JP2001329240A - Adhesive composition, adhesive composition for connecting circuit, circuit-connecting material, connector and semiconductor device - Google Patents
Adhesive composition, adhesive composition for connecting circuit, circuit-connecting material, connector and semiconductor deviceInfo
- Publication number
- JP2001329240A JP2001329240A JP2000150762A JP2000150762A JP2001329240A JP 2001329240 A JP2001329240 A JP 2001329240A JP 2000150762 A JP2000150762 A JP 2000150762A JP 2000150762 A JP2000150762 A JP 2000150762A JP 2001329240 A JP2001329240 A JP 2001329240A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- group
- compound
- circuit
- epoxy
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/35—Mechanical effects
- H01L2924/351—Thermal stress
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、接着剤組成物、回
路接続用接着剤組成物、接続体及び半導体装置に関す
る。The present invention relates to an adhesive composition, an adhesive composition for circuit connection, a connector, and a semiconductor device.
【０００２】[0002]
【従来の技術】半導体素子及び液晶表示素子において、
素子中の種々の部材を結合させる目的で従来から種々の
接着剤が使用されている。接着剤に対する要求は、耐熱
性、高温高湿状態における信頼性等多岐に渡るが、半導
体素子の高集積化、液晶表示素子の大型化、高精細化が
進むにつれて、周辺部材への影響を考慮した低温化、ス
ループットを考慮した短時間接着化が要求されている。
従来から、前記半導体素子や液晶表示素子用の接着剤と
しては、高接着性でかつ高信頼性を示すエポキシ樹脂を
用いた熱硬化性樹脂が用いられてきた。樹脂の構成成分
としては、エポキシ樹脂、エポキシ樹脂と反応性を有す
るフェノール樹脂等の硬化剤、エポキシ樹脂と硬化剤の
反応を促進する熱潜在性触媒が一般に用いられている。
熱潜在性触媒は硬化温度及び硬化速度を決定する重要な
因子となっており、室温での貯蔵安定性と加熱時の硬化
速度の観点から種々の化合物が用いられてきた。実際の
工程での硬化条件は、１７０〜２５０℃の温度で１〜３
時間硬化することにより、所望の接着を得ていた。しか
しながら、最近の半導体素子の高集積化、液晶素子の高
精細化に伴い、素子間及び配線間ピッチが狭小化し、硬
化時の加熱によって、周辺部材に悪影響を及ぼす恐れが
出てきた。さらに低コスト化のためには、スループット
を向上させる必要性があり、低温(１００〜１７０℃)、
短時間(１時間以内)、換言すれば低温速硬化での接着が
要求されている。この低温速硬化を達成するためには、
活性化エネルギーの低い熱潜在性触媒を使用する必要が
あり、室温付近での貯蔵安定性を兼備することが非常に
難しい。貯蔵安定性及び低温硬化性を兼備えた接着剤と
して、エポキシ樹脂の光カチオン重合を用いる方法が特
開平１１−６０８９９号及び特開平１１−１１６７７８
号公報に開示されている。これらは、エポキシ樹脂と光
照射によって強酸を発生する光酸発生剤から構成されて
おり、室温で光照射することにより硬化を行う方法であ
る。2. Description of the Related Art In semiconductor devices and liquid crystal display devices,
Conventionally, various adhesives have been used for the purpose of bonding various members in the element. The requirements for adhesives range from heat resistance, reliability in high-temperature, high-humidity conditions, etc., but as the integration of semiconductor elements, the size of liquid crystal display elements, and the increase in definition increase, consideration will be given to the effects on peripheral members. There is a demand for short-time bonding in consideration of lower temperature and throughput.
Conventionally, as an adhesive for the semiconductor element or the liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used. As a component of the resin, an epoxy resin, a curing agent such as a phenol resin reactive with the epoxy resin, and a heat latent catalyst for accelerating the reaction between the epoxy resin and the curing agent are generally used.
The thermal latent catalyst is an important factor in determining the curing temperature and the curing speed, and various compounds have been used from the viewpoint of storage stability at room temperature and the curing speed when heated. The curing conditions in the actual process are as follows.
The desired adhesion was obtained by curing for a time. However, with recent high integration of semiconductor elements and high definition of liquid crystal elements, the pitch between elements and between wirings has been narrowed, and there has been a possibility that heating during curing may adversely affect peripheral members. In order to further reduce the cost, it is necessary to improve the throughput, low temperature (100 ~ 170 ℃),
Adhesion in a short time (within 1 hour), in other words, at low temperature and fast curing is required. In order to achieve this low temperature rapid curing,
It is necessary to use a heat latent catalyst having a low activation energy, and it is very difficult to have storage stability near room temperature. JP-A-11-60899 and JP-A-11-116778 disclose a method using photocationic polymerization of an epoxy resin as an adhesive having both storage stability and low-temperature curability.
No. 6,086,045. These methods are composed of an epoxy resin and a photoacid generator that generates a strong acid upon irradiation with light, and are cured by irradiating with light at room temperature.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、エポキ
シ樹脂を用いた光カチオン重合では、重合触媒としてブ
レンステッド酸やルイス酸等の強酸が必要であり、硬化
後も系内にこれらが残存してしまう。また、これらの強
酸は、重合後も自由に移動し、被着体である金属基板や
金属及び無機材質で構成される回路電極の腐食を促進し
てしまい接続信頼性の点で劣っている。However, in cationic photopolymerization using an epoxy resin, a strong acid such as Bronsted acid or Lewis acid is required as a polymerization catalyst, and these remain in the system after curing. . In addition, these strong acids move freely even after polymerization, and promote corrosion of a metal substrate as an adherend or a circuit electrode composed of a metal and an inorganic material, which is inferior in connection reliability.
【０００４】本発明は、金属及び無機材質で構成される
被着体の腐食に伴う素子の信頼性低下を防ぎ、かつ低温
短時間で接着可能で、さらに室温での貯蔵安定性に優れ
る接着剤組成物、回路接続用接着剤組成物、接続体及び
半導体装置を提供するものである。[0004] The present invention provides an adhesive which prevents a decrease in the reliability of an element due to corrosion of an adherend made of a metal or an inorganic material, can be bonded in a short time at a low temperature, and has excellent storage stability at room temperature. It is intended to provide a composition, an adhesive composition for circuit connection, a connector, and a semiconductor device.
【０００５】[0005]
【課題を解決するための手段】本発明は、（ａ）エポキ
シ化合物、（ｂ）１５０〜７５０ｎｍの光照射によって
エポキシ化合物と反応する官能基を発生する置換基を含
有する高分子化合物からなり、(ｂ)高分子化合物の数平
均分子量が１，０００〜１００,０００であることを特
徴とする接着剤組成物である。また、本発明は（ｂ）１
５０〜７５０ｎｍの光照射によってフェノール性の水酸
基を発生する高分子化合物であることを特徴とする接着
剤組成物である。また、本発明は（ｂ）１５０〜７５０
ｎｍの光照射によって１級アミノ基または２級アミノ基
を発生する高分子化合物であることを特徴とする接着剤
組成物である。また、本発明は（ｂ）１５０〜７５０ｎ
ｍの光照射によってメルカプト基を発生する高分子化合
物であることを特徴とする接着剤組成物である。また、
本発明は（ａ）エポキシ化合物１００重量部に対して、
（ｂ）光照射によってエポキシ化合物と反応する官能基
を発生する高分子化合物０.０１〜２００重量部を含有
してなる接着剤組成物である。また、本発明は上記いず
れかに記載の接着剤組成物中に、さらに導電性粒子を含
む接着剤組成物である。また、本発明は相対向する回路
電極を有する基板間に介在させ、相対向する回路電極を
有する基板を加圧して加圧方向の電極間を電気的に接続
する回路接続用接着剤組成物であって、前記接着剤は上
記のいずれかに記載の接着剤組成物である回路接続用接
着剤組成物である。また、前記回路接続用接着剤組成物
を用いて接続された接続体である。また、本発明は半導
体素子の電極と半導体搭載用基板の回路電極間に上記の
いずれかに記載の接着剤組成物を介在させ、加圧して加
圧方向の電極間を電気的に接続した半導体装置である。The present invention comprises (a) an epoxy compound, and (b) a polymer compound having a substituent which generates a functional group which reacts with the epoxy compound by irradiation with light of 150 to 750 nm, (b) An adhesive composition characterized in that the number average molecular weight of the polymer compound is 1,000 to 100,000. Further, the present invention provides (b) 1
An adhesive composition, which is a polymer compound that generates a phenolic hydroxyl group upon irradiation with light of 50 to 750 nm. In addition, the present invention relates to (b) 150 to 750.
