JP4572562B2 - Film adhesive - Google Patents
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Description
本発明は、多数の電極や回路が設けられたシートやフィルム間を接着しかつ電気的に接続するフィルム状接着剤に関する。 The present invention relates to a film adhesive that bonds and electrically connects sheets and films provided with a large number of electrodes and circuits.
液晶製品内の電子部品の基板上に形成された電極と回路との接続等、電極（電気端子）や回路をその上に狭ピッチで多数設けたシートやフィルム間を接着しかつ電気的に接続する手段として、導電粒子を含有するフィルム状接着剤が用いられている。フィルム状接着剤は、一般的に、フィルム状の絶縁性接着性樹脂中に導電粒子を分散させたシート状の接着剤であり、接合対象の間に挟まれ、加圧、加熱されて接合対象を接着する。 Adhesion and electrical connection between sheets and films provided with a large number of electrodes (electrical terminals) and circuits on the substrate, such as connection between electrodes and circuits formed on the substrate of electronic components in liquid crystal products As a means to do this, a film adhesive containing conductive particles is used. A film-like adhesive is generally a sheet-like adhesive in which conductive particles are dispersed in a film-like insulating adhesive resin. The film-like adhesive is sandwiched between objects to be joined, pressurized and heated to be joined. Glue.
すなわち、加圧、加熱により、シート状の樹脂が流動し、それぞれの接合対象上の相対峙する電極間の隙間を封止すると同時に、導電粒子の一部が対峙する電極間に噛み込まれて電気的接続が達成される That is, by pressurization and heating, the sheet-like resin flows and seals the gaps between the electrodes facing each other, and at the same time, some of the conductive particles are caught between the electrodes facing each other. Electrical connection is achieved
フィルム状接着剤は、液晶表示装置（ＬＣＤ）等の精密機器周辺の接続に使用されるため高い信頼性が要求されている。そこで、導通／絶縁性能に加え、耐環境性が求められており、例えばＬＣＤへ適用される場合は、６０℃−９０％×１０００時間の高温高湿試験や８５℃×１０００時間の高温放置試験に耐えられる高い耐熱性、耐湿性等が要求される。 A film adhesive is required to have high reliability because it is used for connection around precision equipment such as a liquid crystal display (LCD). Therefore, in addition to conduction / insulation performance, environmental resistance is required. For example, when applied to LCDs, a high-temperature and high-humidity test of 60 ° C.-90% × 1000 hours and a high temperature storage test of 85 ° C. × 1000 hours High heat resistance and moisture resistance that can withstand
従来、フィルム状接着剤を構成する絶縁性接着性樹脂としては主にエポキシ系の熱硬化性樹脂組成物が用いられていた。特に、フィルム形状を維持するための平均分子量約５００００程度の高分子量エポキシ樹脂（フェノキシ樹脂）と、加熱時に速やかに反応し接着性能を発現する平均分子量約４００程度の低分子量エポキシ樹脂及び硬化剤とから成る組成物が広く使用されていた。 Conventionally, epoxy-based thermosetting resin compositions have been mainly used as insulating adhesive resins constituting film adhesives. In particular, a high molecular weight epoxy resin (phenoxy resin) having an average molecular weight of about 50,000 for maintaining the film shape, a low molecular weight epoxy resin having an average molecular weight of about 400 and a curing agent that reacts quickly upon heating and exhibits adhesive performance; Compositions consisting of were widely used.
しかし、ここで用いられるエポキシ樹脂は、高分子量エポキシ、低分子量エポキシのいずれもビスフェノールＡを基本骨格としたものであり、その硬化物のＴｇ（一次相転移点）は１００℃前後と低く、その結果耐熱性に問題を生じ、又高温高湿試験で接続不良を生じる等耐熱・耐湿性に問題があった。 However, the epoxy resin used here is one in which high molecular weight epoxy and low molecular weight epoxy have bisphenol A as the basic skeleton, and the Tg (first phase transition point) of the cured product is as low as around 100 ° C. As a result, there were problems in heat resistance, and there was a problem in heat resistance and humidity resistance, such as poor connection in a high temperature and high humidity test.
そこで、その対策として低分子量エポキシ樹脂を、ビスフェノールＡ型から、剛直な骨格を持つナフタレン型に置き換えることでＴｇを上げ、耐熱・耐湿性を向上した樹脂組成物が提案されている（特開平８−３１５８８５号公報；特許文献１）。すなわち、特許文献１には、（１）フェノキシ樹脂、（２）ナフタレン型エポキシ樹脂、（３）潜在性硬化剤を必須とする接着剤組成物（絶縁性接着性樹脂）と導電性粒子よりなる回路接続材料（フィルム状接着剤）が開示されている。 Therefore, as a countermeasure, a resin composition has been proposed in which the Tg is increased by replacing the low molecular weight epoxy resin with a naphthalene type having a rigid skeleton from the bisphenol A type (Japanese Patent Laid-Open No. Hei 8). No. 315885; Patent Document 1). That is, Patent Document 1 includes (1) a phenoxy resin, (2) a naphthalene-type epoxy resin, (3) an adhesive composition (insulating adhesive resin) essentially including a latent curing agent and conductive particles. A circuit connection material (film adhesive) is disclosed.
ここで（１）フェノキシ樹脂とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）から求められた平均分子量が１００００以上の高分子量エポキシ樹脂に相当し、ビスフェノールＡ型、Ｆ型、ＡＤ型等の種類が用いられており、その結果、良好な接着性等の優れた特徴が得られるが、一方、耐熱・耐湿性の向上には寄与は小さい。従って、この組成物によっても、耐熱・耐湿性の向上は小さく、問題の完全解決には至らなかった。そこで、さらに、耐熱・耐湿性を向上することができる絶縁性接着性樹脂及び該樹脂と導電性粒子よりなるフィルム状接着剤の開発が望まれていた。
本発明は、絶縁性接着性樹脂及び導電性粒子からなり、優れた耐熱・耐湿性を有するフィルム状接着剤を提供することを課題とする。 This invention makes it a subject to provide the film adhesive which consists of insulating adhesive resin and electroconductive particle, and has the outstanding heat resistance and moisture resistance.
本発明者は、鋭意検討の結果、低分子量エポキシ樹脂として剛直な骨格を持つナフタレン型又はビフェニル型エポキシ樹脂を用い、かつ特定の架橋剤を加えることによって、高い耐熱・耐湿性を有する絶縁性接着性樹脂及びフィルム状接着剤が得られることを見出し、本発明を完成した。 As a result of diligent study, the present inventor has used a naphthalene type or biphenyl type epoxy resin having a rigid skeleton as a low molecular weight epoxy resin, and added a specific crosslinking agent, thereby insulating insulating having high heat resistance and moisture resistance. The present invention has been completed by finding that an adhesive resin and a film-like adhesive can be obtained.
