JPH06157876A - Conductive one-pack epoxy resin composition - Google Patents
Conductive one-pack epoxy resin compositionInfo
- Publication number
- JPH06157876A JPH06157876A JP31964892A JP31964892A JPH06157876A JP H06157876 A JPH06157876 A JP H06157876A JP 31964892 A JP31964892 A JP 31964892A JP 31964892 A JP31964892 A JP 31964892A JP H06157876 A JPH06157876 A JP H06157876A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- conductive
- resin composition
- pack type
- type 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は種々の基板に導電層を形
成したり、各種電子部品及びリード線等の導電性を必要
とする部分の接着に用いられる導電性一液型エポキシ樹
脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive one-pack type epoxy resin composition used for forming a conductive layer on various substrates and for bonding various electronic parts, lead wires and the like where conductivity is required. It is about.
【０００２】[0002]
【従来の技術】導電性樹脂組成物はフェノール樹脂、ア
クリル樹脂、ポリエステル樹脂、エポキシ樹脂、ポリイ
ミド樹脂等の合成樹脂に導電性充填剤を混合してイン
キ、塗料、ペースト状等にしたものであり、通常は電気
特性に優れたエポキシ樹脂が多用されている。現在一般
に用いられている導電性エポキシ樹脂組成物には、エポ
キシ樹脂に導電性充填剤を配合した主剤と硬化剤とを使
用直前に混合する二液型と、エポキシ樹脂に導電性充填
剤と硬化剤及び硬化促進剤を予め配合した一液型とがあ
る。二液型の硬化剤としては、一般にポリアミド樹脂或
はアミン類が用いられ、一液型の硬化剤としてはフェノ
ール樹脂、イミダゾール化合物、ジシアンジアミドと尿
素化合物等が用いられている。2. Description of the Related Art A conductive resin composition is prepared by mixing a synthetic resin such as a phenol resin, an acrylic resin, a polyester resin, an epoxy resin or a polyimide resin with a conductive filler to prepare an ink, a paint or a paste. Usually, epoxy resins with excellent electrical characteristics are often used. Currently used conductive epoxy resin compositions include a two-component type in which a main agent prepared by mixing a conductive filler into an epoxy resin and a curing agent are mixed immediately before use, and an epoxy resin containing a conductive filler and a curing agent. There is a one-pack type in which an agent and a curing accelerator are pre-blended. Polyamide resins or amines are generally used as the two-pack type curing agent, and phenol resins, imidazole compounds, dicyandiamide and urea compounds, etc. are used as the one-pack type curing agent.
【０００３】導電性充填剤には金、銀、パラジウム、
銅、ニッケル等の金属微粉末及びその酸化物、カーボン
ブラック或は炭素繊維等の炭素粉末が用いられているが
導電性と価格の面から、通常は粉末或はフレーク状の銀
粉が多用されている。Conductive fillers include gold, silver, palladium,
Fine powders of metals such as copper and nickel and oxides thereof, carbon powders such as carbon black or carbon fibers are used, but powders or flake-shaped silver powders are often used from the viewpoint of conductivity and price. There is.
【０００４】従来の二液型の導電性エポキシ樹脂組成物
では主剤と硬化剤を混合すると、可使時間が短いために
速やかに粘度が上昇し、数時間から数日で樹脂組成物が
硬化してしまうので作業性に問題が生じている。また、
これらの問題点を解決する目的で一液型の導電性エポキ
シ樹脂組成物が種々開発され、用いられているがこれら
に用いられている金属又はその酸化物の粉末、炭素粉末
では安定した導電性を得るために導電性充填剤を多く用
いる必要があった。しかしながら、導電性充填剤を多く
用いると接着性等が低下し、組成物としての物性と安定
した導電性を得るための配合の選択、製造時の工程管理
等に熟練が必要とされている。また製品の高性能、信頼
性等の点から導電性充填剤としては金、銀、白金族の金
属粉末が用いられ、また高充填されている。特にこれら
導電性充填剤において安価な銀粉末が多用されているが
銀はエレクトロマイグレーションが発生しやすいために
絶縁不良を起こすと言った欠点を持つている。In the conventional two-component type conductive epoxy resin composition, when the main agent and the curing agent are mixed, the viscosity is rapidly increased because the pot life is short, and the resin composition is cured in several hours to several days. Therefore, there is a problem in workability. Also,
Various one-component type conductive epoxy resin compositions have been developed and used for the purpose of solving these problems, but the powder of the metal or its oxide used for them and the carbon powder have stable conductivity. Therefore, it was necessary to use a large amount of conductive filler in order to obtain However, when a large amount of conductive filler is used, the adhesiveness and the like are deteriorated, and it is necessary to have skill in selecting the composition for obtaining the physical properties of the composition and stable conductivity, and controlling the process during manufacturing. Further, from the viewpoints of high performance and reliability of the product, gold, silver and platinum group metal powders are used as the conductive filler and are highly filled. In particular, inexpensive silver powder is often used in these conductive fillers, but silver has a drawback that it causes insulation failure because electromigration easily occurs.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的はこのよ
うな導電性エポキシ樹脂組成物の欠点を改良すべく、常
温における貯蔵安定性に優れ、高温時には速やかに硬化
して優れた物性の導電性硬化物を得る導電性一液型エポ
キシ樹脂組成物を開発することにある。SUMMARY OF THE INVENTION The object of the present invention is to improve the drawbacks of such a conductive epoxy resin composition by providing excellent storage stability at room temperature and quick curing at a high temperature to provide a conductive material having excellent physical properties. The purpose is to develop a conductive one-pack type epoxy resin composition for obtaining a cured product.
