JPH08176521A - Electroconductive adhesive - Google Patents
Electroconductive adhesiveInfo
- Publication number
- JPH08176521A JPH08176521A JP32317494A JP32317494A JPH08176521A JP H08176521 A JPH08176521 A JP H08176521A JP 32317494 A JP32317494 A JP 32317494A JP 32317494 A JP32317494 A JP 32317494A JP H08176521 A JPH08176521 A JP H08176521A
- Authority
- JP
- Japan
- Prior art keywords
- pref
- powder
- epoxy resin
- pts
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、導電性接着剤に係わ
り、特に、耐ブリーディング性、高導電性および印刷性
に優れ、電子材料の接続に用いて好適な導電性接着剤に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive adhesive, and more particularly to a conductive adhesive having excellent bleeding resistance, high conductivity and printability, which is suitable for connecting electronic materials.
【０００２】[0002]
【従来の技術】従来の導電性接着剤は、多くの場合、樹
脂、硬化剤、導電性粉末および希釈剤からなり、樹脂と
しては各種エポキシ系、アクリル系、ウレタン系、ポリ
イミド系の樹脂、硬化剤は必要に応じて用いるが、硬化
剤としては、導電性接着剤が主剤と硬化剤系とが各々別
である二液混合型と既に硬化剤が配合されている一液型
によって異なるがそれぞれの樹脂に合った硬化剤が使わ
れ、エポキシ系樹脂の場合、アミ系や酸無水物系の硬化
剤等が使用されている。導電性粉末としてはＡｇ、Ｃ
ｕ、Ｎｉ等あるいはそれらの２成分以上の単独または複
合系の金属粉末、無定形カーボン、グラファイト等が用
いられている。エポキシ系樹脂の場合、希釈剤には大別
してｎ−ブチルセロソルブ等の溶剤と反応性希釈剤とが
あり、前者を使用したものは溶剤型導電性接着剤、後者
を使用した者は無溶剤型導電性接着剤と呼ばれる。エポ
キシ系樹脂よりなる導電性接着剤の場合、反応性希釈剤
を使用するのが主流で、ｎ−ブチルグリシジルエーテ
ル、フェニルグリシジルエーテル等が用いられている。2. Description of the Related Art Conventional conductive adhesives often consist of resins, curing agents, conductive powders and diluents, and various epoxy-based, acrylic-based, urethane-based, polyimide-based resins and cured resins are used as resins. The agent is used as necessary, but as the curing agent, the conductive adhesive is different depending on the two-component mixed type in which the main agent and the curing agent system are different from each other and the one-component type in which the curing agent is already mixed. The curing agent suitable for the resin is used, and in the case of the epoxy resin, the curing agent such as an amide type or an acid anhydride type is used. As conductive powder, Ag, C
u, Ni, etc., or a single or composite metal powder of two or more of them, amorphous carbon, graphite, etc. are used. In the case of epoxy resins, diluents are roughly divided into solvents such as n-butyl cellosolve and reactive diluents. The former uses solvent-type conductive adhesive, and the latter uses solventless conductive. Called adhesive. In the case of a conductive adhesive made of an epoxy resin, a reactive diluent is mainly used, and n-butyl glycidyl ether, phenyl glycidyl ether and the like are used.