本発明は、その請求項１として、
（１）平均分子量が１００００以上のフェノキシ樹脂、
（２）平均分子量が１０００以下のナフタレン型又はビフェニル型エポキシ樹脂
（３）１分子内に３つ以上のエポキシ基を有し、かつ平均分子量が１０００以下である架橋剤、及び
（４）潜在性硬化剤
を必須成分とする絶縁性樹脂に、導電性粒子を含有してなることを特徴とするフィルム状接着剤を提供する。
The present invention, as claim 1 thereof,
(1) a phenoxy resin having an average molecular weight of 10,000 or more,
(2) Naphthalene type or biphenyl type epoxy resin having an average molecular weight of 1000 or less (3) A crosslinking agent having 3 or more epoxy groups in one molecule and an average molecular weight of 1000 or less, and (4) latency Provided is a film adhesive characterized by containing conductive particles in an insulating resin containing a curing agent as an essential component.
ここで、フェノキシ樹脂とは、前記のように、高分子量エポキシ樹脂を意味する。フェノキシ樹脂としては、ビスフェノールＡ、Ｆ、Ｓ、ＡＤ等を骨格とするビスフェノール型フェノキシ樹脂等の他、ビフェニル、ターフェニル、ナフタレン、アントラセン、ベンゾアントラセン、ピレン又はジシクロペンタジエン等の残基（該化合物から１以上の原子又は基を除去した基）が、結合基を通して繋がった剛直な骨格を有するフェノキシ樹脂も用いることができる。 Here, the phenoxy resin means a high molecular weight epoxy resin as described above. Examples of the phenoxy resin include bisphenol type phenoxy resins having a skeleton of bisphenol A, F, S, AD, etc., as well as residues such as biphenyl, terphenyl, naphthalene, anthracene, benzoanthracene, pyrene, or dicyclopentadiene (the compound) It is also possible to use a phenoxy resin having a rigid skeleton in which one or more atoms or groups are removed from each other through a bonding group.
本発明においては（１）として、平均分子量が１００００以上のフェノキシ樹脂が用いられるが、ここで平均分子量とは、ＴＨＦ展開のゲルパーミエーションクロマトグラフィー（ＧＰＣ）から求められたポリスチレン換算の重量平均分子量を意味する。前記の剛直な骨格を有するもの以外のフェノキシ樹脂を用いる場合、例えばビスフェノール型フェノキシ樹脂を用いる場合は、耐熱・耐湿性をさらに向上させるために、平均分子量２００００以上が好ましい。請求項２は、この好ましい態様に該当し、前記のフィルム状接着剤であって、（１）フェノキシ樹脂の平均分子量が２００００以上であることを特徴とするフィルム状接着剤を提供するものである。 In the present invention, a phenoxy resin having an average molecular weight of 10,000 or more is used as (1). Here, the average molecular weight is a weight average molecular weight in terms of polystyrene determined from gel permeation chromatography (GPC) developed in THF. Means. When using a phenoxy resin other than those having a rigid skeleton, for example, when using a bisphenol type phenoxy resin, an average molecular weight of 20000 or more is preferable in order to further improve heat resistance and moisture resistance. Claim 2 corresponds to this preferred embodiment, and provides the film adhesive, wherein (1) the phenoxy resin has an average molecular weight of 20000 or more. .
平均分子量が大きいほどフィルム形成性が高く、また接続温度における樹脂の溶融粘度を高い範囲に設定できる。これらの観点や他の樹脂との相溶性等の点から、平均分子量としては、１００００〜１５００００の範囲が好ましく、１００００〜８００００程度のものがより好ましい。フェノキシ樹脂として、水酸基やカルボキシル基等の極性基を含有するものを用いると、均一な外観や特性を有するフィルムが得られることや、硬化時の反応促進により短時間硬化が得られるので好ましい。 The higher the average molecular weight, the higher the film formability and the higher the melt viscosity of the resin at the connection temperature. From these points of view and compatibility with other resins, the average molecular weight is preferably in the range of 10,000 to 150,000, more preferably about 10,000 to 80,000. It is preferable to use a phenoxy resin containing a polar group such as a hydroxyl group or a carboxyl group because a film having a uniform appearance and characteristics can be obtained and curing can be achieved for a short time by promoting the reaction during curing.
前記の例示した（１）フェノキシ樹脂の中では、剛直な骨格を有するフェノキシ樹脂を用いると、耐熱・耐湿性をさらに向上できるので好ましく、特にビフェニル型エポキシ樹脂やナフタレン型エポキシ樹脂がその入手の容易さや取扱いの容易さの点から好ましい。請求項３は、この特に好ましい態様に該当し、前記のフィルム状接着剤であって、（１）フェノキシ樹脂が、ビフェニル型エポキシ樹脂又はナフタレン型エポキシ樹脂であることを特徴とするフィルム状接着剤を提供するものである。 Among the above-exemplified (1) phenoxy resins, it is preferable to use a phenoxy resin having a rigid skeleton because heat resistance and moisture resistance can be further improved. Particularly, biphenyl type epoxy resins and naphthalene type epoxy resins are easily available. It is preferable from the viewpoint of easy handling. Claim 3 corresponds to this particularly preferable embodiment, and is the film adhesive, wherein (1) the phenoxy resin is a biphenyl type epoxy resin or a naphthalene type epoxy resin. Is to provide.
ビフェニル型フェノキシ樹脂は、例えば、ジヒドロキシビフェニルの水酸基とエピクロロヒドリンを反応させて、高分子量化することにより得られる。このフェノキシ樹脂としては、市販のビフェニル型の高分子量エポキシ樹脂を用いることもできる。 The biphenyl type phenoxy resin can be obtained, for example, by reacting a hydroxyl group of dihydroxybiphenyl with epichlorohydrin to increase the molecular weight. As this phenoxy resin, a commercially available biphenyl type high molecular weight epoxy resin can also be used.
