JPH11236540A - Anisotropic conductive adhesive - Google Patents
Anisotropic conductive adhesiveInfo
- Publication number
- JPH11236540A JPH11236540A JP10040292A JP4029298A JPH11236540A JP H11236540 A JPH11236540 A JP H11236540A JP 10040292 A JP10040292 A JP 10040292A JP 4029298 A JP4029298 A JP 4029298A JP H11236540 A JPH11236540 A JP H11236540A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- anisotropic conductive
- conductive adhesive
- connection
- adhesive
- 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.)
- Pending
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＬＣＤ（液晶ディ
スプレイ）とＴＣＰ（テープキャリヤパッケージ）との
接続や、ＴＣＰとＰＣＢ（プリント回路基板）との接続
などの微細な回路同士の電気的接続に使用される異方導
電性接着剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrical connection between fine circuits such as a connection between an LCD (liquid crystal display) and a TCP (tape carrier package) and a connection between a TCP and a PCB (printed circuit board). The present invention relates to an anisotropic conductive adhesive used.
【０００２】[0002]
【従来の技術】近年、ＬＣＤとＴＣＰ、あるいはＴＣＰ
とＰＣＢの接続など、各種微細回路接続の必要性が飛躍
的に増大してきており、その接続方法として接着性樹脂
中に導電性粒子を分散させた異方導電性接着剤が使用さ
れてきている。この方法は、接続したい部材間に異方導
電性接着剤を挟み加熱加圧することにより、面方向の隣
接端子間では電気的絶縁性を保ち、上下の端子間では電
気的に導通させるものである。2. Description of the Related Art In recent years, LCD and TCP or TCP
The necessity of connecting various microcircuits, such as connection between a PC and a PCB, has been dramatically increased, and an anisotropic conductive adhesive in which conductive particles are dispersed in an adhesive resin has been used as a connection method. . In this method, an anisotropic conductive adhesive is sandwiched between members to be connected and heated and pressed, so that electrical insulation is maintained between adjacent terminals in the surface direction, and electrical conduction is provided between upper and lower terminals. .
【０００３】このような用途に異方導電性接着剤が多用
されてきたのは、被着体の耐熱性がないことや微細な回
路では隣接端子間で電気的にショートしてしまうなど半
田付けなどの従来の接続方法が適用できないことが理由
である。特に最近ではＬＣＤモジュールの大画面化、高
精細化、狭額縁化が急速に進み、これに伴って、接続ピ
ッチの微細化や接続の細幅化も急速に進んできた。[0003] Anisotropic conductive adhesives have often been used for such applications because of the lack of heat resistance of the adherend and the short circuit between adjacent terminals in a fine circuit due to electrical short-circuiting. This is because conventional connection methods such as the above cannot be applied. In particular, in recent years, the LCD module has been rapidly increasing in size, definition, and narrowing of the frame, and accordingly, the connection pitch and the connection width have also rapidly advanced.
【０００４】このため、たとえば、ＬＣＤとＴＣＰ接続
においては、接続時の加熱によるＴＣＰの伸びのために
接続パターンずれが生じたり、接続部が細幅のため接続
時の温度でＬＣＤ内部の部材が熱的影響を受けるなどの
問題が生じてきた。また、ＴＣＰとＰＣＢの接続におい
ては、ＰＣＢが長尺化してきたため接続時の加熱により
ＰＣＢとＬＣＤが反り、ＴＣＰの配線が断線するという
問題も生じてきた。これらの問題を解決するため、十分
な接続信頼性を保ちながら、より低温かつ短時間での接
続が可能な異方導電性接着剤が求められている。For this reason, for example, in the connection between the LCD and the TCP, the connection pattern shifts due to the elongation of the TCP due to the heating at the time of connection, and the members inside the LCD at the temperature at the time of connection because the connection portion is narrow. Problems such as being affected by heat have arisen. Further, in the connection between the TCP and the PCB, since the PCB has become longer, there has been a problem that the PCB and the LCD are warped due to heating during the connection, and the wiring of the TCP is disconnected. In order to solve these problems, there is a demand for an anisotropic conductive adhesive that can be connected at a lower temperature and in a shorter time while maintaining sufficient connection reliability.