【０００３】[0003]
【発明が解決しようとする課題】導電性接着剤は、耐熱
性の弱い材料やはんだが付かない材料に対して使用され
るのは勿論、近年ではＩＣダイボンディング用にも使わ
れ、更に環境保護の観点から、フロン規制に伴うフラッ
クス残査洗浄の問題、アメリカ合衆国による鉛はんだ規
制の動きがあり、導電性接着剤による接続は、はんだ接
続を代替する方法の１つとして提案され期待されてい
る。半導体パッケージの高密度化、高機能化において
も、ファインピッチ化の要求がますます高まってきてお
り、導電性接着剤は、ＬＳＩ新規接続材料としても可能
性が大きくなっている。このように、導電性接着剤は種
々の用途で使用可能な材料として注目されているが、高
導電性、耐熱性、耐湿性、速硬化性、高接着性、耐マイ
グレーション性、耐ブリーディング性、良好な作業性、
印刷性、保存安定性、高純度化および溶剤含量の低減
化、無溶剤化等、その具備すべき特性のレベルは極めて
高く、特に、溶剤含量の低減化、無溶剤化は、ＶＯＣ規
制（揮発性溶剤の使用規制）への対応もあり、溶剤の揮
発が不可能か、あるいは困難な部分への接続用として実
現すべきものであるが、ほとんど実用化されておらず、
上記特性も未だ低いのが現状である。The conductive adhesive is used not only for a material having weak heat resistance or a material to which solder is not applied, but also for IC die bonding in recent years, which further protects the environment. From the viewpoint of the above, there is a problem of residual flux cleaning due to CFC regulation and lead solder regulation by the United States, and the connection by a conductive adhesive is proposed and expected as one of the alternative methods of the solder connection. The demand for finer pitches is increasing more and more even in the case of higher density and higher functionality of semiconductor packages, and conductive adhesives have great potential as new LSI connecting materials. As described above, the conductive adhesive has attracted attention as a material that can be used in various applications, but it has high conductivity, heat resistance, moisture resistance, fast curing, high adhesion, migration resistance, bleeding resistance, Good workability,
The printability, storage stability, high purity, reduction of solvent content, and solvent-free properties are extremely high, and especially, the reduction of solvent content and solvent-free property is regulated by VOC regulations (volatilization). It should be realized as a connection to a part where it is impossible or difficult to volatilize the solvent, but it has not been put into practical use.
At present, the above characteristics are also low.
【０００４】導電性接着剤の主流を占めるエポキシ系に
おいても、溶剤含量を低減化あるいは無溶剤化し、かつ
接着剤の流動性を確保し、加えて、満足すべき上記の特
性を持ったものは未だ世の中にはない。通常反応性希釈
剤の添加により樹脂の粘度を下げ、接着剤の流動性を確
保する方法が行なわれている。しかし、脂肪族および芳
香族のモノあるいはジグリシジルエーテル等の反応性希
釈剤は、希釈効率が悪く、また、多量に添加すると樹脂
組成物の耐熱性、耐溶剤性、耐湿性、接着性等を著しく
低下させ、また、ボイド、クラックの原因となったり、
ブリードが発生したりする問題点があった。また、これ
らの反応性希釈剤は、ｎ−ブチルグリシジルエーテルの
ように高い毒性を持つものがあり、安全性の面から使用
を控えることが好ましいものが少なくなかった。更に、
これらの反応性希釈剤は、エピクロルヒドリンを原料と
するものが多く、そのため塩素イオンなどの不純物を含
み、その結果、アルミニウムなどの腐食され易い被塗物
の場合には、特性低下を来たし信頼性も低下させてい
た。Even in the epoxy system which occupies the mainstream of conductive adhesives, those having a solvent content reduced or solvent-free and ensuring the fluidity of the adhesive and having the above-mentioned satisfactory properties are also available. It's not in the world yet. Usually, a method is used in which the viscosity of the resin is lowered by adding a reactive diluent to secure the fluidity of the adhesive. However, reactive diluents such as aliphatic and aromatic mono- or diglycidyl ether have poor dilution efficiency, and when added in a large amount, the heat resistance, solvent resistance, moisture resistance, adhesiveness, etc. of the resin composition are reduced. Remarkably lowers, causes voids and cracks,
There was a problem that bleeding occurred. Further, some of these reactive diluents have high toxicity such as n-butyl glycidyl ether, and there are many cases where it is preferable to refrain from using them from the viewpoint of safety. Furthermore,
Many of these reactive diluents are made of epichlorohydrin as a raw material, and therefore contain impurities such as chlorine ions, and as a result, in the case of easily corroded materials such as aluminum, the characteristics are deteriorated and the reliability is also low. Had lowered.