【０００６】[0006]
【問題点を解決するための手段】本発明者らは導電性エ
ポキシ樹脂組成物の常温貯蔵安定性と硬化物の性能、特
に銀のエレクトロマイグレーション性を改良し導電性一
液型エポキシ樹脂組成物を完成させた。すなわち本発明
は（Ａ）貴金属被覆繊維状微粉末、（Ｂ）エポキシ樹
脂、（Ｃ）固体分散型潜在性硬化剤を必須成分とするこ
とを特徴とする導電性一液型エポキシ樹脂組成物に関す
るものであり、更には導電性一液型エポキシ樹脂組成物
がシラン系、チタネート系、ジルコニウム系又はアルミ
ニウム系カップリング剤を含むことを特徴とする導電性
一液型エポキシ樹脂組成物に関するものである。SUMMARY OF THE INVENTION The present inventors have improved the storage stability of a conductive epoxy resin composition at room temperature and the performance of a cured product, especially the electromigration property of silver, to improve the conductive one-pack type epoxy resin composition. Was completed. That is, the present invention relates to a conductive one-pack type epoxy resin composition comprising (A) a noble metal-coated fibrous fine powder, (B) an epoxy resin, and (C) a solid dispersion type latent curing agent as essential components. The present invention further relates to a conductive one-pack type epoxy resin composition, wherein the conductive one-pack type epoxy resin composition contains a silane-based, titanate-based, zirconium-based or aluminum-based coupling agent. .
【０００７】以下に本発明に係わる導電性一液型エポキ
シ樹脂組成物について詳細に説明する。本発明おける貴
金属被覆繊維状微粉末とは、繊維長と繊維径の比（アス
ペクト比）が１０以上の繊維形状を有する心材であり、
導電性一液型エポキシ樹脂組成物として用いる場合の加
工性等を考慮すると繊維長１μｍ〜１０ｍｍ、繊維径１
０ｎｍ〜１ｍｍ程度のものが好ましい。繊維形状の心材
としてはアスベスト、ロックウール、石英繊維、アルミ
ナ繊維、炭素繊維、炭化珪素及び炭化ホウ素繊維、ホウ
化アルミニウム繊維、ホウ化チタン繊維、ホウ素繊維、
二酸化チタン繊維、酸化ベリリウム繊維、マグネシウム
パイロボレート繊維、チタン酸アルカリ及びチタン酸ア
ルカリ土類金属繊維等が例示されるが、これらに限定さ
れるものではない。The conductive one-pack type epoxy resin composition according to the present invention will be described in detail below. The noble metal-coated fibrous fine powder in the present invention is a core material having a fiber shape with a fiber length to fiber diameter ratio (aspect ratio) of 10 or more,
Considering processability when used as a conductive one-pack type epoxy resin composition, fiber length 1 μm to 10 mm, fiber diameter 1
It is preferably about 0 nm to 1 mm. As the fiber-shaped core material, asbestos, rock wool, quartz fiber, alumina fiber, carbon fiber, silicon carbide and boron carbide fiber, aluminum boride fiber, titanium boride fiber, boron fiber,
Examples thereof include titanium dioxide fibers, beryllium oxide fibers, magnesium pyroborate fibers, alkali titanates and alkaline earth metal titanates, but are not limited thereto.
【０００８】これら繊維形状の心材に貴金属、即ち金、
銀、白金族の金属を被覆する方法としては無電解めっき
法、湿式中和法、ＣＶＤ法、ＰＶＤ法等の現在常用され
ている表面導電化方法が適用できるが、特に好ましい方
法としては従来から公知の無電解めっき法、即ち錯化剤
を含む貴金属化合物の水溶液又は水分散液に活性化処理
を施した繊維状心材の水分散液を添加し、還元剤を用い
て繊維状心材表面に貴金属の薄膜を被覆形成させる製法
が好適である。Noble metal, that is, gold, is added to these fiber-shaped core materials.
As the method for coating the metal of the silver or platinum group, currently used surface conductive methods such as electroless plating method, wet neutralization method, CVD method and PVD method can be applied. A known electroless plating method, that is, an aqueous dispersion of an activated fibrous core material is added to an aqueous solution or an aqueous dispersion of a noble metal compound containing a complexing agent, and a reducing agent is used to add the precious metal to the surface of the fibrous core material. The manufacturing method of forming a thin film by coating is preferable.
【０００９】本発明における貴金属被覆層は貴金属被覆
層が連結していればよいが、好ましくは均一に被覆され
ていることが好ましい。貴金属被覆層の厚さは特に制限
されないが貴金属被覆層が薄すぎると目的とする導電性
が不充分になり、逆に厚すぎると導電性は満足するもの
の経済性の面では不利益となるため、貴金属被覆層は１
ｎｍ〜１μｍの範囲が好適である。The noble metal coating layer in the present invention may be formed by connecting the noble metal coating layers, but it is preferable that the noble metal coating layers are uniformly coated. The thickness of the noble metal coating layer is not particularly limited, but if the noble metal coating layer is too thin, the target conductivity will be insufficient, and conversely if it is too thick, the conductivity will be satisfactory but it will be disadvantageous in terms of economy. , The precious metal coating layer is 1
The range of nm to 1 μm is suitable.
