JPH11236535A - Electrode connection adhesive and connected structure of fine electrodes - Google Patents
Electrode connection adhesive and connected structure of fine electrodesInfo
- Publication number
- JPH11236535A JPH11236535A JP3948298A JP3948298A JPH11236535A JP H11236535 A JPH11236535 A JP H11236535A JP 3948298 A JP3948298 A JP 3948298A JP 3948298 A JP3948298 A JP 3948298A JP H11236535 A JPH11236535 A JP H11236535A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- electrode
- connection
- electrode connection
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、第１の電子部品上
の電極と第２の電子部品の電極との間に載置し、相対峙
した電極間を電気的に接続、接着する目的に使用される
電極接続用接着剤及びこれを用いた微細電極の接続構造
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an object to mount between an electrode on a first electronic component and an electrode on a second electronic component, and to electrically connect and bond the opposing electrodes. The present invention relates to an electrode connection adhesive used and a fine electrode connection structure using the same.
【０００２】[0002]
【従来の技術】半導体パッケージや回路基板等の電子部
品の小形薄形化に伴い、これらに用いる電極は高密度・
高精細化している。これら微細電極の接続は、従来の半
田やゴムコネクタ等では対応が困難であることから、最
近では異方導電性の接着剤からなる接続部材が多用され
るようになってきた。この方法は、相対峙する電極間に
導電性材料を所定量含有した接着剤よりなる接続部材層
を設け、加圧もしくは加熱加圧手段を講じることによっ
て、上下電極間の電気的接続と同時に隣接電極間には絶
縁性を付与し、相対峙する電極を接着固定するものであ
る。接着剤の硬化手段としては、熱可塑性接着剤による
室温冷却による固化や熱硬化性樹脂による加熱硬化、光
硬化性樹脂による紫外線や可視光硬化等がある。また、
化学反応による接着剤の硬化手段の１つに、ラジカル重
合反応を利用したものが知られている。これは、熱や光
エネルギーによりラジカルを発生させ、接着剤を重合硬
化するものである。厚み方向にのみ導電性を有する異方
導電性フィルム状接着剤に関する先行技術としては、例
えば特開昭５１−２１１９２号公報に開示されているよ
うに、導電粒子を非導電性ベースにより互いに接触しな
い状態に保持した混合体を、導電粒子の大きさにほぼ等
しい厚さのシート状に成形し、導電粒子を介してシート
状の厚み方向にのみ導電性を有する構造としたものがあ
る。また、紫外線照射によるラジカル重合反応を利用し
た異方導電性接着剤としては、特開昭６０−２６２４３
６号公報等に開示されている方法が知られている。これ
らのラジカル重合反応を利用した異方導電性接着剤は、
アクリロイル基を持つモノマやオリゴマを数種組み合わ
せ、紫外線等でラジカルを発生する光重合開始剤を少量
添加した接着剤組成である。しかし、これまでラジカル
重合反応を利用した異方導電性接着剤では、耐熱性と接
着力を両立した接続信頼性の高い接続が得られないとい
う問題があった。具体的には、これまで接着剤硬化物の
耐熱性を向上して高温条件下での充分な接続信頼性を得
るためには、多官能のアクリルモノマ量を多くし、接着
剤中の反応性基であるアクリル基の濃度を高くする必要
があった。しかし、この方法では高弾性で伸びの小さな
硬化物になるため接着力が低下し、接続界面の剥離が進
行しやすく、充分な接続信頼性が得られなかった。ま
た、接着剤にシランカップリング剤を添加することで接
着力を向上することができるが、シランカップリング剤
の反応を進行させ接着力を向上するためには、接続温度
を高くするか接続時間を長くしなければならず、低温短
時間で硬化可能であるという光硬化性接着剤の特長を充
分に生かすことができなかった。2. Description of the Related Art As electronic components such as semiconductor packages and circuit boards become smaller and thinner, the electrodes used for these components have a higher density and higher density.