【０００５】[0005]
【課題を解決するための手段】発明者は、上記した問題
点を解決すべき鋭意努力し、従来の反応性希釈剤に比較
して希釈効果に優れ、毒性が極めて低く、かつ塩素イオ
ンなどの不純物の少ない無置換脂肪族エポキシドを反応
性希釈剤とし、導電性粉末、常温で液状のエポキシ系樹
脂および硬化剤を含有する導電性接着剤を見出した。こ
れにより接着剤の流動性を確保し、その結果良好な印刷
性を実現し、加えて耐ブリーディング性、高導電性にも
優れた使用ができるようになった。The inventor has made diligent efforts to solve the above-mentioned problems and has an excellent diluting effect as compared with conventional reactive diluents, extremely low toxicity, and chlorine ion and the like. We have found an electrically conductive adhesive containing an electrically conductive powder, an epoxy resin that is liquid at room temperature, and a curing agent, using an unsubstituted aliphatic epoxide containing few impurities as a reactive diluent. As a result, the fluidity of the adhesive was ensured, and as a result, good printability was realized, and in addition, it was possible to use the adhesive excellent in bleeding resistance and high conductivity.
【０００６】本発明に用いられる導電性粉末としては、
例えば、Ａｇ、Ｃｕ、Ｎｉ、Ｐｄ等の金属粉末、並びに
表面に合金層を有する金属粉末等が挙げられ、これらは
単独あるいは２種以上を混合して使用することもでき
る。また、これらの粉末の粒径は１〜２０μｍが好まし
く、より好ましくは平均粒径１〜１０μｍである。これ
は、粉の状態を最密充填にしたほうが、導電性にとって
有利であるためであり、粒径が２０μｍを超えると、粉
末が沈降し易く均一分散という点で問題となり好ましく
ない。また、１μｍ未満だと導電性粉末どうしの接触点
が多くなり、接触抵抗のため導電性が劣ってくるので好
ましくない。更に、本発明で用いられる粉末の形状は特
に限定されるものではないが、球状粉、粒状粉あるいは
偏平状粉であることが好ましい。面接触の可能な偏平状
粉が最も好適であり、面接触効果を十分に出すために
は、偏平状粉のアスペクト比は５以上が好ましい。As the conductive powder used in the present invention,
Examples thereof include metal powders such as Ag, Cu, Ni and Pd, and metal powders having an alloy layer on the surface. These may be used alone or in combination of two or more. The particle size of these powders is preferably 1 to 20 μm, and more preferably the average particle size is 1 to 10 μm. This is because it is advantageous for the conductivity that the powder state is the closest packed, and if the particle size exceeds 20 μm, the powder tends to settle and uniform dispersion occurs, which is not preferable. On the other hand, if it is less than 1 μm, the number of contact points between the conductive powders increases, and the contact resistance deteriorates the conductivity, which is not preferable. Further, the shape of the powder used in the present invention is not particularly limited, but it is preferably spherical powder, granular powder or flat powder. The flattened powder capable of surface contact is the most preferable, and the flattened powder preferably has an aspect ratio of 5 or more in order to sufficiently bring out the surface contact effect.
【０００７】本発明に使用する樹脂は、エポキシ系樹脂
であるが他の樹脂に比べ当該樹脂は耐熱と機械的強度と
のバランス、電気特性、接着特性、耐食性等に優れた硬
化樹脂を得ることができること、また、常温で液状であ
ることにより、接着剤として必要な流動性、粘度特性お
よび良好な作業性が得られることによる。本発明で用い
られるエポキシ系樹脂としては、常温で液状のエポキシ
系樹脂として知られる総てのものが使用可能であるが、
電気的特性などの特性バランスがとれていることや、純
度、作業性のよいことから、ビルフェノールＡタイプお
よびビスフェノールＦタイプなどのフェノール系グリシ
ジルエーテル型、１，６−ジヒドロキシナフタレン型が
好適である。このような樹脂としては、例えば、油化シ
ェルエポキシ社製エピコート８２７、ダウケミカル日本
社製のＤ．Ｅ．Ｒ．３３１Ｊ等のビスフェノールＡタイ
プエポキシ樹脂、日本化薬社製のＲＥ−４０４Ｓ等のビ
スフェノールＦタイプエポキシ樹脂、大日本インキ化学
工業社のＨＰ−４０３２Ｄ等の１，６−ジヒドロキシナ
フタレンタイプエポキシ樹脂がある。これらのエポキシ
系樹脂は単独で用いてもよく、また２種以上を混合して
もよい。また、常温で固体のエポキシ系樹脂を、常温で
液体のエポキシ系樹脂あるいは少量の反応性希釈剤とと
もに溶融し、常温で液状となるように調製してもよい。The resin used in the present invention is an epoxy resin, but as compared with other resins, the resin has a balance between heat resistance and mechanical strength, electrical properties, adhesive properties, corrosion resistance and the like. It is also possible to obtain the fluidity, viscosity characteristics and good workability required as an adhesive by being liquid at room temperature. As the epoxy resin used in the present invention, all known epoxy resins which are liquid at room temperature can be used.
