylate.

【００２０】アミン−エポキシアダクト系潜在性硬化促
進剤の製造原料として用いられるアミン類は、エポキシ
基と付加反応しうる活性水素を分子内に１個以上有し、
かつ１級アミノ基、２級アミノ基、３級アミノ基の中か
ら選ばれた置換基を分子内に少なくとも１個以上有する
ものであれば良い。このようなアミン類としては、例え
ば、ジエチレントリアミン、トリエチレンテトラミン、
ｎ−プロピルアミン、２−ヒドロキシエチルアミノプロ
ピルアミン、シクロヘキシルアミン、４，４'−ジアミ
ノ−ジシクロヘキシルメタン、の等の脂肪族アミン類、
４，４'−ジアミノジフェニルメタン、２−メチルアニ
リン等の芳香族アミン類、２−エチル−４−メチルイミ
ダゾール、２−メチルイミダゾール、２−エチル−４−
メチルイミダゾリン、２，４−ジメチルイミダゾリン、
ピペリジン、ピペラジン等の窒素含有複素環化合物等が
挙げられるが、これらに限定されるものではない。これ
らの化合物の中でも特に３級アミノ基を有する化合物は
潜在性が極めて高い硬化促進剤を与える原料であり、そ
のような化合物の例を以下に示すがこれらに限定される
ものではない。例えば、ジメチルアミノプロピルアミ
ン、ジエチルアミノプロピルアミン、ジ−ｎ−プロピル
アミノプロピルアミン、ジブチルアミノプロピルアミ
ン、ジメチルアミノエチルアミン、ジエチルアミノエチ
ルアミン、Ｎ−メチルピペラジン等のようなアミン化合
物や、２−メチルイミダゾール、２−エチルイミダゾー
ル、２−エチル−４−メチルイミダゾール、２−フェニ
ルイミダゾール等のイミダゾール化合物等のような、分
子内に３級アミノ基を有する１級もしくは２級アミン類
などがある。アミン−ウレイドアダクト系潜在性硬化促
進剤、アミン−ウレタンアダクト系潜在性硬化促進剤の
原料となるアミン化合物も同様のものが使用できる。The amines used as raw materials for producing the amine-epoxy adduct latent curing accelerator have at least one active hydrogen in the molecule capable of undergoing an addition reaction with an epoxy group.
In addition, any one having at least one substituent selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule may be used. Examples of such amines include diethylene triamine, triethylene tetramine,
aliphatic amines such as n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4′-diamino-dicyclohexylmethane,
Aromatic amines such as 4,4'-diaminodiphenylmethane, 2-methylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-
Methylimidazoline, 2,4-dimethylimidazoline,
Examples include, but are not limited to, nitrogen-containing heterocyclic compounds such as piperidine and piperazine. Among these compounds, a compound having a tertiary amino group is particularly a raw material that provides a curing accelerator having extremely high potential. Examples of such compounds are shown below, but are not limited thereto. For example, amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as -ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole. The same thing can be used for the amine compound used as a raw material of the amine-ureido adduct latent curing accelerator and the amine-urethane adduct latent curing accelerator.

【００２１】アミン−ウレタンアダクト系潜在性硬化促
進剤の原料となるイソシアネート化合物としては、トリ
レンジイソシアネート、ジフエニルメタンジイソシアネ
ート、ナフタレンジイソシアネート、キシリレンジイソ
シアネート、ジフエニルスルホンジイソシアネート、ト
リフエニルメタンジイソシアネート、へキサメチレンジ
イソシアネート、３−イソシアネートメチル−３，５，
５−トリメチルシクロヘキシルイソシアネート、３−イ
ソシアネートエチル−３，５，５一トリメチルシクロヘ
キシルイソシアネート、３−イソシアネートエチル−
３，５，５−トリエチルシクロヘキシルイソシアネー
ト、ジフエニルプロパンジイソシアネート、フエニレン
ジイソシアネート、シクロヘキシリレンジイソシアネー
ト、３，３’−ジイソシアネートジプロピルエーテル、
トリフェニルメタントリイソシアネート、ジフエニルエ
ーテル−４，４’−ジイソシアネート等のポリイソシア
ネート化合物、これらの二量体又は三量体、これらのポ
リイソシアネート化合物のトリメチロールプロパン、グ
リセリン等の多価アルコールとの付加物などがある。The isocyanate compound used as a raw material of the amine-urethane adduct latent curing accelerator includes tolylene diisocyanate, diphenyl methane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenyl sulfone diisocyanate, triphenyl methane diisocyanate, and hexane. Methylene diisocyanate, 3-isocyanatomethyl-3,5,
5-trimethylcyclohexyl isocyanate, 3-isocyanatoethyl-3,5,5-trimethylcyclohexyl isocyanate, 3-isocyanatoethyl-
3,5,5-triethylcyclohexyl isocyanate, diphenylpropane diisocyanate, phenylene diisocyanate, cyclohexylylene diisocyanate, 3,3′-diisocyanate dipropyl ether,
Polyisocyanate compounds such as triphenylmethane triisocyanate and diphenyl ether-4,4'-diisocyanate, dimers or trimers thereof, and polyisocyanate compounds with polyhydric alcohols such as trimethylolpropane and glycerin There are additional products.

【００２２】本発明に用いられるアダクト型硬化促進剤
の代表的な例を以下に示すがこれらに限定されるもので
はない。アミン−エポキシアダクト系としては、味の素
株式会社からはアミキュアＰＮ−２３、アミキュアＭＹ
−２４、アミキュアＭＹ−Ｄ、アミキュアＭＹ−Ｈ等、
エー・シー・アール株式会社からはハードナーＸ−３６
１５Ｓ、ハードナーＸ−３２９３Ｓ等、旭化成株式会社
からはノバキュアＨＸ−３７４８、ノバキュアＨＸ−３
０８８等、パシフィック アンカー ケミカルからはAn
camine ２０１４ＡＳ、Ancamine ２０１４ＦＧ等がそ
れぞれ上記の商品名で市販されている。また、アミン−
ウレイド型アダクト系としては富士化成株式会社からフ
ジキュアＦＸＥ−１０００、フジキュアＦＸＲ−１０３
０という商品名で市販されている。Representative examples of the adduct-type curing accelerator used in the present invention are shown below, but are not limited thereto. As amine-epoxy adducts, Ajinomoto Co., Ltd. has Amicure PN-23 and Amicure MY.
-24, AMICURE MY-D, AMICURE MY-H, etc.
Hardner X-36 from AC R Co., Ltd.
Novacure HX-3748 and Novacure HX-3 from Asahi Kasei Corporation, such as 15S and Hardner X-3293S.
088 etc. from Pacific Anchor Chemical
Camine 2014AS, Ancamine 2014FG and the like are commercially available under the above trade names, respectively. Also, amine-
As ureide type adduct systems, Fujicure FXE-1000 and Fujicure FXR-103 are available from Fuji Kasei Co., Ltd.
It is marketed under the trade name 0.

【００２３】潜在性硬化促進剤の配合量は、エポキシ樹
脂及びその硬化剤１００重量部に対して、０．１〜２０
重量部、好ましくは１．０〜１５重量部であり、０．１
重量部未満であると硬化速度が極めて遅くなり良好な接
着剤硬化物が得られず、また２０重量部を超えると可使
期間が短くなるため不適である。The compounding amount of the latent curing accelerator is 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin and its curing agent.
Parts by weight, preferably 1.0 to 15 parts by weight,
If the amount is less than 10 parts by weight, the curing speed becomes extremely slow, so that a good cured product of the adhesive cannot be obtained.

【００２４】接着剤には、異種材料間の界面結合をよく
するために、カップリング剤を配合することもできる。
カップリング剤としては、シラン系カップリング剤、チ
タネート系カップリング剤、アルミニウム系カップリン
グ剤が挙げられ、その中でもシランカップリング剤が好
ましい。シランカップリング剤としては、γ−グリシド
キシプロピルトリメトキシシラン、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−ウレイド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
トキシシラン等が挙げられる。前記したシランカップリ
ング剤は、γ−グリシドキシプロピルトリメトキシシラ
ンがＮＵＣ Ａ−１８７、γ−メルカプトプロピルトリ
メトキシシランがＮＵＣ Ａ−１８９、γ−アミノプロ
ピルトリエトキシシランがＮＵＣ Ａ−１１００、γ−
ウレイドプロピルトリエトキシシランがＮＵＣ Ａ−１
１６０、Ｎ−β−アミノエチル−γ−アミノプロピルト
リメトキシシランがＮＵＣ Ａ−１１２０という商品名
で、いずれも日本ユニカ−株式会社から市販されてい
る。カップリング剤の配合量は、添加による効果や耐熱
性およびコストから、樹脂１００重量部に対し０．１〜
１０重量部を配合するのが好ましい。A coupling agent may be added to the adhesive in order to improve the interfacial bonding between different materials.
Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. Among them, the silane coupling agent is preferable. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ- Aminopropyltrimethoxysilane and the like can be mentioned. The above-mentioned silane coupling agents include NUC A-187 for γ-glycidoxypropyltrimethoxysilane, NUC A-189 for γ-mercaptopropyltrimethoxysilane, NUC A-1100 for γ-aminopropyltriethoxysilane, γ −
Ureidopropyltriethoxysilane is NUC A-1
160, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane are commercially available from Nippon Unicar Co., Ltd. under the trade name NUC A-1120. The compounding amount of the coupling agent is 0.1 to 100 parts by weight of the resin, based on the effect of the addition, heat resistance and cost.
It is preferable to add 10 parts by weight.

【００２５】さらに、イオン性不純物を吸着して、吸湿
時の絶縁信頼性をよくするために、イオン捕捉剤を配合
することができる。イオン捕捉剤の配合量は、添加によ
る効果や耐熱性、コストより、エポキシ樹脂及びその硬
化剤１００重量部に対して、１〜１０重量部が好まし
い。イオン捕捉剤としては、銅がイオン化して溶け出す
のを防止するため銅害防止剤として知られる化合物、例
えば、トリアジンチオール化合物、ビスフェノール系還
元剤を配合することもできる。ビスフェノール系還元剤
としては、２，２’−メチレン−ビス−（４−メチル−
６−第３−ブチルフェノール）、４，４’−チオ−ビス
−（３−メチル−６−第３−ブチルフェノール）等が挙
げられる。また、無機イオン吸着剤を配合することもで
きる。無機イオン吸着剤としては、ジルコニウム系化合
物、アンチモンビスマス系化合物、マグネシウムアルミ
ニウム系化合物等が挙げられる。トリアジンチオール化
合物を成分とする銅害防止剤は、三協製薬株式会社か
ら、ジスネットＤＢという商品名で市販されている。ビ
スフェノール系還元剤を成分とする銅害防止剤は、吉富
製薬株式会社から、ヨシノックスＢＢという商品名で市
販されている。また、無機イオン吸着剤は、東亜合成化
学工業株式会社からＩＸＥという商品名で各種市販され
ている。Further, in order to adsorb ionic impurities and improve insulation reliability at the time of moisture absorption, an ion scavenger can be blended. The mixing amount of the ion scavenger is preferably 1 to 10 parts by weight based on 100 parts by weight of the epoxy resin and its curing agent in view of the effect of the addition, heat resistance, and cost. As the ion scavenger, a compound known as a copper harm inhibitor, for example, a triazine thiol compound or a bisphenol-based reducing agent for preventing ionization and dissolution of copper can also be blended. As the bisphenol-based reducing agent, 2,2′-methylene-bis- (4-methyl-
6-tert-butylphenol), 4,4'-thio-bis- (3-methyl-6-tert-butylphenol) and the like. Further, an inorganic ion adsorbent can be blended. Examples of the inorganic ion adsorbent include a zirconium compound, an antimony bismuth compound, and a magnesium aluminum compound. A copper damage inhibitor containing a triazine thiol compound as a component is commercially available from Sankyo Pharmaceutical Co., Ltd. under the trade name Disnet DB. A copper damage inhibitor containing a bisphenol-based reducing agent as a component is commercially available from Yoshitomi Pharmaceutical Co., Ltd. under the trade name Yoshinox BB. Various inorganic ion adsorbents are commercially available from Toa Gosei Chemical Industry Co., Ltd. under the trade name IXE.