【０００５】異方導電接着剤は、熱可塑タイプのものと
熱硬化タイプのものに分類されるが、最近では熱可塑タ
イプのものより、信頼性の優れたエポキシ樹脂系の熱硬
化タイプのものが広く用いられている。しかし、これら
エポキシ樹脂系の熱硬化タイプの異方導電接着剤はその
硬化反応性から、保存性安定性と樹脂の硬化性を両立さ
せるため１５０〜２００℃の温度で３０秒前後加熱、硬
化することが必要とされ、たとえば１５０℃以下の温度
では実用的な接続時間で樹脂を硬化させることは困難で
あった。[0005] Anisotropic conductive adhesives are classified into a thermoplastic type and a thermosetting type. Recently, epoxy resin type thermosetting types having higher reliability than the thermoplastic type have been used. Is widely used. However, these epoxy resin-based thermosetting anisotropic conductive adhesives are heated and cured at a temperature of 150 to 200 ° C. for about 30 seconds in order to achieve both storage stability and resin curability due to their curing reactivity. For example, at a temperature of 150 ° C. or less, it has been difficult to cure the resin in a practical connection time.
【０００６】更に、保存安定性については、例えば、Ｂ
Ｆ3アミン錯体、ジシアンジアミド、有機酸ヒドラジ
ド、イミダゾール化合物等の潜在性硬化剤を配合した系
を用いたもの等が提案されているが、保存安定性に優れ
るものは硬化に長時間または高温を必要とし、低温・短
時間で硬化できるものは逆に保存安定性に劣るといった
問題がありいずれも一長一短があった。Further, regarding the storage stability, for example, B
F 3 amine complexes, dicyandiamide, organic acid hydrazide, and the like that use the system compounded with latent curing agents such as imidazole compounds have been proposed, are excellent in storage stability requires prolonged or high temperature cure On the other hand, those which can be cured at a low temperature and in a short time have a problem that storage stability is inferior, and all of them have advantages and disadvantages.
【０００７】前記問題点に加えて、熱硬化タイプの異方
導電性接着剤を用いた微細な回路同士の接続作業性にお
いて、一度接続したものを位置ずれ等の原因により、被
接続部材を破損または損傷せずに剥離して再度接合（所
謂リペア）したいという要求が多くでてきている。しか
し殆どの熱硬化タイプの異方導電性接着剤は、高接着
力、高信頼性といった長所がある反面、リペアの容易性
という一見矛盾する要求に対しては対応が極めて難し
く、満足するものは得られていない。[0007] In addition to the above problems, in connection workability between fine circuits using a thermosetting anisotropic conductive adhesive, a member to be connected is damaged due to a displacement or the like of a member once connected. Also, there has been a growing demand for peeling without damage and rejoining (so-called repair). However, most thermosetting anisotropic conductive adhesives have the advantages of high adhesive strength and high reliability, but it is extremely difficult to respond to the seemingly contradictory requirements of ease of repair. Not obtained.
【０００８】低温接続を可能とする異方導電性接着剤と
しては、カチオン重合性物質とスルホニウム塩とを配合
した接着性樹脂中に導電性粒子を分散させたもの（特開
平７−９０２３７号公報）や、エポキシ樹脂等と４−
（ジアルキルアミノ）ピリジン誘導体に導電性粒子を分
散させたもの（特開平４−１８９８８３号公報）も提案
されているが、接着剤樹脂の保存性や被接続回路端子の
腐食等の問題があり実用には至っていない。As an anisotropic conductive adhesive which enables low-temperature connection, an adhesive obtained by dispersing conductive particles in an adhesive resin containing a cationically polymerizable substance and a sulfonium salt (JP-A-7-90237) ) Or epoxy resin etc.
A dispersion in which conductive particles are dispersed in a (dialkylamino) pyridine derivative (Japanese Patent Application Laid-Open No. 4-189883) has also been proposed. However, practical use is problematic due to problems such as the preservability of the adhesive resin and the corrosion of connected circuit terminals. Has not been reached.
【０００９】これらの問題を解決し、低温速硬化性と保
存安定性との両立及び、接続信頼性とリペア性との両立
を可能とする異方導電性接着剤として、ラジカル重合性
樹脂、有機過酸化物、熱可塑性エラストマー、及びマレ
イミド樹脂からなる接着剤成分に導電性粒子を分散させ
た熱硬化型異方導電性接着剤が提案されている。この異
方導電性接着剤に於いてラジカル重合性樹脂は、接続信
頼性、接着力、作業性など接着剤の性能の多くを左右す
る主成分であり、ラジカル硬化性樹脂と必要に応じてこ
れに加えられるラジカル重合性モノマーとからなる。し
かしながら、前記樹脂系による異方導電性接着剤が良好
な特性を示すような熱硬化性樹脂とラジカル重合性モノ
マーの組み合わせは、現状では最適化されるには至って
いない。As an anisotropic conductive adhesive which solves these problems and achieves both low-temperature quick-curing and storage stability, and also achieves connection reliability and repairability, radical polymerizable resins and organic A thermosetting anisotropic conductive adhesive in which conductive particles are dispersed in an adhesive component composed of a peroxide, a thermoplastic elastomer, and a maleimide resin has been proposed. In the anisotropic conductive adhesive, the radical polymerizable resin is a main component that determines many of the adhesive properties such as connection reliability, adhesive strength, and workability. And a radical polymerizable monomer added to the polymer. However, the combination of a thermosetting resin and a radically polymerizable monomer such that the resin-based anisotropic conductive adhesive exhibits good characteristics has not been optimized at present.