【００１０】本発明に用いられるエポキシ樹脂とは、平
均して１分子当り２個以上のグリシジル基を有するもの
であればよく、例えばビスフェノールＡ、ビスフェノー
ルＦ、ビスフェノールＡＤ、カテコール、レゾルシン等
の多価フェノール又はグリセリンやポリエチレングリコ
ールのような多価アルコールとエピクロールヒドリンと
を反応させて得られるポリグリシジルエーテル、或はＰ
−オキシ安息香酸、β−オキシナフトエ酸のようなヒド
ロキシカルボン酸のようなヒドロキシカルボン酸とエピ
クロールヒドリンとを反応させて得られるグリシジルエ
ーテルエステル、或はダイマー酸、フタル酸のようなポ
リカルボン酸から得られるポリグリシジルエステル、或
は４，４′−ジアミノジフェニルメタンやｍ−アミノフ
ェノール等から得られるグリシジルアミン化合物、３，
４−エポキシシクロヘキシルメチル−３，４−エポキシ
シクロヘキシルカルボキシレート、３，４−エポキシ−
６−メチルシクロヘキシルメチル−３，４−エポキシ−
６−メチルシクロヘキサンカルボキシレート等の環式脂
肪族エポキシ化合物、更にはエポキシ化ノボラックやエ
ポキシ化ポリオレフィン等が例示されるが、これらに限
定されるものではない。The epoxy resin used in the present invention may be one having an average of two or more glycidyl groups per molecule, and examples thereof include polyhydric compounds such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcin. Polyglycidyl ether obtained by reacting phenol or polyhydric alcohol such as glycerin or polyethylene glycol with epichlorhydrin, or P
-Glycidyl ether ester obtained by reacting hydroxycarboxylic acid such as hydroxycarboxylic acid such as oxybenzoic acid and β-oxynaphthoic acid with epichlorhydrin, or polycarboxylic acid such as dimer acid and phthalic acid Polyglycidyl ester obtained from acid, or glycidyl amine compound obtained from 4,4′-diaminodiphenylmethane, m-aminophenol, or the like, 3,
4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-
6-Methylcyclohexylmethyl-3,4-epoxy-
Examples thereof include cycloaliphatic epoxy compounds such as 6-methylcyclohexanecarboxylate, and epoxidized novolacs and epoxidized polyolefins, but the invention is not limited thereto.
【００１１】本発明に用いられる固体分散型潜在性硬化
剤としては、従来から提案されている潜在性硬化剤を用
いることができ、その代表例としてはジシアンジアミ
ド、アジピン酸ジヒドラジド等のジヒドラジド化合物、
グアナミン類、メラミン類、エポキシ化合物とイミダゾ
ール化合物との付加化合物、エポキシ化合物とジアルキ
ルアミン類との付加化合物、アミンとチオ尿素との付加
化合物、アミンとイソシアネートとの付加化合物等が挙
げられるが、これらに限定されるものではない。As the solid dispersion type latent curing agent used in the present invention, a latent curing agent proposed hitherto can be used, and representative examples thereof include dihydrazide compounds such as dicyandiamide and adipic acid dihydrazide,
Guanamines, melamines, addition compounds of epoxy compounds and imidazole compounds, addition compounds of epoxy compounds and dialkylamines, addition compounds of amines and thioureas, addition compounds of amines and isocyanates, and the like. It is not limited to.
【００１２】また本発明に用いられる固体分散型潜在性
硬化剤は酸無水物等の硬化剤の硬化促進剤としても用い
られる。酸無水物硬化剤としては、例えば無水フタル
酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタ
ル酸、メチルヘキサヒドロ無水フタル酸、無水マレイン
酸、無水ピロメリット酸、無水メチルナジック酸、メチ
ルブテニルテトラヒドロ無水フタル酸、メチルテトラヒ
ドロ無水フタル酸等あげられるが、これらに限定される
ものではない。The solid dispersion type latent curing agent used in the present invention is also used as a curing accelerator for a curing agent such as an acid anhydride. Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, pyromellitic anhydride, methylnadic acid anhydride, methylbutenyltetrahydrophthalic anhydride. Examples thereof include acid and methyltetrahydrophthalic anhydride, but are not limited thereto.
【００１３】本発明の導電性一液型エポキシ樹脂組成物
は所定量のエポキシ樹脂、固体分散型潜在性硬化剤を通
常の撹拌機、らい潰機、三本ロール等を用いて均一に混
合又は混練し、次に所定量の貴金属被覆繊維状微粉末と
前記樹脂組成物とを通常の撹拌機、らい潰機、三本ロー
ル等を用いて均一に混練すれば容易に得ることができ
る。The conductive one-pack type epoxy resin composition of the present invention is prepared by uniformly mixing a predetermined amount of the epoxy resin and the solid dispersion type latent curing agent using a conventional stirrer, crusher, triple roll or the like. It can be easily obtained by kneading and then uniformly kneading a predetermined amount of the noble metal-coated fibrous fine powder and the resin composition by using an ordinary stirrer, mashing machine, three rolls or the like.
【００１４】この場合に、固体分散型潜在性硬化剤の使
用量はエポキシ樹脂に対して１〜１００重量％、好まし
くは１〜５０重量％が望ましい。また酸無水物等の硬化
剤の硬化促進剤としての使用量はエポキシ樹脂に対して
０．１〜２０重量％、好ましくは０．１〜１０重量％が
望ましい。また貴金属被覆繊維状微粉末の使用量は上記
樹脂組成物に対して２０〜９０重量％、好ましくは３０
〜８０重量％が望ましい。貴金属被覆繊維状微粉末の使
用量が２０重量％未満であると殆ど実用的な導電性は得
られず、また９０重量％を越えると塗布性、接着性等が
著しく低下する。In this case, the amount of the solid dispersion type latent curing agent used is 1 to 100% by weight, preferably 1 to 50% by weight based on the epoxy resin. The amount of the curing agent such as acid anhydride used as a curing accelerator is 0.1 to 20% by weight, preferably 0.1 to 10% by weight, based on the epoxy resin. The amount of the noble metal-coated fibrous fine powder used is 20 to 90% by weight, preferably 30%, based on the resin composition.