High definition. Since connection of these fine electrodes is difficult with conventional solder or rubber connectors, connection members made of anisotropically conductive adhesives have recently been used frequently. According to this method, a connection member layer made of an adhesive containing a predetermined amount of a conductive material is provided between opposing electrodes, and a pressing or heating / pressing means is used to simultaneously connect the upper and lower electrodes simultaneously with the adjacent electrodes. An insulating property is provided between the electrodes, and the opposing electrodes are bonded and fixed. Examples of the means for curing the adhesive include solidification by cooling at room temperature with a thermoplastic adhesive, heat curing with a thermosetting resin, and ultraviolet or visible light curing with a photocurable resin. Also,
As one of means for curing an adhesive by a chemical reaction, a method utilizing a radical polymerization reaction is known. In this method, radicals are generated by heat or light energy to polymerize and cure the adhesive. As a prior art relating to an anisotropic conductive film adhesive having conductivity only in the thickness direction, for example, as disclosed in JP-A-51-21192, conductive particles are not brought into contact with each other by a non-conductive base. There is a structure in which the mixture held in a state is formed into a sheet having a thickness substantially equal to the size of the conductive particles, and has a structure having conductivity only in the thickness direction of the sheet via the conductive particles. Further, as an anisotropic conductive adhesive utilizing a radical polymerization reaction by ultraviolet irradiation, JP-A-60-26243
A method disclosed in, for example, Japanese Patent Application Laid-Open No. 6-206 is known. Anisotropic conductive adhesives utilizing these radical polymerization reactions are:
An adhesive composition comprising a combination of several kinds of monomers and oligomers having an acryloyl group and a small amount of a photopolymerization initiator which generates radicals by ultraviolet rays or the like. However, there has been a problem that an anisotropic conductive adhesive utilizing a radical polymerization reaction has not been able to obtain a connection having high heat resistance and adhesive strength and high connection reliability. Specifically, in order to improve the heat resistance of the cured adhesive and obtain sufficient connection reliability under high temperature conditions, the amount of polyfunctional acrylic monomer should be increased and the reactivity in the adhesive It was necessary to increase the concentration of the acrylic group as the base. However, in this method, a cured product having a high elasticity and a small elongation is obtained, so that the adhesive force is reduced, the peeling of the connection interface is apt to proceed, and sufficient connection reliability cannot be obtained. Further, by adding a silane coupling agent to the adhesive, the adhesive strength can be improved. However, in order to promote the reaction of the silane coupling agent and improve the adhesive strength, increase the connection temperature or the connection time. However, the advantage of the photocurable adhesive that it can be cured in a short time at a low temperature cannot be fully utilized.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、かかる状況
に鑑みてなされたもので、接着力並びに接続信頼性に優
れた電極接続用接着剤の新規な構成を提供せんとするも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel structure of an electrode connecting adhesive excellent in adhesive strength and connection reliability.
【０００４】[0004]
【課題を解決するための手段】すなわち本発明は、光酸
発生剤、シランカップリング剤、ラジカル重合性アクリ
ル化合物、光反応開始剤を必須成分とする電極接続用接
着剤および前記電極接続用接着剤を用いた微細電極の接
続構造に関する。That is, the present invention provides an electrode connecting adhesive comprising a photoacid generator, a silane coupling agent, a radically polymerizable acrylic compound, and a photoreaction initiator as essential components, and the electrode connecting adhesive. The present invention relates to a connection structure for fine electrodes using an agent.
【０００５】[0005]
【発明の実施の形態】本発明は、電極接続用接着剤の必
須成分として光酸発生剤、シランカップリング剤、ラジ
カル重合性アクリル化合物、光反応開始剤を用いること
より、低温の接続条件でも接着力が高く接続信頼性の優
れた電極接続用接着剤が得られるようになる。光酸発生
剤は光を吸収し酸を発生する物質で、生成した酸はシラ
ンカップリング剤のアルコキシシラン基の加水分解縮合
反応の反応触媒として働き、光硬化性の電極接続用接着
剤と被着体である基板との接着力を高めることができ
る。よって、従来の加熱のみでシランカップリング剤の
アルコキシシラン基の加水分解縮合反応を進める場合よ
りも低温で速やかに反応が進ので、低温の接続条件で高
い接着力が得られ、低温接続時の接続信頼性を向上でき
る。光酸発生剤としては、種々のスルホニウム塩やヨー
ドニウム塩が使用できるが、触媒活性が高いスルホニウ
ム塩の方がより大きな反応促進硬化が得られるので好ま
しい。シランカップリング剤としては、種々のアルコキ
シシランが使用できるが、あアクリロイル基を含有した
ものは、接着剤成分のラジカル重合性アクリル化合物と
重合反応し、接着剤硬化物の一部となるのでより高い接
着力が得られるので好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention uses a photoacid generator, a silane coupling agent, a radically polymerizable acrylic compound, and a photoreaction initiator as essential components of an adhesive for electrode connection, so that even under low temperature connection conditions. An adhesive for electrode connection with high adhesive strength and excellent connection reliability can be obtained. A photoacid generator is a substance that absorbs light to generate an acid. The generated acid acts as a reaction catalyst for the hydrolysis-condensation reaction of the alkoxysilane group of the silane coupling agent, and is coated with a photocurable adhesive for electrode connection. It is possible to increase the adhesive strength with the substrate as the body. Therefore, since the reaction proceeds more quickly at a lower temperature than when the hydrolysis-condensation reaction of the alkoxysilane group of the silane coupling agent proceeds only by conventional heating, a high adhesive force is obtained under low-temperature connection conditions, Connection reliability can be improved. As the photoacid generator, various sulfonium salts and iodonium salts can be used, but a sulfonium salt having high catalytic activity is preferable because a larger reaction-accelerated curing can be obtained. As the silane coupling agent, various alkoxysilanes can be used, but those containing an acryloyl group undergo a polymerization reaction with the radically polymerizable acrylic compound of the adhesive component and become a part of the cured adhesive. It is preferable because a high adhesive strength can be obtained.