【００１０】即ち、現状では硬化性、作業性、接着性、
接続信頼性等の全てをバランス良く満足する樹脂系は得
られておらず、そのため、より低温、短時間で接続で
き、かつ接着性、接続信頼性、保存安定性、リペア性等
に優れる異方導電性接着剤の要求が強くなっている。That is, at present, curability, workability, adhesiveness,
A resin system that satisfies all of the connection reliability etc. in a well-balanced manner has not been obtained. Therefore, it is possible to connect at a lower temperature and in a shorter time, and it is excellent in adhesiveness, connection reliability, storage stability, repairability, etc. The demand for conductive adhesives has increased.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、従来技術の
このような問題に鑑みて種々の検討の結果なされたもの
であり、その目的とするところは、ＬＣＤとＴＣＰとの
接続や、ＴＣＰとＰＣＢとの接続などの微細回路同士の
電気的接続において、特に低温短時間での接続も可能
で、かつ、接着性、接続信頼性、保存安定性、リペア性
にも優れる加熱硬化型異方導電性接着剤を提供しようと
するものである。SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned problems of the prior art, and has been made as a result of various studies. The purpose of the present invention is to provide a connection between an LCD and a TCP or a TCP. Thermosetting anisotropic, which can be connected in a short time especially at low temperature, and has excellent adhesiveness, connection reliability, storage stability, and repairability in electrical connection between microcircuits such as connection between PCB and PCB It is intended to provide a conductive adhesive.
【００１２】[0012]
【課題を解決するための手段】本発明者は、低温速硬化
性と保存安定性性の両立が可能な、ラジカル重合性樹
脂、有機過酸化物、熱可塑性エラストマー、及びマレイ
ミドを配合した接着剤中に導電性粒子を分散させた熱硬
化型異方導電性接着剤について、該異方導電性接着剤の
諸特性とラジカル重合性樹脂の組成との関係について検
討を重ねた結果、ラジカル重合性樹脂としてフェノール
性水酸基を有する（メタ）アクリロイル化ノボラック樹
脂及び、２−ヒドロキシ−３−フェノキシプロピルアク
リレートとを合わせて用いることにより、種々の環境下
で種々の被着体に対し高い接着力及び接続信頼性を有す
る熱硬化型異方導電性接着剤の得られることを見いだ
し、本発明に至ったものである。SUMMARY OF THE INVENTION The present inventor has developed an adhesive containing a radical polymerizable resin, an organic peroxide, a thermoplastic elastomer, and a maleimide, which can achieve both low-temperature quick-curing and storage stability. As for the thermosetting anisotropic conductive adhesive with conductive particles dispersed in it, the relationship between various properties of the anisotropic conductive adhesive and the composition of the radical polymerizable resin was repeatedly examined. By using (meth) acryloylated novolak resin having a phenolic hydroxyl group as a resin and 2-hydroxy-3-phenoxypropyl acrylate in combination, high adhesion and connection to various adherends under various environments. The present inventors have found that a thermosetting anisotropic conductive adhesive having reliability can be obtained, and have reached the present invention.
【００１３】即ち、本発明はフェノール性水酸基を有す
る（メタ）アクリロイル化ノボラック樹脂、２−ヒドロ
キシ−３−フェノキシプロピルアクリレート、有機過酸
化物、熱可塑性エラストマー及びマレイミドを含む樹脂
組成物中に導電性粒子を分散させた異方導電性接着剤で
ある。That is, the present invention relates to a resin composition containing a (meth) acryloylated novolak resin having a phenolic hydroxyl group, 2-hydroxy-3-phenoxypropyl acrylate, an organic peroxide, a thermoplastic elastomer and a maleimide. This is an anisotropic conductive adhesive in which particles are dispersed.
【００１４】本発明で用いられるラジカル重合性樹脂と
しては、硬化性樹脂として（１）式に示される構造のフ
ェノール性水酸基を有する（メタ）アクリロイル化ノボ
ラック樹脂を用い、ラジカル重合性モノマーとして２−
ヒドロキシ−３−フェノキシプロピルアクリレートを合
わせて用いる。As the radical polymerizable resin used in the present invention, a (meth) acryloylated novolak resin having a phenolic hydroxyl group having a structure represented by the formula (1) is used as a curable resin, and 2- (radical polymerizable monomer) is used as a radical polymerizable monomer.