【００２６】さらに、本発明の接着剤には、接着剤の取
扱性の向上、熱伝導性の向上、溶融粘度の調整、チクソ
トロピック性の付与などを目的として、無機フィラーを
配合することが好ましい。無機フィラーとしては、水酸
化アルミ（水酸化アルミニウム）、水酸化マグネシウ
ム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシ
ウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグ
ネシウム、アルミナ、窒化アルミニウム、ほう酸アルミ
ウイスカ、窒化ホウ素、結晶性シリカ、非晶性シリカ、
アンチモン酸化物などが挙げられる。熱伝導性向上のた
めには、アルミナ、窒化アルミニウム、窒化ホウ素、結
晶性シリカ、非晶性シリカ等が好ましい。溶融粘度の調
整やチクソトロピック性の付与の目的には、水酸化アル
ミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸
マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウ
ム、酸化カルシウム、酸化マグネシウム、アルミナ、結
晶性シリカ、非晶性シリカ等が好ましい。また、上記に
加え耐湿性を向上させるアルミナ、シリカ、水酸化アル
ミ、アンチモン酸化物が好ましい。上記無機フィラー配
合量は、接着剤樹脂分１００体積部に対して１〜２０体
積部が好ましい。配合の効果の点から配合量が１体積部
以上、配合量が多くなると、接着剤の貯蔵弾性率の上
昇、接着性の低下、ボイド残存による電気特性の低下等
の問題を起こすので２０体積部以下とするのが好まし
い。Further, the adhesive of the present invention preferably contains an inorganic filler for the purpose of improving the handleability of the adhesive, improving the thermal conductivity, adjusting the melt viscosity, imparting thixotropic properties, and the like. . As inorganic fillers, aluminum hydroxide (aluminum hydroxide), magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, aluminum borate whisker, boron nitride, Crystalline silica, amorphous silica,
Antimony oxide and the like. For improving the thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica, Crystalline silica and the like are preferred. Further, in addition to the above, alumina, silica, aluminum hydroxide, and antimony oxide which improve moisture resistance are preferable. The amount of the inorganic filler is preferably 1 to 20 parts by volume based on 100 parts by volume of the adhesive resin component. From the viewpoint of the effect of the compounding, if the compounding amount is 1 part by volume or more and the compounding amount is large, problems such as an increase in the storage elastic modulus of the adhesive, a decrease in the adhesiveness, and a decrease in the electrical properties due to the remaining voids are caused. It is preferable to set the following.

【００２７】硬化促進剤を不連続に分散する樹脂相に選
択的に入れることにより接着剤及び接着フィルムの保存
安定性を向上できることを見出した。このためには、接
着剤は、Ｂステージ状態で相分離する２種類の樹脂及び
硬化剤、硬化促進剤を必須成分とする接着剤組成物であ
り、Ｂステージ状態において硬化促進剤が分散相に相溶
性を有し、連続相とは相分離することを特徴とする。It has been found that the storage stability of the adhesive and the adhesive film can be improved by selectively incorporating the curing accelerator into the resin phase which is discontinuously dispersed. For this purpose, the adhesive is an adhesive composition containing two kinds of resins, a curing agent, and a curing accelerator, which are phase-separated in the B-stage state, as an essential component. It has compatibility and is characterized by phase separation from the continuous phase.

【００２８】上記の分散相に使用する樹脂としてはエポ
キシ樹脂、シアネートエステル樹脂、シアネート樹脂、
シリコーン樹脂、エポキシ基やカルボキシル基などの官
能基を有するアクリルゴム、エポキシ基やカルボキシル
基などの官能基を有するブタジエンゴム、シリコーン変
性ポリアミドイミドなどの変性樹脂などが使用できる。
接着性、耐熱性が高い点でエポキシ樹脂が好ましい。エ
ポキシ樹脂としては、前記に記載したものが使用でき
る。また、エポキシ樹脂の硬化剤も前記したものが使用
できる。これらの配合割合も前記の通りである。As the resin used for the above-mentioned dispersed phase, an epoxy resin, a cyanate ester resin, a cyanate resin,
A silicone resin, an acrylic rubber having a functional group such as an epoxy group or a carboxyl group, a butadiene rubber having a functional group such as an epoxy group or a carboxyl group, or a modified resin such as a silicone-modified polyamideimide can be used.
Epoxy resins are preferred because of their high adhesiveness and heat resistance. As the epoxy resin, those described above can be used. Further, as the curing agent for the epoxy resin, those described above can be used. These mixing ratios are also as described above.

【００２９】Ｂステージ状態で上記樹脂相と相分離する
樹脂としては、アクリル酸エステルやメタクリル酸エス
テル及びアクリロニトリルなどの共重合体であるアクリ
ルゴム、スチレンやアクリロニトリルなどを含むブタジ
エンゴム、シリコーン樹脂、シリコーン変性ポリアミド
イミドなどの変性樹脂が挙げられ、前記樹脂層との組み
合わせが適宜決定される。また、重量平均分子量が１０
万以上の高分子量成分を使用した場合、フィルムとして
の取り扱い性が良好である。さらにまた、グリシジルメ
タクリレート又はグリシジルアクリレート２〜６重量％
を含むＴｇが−１０℃以上でかつ重量平均分子量が１０
万以上（特に好ましくは８０万以上）であるアクリル系
共重合体を用いた場合、接着性、耐熱性が高い点で特に
好ましい。グリシジルメタクリレート又はグリシジルア
クリレート２〜６重量％を含むＴｇが−１０℃以上でか
つ重量平均分子量が１０万以上（特に好ましくは８０万
以上）であるアクリル系共重合体としては、前記したも
のが使用できる。Examples of the resin which is phase-separated from the above resin phase in the B-stage state include acrylic rubber which is a copolymer of acrylate, methacrylate and acrylonitrile, butadiene rubber containing styrene and acrylonitrile, silicone resin, silicone A modified resin such as a modified polyamide imide is exemplified, and a combination with the resin layer is appropriately determined. Further, when the weight average molecular weight is 10
When 10,000 or more high molecular weight components are used, the handleability as a film is good. Furthermore, glycidyl methacrylate or glycidyl acrylate is 2 to 6% by weight.
Is not less than -10 ° C and the weight average molecular weight is 10
The use of an acrylic copolymer having a molecular weight of 10,000 or more (especially preferably 800,000 or more) is particularly preferable in terms of high adhesiveness and heat resistance. As the acrylic copolymer having a Tg containing glycidyl methacrylate or glycidyl acrylate of 2 to 6% by weight and having a Tg of -10 ° C or more and a weight average molecular weight of 100,000 or more (especially preferably 800,000 or more), the above-mentioned one is used it can.

【００３０】これらの樹脂相を形成する樹脂はＢステー
ジ状態で相分離する必要があり、また、一方の樹脂が不
連続に分散する分散相を形成し、他方が連続相を形成す
る必要がある。なお本発明でいうＢステージ状態とはＤ
ＳＣを用いて、硬化発熱量を測定した値が、未硬化状態
での組成物の硬化発熱量の１０〜４０％である状態であ
る。Ｂステージ状態となったときに連続相を形成する樹
脂と分散相を形成する樹脂（それぞれの相において、硬
化剤を含むときはそれを含む）は、これらの総量に対し
て連続相を形成する樹脂が２０〜８５重量％であること
が好ましい。The resins forming these resin phases need to be phase-separated in the B-stage state, and one resin must form a dispersed phase in which it is discontinuously dispersed, and the other must form a continuous phase. . The B-stage state in the present invention is D
The value obtained by measuring the calorific value of the composition using SC is 10 to 40% of the curing calorific value of the composition in the uncured state. The resin that forms the continuous phase and the resin that forms the dispersed phase when in the B-stage state (including the curing agent in each phase, if included) form a continuous phase with respect to the total amount of these. Preferably, the resin is 20-85% by weight.

【００３１】硬化促進剤はＢステージ状態で島状に不連
続に分散する分散相と相溶性を有し、海状の相とは相分
離する物質である必要がある。島状の相と同様の極性、
分子構造を有し、他方とは大きく異なる極性、分子構造
を有するものであることが好ましい。例えば島状に不連
続に分散する樹脂相がエポキシ樹脂及び硬化剤を主成分
とする相であり、もう一方の相がアクリルゴムの場合に
は、硬化促進剤はエポキシ化合物とイミダゾール化合物
との付加化合物、エポキシ化合物とジアルキルアミン類
との付加化合物などが好ましい。さらにエポキシ化合物
が長鎖であるものが特に好ましい。特に室温での活性を
低減できる点で、前記したアダクト型の構造をとってい
るものが好ましく、アミン−エポキシ付加化合物、アミ
ン−ウレイド付加化合物、アミン−ウレタン付加化合物
等がある。硬化時に発泡せず、かつ低弾性を有し、耐熱
性、耐湿性が良好な接着剤硬化物を得られる点でアミン
−エポキシ付加化合物が特に好ましい。The curing accelerator must be compatible with the dispersed phase which is discontinuously dispersed in the form of islands in the B-stage state and must be phase-separated from the sea-like phase. Polarity similar to the island phase,
Preferably, it has a molecular structure and a polarity and a molecular structure that are significantly different from the other. For example, when the resin phase that is discontinuously dispersed in an island shape is a phase containing an epoxy resin and a curing agent as main components and the other phase is an acrylic rubber, the curing accelerator is an addition of an epoxy compound and an imidazole compound. Preferred are compounds, addition compounds of epoxy compounds and dialkylamines. Further, those in which the epoxy compound has a long chain are particularly preferred. In particular, those having the adduct-type structure described above are preferable in that the activity at room temperature can be reduced, and examples thereof include an amine-epoxy adduct, an amine-ureide adduct, and an amine-urethane adduct. An amine-epoxy adduct is particularly preferred in that it does not foam during curing, has low elasticity, and provides a cured adhesive product having good heat resistance and moisture resistance.

【００３２】アミン−エポキシアダクト系潜在性硬化促
進剤、アダクト型硬化促進剤の代表的な例は、前記した
とおりのものである。Representative examples of the amine-epoxy adduct latent curing accelerator and the adduct-type curing accelerator are as described above.

【００３３】硬化促進剤（潜在性硬化促進剤を包含す
る）の配合量は好ましくは、分散相の樹脂及び硬化剤の
合計１００重量部に対して０．１〜２０重量部、より好
ましくは１．０〜１５重量部である。０．１重量部未満
であると硬化速度が遅くなる傾向にあり、また２０重量
部を超えると可使期間が短くなる傾向がある。The compounding amount of the curing accelerator (including the latent curing accelerator) is preferably from 0.1 to 20 parts by weight, more preferably from 1 to 20 parts by weight, based on 100 parts by weight of the total of the resin of the disperse phase and the curing agent. 0.0 to 15 parts by weight. If the amount is less than 0.1 part by weight, the curing rate tends to be low, and if it exceeds 20 parts by weight, the usable life tends to be short.

【００３４】硬化促進剤としては上記したアダクト型の
潜在性硬化促進剤が好ましく、その他の硬化促進剤とし
て各種イミダゾール類などを適宜併用することが好まし
く、その量は、所望の保存安定性が得られること考慮し
て決定することが好ましい。イミダゾールとしては、２
−メチルイミダゾール、２−エチル−４−メチルイミダ
ゾール、１−シアノエチル−２−フェニルイミダゾー
ル、１−シアノエチル−２−フェニルイミダゾリウムト
リメリテート等が挙げられる。イミダゾール類は、四国
化成工業株式会社から、２Ｅ４ＭＺ、２ＰＺ−ＣＮ、２
ＰＺ−ＣＳＮという商品名で市販されている。As the curing accelerator, the adduct-type latent curing accelerator described above is preferable, and various imidazoles and the like are preferably used in combination as other curing accelerators, and the amount thereof is determined so as to obtain desired storage stability. It is preferable to determine in consideration of the fact that As imidazole, 2
-Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate and the like. Imidazoles were obtained from Shikoku Chemicals Corporation in 2E4MZ, 2PZ-CN,
It is commercially available under the trade name PZ-CSN.

【００３５】このほかに、流動性の調節、耐湿性の向上
を目的に、フィラーを添加しても良い。このようなフィ
ラーとしては、シリカ、三酸化二アンチモン等がある。In addition, a filler may be added for the purpose of adjusting fluidity and improving moisture resistance. Such fillers include silica, diantimony trioxide, and the like.

【００３６】接着剤には、異種材料間の界面結合をよく
するために、カップリング剤を配合することもできる。
さらに、イオン性不純物を付着して、吸湿時の絶縁信頼
性をよくするために、イオン補足剤を配合することがで
きる。カップリング剤の使用量は、分散相と連続相のそ
れぞれを形成する樹脂成分及び硬化剤成分の総量に対し
て、０．１〜１０重量％が好ましい。イオン補足剤の使
用量は、分散相と連続相のそれぞれを形成する樹脂成分
及び硬化剤成分の総量に対して、１〜１０重量％が好ま
しい。In order to improve the interfacial bonding between different kinds of materials, a coupling agent may be added to the adhesive.
Furthermore, in order to improve the insulation reliability at the time of absorbing moisture by attaching ionic impurities, an ion supplement may be added. The amount of the coupling agent used is preferably 0.1 to 10% by weight based on the total amount of the resin component and the curing agent component forming each of the dispersed phase and the continuous phase. The use amount of the ion scavenger is preferably 1 to 10% by weight based on the total amount of the resin component and the curing agent component forming each of the dispersed phase and the continuous phase.