【０００６】ラジカル重合性アクリル化合物としては、
アクリロイル基を持つ種々のメタクリレートやアクリレ
ート化合物のモノマあるいはオリゴマが用いられる。な
かでも接着剤の硬化物の弾性率や耐熱性からアクリロイ
ル基を２つ持つものを添加することが好ましい。具体的
にはアクリルモノマとしては、例えばポリエチレングリ
コールやポリプロピレングリコールの骨格の両端にアク
リルあるいはメタクリル基があるものやビスフェノール
骨格の両端にアクリルあるいはメタクリル基があるもの
等を用いることができる。また、トリメチロールプロパ
ントリメタクリレートやテトラメチロールメタンテトラ
アクリレート等のアクリロイル基を３つ以上持つものも
適量添加することで耐熱性を向上することができる。ア
クリルオリゴマとしては、ポリエステルアクリレートや
エポキシアクリレート、ウレタンアクリレート等のオリ
ゴマを用いることができる。光反応開始剤としては、ア
セトフェノン、ベンゾイン、ベンゾフェノン等の誘導体
が紫外線による反応開始剤として使用でき、ジカルボニ
ル化合物、チオキサントン、アシルホスフィンオキサイ
ド等の誘導体は、可視光による反応開始剤として使用で
きる。また、これらにアミン化合物等の光反応促進剤を
併用することはより、硬化反応を速やかに進行させるの
で好ましい。The radically polymerizable acrylic compound includes:
Monomers or oligomers of various methacrylate or acrylate compounds having an acryloyl group are used. Above all, it is preferable to add one having two acryloyl groups from the viewpoint of the elastic modulus and heat resistance of the cured product of the adhesive. Specifically, as the acryl monomer, for example, those having an acryl or methacryl group at both ends of a skeleton of polyethylene glycol or polypropylene glycol or those having an acryl or methacryl group at both ends of a bisphenol skeleton can be used. Heat resistance can be improved by adding an appropriate amount of a compound having three or more acryloyl groups such as trimethylolpropane trimethacrylate and tetramethylolmethanetetraacrylate. As the acrylic oligomer, oligomers such as polyester acrylate, epoxy acrylate, and urethane acrylate can be used. As the photoreaction initiator, derivatives such as acetophenone, benzoin, and benzophenone can be used as a reaction initiator by ultraviolet light, and derivatives such as dicarbonyl compounds, thioxanthone, and acylphosphine oxide can be used as reaction initiators by visible light. It is preferable to use a photoreaction accelerator such as an amine compound in combination with these, since the curing reaction proceeds more quickly.
【０００７】また、接着剤成分の一部として、分子量１
０，０００以上のフェノキシ樹脂、ポリエステル、ポリ
ビニルブチラール、フェノール樹脂等の水酸基含有樹脂
を添加すると、高分子化合物による硬化物の靭性の増加
と水酸基による接着性が増し、信頼性が向上する。なか
でもフェノキシ樹脂の水酸基にイソシアネート基を有す
るアクリルモノマを反応させ、側鎖にアクリロイル基を
導入したアクリル変成フェノキシ樹脂を用いると、接続
時に接着剤中のアクリル樹脂と反応するので、より耐熱
性を向上することができる。アクリル変成フェノキシ樹
脂中のビスフェノール構造に対するアクリロイル基の割
合は、０．１から１の範囲で顕著な硬化物の耐熱性の向
上が得られ、硬化物のガラス転移温度は、アクリロイル
基の割合が大きくなるにつれ高くなる。よって、所望の
耐熱性はアクリル変成フェノキシ樹脂中のビスフェノー
ル構造に対するアクリロイル基の割合を調節することで
得ることができる。しかし、アクリロイル基の割合が多
くなるにつれ硬化物の靭性が損なわれる傾向があり、ビ
スフェノール構造に対するアクリロイル基の割合がおお
むね０．１から０．５の範囲で、さらに最適な耐熱性と
靭性の両立が得られる。Further, as a part of the adhesive component, a molecular weight of 1
When a hydroxyl group-containing resin such as phenoxy resin, polyester, polyvinyl butyral, or phenol resin of 000 or more is added, the toughness of the cured product by the polymer compound and the adhesion by the hydroxyl group are increased, and the reliability is improved. Above all, when an acrylic monomer having an isocyanate group is reacted with a hydroxyl group of a phenoxy resin and an acrylic modified phenoxy resin having an acryloyl group introduced into a side chain is used, it reacts with an acrylic resin in an adhesive at the time of connection, so that more heat resistance is obtained. Can be improved. The ratio of the acryloyl group to the bisphenol structure in the acryl-modified phenoxy resin is in the range of 0.1 to 1, whereby a remarkable improvement in the heat resistance of the cured product is obtained, and the glass transition temperature of the cured product has a large ratio of the acryloyl group. It becomes higher as it becomes. Therefore, the desired heat resistance can be obtained by adjusting the ratio of the acryloyl group to the bisphenol structure in the acrylic modified phenoxy resin. However, as the proportion of acryloyl groups increases, the toughness of the cured product tends to be impaired. When the proportion of acryloyl groups to the bisphenol structure is generally in the range of 0.1 to 0.5, more optimal compatibility between heat resistance and toughness is achieved. Is obtained.