Hydroxy-3-phenoxypropyl acrylate is used in combination.
【００１５】[0015]
【化１】 Embedded image
【００１６】更に、必要に応じてビニルエステル樹脂等
のアクリレート類、不飽和ポリエステル樹脂、ジアリル
フタレート樹脂等を加えてもよい。同様に、トリメチロ
ールプロパントリアクリレート（ＴＭＰＴＡ）、ペンタ
エリスリトールジアクリレートモノステアレート、テト
ラエチレングリコールジアクリレートなどのアクリレー
ト類や、スチレン等各種モノマー、その他一般的な反応
性希釈剤を添加してもよい。保存性を確保するために、
予めキノン類、多価フェノール類、フェノール類等の重
合禁止剤を添加することも可能である（例えば、特開平
４−１４６９５１号公報など）。Further, if necessary, acrylates such as vinyl ester resin, unsaturated polyester resin, diallyl phthalate resin and the like may be added. Similarly, acrylates such as trimethylolpropane triacrylate (TMPTA), pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, various monomers such as styrene, and other general reactive diluents may be added. . To ensure preservation,
It is also possible to add in advance a polymerization inhibitor such as quinones, polyhydric phenols, and phenols (for example, JP-A-4-146951).
【００１７】本発明で用いられる（メタ）アクリロイル
化ノボラック樹脂におけるフェノール性水酸基と（メ
タ）アクリロイル基との割合は特に限定するものではな
いが、フェノール性水酸基対（メタ）アクリロイル基の
モル比にして１対９から９対１の範囲が望ましく、２対
８から５対５の範囲でより好適に用いることができる。
（メタ）アクリロイル基の比が上記範囲より多いと硬化
性は良好になるものの、フェノール性水酸基に基づく接
着強度が得られ難く、更に樹脂の軟化点が低下し、水飴
状もしくは粘着性の固形状になるので取り扱いが困難に
なる。また逆に、フェノール性水酸基が上記範囲より多
いと硬化性が不足するため好ましくない。Although the ratio of the phenolic hydroxyl group to the (meth) acryloyl group in the (meth) acryloylated novolak resin used in the present invention is not particularly limited, the molar ratio of the phenolic hydroxyl group to the (meth) acryloyl group is not limited. Thus, the ratio is preferably in the range of 1: 9 to 9: 1, and more preferably in the range of 2: 8 to 5: 5.
When the ratio of the (meth) acryloyl group is more than the above range, the curability becomes good, but the adhesive strength based on the phenolic hydroxyl group is hardly obtained, and the softening point of the resin further decreases, and the syrup or sticky solid Becomes difficult to handle. Conversely, if the phenolic hydroxyl group is more than the above range, the curability will be insufficient, which is not preferable.
【００１８】本発明で用いられるラジカル重合性樹脂全
体に於ける２−ヒドロキシ−３−フェノキシプロピルア
クリレートの割合は、５重量パーセントから５０重量パ
ーセントの範囲にあることが望ましい。この割合が５重
量パーセント以内であると、異方導電性接着剤としたと
きに熱時の流動性の不足や硬化収縮の増加が生じ、十分
な接着力が得られない。また５０％を超えると、硬化物
の架橋密度低下により十分な接続信頼性が得られない。The proportion of 2-hydroxy-3-phenoxypropyl acrylate in the whole radically polymerizable resin used in the present invention is preferably in the range of 5 to 50% by weight. If the proportion is less than 5% by weight, when the anisotropic conductive adhesive is used, insufficient fluidity at the time of heating and an increase in curing shrinkage occur, and a sufficient adhesive strength cannot be obtained. On the other hand, if it exceeds 50%, sufficient connection reliability cannot be obtained due to a decrease in the crosslink density of the cured product.
【００１９】本発明で用いられる有機過酸化物としては
特に限定されるものではなく、例えば１，１，３，３−
テトラメチルブチルパーオキシ−２−エチルヘキサネー
ト、ｔ−ブチルパーオキシ−２−エチルヘキサネート、
ｔ−ヘキシルパーオキシ−２−エチルヘキサネート、
１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−
トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシ
ルパーオキシ）−３，３，５−トリメチルシクロヘキサ
ン、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシ
ジカーボネート等が挙げられる。The organic peroxide used in the present invention is not particularly limited. For example, 1,1,3,3-
Tetramethylbutyl peroxy-2-ethyl hexanate, t-butyl peroxy-2-ethyl hexanate,
t-hexylperoxy-2-ethylhexanate,
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate and the like can be mentioned.