Phenolic glycidyl ether type such as billphenol A type and bisphenol F type and 1,6-dihydroxynaphthalene type are preferable because they have well-balanced characteristics such as electrical characteristics and good purity and workability. . Examples of such a resin include Epicoat 827 manufactured by Yuka Shell Epoxy Co., Ltd. and D.C. manufactured by Dow Chemical Japan. E. FIG. R. There are bisphenol A type epoxy resins such as 331J, bisphenol F type epoxy resins such as RE-404S manufactured by Nippon Kayaku Co., Ltd., and 1,6-dihydroxynaphthalene type epoxy resins such as HP-4032D manufactured by Dainippon Ink and Chemicals. These epoxy resins may be used alone or in combination of two or more. Alternatively, an epoxy resin that is solid at room temperature may be melted with an epoxy resin that is liquid at room temperature or a small amount of a reactive diluent to prepare a liquid at room temperature.
【０００８】また、エポキシ系樹脂の添加量は、導電性
粉末１００重量部に対し、５〜５０重量部が好ましく、
より好ましくは１５〜４０重量部である。エポキシ系樹
脂の添加量が５重量部未満となると、塗膜の強度が低下
し良好な接着性が得られなく、一方５０重量部を超える
と、導電性が急激に低下し必要な導電性が得られなくな
るため好ましくない。The amount of the epoxy resin added is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the conductive powder,
It is more preferably 15 to 40 parts by weight. When the amount of the epoxy resin added is less than 5 parts by weight, the strength of the coating film is lowered and good adhesiveness cannot be obtained. On the other hand, when it exceeds 50 parts by weight, the conductivity is drastically reduced and the required conductivity is reduced. It is not preferable because it cannot be obtained.
【０００９】本発明で用いられる反応性希釈剤として
は、常温で液体であることおよび変異原性のないものが
好ましく、特に、１，２−エポキシデカン、１，２−エ
ポキシドデカン、１，２−エポキシテトラデカン等の炭
素数１０〜１４の無置換脂肪族エポキシドが好適であ
る。このような反応性希釈剤としては、例えば、大日本
インキ化学工業社製のＥＭ−１０２等が挙げられる。ま
た、炭素数１８以上の無置換脂肪族エポキシドは固体と
なるため、トルエン、ｎ−ヘキサン、メチルエチルケト
ン、ｎ−ブチルセロソルブ等の溶剤またはこれらの混合
溶剤で液状化して使用することもできる。無置換脂肪族
エポキシドの添加量は、本発明の接着剤を所望の粘度と
なるように添加すればよいが、エポキシ系樹脂１００重
量部に対し、２〜１００重量部が好ましく、より好まし
くは５〜４０重量部である。２重量部未満となると、十
分な粘度希釈効果が得られ難く、１００重量部を超える
と、印刷に適した粘度特性や耐ブリーディング性、接着
性等が急激に低下するため好ましくない。The reactive diluent used in the present invention is preferably one that is liquid at room temperature and has no mutagenicity, and particularly 1,2-epoxydecane, 1,2-epoxydodecane, 1,2. -C10-14 unsubstituted aliphatic epoxides such as epoxytetradecane are preferred. Examples of such a reactive diluent include EM-102 manufactured by Dainippon Ink and Chemicals, Inc. Further, since the unsubstituted aliphatic epoxide having 18 or more carbon atoms becomes a solid, it can be liquefied with a solvent such as toluene, n-hexane, methyl ethyl ketone, n-butyl cellosolve or a mixed solvent thereof before use. The amount of the unsubstituted aliphatic epoxide added may be such that the adhesive of the present invention has a desired viscosity, but is preferably 2 to 100 parts by weight, more preferably 5 parts by weight, relative to 100 parts by weight of the epoxy resin. ~ 40 parts by weight. If it is less than 2 parts by weight, it is difficult to obtain a sufficient viscosity-diluting effect, and if it exceeds 100 parts by weight, viscosity characteristics suitable for printing, bleeding resistance, adhesiveness, etc. are drastically reduced, which is not preferable.