-80% by weight is desirable. When the amount of the noble metal-coated fibrous fine powder used is less than 20% by weight, practical conductivity is hardly obtained, and when it exceeds 90% by weight, coating properties, adhesiveness, etc. are significantly deteriorated.
【００１５】また、本発明の方法に使用するシラン系、
チタネート系、ジルコニウム系又はアルミニウム系カッ
プリング剤等のカップリング剤は一液型エポキシ樹脂組
成物と貴金属被覆繊維状微粉末との親和性を向上させた
り、或はガラスやセラミックス等と硬化物との接着性及
び接続信頼性を安定化させることができる。The silane-based compound used in the method of the present invention,
A coupling agent such as a titanate-based, zirconium-based or aluminum-based coupling agent improves the affinity between the one-pack type epoxy resin composition and the noble metal-coated fibrous fine powder, or a coupling agent such as glass or ceramics and a cured product. The adhesiveness and connection reliability of can be stabilized.
【００１６】カップリング剤の使用方法としては、一液
型エポキシ樹脂組成物に直接添加し、撹拌混合して用い
る方法又は貴金属被覆繊維状微粉末をカップリング剤で
処理して用いる方法、例えばミキサー或はボールミル等
を用いて貴金属被覆繊維状微粉末に直接添加して撹拌混
合する乾式処理法又は貴金属被覆繊維状微粉末に相溶性
の良いトルエン、メチルエチルケトン等の溶剤で希釈し
たカップリング剤を添加して撹拌混合し、溶剤を除去す
る湿式処理法等が挙げられる。この場合のカップリング
剤の使用量は一液型エポキシ樹脂組成物又は貴金属被覆
繊維状微粉末に対して０．１〜１０重量％が望ましい。The coupling agent may be used by directly adding it to the one-pack type epoxy resin composition and stirring and mixing it, or by treating the precious metal-coated fibrous fine powder with the coupling agent and using it, for example, a mixer. Alternatively, a dry treatment method of directly adding to the noble metal-coated fibrous fine powder by using a ball mill or the like and stirring and mixing, or adding a coupling agent diluted with a solvent such as toluene or methyl ethyl ketone having good compatibility to the noble metal-coated fibrous fine powder. And agitating and mixing to remove the solvent. In this case, the amount of the coupling agent used is preferably 0.1 to 10% by weight based on the one-pack type epoxy resin composition or the noble metal-coated fibrous fine powder.
【００１７】本発明による導電性一液型エポキシ樹脂組
成物は、貯蔵安定性、硬化性等に悪影響を及ぼさない限
り、通常の一液性エポキシ樹脂組成物に用いられる添加
剤、例えば溶剤、着色剤、粘度調整剤、充填剤その他い
ろいろな目的を持つ改質剤等を配合することは何等差し
支えなく、また硬化物の性能、例えば導電性及びエレク
トロマイグレーション等に悪影響を及ぼさない限り、他
の導電性充填剤を配合することは何等差し支えなく、こ
れらの配合もまた本発明の目的に合意しその範囲に包含
されるものである。The conductive one-pack type epoxy resin composition according to the present invention is an additive such as a solvent or a coloring agent used in a conventional one-pack type epoxy resin composition, as long as it does not adversely affect storage stability, curability and the like. There is no problem in blending agents, viscosity modifiers, fillers and other modifiers having various purposes, and unless other adverse effects are exerted on the performance of the cured product such as conductivity and electromigration. There is no problem in blending the functional filler, and these blends are also within the scope of the object of the present invention.
【００１８】[0018]
【実施例】以下に参考例及び実施例を挙げて本発明を詳
しく説明するが、これらの例によって本発明の範囲が制
限されるものではない。例中において部及び％とは特に
説明がない限り重量部及び重量％を意味する。The present invention will be described in detail below with reference to reference examples and examples, but the scope of the present invention is not limited by these examples. In the examples, parts and% mean parts by weight and% by weight, unless otherwise specified.
【００１９】[0019]
【参考例１】エチレンジアミン四酢酸二ナトリウム２
７．９ｇと２８％アンモニア水１７ｍｌを溶解した水溶
液７００ｍｌに硝酸銀１２．４ｇを溶解した水溶液５０
ｍｌを加えて均一に溶解した。この溶液に塩化錫／塩酸
水溶液、塩化パラジウム／塩酸水溶液にて活性化処理し
たチタン酸カリウム繊維（大塚化学製、ティスモＮ）
２．５ｇの水分散液１００ｍｌを添加し、撹拌混合し
た。次に８０％ヒドラジンヒドラート２．５ｍｌの１０
０ｍｌ水溶液を分散液中に加え、反応温度５０℃に保ち
ながら撹拌化で２時間還元反応を行った。冷却後、沈澱
物をろ別、乾燥してチタン酸カリウム繊維の表面に３７
ｎｍの銀が被覆された灰色の導電性繊維状微粉末を１
０．０ｇを得た。得られた導電性繊維状微粉末の表面を
Ｘ線マイクロアナライザーを用いて観察したところ、心
材表面に銀が均一に被覆されていることを確認した。[Reference Example 1] Disodium ethylenediaminetetraacetate 2
An aqueous solution of 12.4 g of silver nitrate dissolved in 700 ml of an aqueous solution of 7.9 g and 17% of 28% ammonia water 50
ml was added and uniformly dissolved. Potassium titanate fibers activated by tin chloride / hydrochloric acid aqueous solution and palladium chloride / hydrochloric acid aqueous solution (Otsuka Chemical, Tismo N)
100 g of an aqueous dispersion of 2.5 g was added and mixed with stirring. Next, 2.5 ml of 80% hydrazine hydrate 10
A 0 ml aqueous solution was added to the dispersion, and the reduction reaction was performed for 2 hours with stirring while maintaining the reaction temperature at 50 ° C. After cooling, the precipitate is filtered off and dried to form 37 on the surface of the potassium titanate fiber.