【００２０】これらの過酸化物は単独で、あるいは硬化
性をコントロールするために二種以上の有機過酸化物を
混合して用いることができる。また、保存性を改良する
ために各種重合禁止剤を予め添加しておくことも可能で
ある。さらに樹脂への溶解作業を容易にするため溶剤等
に希釈して用いることもできる。本発明で用いられる有
機過酸化物の種類や配合量は、各過酸化物を配合した場
合の、接着剤の硬化性と保存性との兼ね合いで決定され
ることは当然である。These peroxides can be used alone or as a mixture of two or more organic peroxides for controlling the curability. It is also possible to add various polymerization inhibitors in advance to improve the storage stability. Further, in order to facilitate the work of dissolving the resin, it may be used after being diluted with a solvent or the like. Naturally, the type and amount of the organic peroxide used in the present invention are determined depending on the balance between the curability and the storage stability of the adhesive when each peroxide is compounded.
【００２１】本発明で用いられる熱可塑性エラストマー
としては特に制限はないが、例えばポリエステル樹脂
類、ポリウレタン樹脂類、ポリイミド樹脂、ポリブタジ
エン、ポリプロピレン、スチレン−ブタジエン−スチレ
ン共重合体、ポリアセタール樹脂、ポリビニルブチラー
ル樹脂、ブチルゴム、クロロプレンゴム、ポリアミド樹
脂、アクリロニトリル−ブタジエン共重合体、アクリロ
ニトリル−ブタジエン−メタクリル酸共重合体、アクリ
ロニトリル−ブタジエン−スチレン共重合体、ポリ酢酸
ビニル樹脂、ナイロン、スチレン−イソプレン共重合
体、スチレン−ブチレン−スチレンブロック共重合体、
スチレン−エチレン−ブチレン−スチレンブロック共重
合体、ポリメチルメタクリレート樹脂などを用いること
ができる。その中で異方導電性接着剤とした際の接着
性、接続信頼性などの特性を考えると、アクリロニトリ
ル−ブタジエン−メタクリル酸共重合体、ポリエステ
ル、ポリアミド樹脂、ナイロン、ポリビニルブチラール
樹脂、スチレン−エチレン−ブチレン−スチレンブロッ
ク共重合体等をより好適に用いることができる。The thermoplastic elastomer used in the present invention is not particularly limited. Examples thereof include polyester resins, polyurethane resins, polyimide resins, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, polyacetal resin, and polyvinyl butyral resin. Butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl acetate resin, nylon, styrene-isoprene copolymer, styrene -Butylene-styrene block copolymer,
Styrene-ethylene-butylene-styrene block copolymer, polymethyl methacrylate resin and the like can be used. Considering properties such as adhesiveness and connection reliability when used as an anisotropic conductive adhesive among them, acrylonitrile-butadiene-methacrylic acid copolymer, polyester, polyamide resin, nylon, polyvinyl butyral resin, styrene-ethylene -Butylene-styrene block copolymer and the like can be more preferably used.
【００２２】本発明に用いられるマレイミドとしては、
ラジカル重合性樹脂と熱可塑性エラストマーとを相溶さ
せる作用を有するものであれば特に制限はないが、一般
的に（２）、（３）式に例示される化学構造を有するも
のを用いる。The maleimide used in the present invention includes:
There is no particular limitation as long as it has a function of making the radical polymerizable resin and the thermoplastic elastomer compatible with each other. Generally, a resin having a chemical structure exemplified by the formulas (2) and (3) is used.
【００２３】[0023]
【化２】 Embedded image
【００２４】[0024]
【化３】 Embedded image
【００２５】異方導電性接着剤の使用条件（接続温度、
接続時間）や、使用するラジカル重合性樹脂及び熱可塑
性エラストマーの種類により、その化学構造を選択ある
いは変更して使用できる。また、ラジカル重合性樹脂と
熱可塑性エラストマーの相溶性の更なる向上、或いは溶
媒溶解性など異方導電性接着剤の作製における作業性向
上等の目的で、アミン化合物、（メタ）アリル化合物、
シアネート化合物等で変性されたマレイミドを用いるこ
ともできる。また変性されたマレイミドを用いるにあた
っては、その変性に用いられた化合物の未反応残留物を
除去したものであっても構わない。Conditions for using the anisotropic conductive adhesive (connection temperature,
The chemical structure can be selected or changed depending on the connection time) and the types of the radical polymerizable resin and the thermoplastic elastomer used. Further, for the purpose of further improving the compatibility between the radical polymerizable resin and the thermoplastic elastomer, or improving the workability in producing an anisotropic conductive adhesive such as solvent solubility, an amine compound, a (meth) allyl compound,
A maleimide modified with a cyanate compound or the like can also be used. When the modified maleimide is used, an unreacted residue of the compound used for the modification may be removed.