【００１０】本発明では反応性希釈剤として無置換脂肪
族エポキシドに限定した理由を更に詳しく説明すると下
記のようになる。即ち、例えばハロゲンで置換された脂
肪族エポキシドだと変異原性が増大するので生体安全性
に問題ができ、また、ハロゲンによる腐食性が問題とな
り、接着剤の一組成として使用した場合、接着した素子
の端子等に問題をおこし、素子の信頼性低下にもつなが
ることになる。また、置換脂肪族エポキシドであるグリ
シジルエーテル、グリジシルエステルでは上記と同様に
変異原性を有するとともに、これらの化合物は塩素を持
つ化合物であるエピクロルヒドリンを原料とするため不
純物の塩素が残存し塩素による腐食が上記と同様に問題
となり好ましくない。また、芳香族グリシジルエーテル
等の芳香族エポキシドは、分子量が概して大きいので希
釈効果が小さく、また、これもグリシジルエーテル類の
ため、上記と同様にエピクロルヒドリンに由来する塩素
による腐食が問題となり好ましくない。In the present invention, the reason why the reactive diluent is limited to the unsubstituted aliphatic epoxide will be described in more detail as follows. That is, for example, a halogen-substituted aliphatic epoxide has increased mutagenicity, which may cause a problem in biosafety. In addition, halogen-induced corrosion causes a problem. This will cause a problem in the terminals of the element, etc., leading to a decrease in the reliability of the element. In addition, glycidyl ether and glycidyl ester, which are substituted aliphatic epoxides, have mutagenicity in the same manner as above, and since these compounds are made from epichlorohydrin, which is a compound with chlorine, chlorine as an impurity remains. Corrosion due to the same problem as described above is not preferable. In addition, since aromatic epoxides such as aromatic glycidyl ethers generally have large molecular weights, the diluting effect is small, and since these are also glycidyl ethers, corrosion due to chlorine derived from epichlorohydrin causes a problem similarly to the above, which is not preferable.
【００１１】本発明で用いられる硬化剤としては、エポ
キシ系樹脂硬化剤として通常知られている総てのものが
使用可能であるが、作業性および保存安定性の観点か
ら、潜在型硬化剤が好適に用いられる。このような硬化
剤としては、例えば、２−エチル−４−メチルイミダゾ
ールなどの第３アミン、３フッ化ホウ素・エチルアミン
錯体などのルイス酸錯体、ジシアンジアミド、アジピン
酸ジヒドラジドなどの有機酸ヒドラジド、マイクロカプ
セル型、芳香族ジアゾニウム塩、ケチミン化合物等が挙
げられる。具体的には、四国化成工業社製のキュアゾー
ルシリーズ、旭化成工業社のノバキュアシリーズ、味の
素社製のアミキュアシリーズ、旭電化工業社製のアデカ
オプトンＣＰ−６６等が知られており、これらを単独ま
たは２種以上混合して使用することができる。硬化剤の
添加量はその種類によって大きく異なり、所望の硬化時
間等によっても差はあるが、その添加量も通常知られて
いる範囲での使用量でよい。As the curing agent used in the present invention, all those generally known as epoxy resin curing agents can be used. From the viewpoint of workability and storage stability, latent type curing agents are used. It is preferably used. Examples of such curing agents include tertiary amines such as 2-ethyl-4-methylimidazole, Lewis acid complexes such as boron trifluoride / ethylamine complex, organic acid hydrazides such as dicyandiamide and adipic acid dihydrazide, and microcapsules. Type, aromatic diazonium salts, ketimine compounds and the like. Specifically, Curezol series manufactured by Shikoku Kasei Kogyo Co., Novacure series manufactured by Asahi Kasei Kogyo Co., Ltd., Amicure series manufactured by Ajinomoto Co., Inc., Adeka Opton CP-66 manufactured by Asahi Denka Co., Ltd., etc. are known. They can be used alone or in combination of two or more. The addition amount of the curing agent varies greatly depending on the type of the curing agent, and also varies depending on the desired curing time and the like, but the addition amount may be within the generally known range.