【０００８】ここで、ビスフェノール構造に対するアク
リロイル基の割合とは、分子中に含まれるビスフェノー
ル構造の数と分子中に含まれるアクリロイル基の数の比
を表している。すなわち、分子中のビスフェノール構造
の数と分子中のアクリロイル基の数が同数のとき、ビス
フェノール構造に対するアクリロイル基の割合は１であ
り、分子中のビスフェノール構造の数に対して分子中の
アクリロイル基の数が１／１０のとき、ビスフェノール
構造に対するアクリロイル基の割合は０．１である。ま
た、固形の高分子化合物を適量添加することで、取り扱
い性やポットライフに優れたフィルム状の電極接続用接
着剤とすることができる。このフィルム状の電極接続用
接着剤の厚みは特に限定するものではないが、接続する
電極部分の凹凸に接着剤が充填することで接着力や耐湿
性が向上することから、ＦＰＣ等の電極部の凹凸以上の
厚みが適当である。また、薄くなると取り扱いが容易で
なく、しわの発生等により製造が困難になってくること
から、０．００５ｍｍ〜１ｍｍが適当である。この接続
工程で接着した硬化物のガラス転移温度は、前記の通り
アクリル変成フェノキシ樹脂のビスフェノール構造に対
するアクリロイル基の割合や、アクリルモノマやアクリ
ルオリゴの構造や配合比で変化するが、ガラス転移温度
が１００℃以上であるとき、８５℃８５％ＲＨの高温高
湿試験や−４０℃〜１００℃の熱衝撃試験等の加速試験
で接続部の剥離が無く、低抵抗な特に良好な接続信頼性
が得られる。また、この電極接続用接着剤に導電粒子を
添加することで、さらに接続抵抗が小さく、高温高湿試
験や熱サイクル試験等における抵抗上昇が抑えられた高
信頼性の接続が得られる。この導電粒子は、Ｎｉ等の金
属粒子や樹脂粒子の表面に、ＮｉやＡｕのめっき層を設
けた金属めっき樹脂粒子を単独または複合して使用する
ことができる。これらの導電粒子の材質は、接続する電
極の堅さや変形性等の特性により最適なものを選択して
用いる。また、粒径は、接続する回路の細かさにより選
択されるが、各粒子の粒径はできるだけ均一である必要
がある。また、本発明の電極接続用接着剤は、上記した
電極の接続材料だけでなく、多層回路部材の層間接続材
等への応用が可能である。Here, the ratio of the acryloyl group to the bisphenol structure indicates the ratio of the number of bisphenol structures contained in the molecule to the number of acryloyl groups contained in the molecule. That is, when the number of bisphenol structures in a molecule and the number of acryloyl groups in a molecule are the same, the ratio of acryloyl groups to bisphenol structures is 1, and the ratio of acryloyl groups in the molecule to the number of bisphenol structures in the molecule is one. When the number is 1/10, the ratio of the acryloyl group to the bisphenol structure is 0.1. In addition, by adding an appropriate amount of a solid polymer compound, a film-shaped adhesive for electrode connection excellent in handleability and pot life can be obtained. The thickness of the film-like electrode connection adhesive is not particularly limited, but the adhesive strength and moisture resistance are improved by filling the unevenness of the electrode part to be connected with the adhesive. It is appropriate that the thickness is not less than the irregularities. Further, when the thickness is reduced, the handling is not easy, and the production becomes difficult due to generation of wrinkles and the like. Therefore, 0.005 mm to 1 mm is appropriate. The glass transition temperature of the cured product adhered in this connection step varies depending on the ratio of acryloyl groups to the bisphenol structure of the acrylic-modified phenoxy resin and the structure and blending ratio of acrylic monomers and oligos, as described above. When the temperature is 100 ° C. or higher, there is no peeling of the connection part in an accelerated test such as a high-temperature and high-humidity test at 85 ° C. and 85% RH or a thermal shock test at −40 ° C. to 100 ° C., and particularly good connection reliability with low resistance is obtained. can get. In addition, by adding conductive particles to the adhesive for electrode connection, a highly reliable connection can be obtained in which the connection resistance is further reduced and the resistance increase in a high-temperature high-humidity test, a heat cycle test, or the like is suppressed. As the conductive particles, metal-plated resin particles in which a Ni or Au plating layer is provided on the surface of metal particles such as Ni or resin particles can be used alone or in combination. The material of these conductive particles is selected and used in accordance with characteristics such as hardness and deformability of the electrode to be connected. The particle size is selected depending on the fineness of the circuit to be connected, but the particle size of each particle needs to be as uniform as possible. The adhesive for electrode connection of the present invention can be applied not only to the above-mentioned electrode connection material but also to an interlayer connection material of a multilayer circuit member.