1 nm of gray conductive fibrous fine powder coated with nm of silver
0.0 g was obtained. When the surface of the obtained conductive fibrous fine powder was observed using an X-ray microanalyzer, it was confirmed that the surface of the core material was uniformly coated with silver.
【００２０】[0020]
【参考例２】エチレンジアミン四酢酸二ナトリウム２
２．６ｇと２８％アンモニア水１５ｍｌを溶解した水溶
液７００ｍｌに硝酸銀１０．３ｇを溶解した水溶液５０
ｍｌを加えて均一に溶解した。この溶液に塩化錫／塩酸
水溶液、塩化パラジウム／塩酸水溶液にて活性化処理し
たホウ酸アルミニウム繊維（四国化成工業製、アルボレ
ックスＧ）３．５ｇの水分散液１００ｍｌを添加し、撹
拌混合した。次に８０％ヒドラジンヒドラート２．２ｍ
ｌの１００ｍｌ水溶液を分散液中に加え、反応温度４０
℃に保ちながら撹拌化で２時間還元反応を行った。冷却
後、沈澱物をろ別、乾燥してホウ酸アルミニウム繊維の
表面に９５ｎｍの銀が被覆された灰色の導電性繊維状微
粉末を１０．２ｇを得た。得られた導電性繊維状微粉末
の表面をＸ線マイクロアナライザーを用いて観察したと
ころ、心材表面に銀が均一に被覆されていることを確認
した。[Reference Example 2] Disodium ethylenediaminetetraacetic acid 2
Aqueous solution 50 in which 10.3 g of silver nitrate is dissolved in 700 ml of an aqueous solution in which 2.6 g and 15 ml of 28% ammonia water are dissolved.
ml was added and uniformly dissolved. To this solution, 100 ml of an aqueous dispersion of 3.5 g of aluminum borate fibers (Alborex G, manufactured by Shikoku Chemicals) activated by a tin chloride / hydrochloric acid aqueous solution and a palladium chloride / hydrochloric acid aqueous solution was added, and mixed with stirring. Then 80% hydrazine hydrate 2.2m
1 ml of 100 ml aqueous solution was added to the dispersion, and the reaction temperature was 40
The reduction reaction was carried out for 2 hours with stirring while maintaining the temperature at ℃. After cooling, the precipitate was filtered off and dried to obtain 10.2 g of gray conductive fibrous fine powder in which the surface of aluminum borate fiber was coated with 95 nm of silver. When the surface of the obtained conductive fibrous fine powder was observed using an X-ray microanalyzer, it was confirmed that the surface of the core material was uniformly coated with silver.
【００２１】[0021]
【参考例３】エチレンジアミン四酢酸二ナトリウム６
９．７ｇと水酸化ナトリウム１１．８ｇを溶解した水溶
液７００ｍｌに硝酸銀１２．４ｇを溶解した水溶液５０
ｍｌを加えて均一に溶解した。この溶液に塩化錫／塩酸
水溶液、塩化パラジウム／塩酸水溶液にて活性化処理し
た二酸化チタン繊維（石原産業製、ＦＴＬ−１００）
２．５ｇの水分散液１００ｍｌを添加し、撹拌混合し
た。次にジ亜リン酸ナトリウム１５．８ｇを溶解した水
溶液１００ｍｌを分散液中に加え、反応温度８０℃に保
ちながら撹拌化で１時間還元反応を行った。冷却後、沈
澱物をろ別、乾燥して二酸化チタン繊維の表面に１５ｎ
ｍの銀が被覆された灰色の導電性繊維状微粉末を９．９
ｇを得た。得られた導電性繊維状微粉末の表面をＸ線マ
イクロアナライザーを用いて観察したところ、心材表面
に銀が均一に被覆されていることを確認した。[Reference Example 3] Disodium ethylenediaminetetraacetic acid 6
An aqueous solution of 12.4 g of silver nitrate dissolved in 700 ml of an aqueous solution of 9.7 g and 11.8 g of sodium hydroxide 50
ml was added and uniformly dissolved. Titanium dioxide fiber activated by tin chloride / hydrochloric acid aqueous solution or palladium chloride / hydrochloric acid aqueous solution (ITL, FTL-100)
100 g of an aqueous dispersion of 2.5 g was added and mixed with stirring. Next, 100 ml of an aqueous solution in which 15.8 g of sodium diphosphite was dissolved was added to the dispersion, and the reduction reaction was carried out for 1 hour with stirring while maintaining the reaction temperature at 80 ° C. After cooling, the precipitate was filtered off and dried to deposit 15n on the surface of the titanium dioxide fiber.
m of silver-coated gray conductive fibrous fine powder for 9.9
g was obtained. When the surface of the obtained conductive fibrous fine powder was observed using an X-ray microanalyzer, it was confirmed that the surface of the core material was uniformly coated with silver.