【００１２】本発明では、上記のもの以外の溶剤、硬化
触媒、カップリング剤等の表面処理剤およびその他の添
加剤を必要に応じ配合してもよい。溶剤としてはセロソ
ルブ系溶剤等の非反応性溶剤で粘度微調整のため添加し
てもよい。ただ、環境問題のためには無溶剤系の本発明
品が好ましく、更に、上記の溶剤を添加した系の導電性
接着剤は、やはり無溶剤系に比べ硬化特性は劣る。特に
接着硬化時、接着層内に気泡ができ易く、導電性にも悪
影響をきたすし、接着強度も低下するし、溶剤が入って
いると、硬化の際、無溶剤の場合に比べ長時間を要す必
要があり、生産効率も悪くなる。In the present invention, a solvent other than the above, a curing catalyst, a surface treating agent such as a coupling agent, and other additives may be blended if necessary. As the solvent, a non-reactive solvent such as a cellosolve-based solvent may be added for fine adjustment of the viscosity. However, the solvent-free product of the present invention is preferable for environmental problems, and the conductive adhesive of the above-mentioned solvent-added system is also inferior in curing property to the solvent-free system. In particular, when the adhesive is cured, bubbles are easily formed in the adhesive layer, the conductivity is adversely affected, the adhesive strength is reduced, and when a solvent is contained, it takes a longer time than the case without a solvent when curing. It needs to be done, and the production efficiency will be poor.
【００１３】次に硬化触媒について述べる。例えば２−
エチル−４−メチルイミダゾール、１−ベンジル−２−
フェニルイミダゾール等のイミダゾール類等が一般的に
硬化を速やかにすすめるために少量添加する場合もあ
る。また、導電性粉末の表面処理を行ない、樹脂との濡
れ性、分散性を改善するために該粉末に対し１ｗｔ％程
度、脂肪酸、各種シランカップリング剤等の表面処理剤
を配合してもよい。その他の添加剤としては、レベリン
グ剤、分散剤等があり、これらも本発明に配合してもよ
い。Next, the curing catalyst will be described. For example, 2-
Ethyl-4-methylimidazole, 1-benzyl-2-
In general, imidazoles such as phenylimidazole may be added in a small amount in order to accelerate curing generally. Further, the surface treatment of the conductive powder may be performed, and in order to improve the wettability and dispersibility with the resin, a surface treatment agent such as fatty acid and various silane coupling agents may be added to the powder in an amount of about 1 wt%. . Other additives include leveling agents, dispersants and the like, which may also be incorporated in the present invention.
【００１４】[0014]
【実施例】以下に実施例および比較例にて詳説するが、
本発明はこれに限定されるものではない。 実施例１ 特開平５−２７９８６３の実施例１に準じて造った銀め
っき銅粉１０ｇに、常温で液状のビスフェノールＦタイ
プエポキシ樹脂ＲＥ４０４Ｓ（日本化薬社製）を１．８
ｇ、硬化剤３フッ化ホウ素・エチルアミン錯体を０．１
５ｇ、反応性希釈剤として１，２−エポキシデカンと
１，２−−エポキシドデカンの混合物ＥＭ−１０２（大
日本インキ化学工業社製）を０．５４ｇ、表面処理剤と
してオレイン酸０．０５ｇを加え、十分練り込み導電性
接着剤（ａ）を造った。[Examples] The following will describe in detail in Examples and Comparative Examples.
The present invention is not limited to this. Example 1 1.8 g of a bisphenol F type epoxy resin RE404S (manufactured by Nippon Kayaku Co., Ltd.), which is liquid at room temperature, was added to 10 g of silver-plated copper powder produced according to Example 1 of JP-A-5-279863.
g, curing agent boron trifluoride / ethylamine complex 0.1
5 g, 0.54 g of a mixture of 1,2-epoxydecane and 1,2-epoxydodecane EM-102 (manufactured by Dainippon Ink and Chemicals, Inc.) as a reactive diluent, and 0.05 g of oleic acid as a surface treatment agent. In addition, the conductive adhesive (a) was sufficiently kneaded to make it.