【００３７】硬化促進剤を不連続に分散する樹脂相に選
択的に入れることによる作用については明確ではない
が、以下のように推測される。島状の分散相に大部分の
硬化促進剤が含まれており、連続相に存在する硬化促進
剤は非常に少ない。分散相において保管中に硬化が進行
しても流動性に及ぼす影響は小さく、一方、硬化温度に
おいては、分散相から開始された反応によってできた活
性基が連続相と反応することで、連続相の硬化も進行す
ると考えられる。The effect of selectively adding the curing accelerator to the resin phase that is discontinuously dispersed is not clear, but is presumed as follows. Most of the curing accelerator is contained in the island-shaped dispersed phase, and the curing accelerator present in the continuous phase is very small. Even if curing progresses during storage in the dispersed phase, the effect on fluidity is small.On the other hand, at the curing temperature, the active group formed by the reaction started from the dispersed phase reacts with the continuous phase to form the continuous phase. It is considered that the curing of the resin also proceeds.

【００３８】本発明におけるフィルム状の接着部材は、
接着剤の各成分を溶剤に溶解ないし分散してワニスと
し、キャリアフィルム上に塗布、加熱し溶剤を除去する
ことにより、接着剤層をキャリアフィルム上に形成して
得られる。加熱温度は、１００〜１８０℃が好ましく、
１３０〜１６０℃が特に好ましい。加熱時間は適宜決定
されるが、好ましくは３〜１５分間、特に好ましくは４
〜１０分間である。この加熱による溶剤除去後の接着剤
は、ＤＳＣ（示差走査熱分析）を用いて測定した全硬化
発熱量の１０〜４０％の発熱を終えた状態とすることが
好ましい。また、フィルム状となった接着剤の残存溶媒
量は、５重量％以下であることが好ましい。キャリアフ
ィルムとしては、ポリテトラフルオロエチレンフィル
ム、ポリエチレンテレフタレートフィルム、離型処理し
たポリエチレンテレフタレートフィルム、ポリエチレン
フィルム、ポリプロピレンフィルム、ポリメチルペンテ
ンフィルム、ポリイミドフィルムなどのプラスチックフ
ィルムが使用できる。キャリアフィルムは、使用時に剥
離して接着フィルムのみを使用することもできるし、キ
ャリアフィルムとともに使用し、後で除去することもで
きる。本発明で用いるキャリアフィルムの例として、ポ
リイミドフィルムは、東レ・デュポン株式会社からカプ
トンという商品名で、鐘淵化学工業株式会社からアピカ
ルという商品名で市販されている。ポリエチレンテレフ
タレートフィルムは、東レ・デュポン株式会社からルミ
ラーという商品名で、帝人株式会社からピューレックス
という商品名で市販されている。The film-like adhesive member according to the present invention comprises:
A varnish is prepared by dissolving or dispersing each component of the adhesive in a solvent, applied to a carrier film, and heated to remove the solvent, thereby forming an adhesive layer on the carrier film. The heating temperature is preferably from 100 to 180 ° C,
130-160 ° C is particularly preferred. The heating time is appropriately determined, but is preferably 3 to 15 minutes, particularly preferably 4 to 15 minutes.
10 minutes. It is preferable that the adhesive after the removal of the solvent by heating has finished heating of 10 to 40% of the total curing calorific value measured using DSC (differential scanning calorimetry). Further, the amount of the residual solvent of the adhesive in the form of a film is preferably 5% by weight or less. As the carrier film, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a release-treated polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film can be used. The carrier film can be peeled off at the time of use to use only the adhesive film, or used together with the carrier film and removed later. As an example of the carrier film used in the present invention, a polyimide film is commercially available from Toray DuPont under the trade name Kapton and from Kanegafuchi Chemical Co., Ltd. under the trade name Apical. Polyethylene terephthalate film is commercially available from Toray DuPont under the trade name Lumirror and from Teijin Limited under the trade name Purex.

【００３９】ワニス化の溶剤は、比較的低沸点の、メチ
ルエチルケトン、アセトン、メチルイソブチルケトン、
２−エトキシエタノール、トルエン、ブチルセルソル
ブ、メタノール、エタノール、２−メトキシエタノール
などを用いるのが好ましい。また、塗膜性を向上するな
どの目的で、高沸点溶剤を加えても良い。高沸点溶剤と
しては、ジメチルアセトアミド、ジメチルホルムアミ
ド、メチルピロリドン、シクロヘキサノンなどが挙げら
れる。ワニスの製造は、無機フィラーの分散を考慮した
場合には、らいかい機、３本ロール及びビーズミル等に
より、またこれらを組み合わせて行なうことができる。
フィラーと低分子量物をあらかじめ混合した後、高分子
量物を配合することにより、混合に要する時間を短縮す
ることも可能となる。また、ワニスとした後、真空脱気
によりワニス中の気泡を除去することが好ましい。Solvents for the varnishing are relatively low boiling point methyl ethyl ketone, acetone, methyl isobutyl ketone,
It is preferable to use 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol and the like. Further, a high boiling point solvent may be added for the purpose of improving the coating properties. Examples of the high boiling point solvent include dimethylacetamide, dimethylformamide, methylpyrrolidone, cyclohexanone and the like. The production of the varnish can be carried out by a mill, a three-roll mill, a bead mill or the like, or a combination thereof, in consideration of the dispersion of the inorganic filler.
By mixing the filler and the low molecular weight material in advance and then blending the high molecular weight material, the time required for mixing can also be reduced. After the varnish is formed, it is preferable to remove bubbles in the varnish by vacuum degassing.

【００４０】フィルム状接着剤のみからなる接着部材の
厚みは、２５〜２５０μｍが好ましいが、これに限定さ
れるものではない。２５μｍよりも薄いと応力緩和効果
に乏しく、厚いと経済的でなくなる。また、複数の接着
フィルムを貼合わせることにより、所望の膜厚の接着部
材を得ることもできる。この場合には、接着フィルム同
士の剥離が発生しないような貼合わせ条件が必要であ
る。The thickness of the adhesive member composed of only the film adhesive is preferably 25 to 250 μm, but is not limited thereto. When the thickness is smaller than 25 μm, the effect of relaxing the stress is poor, and when the thickness is larger, it is not economical. In addition, by bonding a plurality of adhesive films, an adhesive member having a desired thickness can be obtained. In this case, laminating conditions are required so that peeling of the adhesive films does not occur.

【００４１】本発明の接着部材は、コア材の両面に接着
剤を形成したものであってもよい。コア材の厚みは５〜
２００μｍの範囲内であることが好ましいが、これに限
定されるものではない。コア材の両面に形成される接着
剤の厚みは、各々１０〜２００μｍの範囲が好ましい。
これより薄いと接着性や応力緩和効果に乏しく、厚いと
経済的でなくなるが、これに限定されるものではない。The adhesive member of the present invention may be one obtained by forming an adhesive on both sides of a core material. The core material thickness is 5
The thickness is preferably within the range of 200 μm, but is not limited thereto. The thickness of the adhesive formed on both surfaces of the core material is preferably in the range of 10 to 200 μm.
If it is thinner than this, the adhesiveness and stress relaxing effect are poor, and if it is thicker, it is not economical, but it is not limited to this.

【００４２】本発明でコア材に用いられるフィルムとし
ては、耐熱性ポリマまたは液晶ポリマ、フッ素系ポリマ
などを用いた耐熱性熱可塑フィルムが好ましく、ポリア
ミドイミド、ポリイミド、ポリエーテルイミド、ポリエ
ーテルスルホン、全芳香族ポリエステル、ポリテトラフ
ルオロエチレン、エチレンテトラフルオロエチレンコポ
リマー、テトラフルオロエチレン−ヘキサフルオロプロ
ピレンコポリマー、テトラフルオロエチレン−パーフル
オロアルキルビニルエーテルコポリマーなどが好適に用
いられる。また、コア材は、接着部材の弾性率低減のた
めに多孔質フィルムを用いることもできる。好ましくは
軟化点温度が２６０℃以上の特性を有するものが使用さ
れる。軟化点温度が２６０℃未満の熱可塑性フィルムを
コア材に用いた場合は、はんだリフロー時などの高温時
に接着剤との剥離を起こす場合がある。ポリイミドフィ
ルムは、宇部興産株式会社からユーピレックスという商
品名で、東レ・デュポン株式会社からカプトンという商
品名で、鐘淵化学工業株式会社からアピカルという商品
名で市販されている。ポリテトラフルオロエチレンフィ
ルムは、三井・デュポンフロロケミカル株式会社からテ
フロンという商品名で、ダイキン工業株式会社からポリ
フロンという商品名で市販されている。エチレンテトラ
フルオロエチレンコポリマーフィルムは、旭硝子株式会
社からアフロンＣＯＰという商品名で、ダイキン工業株
式会社からネオフロンＥＴＦＥという商品名で市販され
ている。テトラフルオロエチレン−ヘキサフルオロプロ
ピレンコポリマーフィルムは、三井・デュポンフロロケ
ミカル株式会社からテフロンＦＥＰという商品名で、ダ
イキン工業株式会社からネオフロンＦＥＰという商品名
で市販されている。テトラフルオロエチレン−パーフル
オロアルキルビニルエーテルコポリマーフィルムは、三
井・デュポンフロロケミカル株式会社からテフロンＰＦ
Ａという商品名で、ダイキン工業株式会社からネオフロ
ンＰＦＡという商品名で市販されている。液晶ポリマフ
ィルムは、株式会社クラレからベクトラという商品名で
市販されている。さらに、多孔質ポリテトラフルオロエ
チレンフィルムは、住友電気工業株式会社からポアフロ
ンという商品名で、ジャパンゴアテックス株式会社から
ゴアテックスという商品名で市販されている。As the film used for the core material in the present invention, a heat-resistant thermoplastic film or a heat-resistant thermoplastic film using a liquid crystal polymer, a fluorine-based polymer, or the like is preferable. Polyamide imide, polyimide, polyether imide, polyether sulfone, A wholly aromatic polyester, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and the like are suitably used. Further, as the core material, a porous film can be used to reduce the elastic modulus of the adhesive member. Preferably, those having a softening point temperature of 260 ° C. or higher are used. When a thermoplastic film having a softening point temperature of less than 260 ° C. is used as the core material, peeling from the adhesive may occur at a high temperature such as during solder reflow. The polyimide film is commercially available from Ube Industries under the trade name Upilex, from Toray Dupont under the trade name Kapton, and from Kanegabuchi Chemical Co., Ltd. under the trade name Apical. The polytetrafluoroethylene film is commercially available from Mitsui-Dupont Fluorochemicals Co., Ltd. under the trade name Teflon, and from Daikin Industries, Ltd. under the trade name Polyflon. The ethylene tetrafluoroethylene copolymer film is commercially available from Asahi Glass Co., Ltd. under the trade name AFLON COP, and from Daikin Industries, Ltd. under the trade name NEOFLON ETFE. The tetrafluoroethylene-hexafluoropropylene copolymer film is commercially available from DuPont-Mitsui Fluorochemicals Co., Ltd. under the trade name of Teflon FEP, and from Daikin Industries, Ltd. under the trade name of Neoflon FEP. Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film was purchased from Mitsui / Dupont Fluorochemicals Co., Ltd.
It is commercially available from Daikin Industries, Ltd. under the trade name NEOFLON PFA under the trade name A. Liquid crystal polymer films are commercially available from Kuraray Co., Ltd. under the trade name Vectra. Further, a porous polytetrafluoroethylene film is commercially available from Sumitomo Electric Industries, Ltd. under the trade name Poreflon, and from Japan Gore-Tex Corporation under the trade name Gore-Tex.

【００４３】コア材の両面に形成される接着剤は、接着
剤の各成分を溶剤に溶解ないし分散してワニスとするこ
とができる。このワニスをコア材となる耐熱性熱可塑フ
ィルム上に塗布、加熱し溶剤を除去することにより接着
剤層を耐熱性熱可塑フィルム上に形成することができ
る。この工程を耐熱性熱可塑フィルムの両面について行
うことにより、コア材の両面に接着剤を形成した接着部
材を作製することができる。この場合には、両面の接着
剤層同士がブロッキングしないようにカバーフィルムで
表面を保護することが望ましい。しかし、ブロッキング
が起こらない場合には、経済的な理由からカバーフィル
ムを用いないことが好ましく、制限を加えるものではな
い。また、接着剤の各成分を溶剤に溶解ないし分散して
ワニスとしたものを、前述のキャリアフィルム上に塗
布、加熱し溶剤を除去することにより接着剤層をキャリ
アフィルム上に形成し、この接着剤層をコア材の両面に
貼合わせることによりコア材の両面に接着剤を形成した
接着部材を作製することができる。この場合には、キャ
リアフィルムをカバーフィルムとして用いることもでき
る。コア材の両面に形成した接着剤は、フィルム状接着
剤のみからなる接着部材と同様、ＤＳＣを用いて測定し
た全硬化発熱量の１０〜４０％の発熱を終えた状態とす
るのが好ましい。The adhesive formed on both sides of the core material can be made into a varnish by dissolving or dispersing each component of the adhesive in a solvent. The adhesive layer can be formed on the heat-resistant thermoplastic film by applying the varnish on a heat-resistant thermoplastic film serving as a core material, heating and removing the solvent. By performing this step on both sides of the heat-resistant thermoplastic film, an adhesive member having an adhesive formed on both sides of the core material can be produced. In this case, it is desirable to protect the surface with a cover film so that the adhesive layers on both sides do not block each other. However, when blocking does not occur, it is preferable not to use a cover film for economic reasons, and there is no limitation. A varnish obtained by dissolving or dispersing each component of the adhesive in a solvent is coated on the above-mentioned carrier film, and the solvent is removed by heating to form an adhesive layer on the carrier film. By bonding the agent layer to both surfaces of the core material, an adhesive member having an adhesive formed on both surfaces of the core material can be produced. In this case, a carrier film can be used as the cover film. The adhesive formed on both surfaces of the core material is preferably in a state in which heat generation of 10 to 40% of the total curing calorific value measured using DSC has been completed, as in the case of an adhesive member composed of only a film adhesive.