An adhesive composition, which is a polymer compound that generates a primary amino group or a secondary amino group by irradiation with light of nm. In addition, the present invention relates to (b) 150 to 750 n
m is a polymer compound that generates a mercapto group upon irradiation with light. Also,
The present invention relates to (a) 100 parts by weight of the epoxy compound,
(B) An adhesive composition containing 0.01 to 200 parts by weight of a polymer compound that generates a functional group that reacts with an epoxy compound by light irradiation. Further, the present invention is an adhesive composition further comprising conductive particles in the adhesive composition described in any of the above. Further, the present invention provides a circuit connection adhesive composition which is interposed between substrates having opposing circuit electrodes and pressurizes the substrate having opposing circuit electrodes to electrically connect the electrodes in the pressing direction. Further, the adhesive is a circuit-connecting adhesive composition which is the adhesive composition according to any of the above. In addition, a connected body is connected using the adhesive composition for circuit connection. Further, the present invention provides a semiconductor in which the adhesive composition according to any one of the above is interposed between an electrode of a semiconductor element and a circuit electrode of a substrate for mounting a semiconductor, and the pressure is applied to electrically connect the electrodes in the pressing direction. Device.
【０００６】[0006]
【発明の実施の形態】本発明において用いる（a）エポ
キシ樹脂は、分子内に２個以上のエポキシ基を有するも
のであれば特に制限なく、公知のものを使用しうる。こ
のような（a）エポキシ樹脂としては、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
ビスフェノールＳ型エポキシ樹脂、フェノールノボラッ
ク型エポキシ樹脂、クレゾールノボラック型エポキシ樹
脂、ビスフェノールＡノボラック型エポキシ樹脂、ビス
フェノールＦノボラック型エポキシ樹脂、脂環式エポキ
シ樹脂、グリシジルエステル型エポキシ樹脂、グリシジ
ルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹
脂、イソシアヌレート型エポキシ樹脂、脂肪族鎖状エポ
キシ樹脂等があり、これらのエポキシ樹脂は、ハロゲン
化されていてもよく、水素添加されていてもよい。これ
らのエポキシ樹脂は、２種以上を併用してもよい。これ
らの中で、他の各種のエポキシ化合物と比較すると分子
量の異なるグレードが広く入手可能で、接着性や反応性
等を任意に設定できる点から、ビスフェノール型エポキ
シ樹脂が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin (a) used in the present invention is not particularly limited as long as it has two or more epoxy groups in a molecule, and known epoxy resins can be used. As such (a) epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, There are a hydantoin type epoxy resin, an isocyanurate type epoxy resin, an aliphatic chain epoxy resin and the like, and these epoxy resins may be halogenated or hydrogenated. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferred, because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness, reactivity and the like can be arbitrarily set.
【０００７】本発明に用いる（a）エポキシ樹脂のエポ
キシ当量は４３〜１０００が好ましく、５０〜８００が
より好ましく、７３〜６００が特に好ましい。エポキシ
当量が４３未満又は１０００を超えると、後に説明する
電極の接続時に、接着強度が低下する傾向がある。これ
らの（a）エポキシ樹脂は、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、エレクトロンマイグレー
ション防止のために好ましい。The epoxy equivalent of the epoxy resin (a) used in the present invention is preferably 43 to 1,000, more preferably 50 to 800, and particularly preferably 73 to 600. If the epoxy equivalent is less than 43 or more than 1000, the adhesive strength tends to decrease when connecting electrodes described later. These (a) epoxy resins have impurity ions (Na + , Cl
- etc.) and hydrolyzable chlorine and the like using a high-purity product was reduced to 300ppm or less, preferably in order to prevent electron migration.
【０００８】本発明に用いる(ｂ)１５０〜７５０ｎｍの
光照射によってエポキシ化合物と反応する官能基を発生
する高分子化合物は、エポキシ基と反応する基、すなわ
ちフェノール性水酸基、１級アミノ基または２級アミノ
基、メルカプト基を光照射によって生成する高分子化合
物であれば特に制限は受けない。例えば、高分子論文
集、44巻、７４５〜７５１項（１９８７年）に報告され
ている光フリース転位(光Fries転位)を用いることがで
きる。これは、エステル基やチオエステル基、アミド基
を持つ化合物が、光照射によって分子内転位を起こし、
活性水素を持つ基(下式中ＸＨ)を生成する反応である。The polymer compound (b) which generates a functional group which reacts with an epoxy compound by irradiation with light of 150 to 750 nm (b) is a group which reacts with an epoxy group, that is, a phenolic hydroxyl group, a primary amino group or a secondary amino group. There is no particular limitation as long as it is a polymer compound that produces a primary amino group and a mercapto group by light irradiation. For example, the optical Fries dislocation (optical Fries dislocation) reported in the Journal of Polymers, Vol. 44, paragraphs 745 to 751 (1987) can be used. This is because a compound having an ester group, thioester group, or amide group undergoes intramolecular rearrangement by light irradiation,
This is a reaction for generating a group having active hydrogen (XH in the following formula).
【０００９】[0009]
【化１】 Embedded image
【００１０】本発明において用いることができる光フリ
ース転位可能な化合物としては、アリールエステル
(１)、アリールアミド（２）、アリールカーボナート
（３）、アリールチオエステル（４）等が挙げられる。
具体的には、下記一般式(１)〜（５)の少なくとも一種
を分子中に含有することが好ましい。The compound capable of photo-fleece rearrangement that can be used in the present invention includes aryl esters
(1), arylamide (2), arylcarbonate (3), arylthioester (4) and the like.
Specifically, it is preferable that at least one of the following general formulas (1) to (5) is contained in the molecule.
【化２】 （ただし、Ａｒはフェニル基、ナフチル基等の芳香族
基、Ｒ1は水素、炭素数１〜１０のアルキル基、フェニ
ル基、ナフチル基を示す）Embedded image (However, Ar represents an aromatic group such as a phenyl group or a naphthyl group, and R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group.)
【化３】 （ただし、Ａｒはフェニル基、ナフチル基等の芳香族基
を示す）Embedded image (However, Ar represents an aromatic group such as a phenyl group and a naphthyl group.)
【化４】 （ただし、Ａｒはフェニル基、ナフチル基等の芳香族
基、Ｒ2は水素、炭素数１〜１０のアルキル基、フェニ
ル基、ナフチル基を示す）Embedded image (However, Ar represents an aromatic group such as a phenyl group and a naphthyl group, and R 2 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a naphthyl group.)
【化５】 （ただし、Ａｒはフェニル基、ナフチル基等の芳香族
基、Ｒ3及びＲ4は独立に水素、炭素数１〜１０のアルキ
ル基、フェニル基、ナフチル基を示す）Embedded image (However, Ar represents an aromatic group such as a phenyl group or a naphthyl group, and R 3 and R 4 independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group.)
【化６】 （ただし、Ａｒはフェニル基、ナフチル基等の芳香族
基、Ｒ5は水素、炭素数１〜１０のアルキル基、フェニ
ル基、ナフチル基を示す）Embedded image (However, Ar represents an aromatic group such as a phenyl group or a naphthyl group, and R 5 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group.)
【００１１】前記光フリース転位の他、アリルフェニル
エーテル基を使用した光クライゼン転位(光Cleisen転
位)やクルチウス転位(Curtius転位)、スチーブンス転位
(Stevens転位)により、フェノール性水酸基、１級アミ
ノ基または２級アミノ基、メルカプト基を光照射により
任意に発生させることができる。In addition to the above-mentioned optical Fries rearrangement, an optical Claisen rearrangement (optical Cleisen rearrangement), a Curtius rearrangement (Curtius rearrangement), and a Stevens rearrangement using an allylphenyl ether group.