【００２２】[0022]
【参考例４】パラジウム溶液（パラジウム金属５ｇを王
水７０ｍｌに溶解したもの）７０ｍｌに塩化アンモニウ
ム１２ｇ（パラジウムに対して１．２等量倍）を加えて
だいだい色ゲル状溶液を得た。この溶液にアンモニア水
（２５％水溶液）４５ｍｌを加えることにより溶液はピ
ンク色ゲル状溶液となり、溶液のＰＨは約７となった。
この溶液にチタン酸カリウム繊維（大塚化学製、ティス
モＮ）５ｇを加え、撹拌しながら水素化ホウ素ナトリウ
ム水溶液（０．７５重量％）を１００ｍｌを加えたとこ
ろ、ゲル状態が解消して黒色の繊維状微粉末が生成し
た。沈澱物をろ別、乾燥してチタン酸カリウム繊維の表
面に２４ｎｍのパラジウムが被覆された導電性繊維状微
粉末を９．９ｇを得た。得られた導電性繊維状微粉末の
表面をＸ線マイクロアナライザーを用いて観察したとこ
ろ、心材表面にパラジウムが均一に被覆されていること
を確認した。[Reference Example 4] To 70 ml of a palladium solution (5 g of palladium metal dissolved in 70 ml of aqua regia) was added 12 g of ammonium chloride (1.2 equivalent times the amount of palladium) to obtain a dark gel solution. By adding 45 ml of ammonia water (25% aqueous solution) to this solution, the solution became a pink gel solution and the pH of the solution became about 7.
To this solution, 5 g of potassium titanate fiber (manufactured by Otsuka Chemical, Tismo N) was added, and 100 ml of an aqueous sodium borohydride solution (0.75% by weight) was added with stirring. A fine powder was produced. The precipitate was filtered off and dried to obtain 9.9 g of conductive fibrous fine powder in which the surface of potassium titanate fiber was coated with 24 nm of palladium. When the surface of the obtained conductive fibrous fine powder was observed using an X-ray microanalyzer, it was confirmed that the core material surface was uniformly coated with palladium.
【００２３】[0023]
【実施例１〜３】エピコート８０７（油化シェルエポキ
シ製、ビスフェノールＦ型エポキシ樹脂）１００部、ジ
シアンジアミド（油化シェルエポキシ製）８部、アミキ
ュアＰＮ−２３（味の素製、硬化剤）３部を真空らい潰
機にて１０分間混練し、一液型エポキシ樹脂組成物Ａを
得た。この樹脂組成物Ａ３．５ｇと湿式処理法を用いて
２％ＴＴＳ（味の素製、チタネートカップリング剤）処
理した参考例１〜参考例３の銀被覆繊維状微粉末６．５
ｇとを乳鉢中で予備混合後、次に三本ロールにて混練
し、導電性一液型エポキシ樹脂組成物１〜３を得た。こ
の導電性一液型エポキシ樹脂組成物１〜３の硬化時間、
保存安定性、導電性を測定した。測定結果を表−１に示
した。Examples 1 to 3 Epicoat 807 (Oilized shell epoxy, bisphenol F type epoxy resin) 100 parts, dicyandiamide (Oilized shell epoxy) 8 parts, Amicure PN-23 (Ajinomoto, hardener) 3 parts The mixture was kneaded with a vacuum crusher for 10 minutes to obtain a one-pack type epoxy resin composition A. Silver coating fibrous fine powder 6.5 of Reference Example 1 to Reference Example 3 treated with 3.5 g of this resin composition A and 2% TTS (manufactured by Ajinomoto Co., Inc., titanate coupling agent) using a wet treatment method.
g was premixed in a mortar and then kneaded with a three-roll mill to obtain conductive one-pack type epoxy resin compositions 1 to 3. Curing time of the conductive one-pack type epoxy resin compositions 1 to 3,
Storage stability and conductivity were measured. The measurement results are shown in Table-1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】硬化時間の測定は熱板式ゲル化試験器（日
新化学製）を用い、保存安定性は粘度の経日変化を求め
て測定した。また、導電性はスクリーン印刷により４０
μｍの塗膜をポリイミドフィルム上に印刷し、ギャーオ
ーブンにて硬化させた後、表面抵抗計（三菱油化製）を
用いて測定した。The curing time was measured using a hot plate gelation tester (manufactured by Nisshin Chemical Co., Ltd.), and the storage stability was measured by determining the change with time of viscosity. The conductivity is 40 by screen printing.
A μm coating film was printed on a polyimide film, cured in a gear oven, and then measured using a surface resistance meter (manufactured by Mitsubishi Yuka).
【００２６】[0026]
【実施例４〜６】エピコート８２８（油化シェルエポキ
シ製、ビスフェノールＡ型エポキシ樹脂）１００部、Ｈ
Ｎ−５５００（日立化成工業製、酸無水物硬化剤）８５
部、アミキュアＭＹ−２４（味の素製、硬化剤）３部を
真空らい潰機にて１０分間混練し、一液型エポキシ樹脂
組成物Ｂを得た。この樹脂組成物Ｂ４０〜６０％と参考
例１の銀被覆繊維状微粉末６０〜４０％とを真空らい潰
機にて３分間混練し、導電性一液型エポキシ樹脂組成物
４〜６を得た。この導電性一液型エポキシ樹脂組成物４
〜６の硬化時間、保存安定性、導電性を測定した。測定
結果を表−１に示した。Examples 4 to 6 Epicoat 828 (Oilized shell epoxy, bisphenol A type epoxy resin) 100 parts, H
N-5500 (Hitachi Chemical Co., Ltd., acid anhydride curing agent) 85
Parts and 3 parts of Amicure MY-24 (manufactured by Ajinomoto Co., Inc., a curing agent) were kneaded with a vacuum crusher for 10 minutes to obtain a one-pack type epoxy resin composition B. 40-60% of this resin composition B and 60-40% of the silver-coated fibrous fine powder of Reference Example 1 were kneaded with a vacuum crusher for 3 minutes to obtain conductive one-pack type epoxy resin compositions 4-6. It was This conductive one-pack type epoxy resin composition 4
A curing time of ~ 6, storage stability, and conductivity were measured. The measurement results are shown in Table-1.