【０００９】[0009]
【実施例】以下、本発明の実施例に基づいて詳細を説明
するが、本発明はこれに限定されるものではない。本実
施例と比較例に使用した材料と評価方法を以下に示す。
光酸発生剤は芳香族スルホニウム塩（三新化学工業株式
会社製、商品名サンエイド）を使用した。シランカップ
リング剤はγ−メタクリロキシプロピルトリメトキシシ
ラン（東レ・ダウコーニング・シリコーン株式会社製、
商品名ＳＺ６０３０）を使用した。ラジカル重合性アク
リル化合物として、ウレタンアクリレートオリゴマ（新
中村化学工業株式会社製、商品名ＵＡ−１２２Ｐ）を使
用し、多官能のアクリルモノマであるテトラメチロール
メタントリアクリレート（新中村化学工業株式会社製、
商品名Ａ−ＴＭＭ−３Ｌ）を用いた。光反応開始剤とし
てはベンゾフェノン（試薬）を４％、光反応促進剤とし
て４，４−ビスジエチルアミノベンゾフェノン（保土ヶ
谷化学工業株式会社製、商品名ＥＡＢ）を１％添加し
た。水酸基含有樹脂としては、ポリビニルブチラール樹
脂（電気化学工業株式会社製、商品名ＰＶＢ３０００
Ｋ）とフェノキシ樹脂（ユニオンカーバイド株式会社
製、商品名ＰＫＨＣ）を用いた。アクリル変成フェノキ
シ樹脂は、フェノキシ樹脂（ユニオンカーバイド株式会
社製、商品名ＰＫＨＣ）と２−メタクリロイルオキシエ
チルイソシアネート（昭和電工株式会社製、商品名カレ
ンズＭＯＩ）を反応させて得たものを用いた。導電粒子
は、平均粒径５μｍのポリスチレン球状粒子の表面に
０．１μｍのＮｉ層とＡｕ層を設けたものを使用した。
液状の電極接続用接着剤はシリンジ状ディスペンサを用
い、電極上に塗布して接続した。フィルム状の電極接続
用接着剤は、メチルエチルケトンや酢酸エチルの溶剤で
希釈した接着剤をアプリケーターでテフロンフィルム上
に塗布したのち乾燥し、約２０μｍの厚さのフィルム状
に成形した。接続時にはフィルム状の電極接続用接着剤
をテフロンフィルムから電極面に転写し、テフロンフィ
ルムを除去して用いた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited thereto. The materials and evaluation methods used in this example and comparative examples are shown below.
As the photoacid generator, an aromatic sulfonium salt (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sun Aid) was used. The silane coupling agent is γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd.
(Trade name: SZ6030) was used. A urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: UA-122P) is used as the radical polymerizable acrylic compound, and tetramethylol methane triacrylate, a multifunctional acrylic monomer (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Trade name A-TMM-3L) was used. 4% of benzophenone (reagent) was added as a photoreaction initiator, and 1% of 4,4-bisdiethylaminobenzophenone (trade name: EAB, manufactured by Hodogaya Chemical Industry Co., Ltd.) was added as a photoreaction accelerator. As the hydroxyl group-containing resin, polyvinyl butyral resin (trade name: PVB3000, manufactured by Denki Kagaku Kogyo KK)
K) and a phenoxy resin (PKHC, manufactured by Union Carbide Co., Ltd.). As the acrylic modified phenoxy resin, a resin obtained by reacting a phenoxy resin (trade name PKHC, manufactured by Union Carbide Co., Ltd.) with 2-methacryloyloxyethyl isocyanate (trade name, Karenz MOI, manufactured by Showa Denko KK) was used. As the conductive particles, those obtained by providing a 0.1 μm Ni layer and an Au layer on the surface of polystyrene spherical particles having an average particle diameter of 5 μm were used.
The liquid electrode connection adhesive was applied onto the electrodes using a syringe dispenser and connected. The film-form electrode connection adhesive was prepared by applying an adhesive diluted with a solvent such as methyl ethyl ketone or ethyl acetate onto a Teflon film using an applicator and then drying the film to form a film having a thickness of about 20 μm. At the time of connection, a film-like adhesive for electrode connection was transferred from the Teflon film to the electrode surface, and the Teflon film was removed before use.