前記（２）の平均分子量が１０００以下のエポキシ樹脂は、加熱時に速やかに硬化剤と反応し接着性能を発現する役割をするものである。ここで平均分子量とは、（１）の場合と同様に、ＧＰＣから求められた重量平均分子量を意味する。本発明は、（２）の低分子量エポキシ樹脂として、ナフタレン型又はビフェニル型エポキシ樹脂を用いることを特徴とする。剛直な骨格を有するナフタレン型又はビフェニル型エポキシ樹脂を、（２）の低分子量エポキシ樹脂として用いることにより、優れた耐熱・耐湿性が達成される。 The epoxy resin (2) having an average molecular weight of 1000 or less plays a role of rapidly reacting with a curing agent during heating and exhibiting adhesive performance. Here, the average molecular weight means the weight average molecular weight obtained from GPC as in the case of (1). The present invention is characterized in that a naphthalene type or biphenyl type epoxy resin is used as the low molecular weight epoxy resin (2). By using a naphthalene type or biphenyl type epoxy resin having a rigid skeleton as the low molecular weight epoxy resin of (2), excellent heat resistance and moisture resistance are achieved.
ここで、ビフェニル型エポキシ樹脂は、１分子内に少なくとも１個以上のビフェニル環を含んだ骨格を有しており、例えばヒドロキシビフェニルやジヒドロキシビフェニルの水酸基とエピクロロヒドリン等を反応させ、該水酸基の水素原子を置換して得られる。ナフタレン型エポキシ樹脂は、１分子内に少なくとも１個以上のナフタレン環を含んだ骨格を有しており、例えばナフトールやナフタレンジオールの水酸基とエピクロロヒドリン等を反応させ、該水酸基の水素原子を置換して得られる。前記（２）の平均分子量が１０００以下のエポキシ樹脂としては、市販の低分子量エポキシ樹脂を用いることも可能である。 Here, the biphenyl type epoxy resin has a skeleton containing at least one biphenyl ring in one molecule. For example, the hydroxyl group of hydroxybiphenyl or dihydroxybiphenyl is reacted with epichlorohydrin, etc. It is obtained by substituting the hydrogen atom. A naphthalene type epoxy resin has a skeleton containing at least one naphthalene ring in one molecule. For example, a hydroxyl group of naphthol or naphthalene diol is reacted with epichlorohydrin and the like, and a hydrogen atom of the hydroxyl group is converted. Obtained by substitution. As the epoxy resin (2) having an average molecular weight of 1000 or less, a commercially available low molecular weight epoxy resin can also be used.
前記（３）の１分子内に３つ以上のエポキシ基を有し、かつ平均分子量が１０００以下である架橋剤としては、トリフェニルメタン型、テトラフェニルエタン型、クレゾールノボラック型、ナフタレン型等、１分子内に２以上の芳香族環を有する芳香族化合物のエポキシが例示される。 Examples of the crosslinking agent having 3 or more epoxy groups in one molecule of (3) and having an average molecular weight of 1000 or less include triphenylmethane type, tetraphenylethane type, cresol novolak type, naphthalene type, and the like. An epoxy compound of an aromatic compound having two or more aromatic rings in one molecule is exemplified.
架橋剤を使用することにより、接着時の加熱により架橋が起き、その結果耐熱性、耐湿性が向上する。特に架橋剤を、（１）フェノキシ樹脂及び（２）低分子エポキシ樹脂の合計重量に対して５重量％以上８０重量％以下配合することにより、耐熱性、耐湿性の向上が顕著になるので好ましい。請求項４はこの好ましい態様に該当し、前記のフィルム状接着剤であって、（１）フェノキシ樹脂及び（２）エポキシ樹脂の合計重量に対する（３）架橋剤の配合量が、５重量％以上８０重量％以下であることを特徴とするフィルム状接着剤を提供するものである。 By using a cross-linking agent, cross-linking occurs by heating during bonding, and as a result, heat resistance and moisture resistance are improved. In particular, it is preferable to add a crosslinking agent in an amount of 5% by weight to 80% by weight based on the total weight of (1) phenoxy resin and (2) low molecular weight epoxy resin, since the improvement of heat resistance and moisture resistance becomes remarkable. . Claim 4 corresponds to this preferred embodiment, and is the film-like adhesive, wherein the blending amount of (3) cross-linking agent with respect to the total weight of (1) phenoxy resin and (2) epoxy resin is 5% by weight or more. The present invention provides a film adhesive characterized by being 80% by weight or less.
前記の（１）フェノキシ樹脂、（２）低分子量エポキシ樹脂や（３）架橋剤としては、不純物イオン（Ｎａ+ 、Ｃｌ- 等）や、加水分解性塩素等を３００ｐｐｍ以下に低減した高純度品を用いることが、エレクトロマイグレーション防止のために好ましい。 Wherein (1) a phenoxy resin, (2) The low molecular weight epoxy resin and (3) a crosslinking agent, impurity ions (Na +, Cl -, etc.) and high purity product was reduced to 300ppm or less hydrolyzable chlorine and the like Is preferable for preventing electromigration.
前記（４）の潜在性硬化剤とは、低温での貯蔵安定性にすぐれ、室温ではほとんど硬化反応をおこさないが、加熱等により所定の条件とすると速やかに硬化反応をおこす硬化剤である。潜在性硬化剤としては、イミダゾール系、ヒドラジド系、三フッ化ホウ素−アミン錯体、スルホニウム塩、アミンイミド、ポリアミンの塩、ジシアンジアミド及びこれらの変性物が例示される。 The latent curing agent (4) is a curing agent that is excellent in storage stability at low temperatures and hardly undergoes a curing reaction at room temperature, but rapidly undergoes a curing reaction under predetermined conditions by heating or the like. Examples of the latent curing agent include imidazole series, hydrazide series, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide, and modified products thereof.
例示された硬化剤は、アニオンまたはカチオン重合型等のいわゆるイオン重合性の触媒型硬化剤であり、速硬化性を得やすく、また化学当量的な考慮が少なくてよいことから好ましい。特にイミダゾール系硬化剤は、低温での貯蔵安定性にすぐれ、速硬化性等に優れているので好ましい。請求項６は、この好ましい態様に該当し、前記のフィルム状接着剤であって、前記（４）潜在性硬化剤がイミダゾール系硬化剤であることを特徴とするフィルム状接着剤を提供するものである。 The exemplified curing agent is a so-called ion polymerizable catalyst type curing agent such as an anion or cation polymerization type, and is preferable because it can easily obtain fast curability and requires less chemical equivalent consideration. In particular, an imidazole-based curing agent is preferable because it has excellent storage stability at low temperatures and is excellent in rapid curability and the like. Claim 6 corresponds to this preferred embodiment, and provides the film adhesive, wherein (4) the latent curing agent is an imidazole curing agent. It is.