【００４４】本発明の接着剤硬化物の動的粘弾性測定装
置で測定した貯蔵弾性率は、２５℃で２０〜２０００Ｍ
Ｐａ、２６０℃で３〜５０ＭＰａの低弾性率であると好
ましい。貯蔵弾性率の測定は、接着剤硬化物に引張り荷
重をかけて、周波数１０Ｈｚ、昇温速度５〜１０℃／分
で−５０℃から３００℃まで測定する温度依存性測定モ
ードで行った。貯蔵弾性率が２５℃で２０００ＭＰａを
超えるものと２６０℃で５０ＭＰａを超えるものでは、
半導体チップと配線基板であるインターポーザとの熱膨
張係数の差によって発生する熱応力を緩和させる効果が
小さくなり、剥離やクラックを発生する恐れがある。一
方、貯蔵弾性率が２５℃で２０ＭＰａ未満では接着剤の
取扱性や接着剤層の厚み精度が悪くなり、２６０℃で３
ＭＰａ未満ではリフロークラックを発生しやすくなる。The storage elastic modulus of the cured adhesive of the present invention measured by a dynamic viscoelasticity measuring apparatus is 20 to 2000 M at 25 ° C.
It is preferable to have a low elastic modulus of 3 to 50 MPa at Pa and 260 ° C. The storage elastic modulus was measured in a temperature-dependent measurement mode in which a tensile load was applied to the cured adhesive and the temperature was measured from -50 ° C to 300 ° C at a frequency of 10 Hz and a heating rate of 5 to 10 ° C / min. For those having a storage modulus of more than 2000 MPa at 25 ° C. and more than 50 MPa at 260 ° C.,
The effect of alleviating the thermal stress generated by the difference in the thermal expansion coefficient between the semiconductor chip and the interposer as the wiring substrate is reduced, and there is a possibility that peeling or cracking may occur. On the other hand, when the storage elastic modulus is less than 20 MPa at 25 ° C., the handleability of the adhesive and the thickness accuracy of the adhesive layer are deteriorated.
If it is less than MPa, reflow cracks are likely to occur.

【００４５】本発明おける半導体搭載用配線基板は、配
線基板の半導体搭載面に本発明の接着部材を備えたもの
である。本発明の半導体搭載用配線基板に用いる配線基
板としては、セラミック基板や有機基板など基板材質に
限定されることなく用いることができる。セラミック基
板としては、アルミナ基板、窒化アルミ基板などを用い
ることができる。有機基板としては、ガラスクロスにエ
ポキシ樹脂を含浸させたＦＲ−４基板、ビスマレイミド
−トリアジン樹脂を含浸させたＢＴ基板、さらにはポリ
イミドフィルムを基材として用いたポリイミドフィルム
基板などを用いることができる。配線の形状としては、
片面配線、両面配線、多層配線いずれの構造でもよく、
必要に応じて電気的に接続された貫通孔、非貫通孔を設
けてもよい。さらに、配線が半導体装置の外部表面に現
われる場合には、保護樹脂層を設けることが好ましい。
接着部材を配線基板へ張り付ける方法としては、接着部
材を所定の形状に切断し、その切断された接着部材を配
線基板の所望の位置に熱圧着する方法が一般的ではある
が、これに限定されるものではない。The wiring board for mounting a semiconductor according to the present invention has the adhesive member of the present invention on the semiconductor mounting surface of the wiring board. The wiring board used for the wiring board for mounting a semiconductor of the present invention can be used without being limited to a substrate material such as a ceramic substrate and an organic substrate. As the ceramic substrate, an alumina substrate, an aluminum nitride substrate, or the like can be used. As the organic substrate, an FR-4 substrate in which a glass cloth is impregnated with an epoxy resin, a BT substrate in which a bismaleimide-triazine resin is impregnated, and a polyimide film substrate using a polyimide film as a base material can be used. . As the shape of the wiring,
Any structure of single-sided wiring, double-sided wiring, and multilayer wiring may be used.
If necessary, electrically connected through holes and non-through holes may be provided. Further, when the wiring appears on the outer surface of the semiconductor device, it is preferable to provide a protective resin layer.
As a method of attaching the adhesive member to the wiring board, a method of cutting the adhesive member into a predetermined shape and thermocompression bonding the cut adhesive member to a desired position on the wiring board is general, but is not limited thereto. It is not something to be done.

【００４６】本発明の半導体装置は、本発明の接着部材
を用いて互いに接着された半導体チップと配線基板を有
するものであれば、その構造に特に制限はない。例え
ば、本発明の半導体装置の構造としては、半導体チップ
の電極と配線基板とがワイヤボンディングで接続されて
いる構造、半導体チップの電極と配線基板とがテープオ
ートメーテッドボンディング（ＴＡＢ）のインナーリー
ドボンディングで接続されている構造等があるがこれら
に限定されるものではなくいずれでも効果がある。接着
部材を用いて半導体装置を組み立てる方法を図１〜図３
を例に説明するが、本発明はこれらに限定されるもので
はない。接着部材は、図１（ａ）に示すようにフィルム
状の接着剤１である接着部材でも、図１（ｂ）に示すよ
うにコア材２の両面に接着剤１を備えた接着部材でも良
く、図２（ａ）、（ｂ）に示す配線３を形成した配線基
板４の配線側に、所定の大きさに切り抜いた接着部材を
例えば１００〜１５０℃、０．０１〜３ＭＰａ、０．５
〜１０秒の条件で熱圧着し接着部材を備えた半導体搭載
用配線基板を得、接着部材の配線基板と反対側に半導体
チップ５を例えば１２０〜２００℃、０．１〜３ＭＰ
ａ、１〜１０秒の条件で熱圧着し、１５０〜２００℃、
０．５〜２時間加熱して接着部材の接着剤層を硬化させ
た後、図３（ａ）、（ｂ）では半導体チップのパッドと
配線基板上の配線とをボンディングワイヤ６で接続し、
図３（ｃ）、（ｄ）では半導体チップのパッドに基板の
インナーリード６’をボンディングして、封止材７で封
止、外部接続端子８であるはんだボールを設けて半導体
装置を得ることができる。熱圧着の条件は、配線３側に
張り合わせるときの方が、半導体チップ５を張り合わせ
るときよりも緩やかな方が好ましく、特に温度は低い方
が好ましい。半導体チップと配線基板の間に発生する熱
応力は、半導体チップと配線基板の面積差が小さい場合
に著しいが、本発明による半導体装置は低弾性率の電子
部品用接着部材を用いることによりその熱応力を緩和し
て信頼性を確保するものである。さらに、その接着部材
が難燃化されている場合、半導体装置としての難燃性を
有するものである。これらの効果は、半導体チップの面
積が、配線基板の面積の７０％以上である場合に非常に
有効に現われるものである。ここで、半導体チップの面
積及び配線基板の面積とは、半導体チップと配線基板の
互いに向かい合った面の面積を意味する。また、このよ
うに半導体チップと配線基板の面積差が小さい半導体装
置においては、外部接続端子はエリア状に設けられる場
合が多い。The structure of the semiconductor device of the present invention is not particularly limited as long as it has a semiconductor chip and a wiring board bonded to each other using the bonding member of the present invention. For example, the structure of the semiconductor device of the present invention includes a structure in which the electrode of the semiconductor chip and the wiring board are connected by wire bonding, and a structure in which the electrode of the semiconductor chip and the wiring board are inner lead bonding by tape automated bonding (TAB). However, the present invention is not limited to these structures, and any of them is effective. FIGS. 1 to 3 show a method of assembling a semiconductor device using an adhesive member.
However, the present invention is not limited to these. The adhesive member may be an adhesive member that is a film-like adhesive 1 as shown in FIG. 1A, or may be an adhesive member having an adhesive 1 on both sides of a core material 2 as shown in FIG. 1B. On the wiring side of the wiring board 4 on which the wiring 3 shown in FIGS. 2 (a) and 2 (b) is formed, an adhesive member cut out to a predetermined size, for example, at 100 to 150 ° C., 0.01 to 3 MPa, 0.5
The semiconductor chip 5 is thermocompressed under the condition of 10 to 10 seconds to obtain a wiring board for mounting a semiconductor provided with an adhesive member.
a, thermocompression bonding under conditions of 1 to 10 seconds, 150 to 200 ° C,
After heating the adhesive layer of the adhesive member by heating for 0.5 to 2 hours, the pads of the semiconductor chip and the wiring on the wiring board are connected by bonding wires 6 in FIGS.
3C and 3D, the semiconductor device is obtained by bonding the inner lead 6 ′ of the substrate to the pad of the semiconductor chip, sealing with the sealing material 7, and providing the solder ball as the external connection terminal 8. Can be. As for the condition of the thermocompression bonding, it is preferable that the bonding when bonding to the wiring 3 side is gentler than when bonding the semiconductor chip 5, and it is particularly preferable that the temperature is lower. The thermal stress generated between the semiconductor chip and the wiring board is remarkable when the area difference between the semiconductor chip and the wiring board is small. However, the semiconductor device according to the present invention uses a low elastic modulus adhesive member for electronic components to generate the heat stress. This is to relieve stress and ensure reliability. Further, when the adhesive member is made flame-retardant, it has flame retardancy as a semiconductor device. These effects are very effective when the area of the semiconductor chip is 70% or more of the area of the wiring board. Here, the area of the semiconductor chip and the area of the wiring board refer to the area of the mutually facing surfaces of the semiconductor chip and the wiring board. In a semiconductor device having a small area difference between a semiconductor chip and a wiring board, external connection terminals are often provided in an area.

【００４７】本発明の接着部材を用いて半導体チップと
配線基板を接着させた半導体装置は、耐リフロー性、温
度サイクルテスト、耐湿性（耐ＰＣＴ性）等に優れてい
た。さらに接着剤の可使期間が長く、２５℃で３ヶ月保
管後のものを用いて作製した半導体装置も初期とほぼ同
等の特性を示していた。本発明おいて、重量平均分子量
は、ゲルパーミエーションクロマトグラフィーにより、
標準ポリスチレンの検量線を用いて測定したものであ
る。The semiconductor device in which the semiconductor chip and the wiring board were bonded using the bonding member of the present invention was excellent in reflow resistance, temperature cycle test, moisture resistance (PCT resistance) and the like. In addition, the semiconductor device manufactured using the adhesive having a long pot life and stored at 25 ° C. for 3 months also exhibited almost the same characteristics as the initial stage. In the present invention, the weight average molecular weight is determined by gel permeation chromatography.
It was measured using a standard polystyrene calibration curve.