【００１０】接続信頼性の評価は、ポリイミドフィルム
上にライン幅５０μｍピッチ１００μｍ厚さ１８μｍの
平行配列した銅電極を１００本有するＦＰＣと、表面抵
抗２０Ω／□のＩＴＯ電極を有するガラス基板とを電極
接続用接着剤により接続した試料を用いて行った。接続
方法は、圧力２０ｋｇ／ｃｍ2で１３０℃２０秒間のま
たは１５０℃３０秒間の加圧加熱状態で、接着剤に約２
Ｊ／ｃｍ2の紫外線を照射し接続した。紫外線は高圧水
銀ランプを光源とし、光ファイバにより接続部の接着剤
に紫外線を導入する方法で照射した。フィルム状に成形
した硬化済みの接着剤について動的粘弾性測定を行い、
ガラス転移温度を測定し、耐熱性の指標とした。硬化済
み接着剤の作製条件は、１３０℃で紫外線を２Ｊ照射し
た硬化物を使用した。接続抵抗は、１ｍＡの測定電流で
各ラインごとに測定し、平均値を接続抵抗とした。信頼
性評価は、−４０℃と１００℃の各試験槽に交互に試料
を入れる熱サイクル試験１０００サイクルにて行った。
接着力の評価は、ＦＰＣのＩＴＯガラスへの接着性を９
０度剥離試験にて測定した。The connection reliability was evaluated by using an FPC having 100 parallel copper electrodes with a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm on a polyimide film, and a glass substrate having an ITO electrode with a surface resistance of 20 Ω / □. The test was performed using samples connected by a connection adhesive. The connection method is as follows. The pressure is 20 kg / cm 2 at 130 ° C. for 20 seconds or 150 ° C. for 30 seconds.
The connection was made by irradiating ultraviolet rays of J / cm 2 . Ultraviolet rays were irradiated by a method using a high-pressure mercury lamp as a light source and introducing ultraviolet rays into an adhesive at a connection portion by an optical fiber. Perform dynamic viscoelastic measurement on the cured adhesive molded into a film,
The glass transition temperature was measured and used as an index of heat resistance. As a preparation condition of the cured adhesive, a cured product irradiated with 2 J of ultraviolet rays at 130 ° C. was used. The connection resistance was measured for each line at a measurement current of 1 mA, and the average value was defined as the connection resistance. The reliability evaluation was performed by a heat cycle test of 1000 cycles in which samples were alternately put into test tanks at −40 ° C. and 100 ° C.
The evaluation of the adhesion was performed by measuring the adhesion of FPC to ITO glass by 9
It was measured by a 0 degree peel test.
【００１１】実施例１ ウレタンアクリレートオリゴマ６０％（重量、以下同
じ）、テトラメチロールメタントリアクリレート２２
％、シランカップリング剤１０％、光酸発生剤３％、光
反応開始剤４％、光反応促進剤１％を均一混合し、回路
接続用接着剤を作製した。Example 1 60% urethane acrylate oligomer (weight, same hereafter), tetramethylol methane triacrylate 22
%, A silane coupling agent 10%, a photoacid generator 3%, a photoreaction initiator 4%, and a photoreaction accelerator 1% were uniformly mixed to prepare a circuit connection adhesive.
【００１２】実施例２ ポリビニルブチラール樹脂４０％、ウレタンアクリレー
トオリゴマ３０％、テトラメチロールメタントリアクリ
レート１２％、シランカップリング剤１０％、光酸発生
剤３％、光反応開始剤４％、光反応促進剤１％を均一混
合し、フィルム状回路接続用接着剤を作製した。Example 2 40% polyvinyl butyral resin, 30% urethane acrylate oligomer, 12% tetramethylol methane triacrylate, 10% silane coupling agent, 3% photoacid generator, 4% photoreaction initiator, 4% photoreaction 1% of the agent was uniformly mixed to prepare a film-like circuit-connecting adhesive.
【００１３】実施例３ フェノキシ樹脂４０％、ウレタンアクリレートオリゴマ
３０％、テトラメチロールメタントリアクリレート１２
％、シランカップリング剤１０％、光酸発生剤３％、光
反応促進剤１％を均一混合し、フィルム状回路接続用接
着剤を作製した。Example 3 40% phenoxy resin, 30% urethane acrylate oligomer, 12 tetramethylol methane triacrylate
%, A silane coupling agent 10%, a photoacid generator 3%, and a photoreaction accelerator 1% were uniformly mixed to prepare a film-like circuit connection adhesive.
【００１４】実施例４ ビスフェノール構造に対するアクリロイル基の割合が
０．１であるアクリル変成フェノキシ樹脂４０％、ウレ
タンアクリレートオリゴマ３０％、テトラメチロールメ
タントリアクリレート１２％、シランカップリング剤１
０％、光酸発生剤３％、光反応開始剤４％、光反応促進
剤１％を均一混合し、フィルム状回路接続用接着剤を作
製した。Example 4 40% of an acrylic modified phenoxy resin having a ratio of acryloyl group to bisphenol structure of 0.1, urethane acrylate oligomer 30%, tetramethylol methane triacrylate 12%, silane coupling agent 1
0%, 3% of a photoacid generator, 4% of a photoreaction initiator, and 1% of a photoreaction accelerator were uniformly mixed to prepare a film-like circuit-connecting adhesive.
【００１５】実施例５ ビスフェノール構造に対するアクリロイル基の割合が
０．３であるアクリル変成フェノキシ樹脂４０％、ウレ
タンアクリレートオリゴマ３０％、テトラメチロールメ
タントリアクリレート１２％、シランカップリング剤１
０％、光酸発生剤３％、光反応開始剤４％、光反応促進
剤１％を均一混合し、フィルム状回路接続用接着剤を作
製した。Example 5 40% of an acrylic modified phenoxy resin having a ratio of acryloyl group to bisphenol structure of 0.3, urethane acrylate oligomer 30%, tetramethylolmethane triacrylate 12%, silane coupling agent 1
0%, 3% of a photoacid generator, 4% of a photoreaction initiator, and 1% of a photoreaction accelerator were uniformly mixed to prepare a film-like circuit-connecting adhesive.