【００２７】[0027]
【実施例７】エピコート８０７（油化シェルエポキシ
製、ビスフェノールＦ型エポキシ樹脂）１００部、アミ
キュアＭＹ−２４（味の素製、硬化剤）２０部、ＫＢＭ
−４０３（信越シリコーン製、シランカップリング剤）
５．０部を真空らい潰機にて１０分間混練し、一液型エ
ポキシ樹脂組成物Ｃを得た。この樹脂組成物Ｃ３．０ｇ
と参考例３の銀被覆繊維状微粉末７．０ｇとを乳鉢中で
予備混合後、次に三本ロールにて混練し、導電性一液型
エポキシ樹脂組成物７を得た。この導電性一液型エポキ
シ樹脂組成物７の硬化時間、保存安定性、導電性を測定
した。測定結果を表−１に示した。Example 7 Epicoat 807 (Oilized Shell Epoxy, bisphenol F type epoxy resin) 100 parts, Amicure MY-24 (Ajinomoto, hardener) 20 parts, KBM
-403 (Shin-Etsu Silicone, silane coupling agent)
5.0 parts were kneaded with a vacuum crusher for 10 minutes to obtain a one-pack type epoxy resin composition C. This resin composition C 3.0 g
And 7.0 g of the silver-coated fibrous fine powder of Reference Example 3 were premixed in a mortar and then kneaded with a three-roll mill to obtain a conductive one-pack type epoxy resin composition 7. The curing time, storage stability, and conductivity of this conductive one-pack type epoxy resin composition 7 were measured. The measurement results are shown in Table-1.
【００２８】[0028]
【実施例８】実施例１の一液型エポキシ樹脂組成物Ａ
３．５ｇと湿式処理法を用いて２％ＴＴＳ（味の素製、
チタネートカップリング剤）処理した参考例４のパラジ
ウム被覆繊維状微粉末６．５ｇとを乳鉢中で予備混合
後、次に三本ロールにて混練し、導電性一液型エポキシ
樹脂組成物８を得た。この導電性一液型エポキシ樹脂組
成物８の硬化時間、保存安定性、導電性を測定した。測
定結果を表−１に示した。Example 8 One-pack type epoxy resin composition A of Example 1
2% TTS (made by Ajinomoto,
Titanate coupling agent) treated with 6.5 g of the palladium-coated fibrous fine powder of Reference Example 4 was premixed in a mortar and then kneaded with a three-roll to give a conductive one-pack type epoxy resin composition 8. Obtained. The curing time, storage stability, and conductivity of this conductive one-pack type epoxy resin composition 8 were measured. The measurement results are shown in Table-1.
【００２９】[0029]
【比較例１〜２】実施例１の一液型エポキシ樹脂組成物
Ａを２．５ｇ又は１．５ｇと銀粉（福田金属箔粉工業
製、Ａｇｃ−Ｂ）を７．５ｇ又は８．５ｇとを用いた以
外は実施例１と同様に行い、導電性一液型エポキシ樹脂
組成物１及び２を得た。この導電性一液型エポキシ樹脂
組成物１及び２の硬化時間、保存安定性、導電性を測定
した。測定結果を表−１に示した。[Comparative Examples 1 and 2] 2.5 g or 1.5 g of the one-pack type epoxy resin composition A of Example 1 and 7.5 g or 8.5 g of silver powder (Agc-B manufactured by Fukuda Metal Foil & Powder Co., Ltd.). In the same manner as in Example 1 except that was used, conductive one-pack type epoxy resin compositions 1 and 2 were obtained. The curing time, storage stability, and conductivity of the conductive one-pack type epoxy resin compositions 1 and 2 were measured. The measurement results are shown in Table-1.
【００３０】[0030]
【比較例３】エピコート８０７（油化シェルエポキシ
製、ビスフェノールＦ型エポキシ樹脂）３５部、参考例
１の銀被覆繊維状微粉末６５部とを乳鉢中で予備混合
後、次に三本ロールにて混練し、エポキシ樹脂組成物を
得た。この樹脂組成物にトリエチレンテトラミン（東洋
ソーダ製）３．５部を添加し、乳鉢中で均一に混練して
二液型の導電性エポキシ樹脂組成物３を得た。保存安定
性、導電性の測定結果を表−１に示した。[Comparative Example 3] 35 parts of Epicoat 807 (produced by oiled shell epoxy, bisphenol F type epoxy resin) and 65 parts of the silver-coated fibrous fine powder of Reference Example 1 were premixed in a mortar, and then three-rolled. And kneaded to obtain an epoxy resin composition. To this resin composition, 3.5 parts of triethylenetetramine (manufactured by Toyo Soda) was added and uniformly kneaded in a mortar to obtain a two-component conductive epoxy resin composition 3. Table 1 shows the results of measurement of storage stability and conductivity.