By (Stevens rearrangement), a phenolic hydroxyl group, a primary amino group or a secondary amino group, and a mercapto group can be arbitrarily generated by light irradiation.
【００１２】また、Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉ
ｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ １１３巻
４３０３項（１９９１年）に報告されているように、
ニトロベンジルカルバミン酸誘導体を光照射することに
より、アミノ基やメルカプト基を発生させることが可能
である。これらの化合物は、室温で光を照射しない状態
ではエポキシ樹脂と反応性を示さないため、室温での貯
蔵安定性は非常に優れているという特徴を持つ。[0012] Also, Journal of Ameri
As reported in Can Chemical Society 113, 4303 (1991),
By irradiating the nitrobenzyl carbamic acid derivative with light, an amino group or a mercapto group can be generated. Since these compounds do not show reactivity with the epoxy resin when irradiated with no light at room temperature, they have a feature that storage stability at room temperature is extremely excellent.
【００１３】上記の光照射によってエポキシ化合物と反
応する官能基を発生する高分子化合物は、ポリマの主鎖
や側鎖に前記置換基を導入して多官能化して用いるのが
好ましい。ポリマの流動性、架橋密度を考慮すると、本
発明の高分子化合物の数平均分子量は１，０００〜１０
０，０００が好ましく、さらに好ましくは３，０００〜
５０,０００である。The above-mentioned polymer compound which generates a functional group which reacts with the epoxy compound by light irradiation is preferably used after introducing the above substituent into the main chain or side chain of the polymer to make it multifunctional. Considering the fluidity of the polymer and the crosslink density, the number average molecular weight of the polymer compound of the present invention is 1,000 to 10
000 is preferred, and more preferably 3,000 to
50,000.
【００１４】光照射によってエポキシ化合物と反応する
官能基を発生する高分子化合物は、用いるエポキシ樹脂
のエポキシ当量と発生する官能基当量を一致させること
が最も好ましいが、一般的には（ａ）エポキシ化合物１
００重量部に対して、（ｂ）光照射によってエポキシ化
合物と反応する官能基を発生する高分子化合物０.０１
〜２００重量部を含有することが好ましい。For the polymer compound which generates a functional group which reacts with the epoxy compound by light irradiation, it is most preferable to make the epoxy equivalent of the epoxy resin used coincide with the generated functional group equivalent. Compound 1
(B) a polymer compound 0.01 which generates a functional group which reacts with an epoxy compound by light irradiation with respect to 00 parts by weight.
It is preferred that the content be from 200 to 200 parts by weight.
【００１５】本発明の接着剤組成物には、必要に応じて
硬化促進剤を添加できる。このような硬化促進剤として
は、エポキシ基と光照射によって生成する官能基との反
応を促進する活性を示すものであれば特に制限なく使用
することができ、塩基性物質が好ましい。また、光照射
によって塩基性物質を発生する化合物でもよく、保存安
定性の点からとりわけ好ましい。例えば、分子中にベン
ゾインエーテル結合を持つ（４−モルホリノベンゾイ
ル）−１−ベンジル−１−ジメチルアミノプロパン（イ
ルガキュア３６９、Ciba Specialty Chemicals製商品
名）や４−（メチルチオベンゾイル）−１−メチル−１
−モルホリノエタン（イルガキュア９０７、Ciba Speci
alty Chemicals製商品名）などが挙げられる。この他、
フェナシル基等の分子内にカルボニル基を有するジアル
キルフェナシルアンモニウム塩等の4級アンモニウム
塩、コバルト・アミン錯体、鉄-アレーン化合物等を使
用することができる。また必要に応じて、例えば２−メ
チルイミダゾール、２−エチルイミダゾール、２−プロ
ピルイミダゾール等のアルキルイミダゾール化合物、フ
ェニルイミダゾール、ナフチルイミダゾール等のアリー
ルイミダゾール化合物、２−アミノエチルイミダゾー
ル、２−アミノプロピルイミダゾール等のアミノアルキ
ルイミダゾール化合物、アジピン酸ジヒドラジド、エイ
コサン２酸ジヒドラジド、７，１１−オクタデカジエン
−１，１８−ジカルボヒドラジド、１，３−ビス（ヒド
ラジノカルボエチル）−５−イソプロピルヒダントイン
等のヒドラジド化合物、アミンイミド、ポリアミン、ジ
シアンジアミド、第三ホスフィン類、第四アンモニウム
塩、第四ホスホニウム塩等を用いることもできる。これ
らは単独又は２種以上を組み合わせて使用される。これ
らの硬化促進剤は、ポリウレタン、ポリエステル等の高
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されたも
のや、等量のエポキシ樹脂と反応させてアダクト体にさ
れたものであってもよく、そのようなものは、可使時間
延長の点から好ましい。[0015] A curing accelerator can be added to the adhesive composition of the present invention, if necessary. As such a curing accelerator, any one can be used without particular limitation as long as it exhibits an activity of accelerating the reaction between an epoxy group and a functional group generated by light irradiation, and a basic substance is preferable. Further, a compound which generates a basic substance by light irradiation may be used, and is particularly preferable from the viewpoint of storage stability. For example, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane having a benzoin ether bond in the molecule (Irgacure 369, trade name of Ciba Specialty Chemicals) or 4- (methylthiobenzoyl) -1-methyl-1
Morpholinoethane (Irgacure 907, Ciba Speci
alty Chemicals). In addition,
A quaternary ammonium salt such as a dialkylphenacyl ammonium salt having a carbonyl group in the molecule such as a phenacyl group, a cobalt-amine complex, an iron-arene compound, and the like can be used. If necessary, for example, alkyl imidazole compounds such as 2-methylimidazole, 2-ethylimidazole and 2-propylimidazole, arylimidazole compounds such as phenylimidazole and naphthylimidazole, 2-aminoethylimidazole, 2-aminopropylimidazole and the like Hydrazides such as aminoalkylimidazole compounds, adipic dihydrazide, eicosane diacid dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin Compounds, amine imides, polyamines, dicyandiamides, tertiary phosphines, quaternary ammonium salts, quaternary phosphonium salts, and the like can also be used. These are used alone or in combination of two or more. These curing accelerators react with polymer substances such as polyurethane and polyester, microencapsulated by coating with metal thin films such as Ni and Cu, and inorganic substances such as calcium silicate, and react with an equivalent amount of epoxy resin. It may be made into an adduct body, and such a thing is preferable in view of extending the pot life.
【００１６】硬化促進剤を使用する場合、その使用量
は、（Ａ）エポキシ樹脂の１００重量部に対して０．０
１〜２００重量部とすることが好ましく、０．１〜１０
０重量部とすることがより好ましく、０．５〜５０重量
部とすることが特に好ましい。この量が、０．０１重量
部未満では、硬化促進効果が不十分となる傾向があり、
２００重量部を超えると、相溶性が低下する傾向があ
る。When a curing accelerator is used, it is used in an amount of 0.0 to 100 parts by weight of the epoxy resin (A).
It is preferably from 1 to 200 parts by weight, and from 0.1 to 10 parts by weight.
It is more preferably 0 parts by weight, particularly preferably 0.5 to 50 parts by weight. If the amount is less than 0.01 part by weight, the effect of promoting curing tends to be insufficient,
If it exceeds 200 parts by weight, the compatibility tends to decrease.
【００１７】本発明に用いる導電性粒子としては、Ａ
ｕ、Ａｇ、Ｎｉ、Ｃｕ、はんだ等の金属粒子やカーボン
等が挙げられる。また、非導電性のガラス、セラミッ
ク、プラスチック等を核とし、この核に前記金属、金属
粒子やカーボンを被覆したものでもよい。導電性粒子
が、プラスチックを核とし、この核に前記金属、金属粒
子やカーボンを被覆したもの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。またこ
れらの導電性粒子の表面を、さらに高分子樹脂などで被
覆した微粒子は、導電性粒子の配合量を増加した場合の
粒子同士の接触による短絡を抑制し、電極回路間の絶縁
性が向上できることから、適宜これを単独あるいは導電
性粒子と混合して用いてもよい。The conductive particles used in the present invention include A
Metal particles such as u, Ag, Ni, Cu, solder and the like, carbon and the like can be mentioned. Further, the core may be made of non-conductive glass, ceramic, plastic, or the like, and the core may be coated with the metal, metal particles, or carbon. When the conductive particles are made of plastic as a core, and the core is coated with the metal, metal particles or carbon or a hot-melt metal particle,
Heat and pressure are preferable because they have deformability, so that the contact area with the electrode increases during connection and reliability is improved. In addition, fine particles in which the surface of these conductive particles is further coated with a polymer resin, etc., suppress short circuits due to contact between particles when the amount of conductive particles is increased, and improve insulation between electrode circuits. Since it can be used, it may be used alone or as a mixture with conductive particles.