【００４８】[0048]

【実施例】以下、実施例により本発明をさらに具体的に
説明する。 （接着剤ワニス１の調製）エポキシ樹脂としてビスフェ
ノールＡ型エポキシ樹脂（エポキシ当量１７５、東都化
成株式会社製商品名ＹＤ−８１２５を使用）４５重量
部、クレゾールノボラック型エポキシ樹脂（エポキシ当
量２１０、東都化成株式会社製商品名ＹＤＣＮ−７０３
を使用）１５重量部、エポキシ樹脂の硬化剤としてフェ
ノールノボラック樹脂（大日本インキ化学工業株式会社
製商品名プライオーフェンＬＦ２８８２を使用）４０重
量部、エポキシ基含有アクリル系重合体としてエポキシ
基含有アクリルゴム（分子量１００万、グリシジルメタ
クリレート１重量％、Ｔｇ−７℃、帝国化学産業株式会
社製商品名ＨＴＲ−８６０Ｐ−３を使用）２２０重量
部、潜在性硬化促進剤としてアミン−ウレイドアダクト
系硬化促進剤（富士化成株式会社製商品名フジキュアＦ
ＸＲ−１０３０を使用）５重量部からなる組成物に、メ
チルエチルケトンを加えて撹拌混合し、真空脱気した。
この接着剤ワニスを、厚さ７５μｍの離型処理したポリ
エチレンテレフタレートフィルム上に塗布し、１４０℃
で５分間加熱乾燥して膜厚が８０μｍの塗膜とし、接着
剤フィルムを作製した。この接着剤フィルムを１７０℃
で１時間加熱硬化させてその貯蔵弾性率を動的粘弾性測
定装置（レオロジ社製、ＤＶＥ−Ｖ４）を用いて測定
（サンプルサイズ：長さ２０ｍｍ、幅４ｍｍ、膜厚８０
μｍ、昇温速度５℃／分、引張りモード、１０Ｈｚ、自
動静荷重）した結果、２５℃で６００ＭＰａ、２６０℃
で５ＭＰａであった。この接着剤ワニスの固形分は３２
重量％であった。この接着剤ワニスの固形分は、ワニス
粘度が約１００ポイズ（２５℃）になるようにした値で
あり、これより固形分を高めて粘度を上げると厚みのば
らつきが大きくなる（以下同じ）。The present invention will be described more specifically with reference to the following examples. (Preparation of Adhesive Varnish 1) 45 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 175, trade name: YD-8125 manufactured by Toto Kasei Co., Ltd.) as an epoxy resin, cresol novolac type epoxy resin (epoxy equivalent: 210, Toto Kasei YDCN-703 brand name
15 parts by weight, 40 parts by weight of a phenol novolak resin as an epoxy resin curing agent (Plyofen LF2882 manufactured by Dainippon Ink and Chemicals, Inc.), and an epoxy group-containing acrylic rubber as an epoxy group-containing acrylic polymer (Molecular weight 1,000,000, 1% by weight of glycidyl methacrylate, Tg-7 ° C, trade name: HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd.) 220 parts by weight, amine-ureido duct-based curing accelerator as a latent curing accelerator (Fuji Cure F, manufactured by Fuji Chemical Co., Ltd.
XR-1030) To a composition consisting of 5 parts by weight, methyl ethyl ketone was added, mixed with stirring, and degassed under vacuum.
This adhesive varnish was applied on a release-treated polyethylene terephthalate film having a thickness of 75 μm,
For 5 minutes to form a coating film having a thickness of 80 μm, thereby producing an adhesive film. 170 ° C
For 1 hour, and the storage elastic modulus is measured using a dynamic viscoelasticity measuring apparatus (DVE-V4, manufactured by Rheology Co., Ltd.) (sample size: length 20 mm, width 4 mm, film thickness 80).
μm, heating rate 5 ° C./min, tensile mode, 10 Hz, automatic static load).
Was 5 MPa. The solid content of this adhesive varnish is 32
% By weight. The solid content of the adhesive varnish is a value such that the varnish viscosity is about 100 poise (25 ° C.). If the solid content is increased to increase the viscosity, the variation in thickness increases (the same applies hereinafter).

【００４９】（接着剤ワニス２の調製）接着剤ワニス１
の調製において、潜在性硬化促進剤として、アミン−ウ
レイドアダクト系硬化促進剤の代わりにアミン−エポキ
シアダクト系硬化促進剤（味の素株式会社製商品名アミ
キュアＭＹ−２４を使用）５重量部を使用したこと以外
は、接着剤ワニス１の調製に従って、接着剤ワニス２の
調製を行った。また、この接着剤ワニスを利用して、接
着剤ワニス１の調製における方法と同様に接着剤フィル
ムを作製した。この接着剤フィルムを使用して前記と同
様にしてその貯蔵弾性率を動的粘弾性測定装置を用いて
測定した結果、２５℃で３６０ＭＰａ、２６０℃で４Ｍ
Ｐａであった。この接着剤ワニス２の固形分は３０重量
％であった。(Preparation of Adhesive Varnish 2) Adhesive Varnish 1
As a latent curing accelerator, 5 parts by weight of an amine-epoxy adduct-based curing accelerator (trade name Amicure MY-24 manufactured by Ajinomoto Co., Inc.) was used in place of the amine-ureadduct-based curing accelerator. Except for this, the adhesive varnish 2 was prepared according to the preparation of the adhesive varnish 1. Using this adhesive varnish, an adhesive film was produced in the same manner as in the method for preparing the adhesive varnish 1. Using this adhesive film, the storage elastic modulus was measured using a dynamic viscoelasticity measuring device in the same manner as described above. As a result, 360 MPa at 25 ° C. and 4 M at 260 ° C.
Pa. The solid content of the adhesive varnish 2 was 30% by weight.

【００５０】（接着剤ワニス３）接着剤ワニス２の調製
において、潜在性硬化促進剤として、アミン−エポキシ
アダクト系硬化促進剤の使用量を３重量部としたこと以
外は、接着剤ワニス２の調製に従って、接着剤ワニス３
の調製を行った。また、この接着剤ワニスを利用して、
製膜時の乾燥温度を１４０℃から１６０℃としたこと以
外は、接着剤ワニス１の調製における方法と同様に接着
剤フィルムを作製した。この接着剤フィルムを使用して
前記と同様にしてその貯蔵弾性率を動的粘弾性測定装置
を用いて測定した結果、２５℃で３６０ＭＰａ、２６０
℃で４ＭＰａであった。この接着剤ワニスの固形分は２
８重量％であった。(Adhesive Varnish 3) In preparing the adhesive varnish 2, except that the amount of the amine-epoxy adduct-based curing accelerator used as the latent curing accelerator was 3 parts by weight, According to the preparation, adhesive varnish 3
Was prepared. Also, using this adhesive varnish,
An adhesive film was prepared in the same manner as in the preparation of the adhesive varnish 1, except that the drying temperature during film formation was changed from 140 ° C to 160 ° C. Using this adhesive film, the storage elastic modulus was measured using a dynamic viscoelasticity measuring device in the same manner as described above.
It was 4 MPa at ℃. The solid content of this adhesive varnish is 2
It was 8% by weight.

【００５１】（接着剤ワニス４）接着剤ワニス２の調製
において、潜在性硬化促進剤として、アミン−エポキシ
アダクト系硬化促進剤の使用量を１０重量部としたこと
以外は、接着剤ワニス２の調製に従って、接着剤ワニス
４の調製を行った。また、この接着剤ワニスを利用し
て、製膜時の乾燥温度を１４０℃から１２０℃としたこ
と以外は、接着剤ワニス１の調製における方法と同様に
接着剤フィルムを作製した。この接着剤フィルムを使用
して前記と同様にしてその貯蔵弾性率を動的粘弾性測定
装置を用いて測定した結果、２５℃で３６０ＭＰａ、２
６０℃で４ＭＰａであった。この接着剤ワニスの固形分
は２８重量％であった。(Adhesive Varnish 4) In preparing the adhesive varnish 2, except that the amount of the amine-epoxy adduct-based curing accelerator used was 10 parts by weight as a latent curing accelerator, the adhesive varnish 2 was used. According to the preparation, the adhesive varnish 4 was prepared. An adhesive film was prepared in the same manner as in the preparation of the adhesive varnish 1, except that the adhesive varnish was used and the drying temperature during film formation was changed from 140 ° C to 120 ° C. Using this adhesive film, the storage modulus was measured using a dynamic viscoelasticity measuring device in the same manner as described above.
It was 4 MPa at 60 ° C. The solid content of the adhesive varnish was 28% by weight.

【００５２】（接着剤ワニス５）接着剤ワニス１の調製
において、潜在性硬化促進剤として、アミン−ウレイド
アダクト系硬化促進剤の代わりに２−フェニルイミダゾ
ール０．５重量部を使用したこと以外は、接着剤ワニス
１の調製に従って、接着剤ワニス５の調製を行った。ま
た、この接着剤ワニスを利用して、接着剤ワニス１の調
製における方法と同様に接着剤フィルムを作製した。こ
の接着剤フィルムを使用して前記と同様にしてその貯蔵
弾性率を動的粘弾性測定装置を用いて測定した結果、２
５℃で３６０ＭＰａ、２６０℃で４ＭＰａであった。こ
の接着剤ワニスの固形分は２８重量％であった。(Adhesive Varnish 5) In preparing the adhesive varnish 1, except that 0.5 parts by weight of 2-phenylimidazole was used as the latent curing accelerator instead of the amine-ureidoduct-based curing accelerator. According to the preparation of the adhesive varnish 1, the adhesive varnish 5 was prepared. Using this adhesive varnish, an adhesive film was produced in the same manner as in the method for preparing the adhesive varnish 1. Using this adhesive film, the storage elastic modulus was measured using a dynamic viscoelasticity measuring device in the same manner as described above.
It was 360 MPa at 5 ° C. and 4 MPa at 260 ° C. The solid content of the adhesive varnish was 28% by weight.

【００５３】（実施例１）接着剤ワニス１を、厚さ７５
μｍの離型処理したポリエチレンテレフタレートフィル
ム上に塗布し、１４０℃で５分間加熱乾燥して、膜厚が
７５μｍのＢステージ状態の塗膜を形成し、キャリアフ
ィルムを備えた接着フィルムを作製した。この接着フィ
ルムを温度１１０℃、圧力０．３ＭＰａ、速度０．３ｍ
／分の条件でホットロールラミネーターを用いて貼り合
わせ、厚さ１５０μｍの単層フィルム状の接着部材を作
製した。なおこの状態での接着剤の硬化度は、ＤＳＣ
（デュポン社製９１２型ＤＳＣ）を用いて測定（昇温速
度、１０℃／分）した結果、全硬化発熱量の２０％の発
熱を終えた状態であった。また、接着剤のみの残存溶媒
量は、１２０℃で６０分間加熱前後の重量変化より１．
５重量％であった。(Example 1) The adhesive varnish 1 was coated to a thickness of 75
It was applied on a polyethylene terephthalate film having a release treatment of μm and dried by heating at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 75 μm, thereby producing an adhesive film provided with a carrier film. This adhesive film was heated at a temperature of 110 ° C., a pressure of 0.3 MPa, and a speed of 0.3 m.
At a rate of / min, the substrates were bonded using a hot roll laminator to produce a single-layer film-shaped adhesive member having a thickness of 150 μm. The curing degree of the adhesive in this state was determined by DSC
As a result of measurement (temperature rise rate, 10 ° C./min) using (DuPont 912 type DSC), heat generation of 20% of the total curing calorific value was completed. Further, the amount of the residual solvent of only the adhesive was determined from the change in weight before and after heating at 120 ° C. for 60 minutes as 1.
It was 5% by weight.

【００５４】（実施例２）接着剤ワニス１を接着剤ワニ
ス２とした以外は実施例１と同様にして、単層フィルム
状の接着部材を作製した。なおこの状態での接着剤の硬
化度は、ＤＳＣ（デュポン社製９１２型ＤＳＣ）を用い
て測定（昇温速度、１０℃／分）した結果、全硬化発熱
量の２０％の発熱を終えた状態であった。残存溶媒量
は、１．４重量％であった。(Example 2) A single-layer film-shaped adhesive member was produced in the same manner as in Example 1 except that the adhesive varnish 1 was changed to the adhesive varnish 2. The degree of curing of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (heating rate, 10 ° C./min), and as a result, heat generation of 20% of the total curing calorific value was completed. Condition. The residual solvent amount was 1.4% by weight.

【００５５】（実施例３）接着剤ワニス２を、厚さ２５
μｍのポリイミドフィルム（宇部興産株式会社製商品名
ユーピレックスＳＧＡ−２５を使用）上に塗布し、１２
０℃で５分間加熱乾燥して、膜厚が５０μｍのＢステー
ジ状態の塗膜を形成し、さらに接着剤層を形成した反対
面に同じワニスを塗布し、１４０℃で５分間加熱乾燥し
て、膜厚が７０μｍのＢステージ状態の塗膜を形成し、
コア材として用いたポリイミドフィルムの両面に接着剤
層を備えた接着部材を作製した。なおこの状態での接着
剤の硬化度は、ＤＳＣ（デュポン社製９１２型ＤＳＣ）
を用いて測定（昇温速度、１０℃／分）した結果、５０
μｍ層で全硬化発熱量の２５％、７５μｍ層で全硬化発
熱量の２０％の発熱を終えた状態であった。残存溶媒量
は、何れも１．３〜１．６重量％であった。(Example 3) The adhesive varnish 2 was coated with a thickness of 25
μm polyimide film (Ube Industries, Ltd., trade name: Upilex SGA-25)
Heat drying at 0 ° C. for 5 minutes to form a coating film in a B-stage state having a film thickness of 50 μm, further apply the same varnish to the opposite surface on which the adhesive layer was formed, and heat dry at 140 ° C. for 5 minutes. Forming a B-stage coating film having a thickness of 70 μm,
An adhesive member having adhesive layers on both surfaces of a polyimide film used as a core material was produced. The curing degree of the adhesive in this state was measured by DSC (912 type DSC manufactured by DuPont).
As a result of measurement (heating rate, 10 ° C./min) using
The heat generation of 25% of the total curing heat generation was completed in the μm layer, and the heat generation of 20% of the total curing heat generation was completed in the 75 μm layer. The amount of residual solvent was 1.3 to 1.6% by weight in each case.