【００２６】本発明に用いられる導電性粒子は、導電性
を有するものであれば特に制限するものではなく、ニッ
ケル、鉄、銅、アルミニウム、錫、鉛、クロム、コバル
ト、銀、金など各種金属やそれらの合金、または金属酸
化物、カーボン、グラファイト、ガラスやセラミック、
プラスチック粒子の表面に導電物をコートしたもの等が
適用できる。これらの導電性粒子の粒径や材質、配合量
は、接続したい回路の端子間隔や端子形状、回路素材の
厚みや材質等によって適切なものを選ぶことができる。The conductive particles used in the present invention are not particularly limited as long as they have conductivity, and various kinds of metals such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver, and gold can be used. Or their alloys, or metal oxides, carbon, graphite, glass or ceramic,
Plastic particles coated with a conductive material on the surface can be used. Appropriate particles, materials and amounts of these conductive particles can be selected according to the terminal spacing and terminal shape of the circuit to be connected, the thickness and material of the circuit material, and the like.
【００２７】更に、本発明の異方導電性接着剤中には、
必要に応じてカップリング剤を適量添加してもよい。カ
ップリング剤を添加する目的は、異方導電性接着剤の接
着界面の接着性を改質し、接着強度や耐熱性、耐湿性を
向上し接続信頼性を向上するものである。カップリング
剤としては、特にシラン系カップリング剤を好適に添加
使用することができ、例えば、エポキシシラン系、メル
カプトシラン系、アクリルシラン系（例えば、β−
（３，４−エポキシシクロヘキシル）エチルトリメトキ
シシラン、γ−グリシドキシプロピルトリメトキシシラ
ン、γ−メルカプトプロピルトリメトキシシラン、γ−
メタクリロキシプロピルトリメトキシシラン等）を用い
ることができる。Further, in the anisotropic conductive adhesive of the present invention,
If necessary, a suitable amount of a coupling agent may be added. The purpose of adding the coupling agent is to improve the adhesiveness of the adhesive interface of the anisotropic conductive adhesive, improve the adhesive strength, heat resistance and moisture resistance, and improve the connection reliability. As the coupling agent, particularly, a silane coupling agent can be suitably added and used. For example, an epoxy silane type, a mercapto silane type, an acryl silane type (for example, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, etc.) can be used.
【００２８】[0028]
【実施例】以下、本発明を実施例及び比較例により説明
する。 （実施例１） ［異方導電性接着剤フィルムの作製］７００重量部のメ
チルエチルケトン中に、（１）式の構造を有し、フェノ
ール性水酸基とメタアクリロイル基とのモル比が３対７
であるフェノール性水酸基を有するメタアクリロイル化
ノボラック樹脂を８０重量部、２−ヒドロキシ−３−フ
ェノキシプロピルアクリレートを２０重量部、分子量が
２万５千であり軟化点が摂氏１２０度である飽和共重合
ポリエステルを１００重量部、１，１−ジメチルブチル
パーオキシ−２，２−ジメチルプロパネートを５重量
部、ビス（４−マレイミドフェニル）エーテルを１００
重量部を溶解させ、樹脂成分溶液を得た。この樹脂成分
溶液中に、平均粒径５μｍのＮｉ／Ａｕメッキポリスチ
レン粒子７重量部を均一分散させた後、離型処理を施し
たポリエチレンテレフタレートフィルム上に乾燥後の厚
さが４５μｍになるように溶液を流延・乾燥し、異方導
電性接着剤フィルムを得た。The present invention will be described below with reference to examples and comparative examples. (Example 1) [Preparation of anisotropic conductive adhesive film] In 700 parts by weight of methyl ethyl ketone, having a structure of the formula (1), a molar ratio of a phenolic hydroxyl group to a methacryloyl group was 3: 7.
80 parts by weight of a methacryloylated novolak resin having a phenolic hydroxyl group, 20 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, a molecular weight of 25,000 and a softening point of 120 ° C. 100 parts by weight of polyester, 5 parts by weight of 1,1-dimethylbutylperoxy-2,2-dimethylpropanoate, 100 parts by weight of bis (4-maleimidophenyl) ether
The parts by weight were dissolved to obtain a resin component solution. After uniformly dispersing 7 parts by weight of Ni / Au-plated polystyrene particles having an average particle size of 5 μm in this resin component solution, a thickness of 45 μm after drying on a polyethylene terephthalate film subjected to a release treatment is adjusted. The solution was cast and dried to obtain an anisotropic conductive adhesive film.