さらに、これらの潜在性硬化剤を、ポリウレタン系、ポリエステル系等の高分子物質や、Ｎｉ、Ｃｕ等の金属薄膜及びケイ酸カルシウム等の無機物で被覆してマイクロカプセル化したものは可使時間が延長できるため好ましい。これらの潜在性硬化剤は、単独または２種以上の混合体として使用できる。 Furthermore, these latent curing agents are coated with a polymer material such as polyurethane or polyester, a metal thin film such as Ni or Cu, and an inorganic material such as calcium silicate and microencapsulated. This is preferable because it can be extended. These latent curing agents can be used alone or as a mixture of two or more.
前記（２）低分子量エポキシ樹脂及び（４）潜在性硬化剤の配合割合は、（１）フェノキシ樹脂と（２）低分子量エポキシ樹脂の合計重量に対し、（２）が、１０〜８０重量％の範囲、（４）が、５〜４０重量％の範囲が好ましい。（２）が１０重量％以下の場合、硬化速度が低下することがある。一方、（２）が８０重量％以上の場合、シート形成が困難になる場合がある。又、（４）が５重量％以下の場合、硬化速度が低下し、硬化が不十分になる場合があり、一方４０重量％以上の場合、未反応の硬化剤が残留しやすくなり、耐熱、耐湿性を低下させる場合がある。請求項４は、この好ましい態様に該当し、前記のフィルム状接着剤であって、前記（１）フェノキシ樹脂と前記（２）平均分子量１０００以下のエポキシ樹脂の合計重量に対し、前記（２）平均分子量１０００以下のエポキシ樹脂が、１０〜８０重量％の範囲であり、かつ前記（４）潜在性硬化剤が、５〜４０重量％の範囲であることを特徴とするフィルム状接着剤を提供するものである。
The blending ratio of the (2) low molecular weight epoxy resin and (4) latent curing agent is 10 to 80% by weight of (2) based on the total weight of (1) phenoxy resin and (2) low molecular weight epoxy resin. The range of (4) is preferably in the range of 5 to 40% by weight. When (2) is 10% by weight or less, the curing rate may decrease. On the other hand, when (2) is 80% by weight or more, sheet formation may be difficult. In addition, when (4) is 5% by weight or less, the curing rate is lowered and curing may be insufficient. On the other hand, when it is 40% by weight or more, unreacted curing agent tends to remain, heat resistance, May reduce moisture resistance. Claim 4 corresponds to this preferred embodiment, and is the film adhesive, wherein (2) the total weight of (1) the phenoxy resin and (2) the epoxy resin having an average molecular weight of 1000 or less. An epoxy resin having an average molecular weight of 1000 or less is in the range of 10 to 80% by weight, and (4) the latent curing agent is in the range of 5 to 40% by weight. To do.
本発明のフィルム状接着剤の絶縁性樹脂には、前記の（１）及び（２）のエポキシ樹脂の他に、本発明の趣旨を損なわない範囲で、他のエポキシ化合物等を単独にあるいは２種以上混合して添加することが可能である。 As the insulating resin of the film adhesive of the present invention, in addition to the epoxy resins (1) and (2), other epoxy compounds or the like may be used alone or in a range not impairing the gist of the present invention. It is possible to add a mixture of more than one species.
本発明のフィルム状接着剤は、前記のようにして得られる絶縁性樹脂に、導電性粒子を含有させたものである。導電性粒子を含有させることにより、接続時に、接続対象上の多数の相対峙する電極間の間隔にばらつきがあり、一部の電極間に隙間が生じても、この隙間にある導電性粒子により電極間の導通が達成され、良好な電気的接続が得られる。 The film-like adhesive of the present invention is obtained by adding conductive particles to the insulating resin obtained as described above. By including the conductive particles, there is a variation in the distance between a large number of opposed electrodes on the connection target at the time of connection, and even if a gap occurs between some electrodes, the conductive particles in this gap Conduction between the electrodes is achieved and a good electrical connection is obtained.
導電性粒子としては、Ａｕ、Ａｇ、Ｎｉ、Ｃｕ、はんだ等の金属粒子、カーボン粒子、非導電性のガラス、セラミック、プラスチック等に前記の金属やカーボン等を被覆して導通層を形成したもの、微細な金属粒子が鎖状に多数繋がった形状を有する金属粉末、該金属粉末が、鎖の太さ方向に多数繋がり凝集した鎖状二次凝集体からなる金属粉末、及び針状の金属粉末が例示される。プラスチックを核とした場合や熱溶融金属粒子の場合、加熱、加圧により変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。 As conductive particles, metal particles such as Au, Ag, Ni, Cu, solder, etc., carbon particles, non-conductive glass, ceramics, plastics, etc. are coated with the aforementioned metal or carbon to form a conductive layer. A metal powder having a shape in which a large number of fine metal particles are connected in a chain, a metal powder comprising a chain secondary aggregate in which the metal powder is connected in the thickness direction of the chain, and an acicular metal powder Is exemplified. In the case of using plastic as a core or hot-melt metal particles, it is preferable because it has deformability by heating and pressurization, so that the contact area with the electrode is increased at the time of connection and the reliability is improved.
又、微細な金属粒子が鎖状に多数繋がった形状を有する金属粉末、該金属粉末が、鎖の太さ方向に多数繋がり凝集した鎖状二次凝集体からなる金属粉末、又は針状の金属粉末を用いると、金属粉末の充填密度をあまり高くすることなしに、厚み方向の抵抗を低くし、良好な電気的接続を達成できるとともに、面方向の絶縁抵抗をより高く保つことができ、隣り合う電極間の短絡を防ぐ効果がより高くなるので好ましい。特に、これらの金属粉末を含有する導電性粒子を、フィルムの厚み方向に配向させることにより、この効果がさらに顕著になる。請求項７及び請求項８はこの好ましい態様に該当するものである。 Also, a metal powder having a shape in which a large number of fine metal particles are connected in a chain, a metal powder comprising a chain secondary aggregate in which the metal powder is connected in the chain thickness direction and agglomerated, or a needle-shaped metal When powder is used, the resistance in the thickness direction can be lowered and a good electrical connection can be achieved without increasing the packing density of the metal powder so much, and the insulation resistance in the surface direction can be kept higher, so that Since the effect which prevents the short circuit between the electrodes which match is higher, it is preferable. In particular, this effect becomes more remarkable by orienting conductive particles containing these metal powders in the thickness direction of the film. Claims 7 and 8 correspond to this preferred mode.