【００５６】（実施例４）接着剤ワニス２を、厚さ７５
μｍの離型処理したポリエチレンテレフタレートフィル
ム上に塗布し、１４０℃で５分間加熱乾燥して、膜厚が
７５μｍのＢステージ状態の塗膜を形成し、キャリアフ
ィルムを備えた接着フィルムを作製した。この接着フィ
ルムを、厚さ２５μｍのポリイミドフィルム（宇部興産
株式会社製商品名ユーピレックスＳＧＡ−２５を使用）
の両面に温度１１０℃、圧力０．３ＭＰａ、速度０．２
ｍ／分の条件でホットロールラミネーターを用いて貼り
付け、コア材として用いたポリイミドフィルムの両面に
接着剤層を備えた接着部材を作製した。なおこの状態で
の接着剤の硬化度は、ＤＳＣ（デュポン社製９１２型Ｄ
ＳＣ）を用いて測定（昇温速度、１０℃／分）した結
果、両面の接着剤層ともに全硬化発熱量の２０％の発熱
を終えた状態であった。残存溶媒量は、１．４重量％で
あった。Example 4 An adhesive varnish 2 was coated to a thickness of 75
It was applied on a polyethylene terephthalate film having a release treatment of μm and dried by heating at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 75 μm, thereby producing an adhesive film provided with a carrier film. A 25 μm thick polyimide film (using UPILEX SGA-25 manufactured by Ube Industries, Ltd.)
110 ° C, pressure 0.3MPa, speed 0.2 on both sides of
Attachment was performed using a hot roll laminator under the condition of m / min to prepare an adhesive member having an adhesive layer on both surfaces of a polyimide film used as a core material. The degree of cure of the adhesive in this state was measured using a DSC (DuPont 912 type D).
SC) (heating rate, 10 ° C./min), the adhesive layers on both sides were in a state where heat generation of 20% of the total curing heat generation was finished. The residual solvent amount was 1.4% by weight.

【００５７】（実施例５）コア材のポリイミドフィルム
を厚さ２５μｍの液晶ポリマフィルム（株式会社クラレ
製商品名ベクトラＬＣＰ−Ａを使用）にしたこと以外は
実施例４と同様にしてコア材として用いた液晶ポリマフ
ィルム両面に接着剤層を備えた接着部材を作製した。な
おこの状態での接着剤の硬化度は、ＤＳＣ（デュポン社
製９１２型ＤＳＣ）を用いて測定（昇温速度、１０℃／
分）した結果、両面の接着剤層ともに全硬化発熱量の２
０％の発熱を終えた状態であった。残存溶媒量は、１．
４重量％であった。Example 5 A core material was prepared in the same manner as in Example 4 except that the polyimide film of the core material was a liquid crystal polymer film having a thickness of 25 μm (Vectra LCP-A manufactured by Kuraray Co., Ltd.). An adhesive member having an adhesive layer on both sides of the used liquid crystal polymer film was produced. The curing degree of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (heating rate, 10 ° C. /
Minutes), the total amount of heat generated by curing on both adhesive layers was 2
It was in a state where heat generation of 0% was finished. The amount of the remaining solvent was 1.
It was 4% by weight.

【００５８】（実施例６）コア材のポリイミドフィルム
を厚さ２５μｍのテトラフルオロエチレン−ヘキサフル
オロプロピレンコポリマーフィルム（三井・デュポンフ
ロロケミカル株式会社製商品名テフロンＦＥＰを使用）
にしたこと以外は実施例４と同様にしてテトラフルオロ
エチレン−ヘキサフルオロプロピレンコポリマーフィル
ム両面に接着剤層を備えた接着部材を作製した。テトラ
フルオロエチレン−ヘキサフルオロプロピレンコポリマ
ーフィルムについては、濡れ性を向上して接着性を上げ
るのためにその両面を化学処理（株式会社潤工社製商品
名テトラエッチを使用）したものを用いた。なおこの状
態での接着剤の硬化度は、ＤＳＣ（デュポン社製９１２
型ＤＳＣ）を用いて測定（昇温速度、１０℃／分）した
結果、両面の接着剤層ともに全硬化発熱量の２０％の発
熱を終えた状態であった。残存溶媒量は、１．５重量％
であった。(Example 6) A polyimide film as a core material was formed of a tetrafluoroethylene-hexafluoropropylene copolymer film having a thickness of 25 µm (trade name: Teflon FEP manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.)
An adhesive member having an adhesive layer on both surfaces of a tetrafluoroethylene-hexafluoropropylene copolymer film was produced in the same manner as in Example 4 except that the above procedure was adopted. As the tetrafluoroethylene-hexafluoropropylene copolymer film, a film having both surfaces chemically treated (trade name, manufactured by Junko Co., Ltd.) was used in order to improve wettability and increase adhesiveness. The degree of cure of the adhesive in this state was determined by DSC (912 manufactured by DuPont).
As a result of measurement (temperature rise rate, 10 ° C./min), the adhesive layers on both surfaces were in a state where heat generation of 20% of the total curing heat generation was finished. Residual solvent amount is 1.5% by weight
Met.

【００５９】（実施例７）接着剤ワニス２を、厚さ７５
μｍの離型処理したポリエチレンテレフタレートフィル
ム上に塗布し、１４０℃で５分間加熱乾燥して、膜厚が
６０μｍのＢステージ状態の塗膜を形成し、キャリアフ
ィルムを備えた単層フィルム状の接着部材を作製した。
この単層フィルムを、厚さ１００μｍの多孔質ポリテ
トラフルオロエチレンフィルム（住友電気工業株式会社
製商品名ポアフロンＷＰ−１００−１００を使用）の両
面に温度１１０℃、圧力０．３ＭＰａ、速度０．２ｍ／
分の条件でホットロールラミネーターを用いて貼り付
け、コア材として用いた多孔質ポリテトラフルオロエチ
レンフィルムの両面に接着剤層を備えた接着部材を作製
した。なおこの状態での接着剤の硬化度は、ＤＳＣ（デ
ュポン社製９１２型ＤＳＣ）を用いて測定（昇温速度、
１０℃／分）した結果、両面の接着剤層ともに全硬化発
熱量の２０％の発熱を終えた状態であった。残存溶媒量
は、１．４重量％であった。(Example 7) The adhesive varnish 2 was coated to a thickness of 75
Coating on μm-released polyethylene terephthalate film, heating and drying at 140 ° C. for 5 minutes to form a B-stage coating film with a thickness of 60 μm, and a single-layer film-like adhesive with a carrier film A member was manufactured.
This single-layer film is formed on both sides of a porous polytetrafluoroethylene film having a thickness of 100 μm (trade name: Poeflon WP-100-100 manufactured by Sumitomo Electric Industries, Ltd.) at a temperature of 110 ° C., a pressure of 0.3 MPa, and a speed of 0. 2m /
A hot roll laminator was applied under the same conditions as in Example 1 to prepare an adhesive member having an adhesive layer on both sides of a porous polytetrafluoroethylene film used as a core material. The curing degree of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (temperature rising rate,
(10 ° C./min), the adhesive layers on both sides were in a state where heat generation of 20% of the total curing heat generation was finished. The residual solvent amount was 1.4% by weight.

【００６０】（実施例８）接着剤ワニス１を接着剤ワニ
ス３とした以外は実施例１と同様にして、単層フィルム
状の接着部材を作製した。なおこの状態での接着剤の硬
化度は、ＤＳＣ（デュポン社製９１２型ＤＳＣ）を用い
て測定（昇温速度、１０℃／分）した結果、全硬化発熱
量の２０％の発熱を終えた状態であった。(Example 8) A single-layer film-like adhesive member was produced in the same manner as in Example 1 except that the adhesive varnish 1 was changed to the adhesive varnish 3. The degree of curing of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (heating rate, 10 ° C./min), and as a result, heat generation of 20% of the total curing calorific value was completed. Condition.

【００６１】（実施例９）接着剤ワニス１を接着剤ワニ
ス４とした以外は実施例１と同様にして、単層フィルム
状の接着部材を作製した。なおこの状態での接着剤の硬
化度は、ＤＳＣ（デュポン社製９１２型ＤＳＣ）を用い
て測定（昇温速度、１０℃／分）した結果、全硬化発熱
量の２０％の発熱を終えた状態であった。(Example 9) A single-layer film-shaped adhesive member was produced in the same manner as in Example 1 except that the adhesive varnish 1 was changed to the adhesive varnish 4. The degree of curing of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (heating rate, 10 ° C./min), and as a result, heat generation of 20% of the total curing calorific value was completed. Condition.

【００６２】（参考例１）接着剤ワニス１を接着剤ワニ
ス５とした以外は実施例１と同様にして、単層フィルム
状の接着部材を作製した。なお、この状態での接着剤の
硬化度は、ＤＳＣ（デュポン社製９１２型ＤＳＣ）を用
いて測定（昇温速度、１０℃／分）した結果、全硬化発
熱量の２０％の発熱を終えた状態であった。Reference Example 1 A single-layer film-like adhesive member was produced in the same manner as in Example 1 except that the adhesive varnish 1 was changed to the adhesive varnish 5. The degree of curing of the adhesive in this state was measured using a DSC (a 912 type DSC manufactured by DuPont) (heating rate, 10 ° C./min), and as a result, heat generation of 20% of the total curing calorific value was completed. It was in a state.

【００６３】得られた接着部材を用いて図３（ｃ）、
（ｄ）に示すような半導体チップと厚み２５μｍのポリ
イミドフィルムを基材に用いた配線基板を接着部材を用
いて、温度１６０℃、圧力１．５ＭＰａ及び時間３秒の
条件で貼り合せた半導体装置サンプル（片面にはんだボ
ールを形成）を作製し、耐熱性、難燃性、耐湿性、発泡
の有無を調べた。耐熱性の評価方法には、耐リフローク
ラック性と温度サイクル試験を適用した。耐リフローク
ラック性の評価は、サンプル表面の最高温度が２４０℃
でこの温度を２０秒間保持するように温度設定したＩＲ
リフロー炉にサンプルを通し、室温で放置することによ
り冷却する処理を２回繰り返したサンプル中のクラック
を目視と超音波顕微鏡で観察した。クラックの発生して
いないものを○とし、発生していたものを×とした。耐
温度サイクル性は、サンプルを−５５℃雰囲気に３０分
間放置し、その後１２５℃の雰囲気に３０分間放置する
工程を１サイクルとして、１０００サイクル後において
超音波顕微鏡を用いて剥離やクラック等の破壊が発生し
ていないものを○、発生したものを×とした。また、耐
湿性評価は、温度１２１℃、湿度１００％、２気圧の雰
囲気（プレッシャークッカーテスト： ＰＣＴ処理）で
７２時間処理後に剥離を観察することにより行った。接
着部材の剥離の認められなかったものを○とし、剥離の
あったものを×とした。発泡の有無は超音波顕微鏡を用
いて確認し、接着部材に発泡が認められなかったものを
○とし、発泡のあったものを×とした。また可使期間の
評価は、得られた接着部材を２５℃で３ヶ月保管したも
のを用いて同様な半導体装置サンプルを作製し、超音波
顕微鏡を用いて接着剤の回路への埋め込み性を確認し
た。配線基板に設けられた回路との間に空隙がなかった
ものを○、空隙が認められたものを×とした。その結果
を表１に示す。Using the obtained adhesive member, FIG.
(D) A semiconductor device in which a semiconductor chip and a wiring board using a 25 μm-thick polyimide film as a base material are bonded together using an adhesive member at a temperature of 160 ° C., a pressure of 1.5 MPa, and a time of 3 seconds. A sample (with a solder ball formed on one side) was prepared and examined for heat resistance, flame retardancy, moisture resistance, and the presence or absence of foaming. As a method for evaluating heat resistance, a reflow crack resistance and a temperature cycle test were applied. The evaluation of reflow crack resistance is as follows.
IR set to maintain this temperature for 20 seconds
The sample was passed through a reflow furnace and allowed to stand at room temperature to be cooled by cooling twice. Cracks in the sample were visually observed and observed with an ultrasonic microscope.い な い indicates that no cracks occurred, and X indicates that cracks occurred. The temperature cycle resistance is as follows: a sample is left in an atmosphere of -55 ° C for 30 minutes and then left in an atmosphere of 125 ° C for 30 minutes as one cycle, and after 1000 cycles, destruction such as peeling or cracking is performed using an ultrasonic microscope. Indicates that no occurrence occurred, and x indicates occurrence. The moisture resistance was evaluated by observing peeling after treatment for 72 hours in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., a humidity of 100% and a pressure of 2 atm. When the peeling of the adhesive member was not recognized, it was evaluated as ○, and when peeled, it was evaluated as ×. The presence or absence of foaming was confirmed by using an ultrasonic microscope, and the case where no foaming was observed in the adhesive member was evaluated as ○, and the case where foaming was observed was evaluated as ×. For the evaluation of the shelf life, a similar semiconductor device sample was prepared using the obtained adhesive member stored at 25 ° C. for 3 months, and the embedding property of the adhesive in the circuit was confirmed using an ultrasonic microscope. did. When there was no gap between the circuit and the circuit provided on the wiring board, it was rated as "O", and when there was a gap, it was rated as "x". Table 1 shows the results.