【００２９】［評価サンプル作製］被着体は銅箔／ポリ
イミド＝２５／７５μｍに０．５μｍの錫メッキを施し
たＴＣＰ（ピッチ０．３ｍｍ、端子数６０本）と０．８
ｍｍ厚４層板（ＦＲ−４）内層・外層銅箔１８μｍフラ
ッシュ金メッキＰＣＢ（ピッチ０．３０ｍｍ、端子数６
０本）を用い、圧着条件は、１３０℃、３０ｋｇ／ｃｍ
2、１５秒の条件で圧着し、評価サンプルを得た。[Preparation of Evaluation Sample] The adherends were copper (polyimide) = 25/75 μm and 0.5 μm tin-plated TCP (pitch: 0.3 mm, number of terminals: 60) and 0.8
4 mm thick board (FR-4) Inner / outer copper foil 18 μm flash gold-plated PCB (0.30 mm pitch, 6 terminals)
0) and the crimping conditions are 130 ° C., 30 kg / cm
2. Pressure bonding was performed for 15 seconds to obtain an evaluation sample.
【００３０】［評価］ 接着力測定： １３０℃で接着した評価サンプルを用い
て、９０度剥離試験による評価を行った。接続信頼性：
評価サンプル作製直後及び、温度８５℃、湿度８５％
雰囲気中に１００時間放置後の接続抵抗値を測定した。
接続抵抗値を測定できないものについては導通不良（Ｏ
ＰＥＮ）とした。保存安定性： フィルム化された状態
で２５℃の条件下に７日間放置した異方導電性接着剤フ
ィルムを用いて評価サンプルを作製し、サンプル作製直
後の接続抵抗を測定した。これらの評価結果を表２に示
した。なお、使用した原料を表１に示した。[Evaluation] Adhesion force measurement: Evaluation was performed by a 90 ° peel test using an evaluation sample bonded at 130 ° C. Connection reliability:
Immediately after the preparation of the evaluation sample, and at 85 ° C and 85% humidity
The connection resistance value after being left in an atmosphere for 100 hours was measured.
If the connection resistance cannot be measured,
PEN). Storage stability: An evaluation sample was prepared using an anisotropic conductive adhesive film left in a film state at 25 ° C. for 7 days, and the connection resistance was measured immediately after the sample was prepared. Table 2 shows the results of these evaluations. The raw materials used are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【化４】 Embedded image
【００３３】[0033]
【化５】 Embedded image
【００３４】[0034]
【化６】 Embedded image
【００３５】[0035]
【表２】 [Table 2]
【００３６】（実施例２〜６及び比較例１〜４）表２に
示される配合量にて実施例１と同様の操作を行い、それ
ぞれ異方導電性接着剤フィルムを得た。得られた異方導
電性接着剤フィルムを実施例１と同様に評価した結果を
表２に示した。(Examples 2 to 6 and Comparative Examples 1 to 4) The same operation as in Example 1 was performed with the compounding amounts shown in Table 2 to obtain anisotropic conductive adhesive films. The results of evaluating the obtained anisotropic conductive adhesive film in the same manner as in Example 1 are shown in Table 2.
【００３７】[0037]
【発明の効果】本発明によれば、ラジカル重合性樹脂、
有機過酸化物、熱可塑性エラストマー、マレイミドとを
配合した樹脂組成分中に、導電性粒子を分散させること
により得られる異方導電性接着剤を用いて加熱硬化接続
する際、該接着剤中に含まれるマレイミドによってラジ
カル重合性樹脂と熱可塑性エラストマーとが相溶化さ
れ、またマレイミド自身も硬化するため、均一分散した
状態で硬化し、なおかつ、該ラジカル重合性樹脂として
フェノール性水酸基を有する（メタ）アクリロイル化ノ
ボラック樹脂と２−ヒドロキシ−３−フェノキシプロピ
ルアクリレートを用いることにより、これらのラジカル
重合性樹脂に含まれる水酸基に基づく優れた接着力が得
られるため、極めて低温かつ短時間で接続可能であり、
接着性、接続信頼性、保存安定性、リペア性に優れた異
方導電性接着剤が得られる。According to the present invention, a radical polymerizable resin,
Organic peroxide, thermoplastic elastomer, in a resin composition blended with maleimide, when heat-cured connection using an anisotropic conductive adhesive obtained by dispersing conductive particles, in the adhesive Since the radical polymerizable resin and the thermoplastic elastomer are compatibilized by the contained maleimide, and the maleimide itself is also cured, it is cured in a uniformly dispersed state, and has a phenolic hydroxyl group as the radically polymerizable resin (meth). By using an acryloylated novolak resin and 2-hydroxy-3-phenoxypropyl acrylate, an excellent adhesive force based on the hydroxyl group contained in these radically polymerizable resins can be obtained, so that connection can be made at a very low temperature and in a short time. ,
An anisotropic conductive adhesive excellent in adhesiveness, connection reliability, storage stability, and repairability can be obtained.