すなわち、請求項７は、前記のフィルム状接着剤であって、前記導電性粒子が、微細な金属粒子が鎖状に多数繋がった形状を有する金属粉末、前記金属粉末を、鎖の太さ方向に多数繋げ凝集させた鎖状二次凝集体からなる金属粉末、又は針状の金属粉末を含有することを特徴とするフィルム状接着剤を提供するものである。又、請求項８は、請求項７のフィルム状接着剤であって、前記導電性粒子を、フィルムの厚み方向に配向させたことを特徴とするフィルム状接着剤を提供するものである。 That is, claim 7 is the film-like adhesive, wherein the conductive particles are a metal powder having a shape in which a large number of fine metal particles are connected in a chain shape, and the metal powder is used in a chain thickness direction. The present invention provides a film-like adhesive comprising a metal powder composed of a chain-like secondary agglomerate that is connected and aggregated with each other, or a needle-like metal powder. An eighth aspect of the present invention provides the film adhesive according to the seventh aspect, wherein the conductive particles are oriented in the thickness direction of the film.
前記の鎖状又は針状の金属粉末は、例えば、強磁性を有する金属単体、強磁性を有する２種類以上の金属の合金、強磁性を有する金属と他の金属の合金、強磁性を有する金属を含む複合体から形成される。これらの金属粉末を用いることにより、後述する磁場による金属粉末の配向を行うことができるので好ましい。請求項９はこの好ましい態様に該当するものであり、導電性粒子として鎖状又は針状の金属粉末を用いるフィルム状接着剤であって、前記鎖状又は針状の金属粉末が、強磁性を有する金属単体、強磁性を有する２種類以上の金属の合金、強磁性を有する金属と他の金属の合金、又は強磁性を有する金属を含む複合体から形成されることを特徴とするフィルム状接着剤を提供するものである。 The chain or needle-shaped metal powder includes, for example, a single metal having ferromagnetism, an alloy of two or more metals having ferromagnetism, an alloy of a metal having ferromagnetism and another metal, and a metal having ferromagnetism It is formed from the composite_body | complex containing. Use of these metal powders is preferable because the metal powder can be oriented by a magnetic field described later. Claim 9 corresponds to this preferred embodiment, and is a film-like adhesive using chain-like or needle-like metal powder as conductive particles, wherein the chain-like or needle-like metal powder has ferromagnetic properties. A film-like adhesive formed from a single metal having an alloy, an alloy of two or more metals having ferromagnetism, an alloy of a metal having ferromagnetism and another metal, or a composite containing a metal having ferromagnetism An agent is provided.
ここで、強磁性を有する金属を含む複合体としては、強磁性を有する金属単体や強磁性を有する２種以上の金属の合金にて形成した鎖の表面を、Ｃｕ、Ｒｂ、Ｒｈ、Ｐｄ、Ａｇ、Ｒｅ、ＰｔおよびＡｕからなる群より選ばれた少なくとも１種の金属で被覆した複合体が例示される。強磁性を有する金属としては、鉄、ニッケル、コバルトが例示される。 Here, as a composite containing a metal having ferromagnetism, the surface of a chain formed of a single metal having ferromagnetism or an alloy of two or more metals having ferromagnetism is formed by Cu, Rb, Rh, Pd, Examples include composites coated with at least one metal selected from the group consisting of Ag, Re, Pt and Au. Examples of the metal having ferromagnetism include iron, nickel, and cobalt.
鎖状又は針状の金属粉末を、フィルムの厚み方向に配向させる方法は特に限定されないが、該金属粉末が、前記のような強磁性を有するものである場合は、該鎖状又は針状の金属粉末を絶縁性樹脂溶液に分散し、得られた分散溶液を、下地面と交差する方向に磁場を印加した下地上に塗布して該金属粉末を配向させ、該下地上で溶媒の除去等により固化、硬化させて配向を固定する方法が好ましく例示される。 The method for orienting the chain or needle-like metal powder in the thickness direction of the film is not particularly limited. However, when the metal powder has ferromagnetism as described above, the chain or needle-like metal powder is used. Metal powder is dispersed in an insulating resin solution, and the obtained dispersion solution is applied on a base to which a magnetic field is applied in a direction crossing the base surface to orient the metal powder, and the solvent is removed on the base. Preferably, the method of fixing the orientation by solidifying and curing is preferred.
又は、強磁性を有する鎖状又は針状の金属粉末を、下地面と交差する方向に磁場を印加した下地上に散布して、鎖状又は針状の金属粉末を、前記磁場の方向に配向させるとともに、その上に、絶縁性樹脂溶液を塗布して固化または硬化させて配向を固定する方法も使用することができる。これらの製造方法によれば、金属粉末を膜の厚み方向に配向させた異方導電膜を、より効率よく形成することができる。 Alternatively, a chain-like or needle-like metal powder having ferromagnetism is dispersed on a base to which a magnetic field is applied in a direction intersecting the base surface, and the chain-like or needle-like metal powder is oriented in the direction of the magnetic field. In addition, a method of fixing the orientation by applying an insulating resin solution thereon to be solidified or cured can also be used. According to these manufacturing methods, the anisotropic conductive film in which the metal powder is oriented in the thickness direction of the film can be formed more efficiently.
鎖状又は針状の金属粉末の長さや太さは、電極の間隔等に基づき適宜選択され、特に限定されないが、長さ／太さが３以上の場合、良好な電気的接続を達成しながら、面方向の絶縁抵抗をより高く保つとの効果が充分達成されるので好ましい。鎖状又は針状の金属粉末の、製造方法も特に限定されないが、特開２００３−３３１９５１号公報に記載の方法等が好ましく例示される。 The length or thickness of the chain or needle-shaped metal powder is appropriately selected based on the distance between the electrodes and the like, and is not particularly limited. However, when the length / thickness is 3 or more, while achieving good electrical connection It is preferable because the effect of keeping the insulation resistance in the plane direction higher can be sufficiently achieved. A production method of the chain or needle-shaped metal powder is not particularly limited, but a method described in JP-A-2003-331951 is preferably exemplified.
導電性粒子の配合量は、フィルム状接着剤の全体積に対して、０．０１〜３０体積％の範囲から選ばれ、用途により使い分ける。過剰な導電性粒子による隣接回路の短絡等を防止するためには、０．０１〜１０体積％とするのがより好ましい。 The compounding quantity of electroconductive particle is selected from the range of 0.01-30 volume% with respect to the whole volume of a film adhesive, and uses it properly by a use. In order to prevent a short circuit of an adjacent circuit due to excessive conductive particles, the content is more preferably 0.01 to 10% by volume.