【００１６】実施例６〜実施例１０ 実施例１から５に導電粒子を５体積％添加したものをそ
れぞれ実施例６から実施例１０とした。Examples 6 to 10 Examples 6 to 10 were obtained by adding conductive particles of 5% by volume to Examples 1 to 5, respectively.
【００１７】比較例１〜比較例１０ 実施例１から１０の光酸発生剤を添加していないものを
それぞれ比較例１から１０とした。各実施例と比較例の
ガラス転移温度、１３０℃２０秒接続での接着力、１５
０℃３０秒接続での接着力、初期接続抵抗、信頼性試験
後の接続抵抗を表１に示した。本発明にかかる電極接続
用接着剤はいづれも比較的低い温度の接続条件でも接着
力にすぐれ、かつ接続信頼性に優れている。Comparative Examples 1 to 10 Comparative Examples 1 to 10 were prepared without adding the photoacid generator of Examples 1 to 10. Glass transition temperature of each Example and Comparative Example, adhesive strength at 130 ° C. for 20 seconds connection, 15
Table 1 shows the adhesive strength at 0 ° C. for 30 seconds, the initial connection resistance, and the connection resistance after the reliability test. The adhesive for electrode connection according to the present invention has excellent adhesive strength even under relatively low temperature connection conditions, and is excellent in connection reliability.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】請求項１記載の電極接続用接着剤は、低
温の接続条件で高い接着力が得られ、接続信頼性の高い
接続を得るのに好適である。請求項２記載の電極接続用
接着剤は、請求項１記載の効果を奏し、さらに低温の接
続条件で接着性が優れる。請求項３記載の電極接続用接
着剤は、請求項１乃至２記載の効果を奏し、さらに接着
力と接続信頼性が優れる。請求項４記載の電極接続用接
着剤は、請求項１乃至３記載の効果を奏し、接着力と接
続信頼性に優れたフィルム状の電極接続用接着剤を得る
のに好適である。請求項５記載の電極接続用接着剤は、
請求項１乃至４記載の効果を奏し、さらに接着力と接続
信頼性に優れたフィルム状の電極接続用接着剤が得られ
る。請求項６記載の電極接続用接着剤は、請求項１乃至
５記載の効果を奏し、さらに耐熱性が高い電極接続用接
着剤が得られる。請求項７記載の電極接続用接着剤は、
請求項１乃至６記載の効果を奏し、耐熱信頼性が高い電
極接続用接着剤が得られる。請求項８記載の電極接続用
接着剤は、請求項１乃至７記載の効果を奏し、信頼性試
験後の接続抵抗の上昇量が少ない電極接続用接着剤が得
られる。請求項９記載の電極接続用接着剤は、請求項１
乃至８記載の効果を奏し、接着力と接続信頼性が高い微
細電極の接続構造を提供することができる。The adhesive for electrode connection according to the first aspect is suitable for obtaining a high adhesive strength under low-temperature connection conditions and for obtaining a connection with high connection reliability. The adhesive for electrode connection according to the second aspect has the effect of the first aspect, and further has excellent adhesiveness under low-temperature connection conditions. The adhesive for electrode connection according to the third aspect has the effects described in the first and second aspects, and further has excellent adhesive strength and connection reliability. The electrode connecting adhesive according to the fourth aspect has the effects described in the first to third aspects, and is suitable for obtaining a film-shaped electrode connecting adhesive excellent in adhesive strength and connection reliability. The adhesive for electrode connection according to claim 5,
The effects described in claims 1 to 4 are exhibited, and a film-like electrode connection adhesive excellent in adhesive strength and connection reliability can be obtained. The adhesive for electrode connection according to the sixth aspect has the effects of the first to fifth aspects, and an adhesive for electrode connection having higher heat resistance can be obtained. The adhesive for electrode connection according to claim 7,
The effects of claims 1 to 6 are achieved, and an electrode connection adhesive having high heat resistance reliability can be obtained. The electrode connection adhesive according to the eighth aspect has the effects described in the first to seventh aspects, and an electrode connection adhesive having a small increase in connection resistance after a reliability test can be obtained. The adhesive for electrode connection according to the ninth aspect is the first aspect.
8 to provide a connection structure of a fine electrode with high adhesive strength and high connection reliability.
【図１】本発明にかかる導電粒子を含有した電極接続用
接着剤を用いた電極接続構造の断面図。FIG. 1 is a cross-sectional view of an electrode connection structure using an electrode connection adhesive containing conductive particles according to the present invention.