【００６４】[0064]

【表１】 [Table 1]

【００６５】実施例１はアミン−ウレイドアダクト系潜
在性硬化促進剤を用いたものであり、可使期間は長く良
好であったが、硬化時の発泡が認められた。実施例２〜
９はアミン−エポキシアダクト系潜在性硬化促進剤を用
いたものであり、可使期間が長く、硬化時の発泡もなく
良好な結果を示した。これらの接着剤硬化物は、本発明
で好ましいと規定した２５℃及び２６０℃での貯蔵弾性
率を示しており、さらにこれらの接着部材を用いた半導
体装置は、耐リフロークラック性、耐温度サイクル性、
耐湿性が良好であった。また、実施例３〜７はコア材を
備えた接着部材であるが、取扱性が良好であった。参考
例１は硬化促進剤にアダクトがないイミダゾール化合物
を使用した例であり、可使期間が短かった。Example 1 uses an amine-ureido duct type latent curing accelerator, and has a long usable life and is good, but foaming during curing was observed. Example 2
No. 9 used an amine-epoxy adduct-based latent curing accelerator, had a long pot life, and exhibited good results without foaming during curing. These cured adhesives exhibit storage elastic moduli at 25 ° C. and 260 ° C., which are specified as preferred in the present invention. Furthermore, semiconductor devices using these adhesives have reflow crack resistance and temperature cycle resistance. sex,
The moisture resistance was good. Examples 3 to 7 are the adhesive members provided with the core material, but the handleability was good. Reference Example 1 is an example in which an imidazole compound having no adduct was used as the curing accelerator, and the pot life was short.

【００６６】実施例１０ エポキシ樹脂としてビスフェノールＡ型エポキシ樹脂
（エポキシ当量１９０、油化シェルエポキシ株式会社製
のエピコート８２８を使用）４５重量部、クレゾールノ
ボラック型エポキシ樹脂（エポキシ当量１９５、住友化
学工業株式会社製のＥＳＣＮ１９５を使用）１５重量
部、エポキシ樹脂の硬化剤としてフェノールノボラック
樹脂（大日本インキ化学工業株式会社製のプライオーフ
ェンＬＦ２８８２を使用）４０重量部、シランカップリ
ング剤としてγ−グリシドキシプロピルトリメトキシシ
ラン（日本ユニカー株式会社製のＮＵＣＡ−１８７を使
用）０．７重量部からなる組成物に、メチルエチルケト
ンを加えて攪拌混合し、これにグリシジルメタクリレー
ト又はグリシジルアクリレート２〜６重量％を含むアク
リルゴム（重量平均分子量１００万、帝国化学産業株式
会社製のＨＴＲ−８６０Ｐ−３を使用）１５０重量部、
硬化促進剤としてエポキシアミンアダクト化合物である
味の素株式会社製のアミキュアＭＹ−２４を４重量部添
加し、攪拌モータで３０分混合し、ワニスを得た。この
ワニスをキャリアフィルム（厚さ７５μｍの表面処理し
たポリエチレンテレフタレートフィルム）上に塗布し
て、１４０℃で５分間加熱乾燥し、厚さ７５μｍのＢス
テージ状態の塗膜を形成し、接着フィルムを作成した。
アミキュアＭＹ−２４はエポキシ樹脂及び硬化剤の混合
物には均一に溶解したが、アクリルゴムには溶解せず、
粒子状に析出した。また、上記接着剤は硬化後にエポキ
シ樹脂が分散相、アクリルゴムが連続相に相分離した。Example 10 45 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 190, epoxy coat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was used as an epoxy resin, and a cresol novolac type epoxy resin (epoxy equivalent: 195, Sumitomo Chemical Co., Ltd.) 15 parts by weight of ESCN195 manufactured by the company), 40 parts by weight of phenol novolak resin (using Plyofen LF2882 manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent for epoxy resin, and γ-glycidoxy as a silane coupling agent To a composition consisting of 0.7 parts by weight of propyltrimethoxysilane (using NUCA-187 manufactured by Nippon Unicar Co., Ltd.), methyl ethyl ketone is added and mixed with stirring, and contains 2 to 6% by weight of glycidyl methacrylate or glycidyl acrylate. A Rirugomu (weight average molecular weight of 1,000,000, use the HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd.) 150 parts by weight,
As a curing accelerator, 4 parts by weight of Amicour MY-24, an epoxyamine adduct compound manufactured by Ajinomoto Co., was added and mixed with a stirring motor for 30 minutes to obtain a varnish. This varnish is applied on a carrier film (75 μm thick surface-treated polyethylene terephthalate film) and dried by heating at 140 ° C. for 5 minutes to form a 75 μm thick B-stage coating film to form an adhesive film. did.
AMICURE MY-24 was uniformly dissolved in the mixture of the epoxy resin and the curing agent, but was not dissolved in the acrylic rubber.
It precipitated in the form of particles. After curing, the adhesive separated into an epoxy resin dispersed phase and an acrylic rubber phase separated into a continuous phase.

【００６７】実施例１１ 硬化促進剤としてアミン−ウレイド系のアダクト系化合
物である富士化成株式会社のフジキュアＦＸＲ−１０３
０を使用した他は実施例１０と同様にして作製した。フ
ジキュアＦＸＲ−１０３０はエポキシ樹脂及び硬化剤の
混合物には均一に溶解したが、アクリルゴムには溶解せ
ず、粒子状に析出した。Example 11 As a curing accelerator, an amine-ureido-based adduct compound, Fuji Cure FXR-103 manufactured by Fuji Kasei Co., Ltd.
Except that 0 was used, it was produced in the same manner as in Example 10. Fujicure FXR-1030 was uniformly dissolved in the mixture of the epoxy resin and the curing agent, but did not dissolve in the acrylic rubber, but precipitated in the form of particles.

【００６８】参考例２ 硬化促進剤として１−シアノエチル−２−フェニルイミ
ダゾール（四国化成工業株式会社製キュアゾール２ＰＺ
−ＣＮを使用）０．５重量部を使用した他は実施例１と
同様にしてフィルムを作製した。キュアゾール２ＰＺ−
ＣＮは、エポキシ樹脂、アクリルゴム両方に溶解した。Reference Example 2 1-cyanoethyl-2-phenylimidazole (Curesol 2PZ manufactured by Shikoku Chemicals Co., Ltd.) was used as a curing accelerator.
A film was prepared in the same manner as in Example 1 except that 0.5 part by weight was used. Cureazole 2PZ-
CN was dissolved in both the epoxy resin and the acrylic rubber.

【００６９】可使期間の評価は、得られた接着部材を２
５℃で１〜６ヶ月保管したものを用いて、半導体チップ
と厚み２５μｍのポリイミドフィルムを基材に用いた配
線基板とを、温度１６０℃、圧力１．５ＭＰａ及び時間
３秒の条件で貼りあわせ、超音波顕微鏡を用いて接着剤
の回路への埋め込み性を確認した。配線基板に設けられ
た回路との間に空隙がなかった物を○、空隙が認められ
たものを×とした。その結果を表１に示す。The evaluation of the pot life was made by comparing the obtained adhesive member with two.
A semiconductor chip and a wiring substrate using a polyimide film having a thickness of 25 μm as a base material are bonded at a temperature of 160 ° C., a pressure of 1.5 MPa and a time of 3 seconds by using a device stored at 5 ° C. for 1 to 6 months. The embedding property of the adhesive into the circuit was confirmed using an ultrasonic microscope.物 indicates that there was no gap between the circuit and the circuit provided on the wiring board, and x indicates that there was a gap. Table 1 shows the results.

【００７０】[0070]

【表２】 実施例１０はアミン−エポキシアダクト系潜在性硬化促
進剤を用いたものであり、可使期間は長く良好であっ
た。実施例１１はアミン−ウレイドアダクト系潜在性硬
化促進剤を用いたものであり、可使期間は長く良好であ
った。参考例２は、分子量が小さく、ゴム、エポキシの
両方に溶解性のあるイミダゾール系の硬化促進剤を使用
したものであり、可使期間が短い。[Table 2] In Example 10, an amine-epoxy adduct-based latent curing accelerator was used, and the pot life was long and good. In Example 11, an amine-ureido duct-based latent curing accelerator was used, and the pot life was long and good. Reference Example 2 uses an imidazole-based curing accelerator having a small molecular weight and being soluble in both rubber and epoxy, and has a short pot life.

【００７１】[0071]

【発明の効果】本発明における接着剤は潜在性硬化促進
剤を用いることでＢステージフィルムの保存安定性を高
めることができた。アミンアダクト系のＭＹ−２４及び
ＦＸＲ−１０３０を用いたものは耐熱性、耐湿性が良好
であった。特にアミン−エポキシアダクト系潜在性硬化
促進剤を使用した場合には、接着剤硬化時の硬化速度が
十分に大きいために発泡することなく完全な硬化物を得
ることができる。特にアダクト型、アミンアダクト系、
アミン−エポキシアダクト系の潜在性硬化促進剤を使用
した本発明の接着剤を用いた接着部材は、耐熱性、耐湿
性が良好である。これらの効果により、優れた信頼性を
発現する半導体装置に必要な接着材料を効率良く提供す
ることができる。According to the present invention, the storage stability of the B-stage film can be improved by using a latent curing accelerator as the adhesive in the present invention. Those using the amine adduct MY-24 and FXR-1030 were excellent in heat resistance and moisture resistance. In particular, when an amine-epoxy adduct latent curing accelerator is used, a completely cured product can be obtained without foaming because the curing speed at the time of curing the adhesive is sufficiently high. Especially adduct type, amine adduct type,
An adhesive member using the adhesive of the present invention using an amine-epoxy adduct latent curing accelerator has excellent heat resistance and moisture resistance. With these effects, it is possible to efficiently provide an adhesive material necessary for a semiconductor device exhibiting excellent reliability.

【００７２】請求項１１〜１４の接着剤を用いた接着フ
ィルムは可使期間が長いため、長期にわたり保存でき、
生産管理がしやすい点で従来の接着フィルムに比べて大
きな効果が有る。よって、保存安定性に優れる接着剤、
接着フィルムを作成することができる。請求項１２に記
載の接着剤によって、さらに、接着性、耐熱性とフィル
ムとしての取り扱い性に優れる接着フィルムを作成する
ことができる。請求項１３に記載の接着剤は、これを用
いることによって接着性、耐熱性がさらに高い接着フィ
ルムを作成できる点で優れる。また、請求項１４に記載
の接着剤組成物は、さらに硬化時に発泡せず、かつ低弾
性を有し耐熱性、耐湿性が良好な接着剤、接着フィルム
を作成できる点で優れる。よって、これらの発明によ
り、保存安定性が特に高い接着フィルム、半導体搭載用
配線基板及び半導体装置を作成することができる。The adhesive film using the adhesive according to any one of claims 11 to 14 can be stored for a long period of time because of its long working life.
There is a great effect compared to the conventional adhesive film in that the production control is easy. Therefore, adhesives with excellent storage stability,
An adhesive film can be made. With the adhesive according to the twelfth aspect, it is possible to produce an adhesive film having further excellent adhesiveness, heat resistance and handleability as a film. The adhesive according to the thirteenth aspect is excellent in that an adhesive film having higher adhesiveness and heat resistance can be prepared by using the adhesive. Further, the adhesive composition according to claim 14 is excellent in that an adhesive and an adhesive film which do not foam at the time of curing, have low elasticity, and have good heat resistance and moisture resistance can be produced. Therefore, according to these inventions, an adhesive film, a wiring board for mounting a semiconductor, and a semiconductor device having particularly high storage stability can be manufactured.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 （ａ）は本発明による接着剤単層からなるフ
ィルム状の接着部材を示す断面図、（ｂ）は本発明によ
るコア材の両面に接着剤を備えた接着部材を示す断面
図。FIG. 1A is a cross-sectional view showing a film-like adhesive member comprising a single layer of an adhesive according to the present invention, and FIG. 1B is a cross-sectional view showing an adhesive member having an adhesive on both sides of a core material according to the present invention. .

【図２】 （ａ）は本発明による接着剤単層からなるフ
ィルム状の接着部材を用いた半導体搭載用配線基板を示
す断面図、（ｂ）は本発明によるコア材の両面に接着剤
を備えた接着部材を用いた半導体搭載用配線基板を示す
断面図。FIG. 2A is a cross-sectional view showing a wiring board for mounting a semiconductor using a film-like adhesive member composed of an adhesive single layer according to the present invention, and FIG. 2B is a sectional view showing an adhesive on both sides of a core material according to the present invention. Sectional drawing which shows the wiring board for semiconductor mounting using the provided adhesive member.