本発明のフィルム状接着剤中には、さらに、本発明の趣旨を損なわない範囲で、充填剤、軟化剤、促進剤、老化防止剤、着色剤、難燃剤、チキソトロピック剤、カップリング剤及びフェノール樹脂やメラミン樹脂、イソシアネート類等の硬化剤等を含有することもできる。これらの中では、導電性粒子やシリカ等の充填剤及びシラン、チタン、クロム、ジルコニウム、アルミニウム等の各系のカップリング剤が特に有効である。カップリング剤としては、アミノ基やエポキシ基及びイソシアネート基含有物が、接着性の向上の点から特に好ましい。 In the film-like adhesive of the present invention, a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, and the like, as long as the gist of the present invention is not impaired. A curing agent such as a phenol resin, a melamine resin, or an isocyanate can also be contained. Among these, conductive particles, fillers such as silica, and coupling agents of various systems such as silane, titanium, chromium, zirconium, and aluminum are particularly effective. As a coupling agent, an amino group, an epoxy group and an isocyanate group-containing material are particularly preferable from the viewpoint of improving adhesiveness.
本発明のフィルム状接着剤は、前記の各成分を混合することにより得ることができる。例えば、前記の（１）〜（４）の成分等を溶解し、導電性粒子等を分散する溶媒中に、各成分を溶解、均一分散し、分散溶液を得た後、該分散溶液のうすい膜を形成し、その後、溶媒を乾燥等により除去することにより、フィルム状接着剤が得られる。用いられる溶媒の種類や該分散溶液の濃度等は、前記の成分を溶解、分散し、うすい膜を形成できる範囲であれば特に限定されない。フィルム状接着剤の厚みも特に限定されないが、通常１０〜３０μｍ程度である。 The film adhesive of this invention can be obtained by mixing said each component. For example, the components (1) to (4) are dissolved, and each component is dissolved and uniformly dispersed in a solvent that disperses the conductive particles and the like. After obtaining a dispersion solution, the dispersion solution is diluted. A film adhesive is obtained by forming a film and then removing the solvent by drying or the like. The type of solvent used, the concentration of the dispersion solution, and the like are not particularly limited as long as the components can be dissolved and dispersed to form a thin film. Although the thickness of a film adhesive is not specifically limited, Usually, it is about 10-30 micrometers.
本発明のフィルム状接着剤を、接合対象の間に挟み、加圧、加熱することにより、該接合対象を接着し、該接合対象上の相対峙する電極、回路間を電気的に接続することができる。加圧の条件や加熱の条件は、電極、回路間の電気的接続が充分達成される範囲で選ばれ、加熱の条件は、絶縁性樹脂が硬化して充分な接着が達成される範囲で選ばれるが、具体的な範囲は、電極、回路のサイズや、絶縁性樹脂の種類により変動し特に限定されない。 The film-like adhesive of the present invention is sandwiched between the objects to be joined, pressurized, and heated to adhere the objects to be joined and to electrically connect the electrodes and circuits facing each other on the objects to be joined. Can do. Pressing conditions and heating conditions are selected within a range in which electrical connection between electrodes and circuits is sufficiently achieved, and heating conditions are selected in a range in which insulating resin is cured and sufficient adhesion is achieved. However, the specific range varies depending on the size of the electrode and circuit and the type of the insulating resin, and is not particularly limited.
接合対象は、多数の電極を狭ピッチでその表面に有する基板等であり、該基板としては、半導体、ガラス、セラミック等の無機物、ポリイミド、ポリカーボネート等の有機物、ガラス／エポキシ等の無機物と有機物の組み合わせ等が適用できる。本発明のフィルム状接着剤は、例えば、フレキシブルプリント配線板（ＦＰＣ）の端子、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）テープの端子やドライバＩＣの端子と、ガラス基板上に形成されたＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）やアルミニウム、クロムの電極パターンの接続等に用いられ、接続された電気部品は、高い信頼性を有するものとして、液晶製品等に使用される。 The object to be joined is a substrate having a large number of electrodes on its surface at a narrow pitch, such as semiconductors, inorganic materials such as glass and ceramics, organic materials such as polyimide and polycarbonate, inorganic materials such as glass / epoxy and organic materials. Combinations can be applied. The film adhesive of the present invention includes, for example, a terminal of a flexible printed wiring board (FPC), a terminal of a TAB (Tape Automated Bonding) tape, a terminal of a driver IC, and an ITO (Indium Tin Oxide) formed on a glass substrate. The connected electrical components are used for liquid crystal products and the like as having high reliability.
本発明のフィルム状接着剤は、多数の電極や回路が設けられたシートやフィルム間を接着しかつ電気的に接続するために使用されるが、優れた耐熱性、耐湿性を有する。従って、本発明のフィルム状接着剤を使用して得られた電気部品が、高温、高湿の環境下で長時間使用されても、その特性の変化は小さいので、液晶製品等高い信頼性が要求される用途に使用することができる。 The film adhesive of the present invention is used for bonding and electrically connecting sheets and films provided with a large number of electrodes and circuits, and has excellent heat resistance and moisture resistance. Therefore, even if the electrical component obtained using the film adhesive of the present invention is used for a long time in an environment of high temperature and high humidity, the change in its characteristics is small, so that it has high reliability such as liquid crystal products. Can be used for required applications.
次に発明を実施するための最良の形態を実施例により説明する。実施例は、本発明の範囲を限定するものではない。 Next, the best mode for carrying out the invention will be described by way of examples. The examples are not intended to limit the scope of the invention.
〔塗工溶液の作製〕
導電粒子としては３μｍから１５μｍまでの鎖長分布を有する鎖状ニッケル微粒子（平均粒径２００ｎｍのニッケル微粒子が直鎖状に連結したもの）を用いた。絶縁性樹脂としては、分子量４８０００のビスフェノールＡ型エポキシ樹脂〔ＪＥＲ（株）製、エピコート１２５６〕と、ナフタレン型エポキシ樹脂〔大日本インキ化学工業（株）製、ＨＰ４０３２Ｄ〕、架橋剤〔ＪＥＲ（株）製、エピコート１０３２〕及びマイクロカプセル型のイミダゾール系硬化剤〔旭化成エポキシ（株）製、ノバキュアＨＸ３９４１〕を重量比で４０／３０／２０／１０の割合で用い、シクロヘキサノンに溶解し固形分５０％の溶液を作製した。この溶液に、固形分の総量（Ｎｉ粉末＋樹脂）に占める割合で表される金属充填率が、０．５体積％となるように前記Ｎｉ粉末を添加した後、遠心ミキサーを用いて攪拌することでＮｉ粉末を均一分散し、接着剤用の複合材料を調製した。
[Preparation of coating solution]
As the conductive particles, chain nickel fine particles having a chain length distribution of 3 μm to 15 μm (nickel particles having an average particle diameter of 200 nm connected in a straight line) were used. Examples of the insulating resin include a bisphenol A type epoxy resin having a molecular weight of 48000 [Epicoat 1256 manufactured by JER Co., Ltd.], a naphthalene type epoxy resin [manufactured by Dainippon Ink and Chemicals, HP 4032D], and a crosslinking agent [JER Co., Ltd. ), Epicoat 1032] and microcapsule type imidazole curing agent (Asahi Kasei Epoxy Co., Ltd., NovaCure HX3941) in a weight ratio of 40/30/20/10, dissolved in cyclohexanone and having a solid content of 50% A solution of was prepared. The Ni powder is added to this solution so that the metal filling rate represented by the ratio of the total solid content (Ni powder + resin) is 0.5% by volume, and then stirred using a centrifugal mixer. In this way, Ni powder was uniformly dispersed to prepare a composite material for an adhesive.