【００１８】この導電性粒子の平均粒径は、分散性、導
電性の点から１〜１８μｍであることが好ましい。導電
性粒子の使用量は、特に制限は受けないが、（Ａ）エポ
キシ樹脂、（Ｂ）光照射によって塩基性物質を発生する
化合物、必要に応じて用いる硬化促進剤及び必要に応じ
て用いる添加剤のトータル１００体積に対して０．１〜
３０体積％とすることが好ましく、０．１〜１０体積％
とすることがより好ましい。この値が、０．１体積％未
満であると導電性が劣る傾向があり、３０体積％を超え
ると回路の短絡が起こる傾向がある。なお、体積％は２
３℃の硬化前の各成分の体積をもとに決定されるが、各
成分の体積は、比重を利用して重量から体積に換算する
ことができる。また、メスシリンダー等にその成分を溶
解したり膨潤させたりせず、その成分をよくぬらす適当
な溶媒（水、アルコール等）を入れたものに、その成分
を投入し増加した体積をその体積として求めることもで
きる。The average particle size of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The amount of the conductive particles used is not particularly limited, but (A) an epoxy resin, (B) a compound that generates a basic substance by light irradiation, a curing accelerator used as needed, and an additive used as needed. 0.1 to 100 total volume of the agent
Preferably, it is 30% by volume, and 0.1 to 10% by volume.
Is more preferable. If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur. The volume% is 2
Determined based on the volume of each component before curing at 3 ° C., the volume of each component can be converted from weight to volume using specific gravity. In addition, put the component in a suitable solvent (water, alcohol, etc.) that does not dissolve or swell the component in a graduated cylinder, etc. You can also ask.
【００１９】本発明の接着剤組成物には、カップリング
剤等の密着向上剤、レベリング剤などの添加剤を適宜添
加してもよい。さらには、一組成物には（メタ）アクリ
レート誘導体、スチレン誘導体、マレイミド誘導体など
のラジカル重合性モノマと熱あるいは光によりラジカル
を発生する公知のラジカル発生剤及び増感剤を含んでい
てもよい。また、ビニルエーテル誘導体、オキセタン誘
導体等のカチオン重合性モノマとヨードニウム塩、スル
ホニウム塩、鉄-アレーン錯体等の光酸発生剤及び増感
剤を併用することができる。The adhesive composition of the present invention may optionally contain additives such as an adhesion improver such as a coupling agent and a leveling agent. Further, one composition may contain a radical polymerizable monomer such as a (meth) acrylate derivative, a styrene derivative, and a maleimide derivative, and a known radical generator and a sensitizer that generates a radical by heat or light. Further, a cationic polymerizable monomer such as a vinyl ether derivative or an oxetane derivative may be used in combination with a photoacid generator and a sensitizer such as an iodonium salt, a sulfonium salt, or an iron-arene complex.
【００２０】本発明の接着剤組成物は、増粘化やフィル
ム化を目的として、種々のポリマを適宜添加してもよ
い。使用するポリマは特に制限を受けないが、(a)エポ
キシ樹脂、(b)光照射によってエポキシ化合物と反応す
る官能基を発生する化合物及び導電性粒子に悪影響を及
ぼさないことが必須である。このようなポリマとして
は、ビスフェノールＡ型フェノキシ樹脂やビスフェノー
ルＦ型フェノキシ樹脂、ビスフェノールＡ・ビスフェノ
ールＦ共重合型フェノキシ樹脂等の汎用フェノキシ樹脂
類、ポリメタクリレート類、ポリアクリレート類、ポリ
イミド類、ポリウレタン類、ポリエステル類、ポリビニ
ルブチラール、ＳＢＳ及びそのエポキシ変性体、ＳＥＢ
Ｓ及びその変性体などを用いることができる。これらは
単独あるいは２種類以上を混合して用いることができ
る。さらに、これらポリマ中にはシロキサン結合やフッ
素置換基が含まれていても良い。これらは、混合する樹
脂同士が完全に相溶するか、もしくはミクロ相分離が生
じて白濁する状態であれば接着剤組成物としては好適に
用いることができる。上記ポリマの分子量は大きいほど
フィルム形成性が容易に得られ、また接着剤としての流
動性に影響する溶融粘度を広範囲に設定できる。分子量
は特に制限を受けるものではないが、一般的な重量平均
分子量としては５，０００〜１５０，０００が好まし
く、１０，０００〜８０，０００が特に好ましい。この
値が、５，０００未満ではフィルム形成性が劣る傾向が
あり、また１５０，０００を超えると他の成分との相溶
性が悪くなる傾向がある。使用量としてはエポキシ樹脂
１００重量部に対して２０〜３２０重量部とすることが
好ましい。この使用量が、２０重量部未満又は３２０重
量部を超える場合は、流動性や接着性が低下する傾向が
ある。The adhesive composition of the present invention may be appropriately added with various polymers for the purpose of thickening or forming a film. The polymer used is not particularly limited, but it is essential that (a) an epoxy resin, (b) a compound that generates a functional group that reacts with an epoxy compound by light irradiation, and the conductive particles have no adverse effect. Such polymers include general-purpose phenoxy resins such as bisphenol A phenoxy resin and bisphenol F phenoxy resin, bisphenol A / bisphenol F copolymerization phenoxy resin, polymethacrylates, polyacrylates, polyimides, polyurethanes, Polyesters, polyvinyl butyral, SBS and its epoxy modified products, SEB
S and its modified products can be used. These can be used alone or in combination of two or more. Further, these polymers may contain a siloxane bond or a fluorine substituent. These can be suitably used as an adhesive composition as long as the resins to be mixed are completely compatible with each other or are in a state where microphase separation occurs and the mixture becomes cloudy. The larger the molecular weight of the polymer, the more easily the film can be formed, and the melt viscosity which affects the fluidity as an adhesive can be set in a wide range. Although the molecular weight is not particularly limited, a general weight average molecular weight is preferably from 5,000 to 150,000, and particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film-forming properties tend to be poor, and if it exceeds 150,000, the compatibility with other components tends to be poor. The amount used is preferably 20 to 320 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 20 parts by weight or more than 320 parts by weight, fluidity and adhesiveness tend to decrease.
【００２１】本発明の接着剤組成物は、常温で液状であ
る場合にはペースト状で使用することができる。室温で
固体の場合には、加熱して使用する他、溶剤を使用して
ペースト化してもよい。使用できる溶剤としては、接着
剤組成物及び添加剤と反応性がなく、かつ十分な溶解性
を示すものであれば、特に制限は受けないが、常圧での
沸点が５０〜１５０℃であるものが好ましい。沸点が５
０℃以下の場合、室温で放置すると揮発する恐れがあ
り、開放系での使用が制限される。また、沸点が１５０
℃以上だと、溶剤を揮発させることが難しく、接着後の
信頼性に悪影響を及ぼす恐れがある。The adhesive composition of the present invention can be used in the form of a paste when it is liquid at normal temperature. When it is solid at room temperature, it may be used by heating or pasting using a solvent. The solvent that can be used is not particularly limited as long as it has no reactivity with the adhesive composition and the additive, and shows sufficient solubility, but the boiling point at normal pressure is 50 to 150 ° C. Are preferred. Boiling point is 5
If the temperature is lower than 0 ° C., the mixture may be volatilized when left at room temperature, and use in an open system is restricted. In addition, the boiling point is 150
If the temperature is higher than ° C, it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.