【００１５】実施例２ 実施例１と同様にして、導電性接着剤を得た後、溶剤と
してｎ−ブチルセロソルブ０．２ｇを添加し、導電性接
着剤（ｂ）を造った。Example 2 In the same manner as in Example 1, after obtaining a conductive adhesive, 0.2 g of n-butyl cellosolve was added as a solvent to prepare a conductive adhesive (b).
【００１６】比較例１ 反応性希釈剤として、芳香族エポキシドの一つであるＯ
−ｓｅｃ−ブチルフェノールグリシジルエーテルを用い
た以外は実施例１と同様にして、導電性接着剤（ｃ）を
造った。Comparative Example 1 As a reactive diluent, one of aromatic epoxides, O
A conductive adhesive (c) was produced in the same manner as in Example 1 except that -sec-butylphenol glycidyl ether was used.
【００１７】比較例２ 反応性希釈剤として、置換脂肪族エポキシドの一つであ
る脂肪族ポリグリシジルエーテルを用いた以外は実施例
１と同様にして、導電性接着剤（ｄ）を造った。Comparative Example 2 A conductive adhesive (d) was prepared in the same manner as in Example 1 except that aliphatic polyglycidyl ether, which is one of substituted aliphatic epoxides, was used as the reactive diluent.
【００１８】比較例３ 反応性希釈剤として、芳香族エポキシドの一つであるジ
グリシジル−ｏ−トルイジンを用いた以外は実施例１と
同様にして、導電性接着剤（ｅ）を造った。Comparative Example 3 A conductive adhesive (e) was prepared in the same manner as in Example 1 except that diglycidyl-o-toluidine, which is one of aromatic epoxides, was used as the reactive diluent.
【００１９】比較例４ 反応性希釈剤として、置換脂肪族エポキシドの一つであ
る第３級脂肪酸モノグリシジルエステルを用いた以外は
実施例１と同様にして、導電性接着剤（ｆ）を造った。Comparative Example 4 A conductive adhesive (f) was prepared in the same manner as in Example 1 except that a tertiary fatty acid monoglycidyl ester which is one of substituted aliphatic epoxides was used as the reactive diluent. It was
【００２０】実施例３ 市販のフレーク銀粉１０ｇに、常温で液状のビスフェノ
ールＡタイプエポキシ樹脂Ｄ．Ｅ．Ｒ．３８３Ｊ（ダウ
ケミカル日本社製）を１．８ｇ、潜在型硬化剤アミキュ
アＡＨ１５４（味の素社製、商品名）、を０．１７ｇ、
１，２−エポキシデカンと１，２−エポキシドデカンの
混合物０．５４ｇを加え十分練り込み、導電性接着剤
（ｇ）を造った。Example 3 10 g of commercially available flake silver powder was added to a bisphenol A type epoxy resin D. E. FIG. R. 1.83 g of 383J (manufactured by Dow Chemical Japan), 0.17 g of latent curing agent Amicure AH154 (manufactured by Ajinomoto Co., product name),
A conductive adhesive (g) was prepared by adding 0.54 g of a mixture of 1,2-epoxydecane and 1,2-epoxydodecane and thoroughly kneading the mixture.
【００２１】比較例５ 反応性希釈剤として、Ｏ−ｓｅｃ−ブチルフェノールグ
リシジルエーテルを用いた以外は実施例２と同様にし
て、導電性接着剤（ｈ）を造った。Comparative Example 5 A conductive adhesive (h) was prepared in the same manner as in Example 2 except that O-sec-butylphenol glycidyl ether was used as the reactive diluent.