〔フィルム状接着剤の作製〕
前記で調製した複合材料を、離型処理したＰＥＴフィルム上にドクターナイフを用いて塗布した後、磁束密度１００ｍＴの磁場中、６０℃、３０分間で乾燥し、固化させることによって、塗布膜中の鎖状粒子が磁場方向に配向した、総厚み２０μｍのフィルム状接着剤を得た。
[Production of film adhesive]
The composite material prepared above is applied onto a release-treated PET film using a doctor knife, and then dried and solidified in a magnetic field with a magnetic flux density of 100 mT at 60 ° C. for 30 minutes. A film adhesive having a total thickness of 20 μm in which chain-like particles were oriented in the magnetic field direction was obtained.
〔抵抗評価〕
幅１５μｍ、長さ１００μｍ、高さ１６μｍのＡｕメッキバンプが１５μｍ間隔で７２６個配列されたＩＣチップと、幅２０μｍ、スペース１０μｍで同数のＩＴＯ電極が形成されたガラス基板とを用意した。このＩＣチップと回路基板との間に、前記で得られたフィルム状接着剤を挟み、２００℃に加熱しながら、１バンプ当たり３０ｇｆの圧力で１５秒間加圧して接着させ、ＩＣ−ガラス基板接合体を得た。その後、ＩＴＯ電極、前記フィルム状接着剤により形成された異方導電膜及びＡｕバンプを介して導電接続された連続する６４４個の電極間の、導体抵抗も含めた抵抗値（単位ｋΩ）を、デジタルマルチメーターを用いて測定した。その結果を表１に示す。
(Evaluation of resistance)
An IC chip in which 726 Au plated bumps having a width of 15 μm, a length of 100 μm, and a height of 16 μm were arranged at intervals of 15 μm and a glass substrate on which the same number of ITO electrodes were formed with a width of 20 μm and a space of 10 μm were prepared. The film adhesive obtained above is sandwiched between the IC chip and the circuit board, and heated and heated at 200 ° C. for 15 seconds with a pressure of 30 gf per bump to bond the IC-glass substrate. Got the body. Thereafter, a resistance value including a conductor resistance (unit kΩ) between the 644 continuous electrodes conductively connected through the ITO electrode, the anisotropic conductive film formed by the film adhesive and the Au bump, Measurement was performed using a digital multimeter. The results are shown in Table 1.
〔耐熱試験〕
前記のＩＣ−ガラス基板接合体を１００℃に設定した恒温槽内に投入し、１００時間経過後に取り出し、再び前記と同様にして抵抗値を測定した。その結果を表１に示す。
[Heat resistance test]
The IC-glass substrate assembly was put into a thermostat set at 100 ° C., taken out after 100 hours, and the resistance value was measured again in the same manner as described above. The results are shown in Table 1.
〔Ｔｇ測定〕
前記で得られたフィルム状接着剤を２００℃で３０秒間加熱硬化した試料を準備し、粘弾性測定装置（セイコーインスツルメンツ社製、商品名：ＤＭＳ−６１００）により求めた。
[Tg measurement]
A sample obtained by heating and curing the film-like adhesive obtained above at 200 ° C. for 30 seconds was prepared and obtained by a viscoelasticity measuring apparatus (trade name: DMS-6100, manufactured by Seiko Instruments Inc.).
上記分子量４８０００のビスフェノールＡ型エポキシ樹脂の代わりに、分子量３９０００のビフェニル系エポキシ樹脂を用いたこと以外は実施例１と同様にして総厚みが２０μｍのフィルム状接着剤を作製し、実施例１と同様にして抵抗評価、耐熱試験及びＴｇ測定を行った。その結果を表１に示す。 A film adhesive having a total thickness of 20 μm was prepared in the same manner as in Example 1 except that a biphenyl type epoxy resin having a molecular weight of 39000 was used instead of the bisphenol A type epoxy resin having a molecular weight of 48000. Similarly, resistance evaluation, heat resistance test, and Tg measurement were performed. The results are shown in Table 1.
導電粒子として、直径が３．５μｍで、表面を金メッキした球状樹脂粒子を７体積％加えたこと以外は実施例１と同様にして総厚みが２０μｍのフィルム状接着剤を作製し、実施例１と同様にして抵抗評価、耐熱試験及びＴｇ測定を行った。その結果を表１に示す。 A film-like adhesive having a total thickness of 20 μm was prepared in the same manner as in Example 1 except that 7% by volume of spherical resin particles having a diameter of 3.5 μm and gold-plated surfaces were added as conductive particles. In the same manner, resistance evaluation, heat resistance test and Tg measurement were performed. The results are shown in Table 1.
比較例１
架橋剤を用いずに、代わりにビスフェノールＡ型エポキシ樹脂〔大日本インキ化学工業（株）製、８５０ＣＲＰ〕用いたこと以外は実施例１と同様にして総厚みが２０μｍのフィルム状接着剤を作製し、実施例１と同様にして抵抗評価、耐熱試験及びＴｇ測定を行った。その結果を表１に示す。
Comparative Example 1
A film adhesive having a total thickness of 20 μm was prepared in the same manner as in Example 1 except that a bisphenol A type epoxy resin (Dainippon Ink & Chemicals, Inc., 850CRP) was used instead of a crosslinking agent. In the same manner as in Example 1, resistance evaluation, heat resistance test, and Tg measurement were performed. The results are shown in Table 1.