【００２２】本発明の接着剤組成物はフィルム状にして
用いることもできる。接着剤組成物に必要により溶剤等
を加えるなどした溶液を、フッ素樹脂フィルム、ポリエ
チレンテレフタレートフィルム、離形紙等の剥離性基材
上に塗布し、あるいは不織布等の基材に前記溶液を含浸
させて剥離性基材上に載置し、溶剤等を除去してフィル
ムとして使用することができる。フィルムの形状で使用
すると取扱性等の点から一層便利である。The adhesive composition of the present invention can be used in the form of a film. A solution obtained by adding a solvent or the like as necessary to the adhesive composition is coated on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. It can be used as a film after being placed on a peelable substrate by removing a solvent or the like. Use in the form of a film is more convenient in terms of handling properties and the like.
【００２３】照射に用いる光は、１５０〜７００ｎｍの
波長域で照射強度を持つランプを使用することができ、
一般に広く使用されている紫外線照射装置を用いること
ができる。例えば、水銀ランプ、メタルハライドラン
プ、無電極ランプ等が挙げられる。光照射時間は、ラン
プの波長域及び照射光強度と密接に関係があり、特に制
限は受けないが、スループットを考慮すると1時間以内
であることが好ましい。As the light used for irradiation, a lamp having an irradiation intensity in a wavelength range of 150 to 700 nm can be used.
A generally used ultraviolet irradiation device can be used. For example, a mercury lamp, a metal halide lamp, an electrodeless lamp and the like can be mentioned. The light irradiation time is closely related to the wavelength range of the lamp and the irradiation light intensity, and is not particularly limited, but is preferably within one hour in consideration of the throughput.
【００２４】本発明の接着剤組成物は光照射のみで被着
体と接着させる方法以外に光照射と同時あるいは光照射
後に硬化反応を促進する目的で加熱及び加圧を併用して
接着させても良い。これらを併用することにより、より
低温短時間での接着が可能となる。加熱温度は、接着剤
組成物の分解点以下であれば特に制限は受けないが、５
０〜１７０℃の温度が好ましい。圧力は、被着体に損傷
を与えない範囲であれば、特に制限は受けないが、一般
的には０.１〜１０ＭＰａが好ましい。これらの加熱及
び加圧は、０.５秒〜３時間の範囲で行うことが好まし
い。The adhesive composition of the present invention may be adhered to the adherend using heat and pressure simultaneously with or after light irradiation in order to accelerate the curing reaction, in addition to the method of adhering to the adherend only by light irradiation. Is also good. By using these together, bonding at a lower temperature and in a shorter time becomes possible. The heating temperature is not particularly limited as long as it is lower than the decomposition point of the adhesive composition.
Temperatures between 0 and 170C are preferred. The pressure is not particularly limited as long as the pressure does not damage the adherend, but is generally preferably 0.1 to 10 MPa. These heating and pressurizing are preferably performed in a range of 0.5 seconds to 3 hours.
【００２５】本発明の接着剤組成物は、熱膨張係数の異
なる異種の被着体の接着剤として使用することができ
る。具体的には、異方導電接着剤、銀ペースト、銀フィ
ルム等に代表される回路接続材料、ＣＳＰ用エラストマ
ー、ＣＳＰ用アンダーフィル材、ＬＯＣテープ等に代表
される半導体素子接着材料として使用することができ
る。The adhesive composition of the present invention can be used as an adhesive for adherends of different types having different coefficients of thermal expansion. Specifically, it is used as a circuit connection material typified by an anisotropic conductive adhesive, silver paste, silver film, etc., a CSP elastomer, a CSP underfill material, and a semiconductor element adhesion material typified by a LOC tape. Can be.
【００２６】以下に、本発明の接着剤組成物及び導電粒
子を使用して作製した異方導電フィルムと電極の接続の
一例について説明する。異方導電フィルムを、基板上の
相対時する電極間に存在させ、２００〜７００ｎｍの光
を照射した後、加熱加圧することにより両電極の接触と
基板間の接着を得、電極との接続を行える。電極を形成
する基板としては、半導体、ガラス、セラミック等の無
機質、ポリイミド、ポリカーボネート等の有機物、ガラ
ス／エポキシ等のこれら複合の各組み合わせが適用でき
る。本発明の接着剤組成物及びこれを電極の接続に用い
る回路接続用接着剤組成物を用いると、従来困難であっ
た、熱膨張係数が大きく異なる材質の接続が可能となる
ことから、広範な材料の接続へ応用できる。Hereinafter, an example of connection between an anisotropic conductive film produced using the adhesive composition and the conductive particles of the present invention and an electrode will be described. The anisotropic conductive film is present between the opposing electrodes on the substrate, irradiated with light of 200 to 700 nm, and then heated and pressed to obtain the contact between the two electrodes and the adhesion between the substrates. I can do it. As a substrate on which electrodes are formed, inorganic materials such as semiconductors, glass, and ceramics, organic materials such as polyimide and polycarbonate, and combinations of these composite materials such as glass / epoxy can be used. The use of the adhesive composition of the present invention and the adhesive composition for circuit connection that uses the adhesive composition for connecting electrodes enables connection of materials having significantly different coefficients of thermal expansion, which has been difficult in the past. Applicable to connection of materials.
【００２７】本発明の接着剤組成物、回路接続用接着剤
組成物は、比較的低温での接続が可能なため、接続時に
熱応力が小さく、微細回路接続後の信頼性を飛躍的に向
上でき、マージンを大きくとれるので、回路の接続作業
の効率が向上し、かつ歩留まりも向上する。Since the adhesive composition and the adhesive composition for circuit connection of the present invention can be connected at a relatively low temperature, the thermal stress at the time of connection is small, and the reliability after connecting a fine circuit is dramatically improved. As a result, a large margin can be obtained, so that the efficiency of circuit connection work is improved and the yield is also improved.
【００２８】[0028]
【実施例】以下に、本発明を実施例に基づいて具体的に
説明するが、本発明はこれに限定されるものではない。 (ポリｐ−ビニルベンゾエートの合成)１Lのナス型フラ
スコにポリｐ−ビニルフェノール(丸善石油化学株式会
社製、商品名マルカリンカーＭ、重量平均分子量４，０
００〜６，０００)３０ｇをテトラヒドロフラン３００
ｇ、ピリジン２０ｇの混合溶媒中に室温でマグネチック
スターラーを用いて室温でかくはんして溶解させた。ポ
リマが完全に溶解した後、氷浴で冷却しながらテトラヒ
ドロフラン７０ｇに塩化ベンゾイル３５．８ｇを溶解さ
せた溶液を３０分かけて滴下した。滴下開始３分後に、
ピリジン塩酸塩の析出が認められた。滴下終了後、氷浴
中で1時間かくはんした。この後、リービッヒ冷却管を
セットし、オイルバスにて６０℃に加熱しながら２時間
反応させた。反応後、室温まで冷却し、析出したピリジ
ン塩酸塩を吸引ろ過により取り除いた。この後、ロータ
リーエバポレーターを用いて反応液が半分になるまで濃
縮した。得られた濃縮液を１０００重量部のｎ-へキサ
ン中に添加すると、白色沈殿物を得た。この沈殿物を吸
引ろ過し、飽和炭酸水素ナトリウム水溶液で３度洗浄し
て、真空下６０℃で一晩乾燥して目的のポリｐ−ビニル
ベンゾエートを得た。収量５２．６ｇ(収率９４％)であ
った。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. (Synthesis of poly p-vinyl benzoate) In a 1-L eggplant-shaped flask, put poly-p-vinyl phenol (trade name Marcalinker M, manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight of 4.0
(00 to 6,000) 30 g of tetrahydrofuran 300
g and pyridine in a mixed solvent of 20 g at room temperature using a magnetic stirrer to stir at room temperature to dissolve. After the polymer was completely dissolved, a solution of 35.8 g of benzoyl chloride in 70 g of tetrahydrofuran was added dropwise over 30 minutes while cooling in an ice bath. Three minutes after the start of dripping,
Precipitation of pyridine hydrochloride was observed. After completion of the dropwise addition, the mixture was stirred in an ice bath for 1 hour. Thereafter, a Liebig condenser tube was set, and a reaction was performed for 2 hours while heating to 60 ° C. in an oil bath. After the reaction, the mixture was cooled to room temperature, and the precipitated pyridine hydrochloride was removed by suction filtration. Thereafter, the reaction solution was concentrated using a rotary evaporator until the reaction solution became half. When the obtained concentrate was added to 1000 parts by weight of n-hexane, a white precipitate was obtained. The precipitate was filtered by suction, washed three times with a saturated aqueous solution of sodium hydrogen carbonate, and dried under vacuum at 60 ° C. overnight to obtain the desired poly (p-vinylbenzoate). The yield was 52.6 g (94% yield).