【図３】 （ａ）は本発明による接着剤単層からなるフ
ィルム状の接着部材を用いて半導体チップと配線基板を
接着させ、半導体チップのパッドと基板上の配線とをボ
ンディングワイヤで接続した半導体装置の断面図、
（ｂ）は本発明によるコア材の両面に接着剤を備えた接
着部材を用いて半導体チップと配線基板を接着させ、半
導体チップのパッドと基板上の配線とをボンディングワ
イヤで接続した半導体装置の断面図、（ｃ）は本発明に
よる接着剤単層からなるフィルム状の接着部材を用いて
半導体チップと配線基板を接着させ、半導体チップのパ
ッドに基板のインナーリードをボンディングした半導体
装置の断面図、（ｄ）は本発明によるコア材の両面に接
着剤を備えた接着部材を用いて半導体チップと配線基板
を接着させ、半導体チップのパッドに基板のインナーリ
ードをボンディングした半導体装置の断面図。FIG. 3 (a) shows that a semiconductor chip and a wiring board are bonded using a film-like bonding member composed of an adhesive single layer according to the present invention, and pads of the semiconductor chip and wiring on the board are connected by bonding wires. Sectional view of a semiconductor device,
(B) shows a semiconductor device in which a semiconductor chip and a wiring board are adhered by using an adhesive member provided with an adhesive on both sides of a core material according to the present invention, and pads of the semiconductor chip and wiring on the board are connected by bonding wires. FIG. 4C is a cross-sectional view of a semiconductor device in which a semiconductor chip and a wiring substrate are bonded using a film-like bonding member made of a single layer of an adhesive according to the present invention, and inner leads of the substrate are bonded to pads of the semiconductor chip. And (d) is a cross-sectional view of a semiconductor device in which a semiconductor chip and a wiring board are adhered to each other using an adhesive member provided with an adhesive on both sides of a core material according to the present invention, and inner leads of the substrate are bonded to pads of the semiconductor chip.

【符号の説明】[Explanation of symbols]

１ ． 接着剤 ２ ． コア材（耐熱性熱可塑フィルム） ３ ． 配線 ４ ． 配線基板 ５ ． 半導体チップ ６ ． ボンディングワイヤ ６’． インナリード ７ ． 封止材 ８ ． 外部接続端子 1. Adhesive 2. 2. Core material (heat-resistant thermoplastic film) Wiring 4. Wiring board 5. Semiconductor chip 6. Bonding wire 6 '. Inner lead 7. Sealing material 8. External connection terminal

───────────────────────────────────────────────────── フロントページの続き (72)発明者 栗谷 弘之 茨城県下館市大字小川1500番地 日立化成 工業株式会社総合研究所内 (72)発明者 神代 恭 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 (72)発明者 山本 和徳 茨城県下館市大字小川1500番地 日立化成 工業株式会社総合研究所内 (72)発明者 住谷 圭二 茨城県日立市東町四丁目13番１号 日立化 成工業株式会社総合研究所内 Ｆターム(参考） 4J004 AA02 AA10 AA13 AA17 AA18 AB05 CA03 CA06 CC02 FA05 4J040 DF041 DF042 DF051 DF052 EC061 EC231 EC232 GA11 HA136 HA306 HC01 JA09 JB02 KA16 KA17 KA42 LA01 LA02 LA06 NA20 PA23 5F044 LL11 MM06 5F061 AA01 BA04 CA21  ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroyuki Kuritani 1500 Ogawa, Oji, Shimodate, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. Inside the Shimodate Research Laboratory (72) Inventor Kazunori Yamamoto 1500 Ogawa, Shimodate-shi, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. F-term within the Research Institute (reference) 4J004 AA02 AA10 AA13 AA17 AA18 AB05 CA03 CA06 CC02 FA05 4J040 DF041 DF042 DF051 DF052 EC061 EC231 EC232 GA11 HA136 HA306 HC01 JA09 JB02 KA16 KA17 KA42 LA01 LA02 LA04 NA06 PA11

Claims (25)

【特許請求の範囲】[Claims] 【請求項１】 （１）エポキシ樹脂及びその硬化剤１０
０重量部、（２）グリシジル（メタ）アクリレート０．
５〜６重量％を含むＴｇ（ガラス転移温度）が−１０℃
以上でかつ重量平均分子量が１０万以上であるエポキシ
基含有アクリル共重合体７５〜３００重量部、（３）潜
在性硬化促進剤０．１〜２０重量部を含有する接着剤。(1) Epoxy resin and its curing agent 10
0 parts by weight, (2) glycidyl (meth) acrylate
Tg (glass transition temperature) containing 5 to 6% by weight is -10C
An adhesive containing 75 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a weight average molecular weight of 100,000 or more and (3) 0.1 to 20 parts by weight of a latent curing accelerator. 【請求項２】 （１）エポキシ樹脂及びその硬化剤１０
０重量部、（２）エポキシ樹脂と相溶性がありかつ重量
平均分子量が３万以上の高分子量樹脂５〜４０重量部、
（３）グリシジル（メタ）アクリレート０．５〜６重量
％を含むＴｇ（ガラス転移温度）が−１０℃以上でかつ
重量平均分子量が１０万以上であるエポキシ基含有アク
リル共重合体７５〜３００重量部、（４）潜在性硬化促
進剤０．１〜２０重量部を含有する接着剤。(1) Epoxy resin and its curing agent 10
0 parts by weight, (2) 5 to 40 parts by weight of a high molecular weight resin compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more,
(3) 75 to 300 weight percent of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 100,000 or more containing glycidyl (meth) acrylate of 0.5 to 6% by weight. (4) An adhesive containing 0.1 to 20 parts by weight of a latent curing accelerator. 【請求項３】 潜在性硬化促進剤がアダクト型である請
求項１ないし請求項２のいずれかに記載の接着剤。3. The adhesive according to claim 1, wherein the latent curing accelerator is an adduct type. 【請求項４】 潜在性硬化促進剤がアミンアダクトであ
る請求項３に記載の接着剤。4. The adhesive according to claim 3, wherein the latent curing accelerator is an amine adduct. 【請求項５】 潜在性硬化促進剤がアミン−エポキシア
ダクトである請求項４に記載の接着剤。5. The adhesive according to claim 4, wherein the latent curing accelerator is an amine-epoxy adduct. 【請求項６】 無機フィラーを、接着剤樹脂分１００体
積部に対して１〜２０体積部含む請求項１から請求項５
のいずれかに記載の接着剤。6. An inorganic filler containing 1 to 20 parts by volume based on 100 parts by volume of an adhesive resin component.
The adhesive according to any one of the above. 【請求項７】 無機フィラーがアルミナ、シリカ、水酸
化アルミ、アンチモン酸化物のいずれかである請求項６
に記載の接着剤。7. The inorganic filler is one of alumina, silica, aluminum hydroxide, and antimony oxide.
The adhesive according to item 1. 【請求項８】 接着剤を、ＤＳＣを用いて測定した場合
の全硬化発熱量の１０〜４０％の発熱を終えた状態にし
た請求項１から請求項７のいずれかに記載の接着剤。8. The adhesive according to claim 1, wherein the adhesive has been heated to 10 to 40% of the total curing calorific value when measured using DSC. 【請求項９】 残存溶媒量が５重量％以下である請求項
１から請求項８のいずれかに記載の接着剤。9. The adhesive according to claim 1, wherein the amount of the residual solvent is 5% by weight or less. 【請求項１０】 動的粘弾性測定装置を用いて測定した
場合の接着剤硬化物の貯蔵弾性率が２５℃で２０〜２０
００ＭＰａであり、２６０℃で３〜５０ＭＰａである請
求項１から請求項９のいずれかに記載の接着剤。10. The cured adhesive has a storage elastic modulus of from 20 to 20 at 25 ° C. as measured using a dynamic viscoelasticity measuring device.
The adhesive according to any one of claims 1 to 9, wherein the adhesive has a pressure of 3 MPa to 50 MPa at 260 ° C. 【請求項１１】 Ｂステージ状態で相分離する２種類の
樹脂及び硬化剤、硬化促進剤を必須成分とする接着剤組
成物であり、Ｂステージ状態において硬化促進剤が分散
相に相溶性を有し、連続相とは相分離することを特徴と
する接着剤。11. An adhesive composition comprising two kinds of resins, a curing agent and a curing accelerator which are phase-separated in a B-stage state as essential components, wherein the curing accelerator has compatibility with the dispersed phase in the B-stage state. And an adhesive characterized by phase separation from the continuous phase. 【請求項１２】 Ｂステージ状態で、分散相がエポキシ
樹脂及び硬化剤を主成分とする相となり、連続相が重量
平均分子量１０万以上の高分子量成分を主成分とする相
となることを特徴とする請求項１１記載の接着剤。12. In the B-stage state, the dispersed phase is a phase mainly composed of an epoxy resin and a curing agent, and the continuous phase is a phase mainly composed of a high molecular weight component having a weight average molecular weight of 100,000 or more. The adhesive according to claim 11, wherein 【請求項１３】 重量平均分子量１０万以上の高分子量
成分がグリシジルメタクリレート又はグリシジルアクリ
レート２〜６重量％を含むアクリル系共重合体であるこ
とを特徴とする請求項１２記載の接着剤。13. The adhesive according to claim 12, wherein the high molecular weight component having a weight average molecular weight of 100,000 or more is an acrylic copolymer containing 2 to 6% by weight of glycidyl methacrylate or glycidyl acrylate. 【請求項１４】 硬化促進剤がエポキシアミンアダクト
化合物である請求項１１〜１３いずれかに記載の接着
剤。14. The adhesive according to claim 11, wherein the curing accelerator is an epoxyamine adduct compound. 【請求項１５】 請求項１〜請求項１４のいずれかに記
載の接着剤をキャリアフィルム上に形成して得られるフ
ィルム状の接着部材。15. A film-like adhesive member obtained by forming the adhesive according to claim 1 on a carrier film. 【請求項１６】 請求項１〜請求項１４のいずれかに記
載の接着剤をコア材の両面に形成して得られる接着部
材。16. An adhesive member obtained by forming the adhesive according to claim 1 on both surfaces of a core material. 【請求項１７】 コア材が耐熱性熱可塑フィルムである
請求項１６に記載の接着部材。17. The adhesive member according to claim 16, wherein the core material is a heat-resistant thermoplastic film. 【請求項１８】 耐熱性熱可塑フィルム材料の軟化点が
２６０℃以上である請求項１７に記載の接着部材。18. The adhesive member according to claim 17, wherein the heat-resistant thermoplastic film material has a softening point of 260 ° C. or higher. 【請求項１９】 コア材または耐熱性熱可塑フィルムが
多孔質フィルムである請求項１７又は請求項１８のいず
れかに記載の接着部材。19. The adhesive member according to claim 17, wherein the core material or the heat-resistant thermoplastic film is a porous film. 【請求項２０】 耐熱性熱可塑フィルムが液晶ポリマで
ある請求項１７〜請求項１９のいずれかに記載の接着部
材。20. The adhesive member according to claim 17, wherein the heat-resistant thermoplastic film is a liquid crystal polymer. 【請求項２１】 耐熱性熱可塑フィルムがポリアミドイ
ミド、ポリイミド、ポリエーテルイミドまたはポリエー
テルスルホンのいずれかである請求項１７〜請求項２０
のいずれかに記載の接着部材。21. The heat-resistant thermoplastic film is any of polyamide imide, polyimide, polyether imide or polyether sulfone.
The adhesive member according to any one of the above. 【請求項２２】 耐熱性熱可塑フィルムがポリテトラフ
ルオロエチレン、エチレンテトラフルオロエチレンコポ
リマー、テトラフルオロエチレン−ヘキサフルオロプロ
ピレンコポリマー、テトラフルオロエチレン−パーフル
オロアルキルビニルエーテルコポリマーのいずれかであ
る請求項１７〜請求項２０のいずれかに記載の接着部
材。22. The heat-resistant thermoplastic film is any one of polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. Item 21. The adhesive member according to any one of items 20. 【請求項２３】 配線基板の半導体チップ搭載面に請求
項１５〜請求項２２のいずれかに記載の接着部材を備え
た半導体搭載用配線基板。23. A wiring board for mounting a semiconductor, comprising the adhesive member according to claim 15 on a semiconductor chip mounting surface of the wiring board. 【請求項２４】 半導体チップと配線基板を請求項１５
〜請求項２２のいずれかに記載の接着部材を用いて接着
させた半導体装置。24. A semiconductor chip and a wiring board.
A semiconductor device bonded using the bonding member according to claim 22. 【請求項２５】 半導体チップの面積が、配線基板の面
積の７０％以上である半導体チップと配線基板を請求項
１５〜請求項２２のいずれかに記載の接着部材を用いて
接着させた半導体装置。25. A semiconductor device wherein a semiconductor chip having an area of a semiconductor chip which is 70% or more of an area of a wiring board and a wiring board are bonded by using the bonding member according to claim 15. .
JP2000180777A 1999-06-18 2000-06-16 Adhesive, adhesive member, wiring board for semiconductor mounting provided with adhesive member, and semiconductor device using the same Expired - Fee Related JP3617417B2 (en)

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