１ 電極接続用接着剤 ２ 接着剤 ３ 導電粒子 ４ 第１の電極 ５ 第２の電極 DESCRIPTION OF SYMBOLS 1 Adhesive for electrode connection 2 Adhesive 3 Conductive particles 4 First electrode 5 Second electrode
フロントページの続き (72)発明者 松田 和也 茨城県下館市大字五所宮1150番地 日立化 成工業株式会社五所宮工場内 (72)発明者 藤井 正規 茨城県下館市大字五所宮1150番地 日立化 成工業株式会社五所宮工場内 (72)発明者 保田 裕司 茨城県下館市大字五所宮1150番地 日立化 成工業株式会社五所宮工場内Continued on the front page (72) Inventor Kazuya Matsuda 1150 Goshomiya, Oaza, Shimodate City, Ibaraki Pref.Hitachi Kasei Kogyo Co., Ltd. (72) Inventor, Yuji Yasuda, Gozomiya, Shimodate, Ibaraki, 1150 Goshomiya Plant, Hitachi Chemical Co., Ltd.
Claims (9)
の電極との間に載置し、相対峙した電極間を電気的に接
続、接着する目的に使用される電極接続用接着剤におい
て、光酸発生剤、シランカップリング剤、ラジカル重合
性アクリル化合物、光反応開始剤を必須成分としてなる
電極接続用接着剤。An electrode connecting member which is placed between an electrode on a first electronic component and an electrode of a second electronic component, and is used for electrically connecting and bonding opposing electrodes. An adhesive for electrode connection comprising, as essential components, a photoacid generator, a silane coupling agent, a radically polymerizable acrylic compound, and a photoreaction initiator.
１記載の電極接続用接着剤。2. The electrode connecting adhesive according to claim 1, wherein the photoacid generator is a sulfonium salt.
有アルコキシシランである請求項１又は２記載の電極接
続用接着剤。3. The adhesive for electrode connection according to claim 1, wherein the silane coupling agent is an acryloyl group-containing alkoxysilane.
をさらに添加した請求項１乃至３のいづれかに記載の電
極接続用接着剤。4. The electrode connecting adhesive according to claim 1, further comprising a hydroxyl group-containing resin having a molecular weight of 10,000 or more.
求項４記載の電極接続用接着剤。5. The adhesive for electrode connection according to claim 4, wherein the hydroxyl group-containing resin is a phenoxy resin.
樹脂である請求項５記載の電極接続用接着剤。6. The electrode connecting adhesive according to claim 5, wherein the phenoxy resin is an acrylic modified phenoxy resin.
ある請求項１乃至６のいづれかに記載の電極接続用接着
剤。7. The adhesive for electrode connection according to claim 1, wherein the cured product has a glass transition temperature of 100 ° C. or higher.
れかに記載の電極接続用接着剤。8. The electrode connecting adhesive according to claim 1, further comprising conductive particles.
を用いた微細電極の接続構造。9. A connection structure for fine electrodes using the adhesive for electrode connection according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03948298A JP4151101B2 (en) | 1998-02-23 | 1998-02-23 | Electrode connecting adhesive, fine electrode connecting structure using the same, and electrode connecting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03948298A JP4151101B2 (en) | 1998-02-23 | 1998-02-23 | Electrode connecting adhesive, fine electrode connecting structure using the same, and electrode connecting method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008076341A Division JP2008258607A (en) | 2008-03-24 | 2008-03-24 | Adhesive for electrode connection, connection structure of fine electrode using this, and connection method of electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11236535A true JPH11236535A (en) | 1999-08-31 |
| JP4151101B2 JP4151101B2 (en) | 2008-09-17 |
Family
ID=12554288
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03948298A Expired - Fee Related JP4151101B2 (en) | 1998-02-23 | 1998-02-23 | Electrode connecting adhesive, fine electrode connecting structure using the same, and electrode connecting method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4151101B2 (en) |
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| WO2015137008A1 (en) * | 2014-03-11 | 2015-09-17 | デクセリアルズ株式会社 | Anisotropic conductive adhesive, method for producing connector and method for connecting electronic component |
| JP2015172109A (en) * | 2014-03-11 | 2015-10-01 | デクセリアルズ株式会社 | Anisotropic conductive adhesive, method for producing connector and method for connecting electronic components |
| KR20160130977A (en) * | 2014-03-11 | 2016-11-15 | 데쿠세리아루즈 가부시키가이샤 | Anisotropic conductive adhesive, method for producing connector and method for connecting electronic component |
| WO2017061545A1 (en) * | 2015-10-07 | 2017-04-13 | 積水化学工業株式会社 | Poly(vinyl acetal) resin composition, adhesive sheet, interlaminar filling material for touch panel, and laminate |
| JPWO2017061545A1 (en) * | 2015-10-07 | 2018-07-26 | 積水化学工業株式会社 | Polyvinyl acetal resin composition, adhesive sheet, interlayer filling material for touch panel, and laminate |
| JP2018065916A (en) * | 2016-10-19 | 2018-04-26 | デクセリアルズ株式会社 | Method for producing connection body |
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