【００２９】（実施例１）フェノキシ樹脂（ＰＫＨＣ、
ユニオンカーバイド社製商品名、平均分子量４５，００
０）４０ｇを、重量比でトルエン／酢酸エチル＝５０／
５０の混合溶剤６０ｇに溶解して、固形分４０重量％の
溶液とした。エポキシ樹脂として、ビスフェノール型液
状エポキシ樹脂（エピコート８２８、油化シェルエポキ
シ株式会社製商品名、ビスフェノールＡ型エポキシ樹
脂、エポキシ当量１８４）を用い、光照射によってフェ
ノール性水酸基を生成するポリ−ｐ−ビニルベンゾエー
ト及び反応促進剤としてイミダゾール化合物(キュアゾ
ール2ＰＺ-ＣＮ、四国化成工業株式会社製商品名)を用
いた。またポリスチレンを核とする粒子の表面に、厚み
０．２μｍのニッケル層を設け、このニッケル層の外側
に、厚み０．０２μｍの金層を設け、平均粒径５μｍ、
比重２．５の導電性粒子を作製した。固形重量比でフェ
ノキシ樹脂５０、エポキシ樹脂５０、ポリ−ｐ−ビニル
ベンゾエート６０、反応促進剤２となるように配合し、
さらに導電性粒子を１．５体積％配合分散させ、厚み８
０μｍのフッ素樹脂フィルムに塗工装置を用いて塗布
し、７０℃、１０分の熱風乾燥によって接着剤層の厚み
が２０μｍのフィルム状接着剤を得た。上記製法によっ
て得たフィルム状接着剤を用いて、ライン幅５０μｍ、
ピッチ１００μｍ、厚み１８μｍの銅回路を５００本有
するフレキシブル回路板（ＦＰＣ）と、０．２μｍの酸
化インジウム（ＩＴＯ）の薄層を形成したガラス（厚み
１．１ｍｍ、表面抵抗２０Ω／□）とを、紫外線照射併
用型熱圧着装置（加熱方式：コンスタントヒート型、東
レエンジニアリング株式会社製）を用いて１４０℃、２
ＭＰａで２０秒間の加熱加圧およびＩＴＯガラス側から
の紫外線照射を同時に行って幅２ｍｍにわたり接続し、
時間経過後圧力開放して、接続体を作製した。接着剤に
照射される紫外線照射量は２．０Ｊ／ｃｍ2(３６６ｎｍ
換算)とした。この時、あらかじめＩＴＯガラス上に、
フィルム状回路接続材料の接着面を貼り付けた後、７０
℃、０．５ＭＰａで５秒間加熱加圧して仮接続し、その
後、フッ素樹脂フィルムを剥離してもう一方の被着体で
あるＦＰＣと接続した。また２０秒間の接続の際、加熱
加圧のみを開始して３秒経過した後１７秒間の紫外線照
射を開始し、加熱加圧２０秒後に２工程が同時に終了す
るようにした。(Example 1) Phenoxy resin (PKHC,
Union Carbide trade name, average molecular weight 45,000
0) 40 g of toluene / ethyl acetate = 50 /
It was dissolved in 60 g of a mixed solvent of 50 to obtain a solution having a solid content of 40% by weight. As the epoxy resin, a bisphenol type liquid epoxy resin (Epicoat 828, trade name of Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: 184) is used, and poly-p-vinyl which generates a phenolic hydroxyl group by light irradiation is used. Benzoate and an imidazole compound (Curesol 2PZ-CN, trade name, manufactured by Shikoku Chemicals Co., Ltd.) were used as a reaction accelerator. Further, a nickel layer having a thickness of 0.2 μm was provided on the surface of the particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm was provided outside the nickel layer.
Conductive particles having a specific gravity of 2.5 were produced. The phenoxy resin 50, the epoxy resin 50, the poly-p-vinyl benzoate 60, and the reaction accelerator 2 are blended at a solid weight ratio,
Further, 1.5% by volume of conductive particles were mixed and dispersed, and the thickness was 8
It was applied to a 0 μm fluororesin film using a coating apparatus, and dried with hot air at 70 ° C. for 10 minutes to obtain a film adhesive having an adhesive layer thickness of 20 μm. Using the film-like adhesive obtained by the above manufacturing method, a line width of 50 μm,
A flexible circuit board (FPC) having 500 copper circuits with a pitch of 100 μm and a thickness of 18 μm, and glass (thickness: 1.1 mm, surface resistance: 20 Ω / □) formed with a thin layer of 0.2 μm indium oxide (ITO) At 140 ° C. using a thermocompression device combined with ultraviolet irradiation (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.).
At the same time, heating and pressurizing at 20 MPa and UV irradiation from the ITO glass side were performed simultaneously to connect over a width of 2 mm,
After a lapse of time, the pressure was released to produce a connection body. The amount of ultraviolet irradiation applied to the adhesive is 2.0 J / cm 2 (366 nm).
Conversion). At this time, beforehand on the ITO glass,
After attaching the adhesive surface of the film-like circuit connection material, 70
Temporary connection was performed by heating and pressing at 0.5 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film was peeled off and connected to another FPC as an adherend. Further, at the time of connection for 20 seconds, ultraviolet irradiation for 17 seconds was started after elapse of 3 seconds after only heating / pressing was started, and the two processes were simultaneously finished after 20 seconds of heating / pressing.
【００３０】（実施例２）実施例１で使用したフィルム
状接着剤を、ＩＴＯガラス上に７０℃、０．５ＭＰａで
５秒間加熱加圧して仮接続した後、フッ素樹脂フィルム
を剥離して高圧水銀灯を用いて３.０Ｊ/ｃｍ2(３６６ｎ
ｍ換算)の紫外線を照射した。この後、実施例1と同様の
ＦＰＣを熱圧着装置（加熱方式：コンスタントヒート
型、東レエンジニアリング株式会社製）を用いて１４０
℃、２ＭＰａで２０秒間の加熱加圧を行って幅２ｍｍに
わたり接続し、時間経過後圧力開放して、接続体を作製
した。もう一方の被着体であるＦＰＣと接続した。(Example 2) The film adhesive used in Example 1 was temporarily connected to the ITO glass by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film was peeled off and the high pressure was applied. Using a mercury lamp, 3.0 J / cm 2 (366 n
(equivalent to m). Thereafter, the same FPC as in Example 1 was applied using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.)
The connection was performed over a width of 2 mm by applying heat and pressure at 2 ° C. and 2 MPa for 20 seconds, and after a lapse of time, the pressure was released to produce a connected body. It was connected to the other adherend, FPC.