比較例２
架橋剤を用いずに、代わりにビスフェノールＡ型エポキシ樹脂〔大日本インキ化学工業（株）製８５０ＣＲＰ〕用い、導電粒子として直径が３．５μｍで、表面を金メッキした球状樹脂粒子を７体積％加えたこと以外は実施例１と同様にして総厚みが２０μｍのフィルム状接着剤を作製し、実施例１と同様にして抵抗評価、耐熱試験及びＴｇ測定を行った。その結果を表１に示す。
Comparative Example 2
Instead of using a crosslinking agent, bisphenol A type epoxy resin [850CRP manufactured by Dainippon Ink & Chemicals, Inc.] was used instead, and 7% by volume of spherical resin particles having a diameter of 3.5 μm and gold-plated surfaces were added. A film adhesive having a total thickness of 20 μm was prepared in the same manner as in Example 1 except that the resistance evaluation, heat resistance test, and Tg measurement were performed in the same manner as in Example 1. The results are shown in Table 1.
表１の結果は、本発明例（実施例１〜３）のフィルム状接着剤を用いて接着された場合は、高温の環境下に長時間置かれた場合でも抵抗値の増加は小さく、又高いＴｇが得られており、優れた耐熱性が達成できると考えられる。特にビフェニル型エポキシを（１）フェノキシ樹脂として用いた、実施例２は、この効果が大きい。一方、本発明の範囲外の比較例１、２では、同条件での抵抗値の増加は比較的大きいとともに、Ｔｇが低く、耐熱性に関して本発明例より劣ることが示されている。この結果より明らかなように、本発明例のフィルム状接着剤を用いることにより、優れた耐熱性を達成することができる。
The results in Table 1 show that when the film-like adhesives of the present invention examples (Examples 1 to 3) are adhered, the increase in resistance value is small even when placed in a high temperature environment for a long time. A high Tg is obtained, and it is considered that excellent heat resistance can be achieved. In particular, Example 2 using biphenyl type epoxy as (1) phenoxy resin has a great effect. On the other hand, in Comparative Examples 1 and 2 outside the scope of the present invention, the increase in resistance value under the same conditions is relatively large and Tg is low, indicating that the heat resistance is inferior to that of the present invention. As is clear from this result, excellent heat resistance can be achieved by using the film adhesive of the present invention example.
Claims (8)
（２）平均分子量が１０００以下でかつ１分子内に２つのエポキシ基を有するナフタレン型又はビフェニル型エポキシ樹脂、
（３）１分子内に３つ以上のエポキシ基を有し、かつ平均分子量が１０００以下である架橋剤、及び
（４）潜在性硬化剤
を必須成分とする絶縁性樹脂に、導電性粒子を含有してなることを特徴とするフィルム状接着剤。 (1) A phenoxy resin selected from a biphenyl type epoxy resin and a naphthalene type epoxy resin having an average molecular weight of 10,000 or more,
(2) Naphthalene type or biphenyl type epoxy resin having an average molecular weight of 1000 or less and having two epoxy groups in one molecule ;
(3) Conductive particles are added to an insulating resin having three or more epoxy groups in one molecule and an average molecular weight of 1000 or less, and (4) an latent resin as an essential component. A film adhesive characterized by containing.
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| JP2007091959A (en) | 2005-09-30 | 2007-04-12 | Sumitomo Electric Ind Ltd | Anisotropically conductive adhesive |
| JP4684087B2 (en) * | 2005-11-21 | 2011-05-18 | 旭化成イーマテリアルズ株式会社 | Connected structure |
| JP4935252B2 (en) * | 2005-12-21 | 2012-05-23 | 住友電気工業株式会社 | Multi-fiber cable connection structure, multi-core cable, and method for manufacturing multi-core cable connection structure |
| JP5178509B2 (en) * | 2006-03-27 | 2013-04-10 | 日立造船株式会社 | Method for producing conductive material using carbon nanotube, and electric double layer capacitor using conductive material |
| JP2007302864A (en) * | 2006-04-11 | 2007-11-22 | Hitachi Chem Co Ltd | Adhesive film, and circuit element connecting structure using the same |
| KR101171646B1 (en) * | 2006-04-26 | 2012-08-07 | 히다치 가세고교 가부시끼가이샤 | Adhesive tape and solar cell module using the same |
| JP4744496B2 (en) * | 2007-04-16 | 2011-08-10 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
| JP5147049B2 (en) * | 2007-07-25 | 2013-02-20 | 旭化成イーマテリアルズ株式会社 | Anisotropic conductive film |
| JP2010132840A (en) * | 2008-12-08 | 2010-06-17 | Asahi Kasei E-Materials Corp | Epoxy resin composition for adhesive sheet |
| JP6307966B2 (en) * | 2014-03-25 | 2018-04-11 | 日立化成株式会社 | Adhesive composition, anisotropic conductive adhesive composition, circuit connection material and connector |
| JP2016164984A (en) * | 2016-03-02 | 2016-09-08 | デクセリアルズ株式会社 | Solar cell module, method for manufacturing the same, and conductive adhesive film |
| JP2023172562A (en) * | 2022-05-24 | 2023-12-06 | 株式会社レゾナック | Adhesive composition, circuit connection material, and connection body |
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| JPH04217675A (en) * | 1990-10-30 | 1992-08-07 | Dainippon Ink & Chem Inc | Epoxy resin and its intermediate, production thereof and epoxy resin composition |
| JPH05320610A (en) * | 1992-05-26 | 1993-12-03 | Hitachi Chem Co Ltd | Adhesive composition, production of adhesive film therefrom, and connection of electrode and metal foil with adhesive prepared using the same |
| JPH08315885A (en) * | 1995-05-16 | 1996-11-29 | Hitachi Chem Co Ltd | Circuit connecting material |
| JP2003002949A (en) * | 2001-06-26 | 2003-01-08 | Matsushita Electric Works Ltd | Liquid epoxy resin composition for sealing semiconductor and semiconductor device |
| JP2003331951A (en) * | 2001-11-09 | 2003-11-21 | Sumitomo Electric Ind Ltd | Anisotropic conductive film and manufacturing method of the same |
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| JPH04217675A (en) * | 1990-10-30 | 1992-08-07 | Dainippon Ink & Chem Inc | Epoxy resin and its intermediate, production thereof and epoxy resin composition |
| JPH05320610A (en) * | 1992-05-26 | 1993-12-03 | Hitachi Chem Co Ltd | Adhesive composition, production of adhesive film therefrom, and connection of electrode and metal foil with adhesive prepared using the same |
| JPH08315885A (en) * | 1995-05-16 | 1996-11-29 | Hitachi Chem Co Ltd | Circuit connecting material |
| JP2003002949A (en) * | 2001-06-26 | 2003-01-08 | Matsushita Electric Works Ltd | Liquid epoxy resin composition for sealing semiconductor and semiconductor device |
| JP2003331951A (en) * | 2001-11-09 | 2003-11-21 | Sumitomo Electric Ind Ltd | Anisotropic conductive film and manufacturing method of the same |
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