【００２２】実施例４および比較例６ 実施例１〜３および比較例１〜５の導電性接着剤（ａ）
〜（ｈ）について、比抵抗、Ｅ型粘度計０．５ｒ．ｐ．
ｍ．における粘度および耐ブリーディング性を比較し
た。耐ブリーディング性は、特開平４−３９８０９に開
示されたブリード試験に準じ導電性接着剤をスライドガ
ラス上に幅５ｍｍ、長さ４０ｍｍ、厚さ５０μｍとなる
ようにスクリーンに印刷し、１５０℃で１時間処理して
硬化させた後、２ａｔｍのプレッシャー・クッカ・テス
トを８時間行った時のガラス界面を、２０倍の倍率にて
顕微鏡観察により評価した。その結果を表１に示す。Example 4 and Comparative Example 6 Conductive adhesives (a) of Examples 1 to 3 and Comparative Examples 1 to 5
~ (H), specific resistance, E-type viscometer 0.5r. p.
m. And the bleeding resistance were compared. The bleeding resistance was measured by printing a conductive adhesive on a glass slide to a width of 5 mm, a length of 40 mm and a thickness of 50 μm in accordance with the bleeding test disclosed in JP-A-4-39809 and then at 150 ° C. After being treated by time and cured, a glass interface at a pressure cooker test of 2 atm for 8 hours was evaluated under a microscope at a magnification of 20 times. Table 1 shows the results.
【００２３】[0023]
【表１】 表１中のブリードの有無の判断は◎印はなし、○印は一
部あり、△印は多数あり、×印は著しく多数ありの記号
にて評価した。[Table 1] In Table 1, the presence / absence of bleeding was evaluated by the symbols with no ◎, some with ○, many with △, and markedly with ×.
【００２４】[0024]
【発明の効果】本発明によれば、従来にはない高い耐ブ
リーディング性、高導電性および印刷性に優れ、電子材
料の接続に用いて良好な結果を得るものである。According to the present invention, it has excellent bleeding resistance, high conductivity and printability which have not been hitherto obtained, and it can be used for connecting electronic materials with good results.
Claims (1)
キシ系樹脂、Ｃ）硬化剤、Ｄ）無置換脂肪族エポキシド
を含有することを特徴とする導電性接着剤。1. A conductive adhesive containing A) a conductive powder, B) an epoxy resin which is liquid at room temperature, C) a curing agent, and D) an unsubstituted aliphatic epoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32317494A JPH08176521A (en) | 1994-12-26 | 1994-12-26 | Electroconductive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32317494A JPH08176521A (en) | 1994-12-26 | 1994-12-26 | Electroconductive adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08176521A true JPH08176521A (en) | 1996-07-09 |
Family
ID=18151907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32317494A Pending JPH08176521A (en) | 1994-12-26 | 1994-12-26 | Electroconductive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08176521A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980066134A (en) * | 1997-01-20 | 1998-10-15 | 구광시 | Anisotropic conductive film with excellent storage stability at room temperature |
| JPH10329970A (en) * | 1997-06-03 | 1998-12-15 | Hokushin Ind Inc | Conveyance roll and its manufacture |
| EP0906927A1 (en) * | 1997-10-02 | 1999-04-07 | Hexcel Corporation | Epoxy resin curing agents |
| WO2006064678A1 (en) * | 2004-12-16 | 2006-06-22 | Sumitomo Electric Industries, Ltd. | Adhesive for circuit connection |
| CN102408856A (en) * | 2011-08-09 | 2012-04-11 | 烟台德邦电子材料有限公司 | Conductive adhesive for LED (light emitting diode) packaging and preparation method thereof |
-
1994
- 1994-12-26 JP JP32317494A patent/JPH08176521A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980066134A (en) * | 1997-01-20 | 1998-10-15 | 구광시 | Anisotropic conductive film with excellent storage stability at room temperature |
| JPH10329970A (en) * | 1997-06-03 | 1998-12-15 | Hokushin Ind Inc | Conveyance roll and its manufacture |
| EP0906927A1 (en) * | 1997-10-02 | 1999-04-07 | Hexcel Corporation | Epoxy resin curing agents |
| WO2006064678A1 (en) * | 2004-12-16 | 2006-06-22 | Sumitomo Electric Industries, Ltd. | Adhesive for circuit connection |
| JP2006196850A (en) * | 2004-12-16 | 2006-07-27 | Sumitomo Electric Ind Ltd | Adhesive for connecting circuit |
| US7588698B2 (en) | 2004-12-16 | 2009-09-15 | Sumitomo Electric Industries, Ltd. | Circuit connecting adhesive |
| CN102408856A (en) * | 2011-08-09 | 2012-04-11 | 烟台德邦电子材料有限公司 | Conductive adhesive for LED (light emitting diode) packaging and preparation method thereof |
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