【００３１】（比較例１）フェノキシ樹脂（ＰＫＨＣ、
ユニオンカーバイド社製商品名、平均分子量４５，００
０）４０ｇを、重量比でトルエン／酢酸エチル＝５０／
５０の混合溶剤６０ｇに溶解して、固形分４０重量％の
溶液とした。光カチオン重合性化合物として、脂環式エ
ポキシ樹脂（ＥＰＨＥ３１５０、ダイセル化学工業株式
会社製商品名、エポキシ当量１８５）を用いた。光カチ
オン重合開始剤としてはトリアリールスルホニウムのヘ
キサフルオロリン塩混合物（サイラキュアＵＶＩ−６９
９０、ユニオンカーバイド社製商品名）を用いた。また
ポリスチレンを核とする粒子の表面に、厚み０．２μｍ
のニッケル層を設け、このニッケル層の外側に、厚み
０．０２μｍの金層を設け、平均粒径５μｍ、比重２．
５の導電性粒子を作製した。固形重量比でフェノキシ樹
脂５０、光カチオン重合性化合物５０、光カチオン重合
開始剤５となるように配合し、さらに導電性粒子を３体
積％配合分散させ、厚み８０μｍのフッ素樹脂フィルム
に塗工装置を用いて塗布し、７０℃、１０分の熱風乾燥
によって接着剤層の厚みが２０μｍのフィルム状接着剤
を得た。上記によって得たフィルム状接着剤を用いて、
実施例1と同様にＩＴＯ及びＦＰＣと接着させた。Comparative Example 1 Phenoxy resin (PKHC,
Union Carbide trade name, average molecular weight 45,000
0) 40 g of toluene / ethyl acetate = 50 /
It was dissolved in 60 g of a mixed solvent of 50 to obtain a solution having a solid content of 40% by weight. As the cationic photopolymerizable compound, an alicyclic epoxy resin (EPHE3150, trade name, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 185) was used. As the cationic photopolymerization initiator, a triarylsulfonium hexafluorophosphate salt mixture (Siracure UVI-69)
90, manufactured by Union Carbide Co., Ltd.). In addition, the thickness of 0.2 μm
A nickel layer having a thickness of 0.02 μm is provided outside the nickel layer, the average particle diameter is 5 μm, and the specific gravity is 2.
5 were prepared. A phenoxy resin 50, a photocationic polymerizable compound 50, and a photocationic polymerization initiator 5 are blended so as to be a solid weight ratio, and 3 vol% of conductive particles are further blended and dispersed, and the coating apparatus is applied to a fluororesin film having a thickness of 80 μm. And dried by hot air at 70 ° C. for 10 minutes to obtain a film adhesive having an adhesive layer thickness of 20 μm. Using the film adhesive obtained above,
It adhered to ITO and FPC like Example 1.
【００３２】（比較例２）フェノキシ樹脂（ＰＫＨＣ、
ユニオンカーバイド社製商品名、平均分子量４５，００
０）４０ｇを、重量比でトルエン／酢酸エチル＝５０／
５０の混合溶剤６０ｇに溶解して、固形分４０重量％の
溶液とした。光カチオン重合性化合物として、脂環式エ
ポキシ樹脂（ＥＰＨＥ３１５０、ダイセル化学工業株式
会社製商品名、エポキシ当量１８５）を用いた。光カチ
オン重合開始剤としてはトリアリールスルホニウムのヘ
キサフルオロリン塩混合物（サイラキュアＵＶＩ−６９
９０、ユニオンカーバイド社製商品名）を用いた。また
ポリスチレンを核とする粒子の表面に、厚み０．２μｍ
のニッケル層を設け、このニッケル層の外側に、厚み
０．０２μｍの金層を設け、平均粒径５μｍ、比重２．
５の導電性粒子を作製した。固形重量比でフェノキシ樹
脂５０、光カチオン重合性化合物５０、光カチオン重合
開始剤５となるように配合し、さらに導電性粒子を３体
積％配合分散させ、厚み８０μｍのフッ素樹脂フィルム
に塗工装置を用いて塗布し、７０℃、１０分の熱風乾燥
によって接着剤層の厚みが２０μｍのフィルム状接着剤
を得た。上記によって得たフィルム状接着剤を用いて、
実施例２と同様にＩＴＯ及びＦＰＣと接着させ接続体を
作製した。Comparative Example 2 Phenoxy resin (PKHC,
Union Carbide trade name, average molecular weight 45,000
0) 40 g of toluene / ethyl acetate = 50 /
It was dissolved in 60 g of a mixed solvent of 50 to obtain a solution having a solid content of 40% by weight. As the cationic photopolymerizable compound, an alicyclic epoxy resin (EPHE3150, trade name, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 185) was used. As the cationic photopolymerization initiator, a triarylsulfonium hexafluorophosphate salt mixture (Siracure UVI-69)
90, manufactured by Union Carbide Co., Ltd.). In addition, the thickness of 0.2 μm
A nickel layer having a thickness of 0.02 μm is provided outside the nickel layer, the average particle diameter is 5 μm, and the specific gravity is 2.
5 were prepared. A phenoxy resin 50, a photocationic polymerizable compound 50, and a photocationic polymerization initiator 5 are blended so as to be a solid weight ratio, and 3 vol% of conductive particles are further blended and dispersed, and the coating apparatus is applied to a fluororesin film having a thickness of 80 μm. And dried by hot air at 70 ° C. for 10 minutes to obtain a film adhesive having an adhesive layer thickness of 20 μm. Using the film adhesive obtained above,
In the same manner as in Example 2, it was bonded to ITO and FPC to produce a connection body.
【００３３】実施例１〜２、比較例１〜２で作製した接
続体について接続直後の初期抵抗及び８０℃、９５％Ｒ
Ｈの条件で２４０時間、高温高湿状態に曝した後の接続
抵抗を評価した。接続抵抗の評価は、フィルム状接着剤
を用いて接続した後、上記接続部を含むＦＰＣの隣接回
路間の抵抗値を、マルチメータで測定した。測定電流は
１ｍＡとし、抵抗値は隣接回路間の抵抗１５０点の平均
で示した。その結果を表１に示した。The initial resistance immediately after connection and the temperature of 80 ° C. and 95% R for the connection bodies prepared in Examples 1 and 2 and Comparative Examples 1 and 2
The connection resistance after exposure to a high temperature and high humidity state for 240 hours under the condition of H was evaluated. The connection resistance was evaluated by connecting with an adhesive film and measuring the resistance value between adjacent circuits of the FPC including the connection portion with a multimeter. The measurement current was 1 mA, and the resistance value was represented by an average of 150 resistance points between adjacent circuits. The results are shown in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】実施例１〜２で得た接続体については、耐
湿試験後も初期の接続抵抗を持続しており、良好な接着
剤であることを示した。これに対して、光カチオン重合
を用いていた比較例１の場合、耐湿試験後の接続抵抗は
初期の接続抵抗を維持できず、高い値となり信頼性が低
いことが分かる。また、比較例２の場合、光照射後に接
着剤が硬化し、接着効果を発現していないことを示し
た。The connection bodies obtained in Examples 1 and 2 maintained the initial connection resistance even after the moisture resistance test, indicating that they were good adhesives. On the other hand, in the case of Comparative Example 1 using photocationic polymerization, the connection resistance after the moisture resistance test was not able to maintain the initial connection resistance, indicating a high value and low reliability. In addition, in the case of Comparative Example 2, it was shown that the adhesive was cured after light irradiation, and the adhesive effect was not exhibited.
【００３６】（実施例３）実施例１〜２で得たフィルム
化前の配合物をサンプル管中に保管し、室温で３日間放
置してその流動性を目視で観察した。この結果、いずれ
の配合物も配合直後の流動性を確保していた。Example 3 The formulations before film formation obtained in Examples 1 and 2 were stored in a sample tube and left at room temperature for 3 days to visually observe the fluidity. As a result, all of the blends ensured fluidity immediately after blending.
【００３７】（比較例３）ポリｐ−ビニルベンゾエート
の代わりにポリｐ-ビニルフェノールを用いた以外は実
施例１と同様の配合を行い、フィルム化前の配合物を得
た。これを実施例３と同様に室温における流動性を観察
したところ、室温放置1日後に流動性が低下し、３日後
には流動性を失っていた。(Comparative Example 3) The same formulation as in Example 1 was carried out except that poly-p-vinylphenol was used instead of poly-p-vinylbenzoate, to obtain a compound before forming into a film. When the fluidity at room temperature was observed in the same manner as in Example 3, the fluidity was lowered one day after standing at room temperature and lost after three days.
【００３８】（比較例４）ポリｐ−ビニルベンゾエート
の替わりに４,４'-ジフェニルメタンジアミンを用いた
以外は実施例３と同様の配合を行い、フィルム化前の配
合物を得た。これを実施例３と同様に室温における流動
性を観察したところ、配合直後から流動性の低下を確認
し、室温放置1日後には流動性を失っていた。(Comparative Example 4) The same formulation as in Example 3 was carried out except that 4,4'-diphenylmethanediamine was used instead of poly p-vinylbenzoate, to obtain a formulation before forming a film. When the fluidity at room temperature was observed in the same manner as in Example 3, a decrease in the fluidity was confirmed immediately after the compounding, and the fluidity was lost one day after standing at room temperature.