Claims (2)
可塑性エラストマー、マレイミドを含む樹脂組成物中に
導電性粒子を分散させた異方導電性接着剤に於いて、該
ラジカル重合性樹脂が、フェノール性水酸基を有する
（メタ）アクリロイル化ノボラック樹脂及び２−ヒドロ
キシ−３−フェノキシプロピルアクリレートを含むこと
を特徴とする異方導電性接着剤。1. An anisotropic conductive adhesive in which conductive particles are dispersed in a resin composition containing a radical polymerizable resin, an organic peroxide, a thermoplastic elastomer, and maleimide, wherein the radical polymerizable resin is An anisotropic conductive adhesive comprising: a (meth) acryloylated novolak resin having a phenolic hydroxyl group; and 2-hydroxy-3-phenoxypropyl acrylate.
ロキシ−３−フェノキシプロピルアクリレートの割合が
５重量パーセントから５０重量パーセントの範囲内にあ
ることを特徴とする請求項１記載の異方導電性接着剤。2. An anisotropic conductive material according to claim 1, wherein the proportion of 2-hydroxy-3-phenoxypropyl acrylate in the radically polymerizable resin is in the range of 5 to 50% by weight. Adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10040292A JPH11236540A (en) | 1998-02-23 | 1998-02-23 | Anisotropic conductive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10040292A JPH11236540A (en) | 1998-02-23 | 1998-02-23 | Anisotropic conductive adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11236540A true JPH11236540A (en) | 1999-08-31 |
Family
ID=12576540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10040292A Pending JPH11236540A (en) | 1998-02-23 | 1998-02-23 | Anisotropic conductive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11236540A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004055126A1 (en) * | 2002-12-13 | 2004-07-01 | Ls Cable Ltd. | Anisotropic-electroconductive adhesive, circuit connection method and structure using the same |
| WO2006082672A1 (en) * | 2005-02-03 | 2006-08-10 | Sony Chemical & Information Device Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| KR100710957B1 (en) * | 2006-01-03 | 2007-04-24 | 엘에스전선 주식회사 | Anisotropic-electroconductive adhesive, circuit connection using the same, and circuit connection structure |
| JP4599666B2 (en) * | 2000-06-29 | 2010-12-15 | 日立化成工業株式会社 | Conductive resin paste composition and semiconductor device using the same |
| KR101184910B1 (en) | 2009-11-02 | 2012-09-20 | 회명산업 주식회사 | Anisotropic conductive adhesive having superior repairability and fast adhesiveness |
| JP2014070179A (en) * | 2012-09-28 | 2014-04-21 | Tamura Seisakusho Co Ltd | Adhesive composition, solar cell module, and method of connecting between solar cell and wiring |
| US9899122B2 (en) | 2014-11-27 | 2018-02-20 | Samsung Sdi Co., Ltd. | Display device connected by anisotropic conductive film |
-
1998
- 1998-02-23 JP JP10040292A patent/JPH11236540A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4599666B2 (en) * | 2000-06-29 | 2010-12-15 | 日立化成工業株式会社 | Conductive resin paste composition and semiconductor device using the same |
| WO2004055126A1 (en) * | 2002-12-13 | 2004-07-01 | Ls Cable Ltd. | Anisotropic-electroconductive adhesive, circuit connection method and structure using the same |
| CN1304510C (en) * | 2002-12-13 | 2007-03-14 | Lg电线有限公司 | Anisotropic-electroconductive adhesive, circuit connection method and structure using the same |
| WO2006082672A1 (en) * | 2005-02-03 | 2006-08-10 | Sony Chemical & Information Device Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US8034849B2 (en) * | 2005-02-03 | 2011-10-11 | Sony Corporation | Adhesive composition and adhesive sheet |
| KR100710957B1 (en) * | 2006-01-03 | 2007-04-24 | 엘에스전선 주식회사 | Anisotropic-electroconductive adhesive, circuit connection using the same, and circuit connection structure |
| KR101184910B1 (en) | 2009-11-02 | 2012-09-20 | 회명산업 주식회사 | Anisotropic conductive adhesive having superior repairability and fast adhesiveness |
| JP2014070179A (en) * | 2012-09-28 | 2014-04-21 | Tamura Seisakusho Co Ltd | Adhesive composition, solar cell module, and method of connecting between solar cell and wiring |
| US9899122B2 (en) | 2014-11-27 | 2018-02-20 | Samsung Sdi Co., Ltd. | Display device connected by anisotropic conductive film |
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