【００３９】[0039]
【発明の効果】本発明によれば、エポキシ樹脂の光カチ
オン重合のように重合触媒として強酸を用いる必要がな
いため回路電極の腐食が無く、しかも低温短時間で接着
可能となり、接続信頼性に優れる。また、貯蔵安定性に
優れる接着剤組成物、回路接続用接着剤組成物を提供す
ることができる。According to the present invention, there is no need to use a strong acid as a polymerization catalyst as in the photocationic polymerization of an epoxy resin, so there is no corrosion of circuit electrodes, and bonding can be performed at a low temperature in a short time, and connection reliability can be improved. Excellent. Further, it is possible to provide an adhesive composition having excellent storage stability and an adhesive composition for circuit connection.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 湯佐 正己 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 Ｆターム(参考） 4J040 DE012 EC061 EC071 EC081 EC091 EC121 EC131 EC151 EC171 EC261 GA04 GA07 GA22 GA23 JB08 KA16 LA01 LA05 LA11 MA01 MA02 NA20 5F047 AA17 BA34 BA40 BB03 BB11 BB16 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaki Yusa 48 Wadai, Tsukuba-shi, Ibaraki F-term in Hitachi Chemical Co., Ltd. Research Laboratory 4J040 DE012 EC061 EC071 EC081 EC091 EC121 EC131 EC151 EC171 EC261 GA04 GA07 GA22 GA23 JB08 KA16 LA01 LA05 LA11 MA01 MA02 NA20 5F047 AA17 BA34 BA40 BB03 BB11 BB16
Claims (9)
７５０ｎｍの光照射によってエポキシ化合物と反応する
官能基を発生する高分子化合物からなり、該高分子化合
物の数平均分子量が１，０００〜１００,０００である
ことを特徴とする接着剤組成物。(1) an epoxy compound; (b) 150-
An adhesive composition comprising a polymer compound that generates a functional group that reacts with an epoxy compound upon irradiation with light of 750 nm, wherein the number average molecular weight of the polymer compound is 1,000 to 100,000.
ってフェノール性の水酸基を発生する高分子化合物であ
ることを特徴とする請求項１に記載の接着剤組成物。2. The adhesive composition according to claim 1, wherein (b) a polymer compound that generates a phenolic hydroxyl group upon irradiation with light of 150 to 750 nm.
って１級アミノ基または２級アミノ基を発生する高分子
化合物であることを特徴とする請求項１に記載の接着剤
組成物。3. The adhesive composition according to claim 1, wherein (b) a polymer compound that generates a primary amino group or a secondary amino group when irradiated with light of 150 to 750 nm.
ってメルカプト基を発生する高分子化合物であることを
特徴とする請求項１に記載の接着剤組成物。4. The adhesive composition according to claim 1, wherein (b) a polymer compound which generates a mercapto group upon irradiation with light of 150 to 750 nm.
して、（ｂ）光照射によってエポキシ化合物と反応する
官能基を発生する高分子化合物０.０１〜２００重量部
を含有してなる請求項１ないし請求項４のいずれかに記
載の接着剤組成物。5. The method according to claim 1, wherein (a) 100 to 100 parts by weight of the epoxy compound, (b) 0.01 to 200 parts by weight of a polymer compound which generates a functional group which reacts with the epoxy compound by light irradiation. The adhesive composition according to any one of claims 1 to 4.
載の接着剤組成物中に、さらに導電性粒子を含む接着剤
組成物。6. An adhesive composition according to any one of claims 1 to 5, further comprising conductive particles.
在させ、相対向する回路電極を有する基板を加圧して加
圧方向の電極間を電気的に接続する接着剤組成物であっ
て、前記接着剤は請求項１ないし請求項６のいずれかに
記載の接着剤組成物である回路接続用接着剤組成物。7. An adhesive composition which is interposed between substrates having opposing circuit electrodes and presses the substrates having opposing circuit electrodes to electrically connect the electrodes in the pressing direction, An adhesive composition for circuit connection, wherein the adhesive is the adhesive composition according to any one of claims 1 to 6.
物を用いて接続された接続体。8. A connected body using the adhesive composition for circuit connection according to claim 7.
回路電極間に請求項１ないし請求項６のいずれかに記載
の接着剤組成物を介在させ、加圧して加圧方向の電極間
を電気的に接続した半導体装置。9. The adhesive composition according to claim 1, which is interposed between an electrode of a semiconductor element and a circuit electrode of a substrate for mounting a semiconductor, and pressurizes the electrode composition in the direction of pressurization. An electrically connected semiconductor device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000150762A JP5011599B2 (en) | 2000-05-23 | 2000-05-23 | Adhesive composition, adhesive composition for circuit connection, circuit connection material, connector and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000150762A JP5011599B2 (en) | 2000-05-23 | 2000-05-23 | Adhesive composition, adhesive composition for circuit connection, circuit connection material, connector and semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001329240A true JP2001329240A (en) | 2001-11-27 |
| JP5011599B2 JP5011599B2 (en) | 2012-08-29 |
Family
ID=18656410
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000150762A Expired - Fee Related JP5011599B2 (en) | 2000-05-23 | 2000-05-23 | Adhesive composition, adhesive composition for circuit connection, circuit connection material, connector and semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5011599B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097441A (en) * | 2000-09-21 | 2002-04-02 | Hitachi Chem Co Ltd | Adhesive composition, circuit-connecting material, adhesive composition for connecting circuit, connected body, and semiconductor device |
| JP2013041895A (en) * | 2011-08-11 | 2013-02-28 | Furukawa Electric Co Ltd:The | Connection sheet |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4888197A (en) * | 1972-02-25 | 1973-11-19 | ||
| JPS6253327A (en) * | 1985-08-31 | 1987-03-09 | Res Dev Corp Of Japan | Curable composition |
| JPH04264178A (en) * | 1991-02-18 | 1992-09-18 | Nissei Kagaku Kogyosho:Kk | Photosetting adhesive composition for transparent material |
| JPH05331366A (en) * | 1992-03-31 | 1993-12-14 | Res Dev Corp Of Japan | Curable composition and method for curing the same |
| JPH07292074A (en) * | 1994-04-28 | 1995-11-07 | Sannopuko Kk | Curable resin composition |
| JPH07309931A (en) * | 1994-05-19 | 1995-11-28 | Kansai Paint Co Ltd | Curable resin composition |
| JP2000063489A (en) * | 1998-08-21 | 2000-02-29 | Shikoku Chem Corp | Epoxy resin composition |
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2000
- 2000-05-23 JP JP2000150762A patent/JP5011599B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4888197A (en) * | 1972-02-25 | 1973-11-19 | ||
| JPS6253327A (en) * | 1985-08-31 | 1987-03-09 | Res Dev Corp Of Japan | Curable composition |
| JPH04264178A (en) * | 1991-02-18 | 1992-09-18 | Nissei Kagaku Kogyosho:Kk | Photosetting adhesive composition for transparent material |
| JPH05331366A (en) * | 1992-03-31 | 1993-12-14 | Res Dev Corp Of Japan | Curable composition and method for curing the same |
| JPH07292074A (en) * | 1994-04-28 | 1995-11-07 | Sannopuko Kk | Curable resin composition |
| JPH07309931A (en) * | 1994-05-19 | 1995-11-28 | Kansai Paint Co Ltd | Curable resin composition |
| JP2000063489A (en) * | 1998-08-21 | 2000-02-29 | Shikoku Chem Corp | Epoxy resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097441A (en) * | 2000-09-21 | 2002-04-02 | Hitachi Chem Co Ltd | Adhesive composition, circuit-connecting material, adhesive composition for connecting circuit, connected body, and semiconductor device |
| JP4635312B2 (en) * | 2000-09-21 | 2011-02-23 | 日立化成工業株式会社 | Adhesive composition, circuit connection material, adhesive composition for circuit connection, connector and semiconductor device |
| JP2013041895A (en) * | 2011-08-11 | 2013-02-28 | Furukawa Electric Co Ltd:The | Connection sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5011599B2 (en) | 2012-08-29 |
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