【００３１】[0031]
【比較例４】実施例１の一液型エポキシ樹脂組成物Ａを
２．０ｇと約１μｍのパラジウム粉（高純度化学研究所
製）を８．０ｇとを用いた以外は実施例１と同様に行
い、導電性一液型エポキシ樹脂組成物４を得た。この導
電性一液型エポキシ樹脂組成物４の硬化時間、保存安定
性、導電性を測定した。測定結果を表−１に示した。Comparative Example 4 The same as Example 1 except that 2.0 g of the one-pack type epoxy resin composition A of Example 1 and 8.0 g of palladium powder of about 1 μm (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were used. Then, a conductive one-pack type epoxy resin composition 4 was obtained. The curing time, storage stability, and conductivity of this conductive one-pack type epoxy resin composition 4 were measured. The measurement results are shown in Table-1.
【００３２】[0032]
【実施例９】実施例１、５、７の導電性一液型エポキシ
樹脂組成物、比較例１、２の導電性一液型エポキシ樹脂
組成物、比較例３の二液型導電性エポキシ樹脂組成物を
スクリーン印刷により線幅０．２５ｍｍ、ピッチ０．４
ｍｍの交差指型電極をポリイミドフィルム上に印刷し、
硬化させた。次に、この印刷面をＵＶ絶縁ペースト（ア
サヒ化学研究所製、ＵＶＦ１０Ｇ）で被覆し、硬化させ
てエレクトロマイグレーション試験を行った。エレクト
ロマイグレーション試験は６０℃、９５％の恒温恒湿雰
囲気下で３０Ｖの電圧を印可し、絶縁抵抗（抵抗値が１
０の６乗オーム以下となった場合）の経日変化を求めて
測定した。測定結果を表−２に示した。[Example 9] Conductive one-pack type epoxy resin composition of Examples 1, 5 and 7, conductive one-pack type epoxy resin composition of Comparative Examples 1 and 2, two-pack type conductive epoxy resin of Comparative Example 3 The composition was screen-printed to have a line width of 0.25 mm and a pitch of 0.4.
mm interdigitated electrodes are printed on the polyimide film,
Cured. Next, this printed surface was covered with a UV insulating paste (UVF10G, manufactured by Asahi Chemical Research Institute) and cured to carry out an electromigration test. In the electromigration test, a voltage of 30 V was applied in a constant temperature and humidity atmosphere of 60 ° C. and 95%, and insulation resistance (resistance value was 1
It was measured by obtaining the change over time in the case of 0 to the sixth power ohm or less). The measurement results are shown in Table-2.
【００３３】[0033]
【表２】 [Table 2]
【００３４】表−１及び表−２の実施例の結果より本発
明の導電性一液型エポキシ樹脂組成物は比較例に比べて
長期間の保存安定性と低添加量での導電性に優れ、また
エレクトロマイグレーション性にも優れていることが判
る。From the results of the examples in Tables 1 and 2, the conductive one-pack type epoxy resin composition of the present invention is superior in storage stability for a long period of time and conductivity at a low addition amount as compared with Comparative Examples. It is also found that the electromigration property is also excellent.
【００３５】[0035]
【発明の効果】本発明の導電性一液型エポキシ樹脂組成
物は、常温での貯蔵安定性に優れ、かつ従来の粉末又は
フレーク状の貴金属を配合した一液型エポキシ樹脂組成
物に比べ、貴金属被覆繊維状微粉末の配合量が少なくて
も安定した導電性が得られ、また種々の基板に導電層を
形成したり、各種電子部品及びリード線等の導電性を必
要とする部分に用いるとエレクトロマイグレーション
性、更には密着性に優れた導電性硬化物を与えるもので
ある。従って、一度に導電性樹脂組成物を調整して貯蔵
することができ、二液型のようにその都度煩雑な操作を
必要としない利点がある。EFFECT OF THE INVENTION The conductive one-pack type epoxy resin composition of the present invention has excellent storage stability at room temperature, and is superior to conventional one-pack type epoxy resin compositions containing powder or flake-shaped noble metal. Stable conductivity can be obtained even with a small amount of noble metal-coated fibrous fine powder, and it is used for forming conductive layers on various substrates and for parts that require conductivity such as various electronic parts and lead wires. And an electroconductive cured product having excellent electromigration property and adhesiveness. Therefore, the conductive resin composition can be prepared and stored at one time, and there is an advantage that a complicated operation is not required each time unlike the two-pack type.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/09 Ｄ 6921−4Ｅ (72)発明者 高橋 三雄 神奈川県川崎市川崎区鈴木町１−１ 味の 素株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication location H05K 1/09 D 6921-4E (72) Inventor Mitsuo Takahashi 1-Suzuki-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa 1 Central Research Institute of Ajinomoto Co., Inc.
Claims (3)
ポキシ樹脂、（Ｃ）固体分散型潜在性硬化剤を必須成分
とすることを特徴とする導電性一液型エポキシ樹脂組成
物1. A conductive one-pack type epoxy resin composition comprising (A) a noble metal-coated fibrous fine powder, (B) an epoxy resin, and (C) a solid dispersion type latent curing agent as essential components.
ることを特徴とする請求項１記載の導電性一液型エポキ
シ樹脂組成物。2. The conductive one-pack type epoxy resin composition according to claim 1, wherein the noble metal of the noble metal-coated fibrous fine powder is silver.
又はアルミニウム系カップリング剤等のカップリング剤
を含むことを特徴とする請求項１及び請求項２記載の導
電性一液型エポキシ樹脂組成物。3. The conductive one-pack type epoxy resin composition according to claim 1, further comprising a coupling agent such as a silane-based, titanate-based, zirconium-based or aluminum-based coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31964892A JPH06157876A (en) | 1992-11-30 | 1992-11-30 | Conductive one-pack epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31964892A JPH06157876A (en) | 1992-11-30 | 1992-11-30 | Conductive one-pack epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06157876A true JPH06157876A (en) | 1994-06-07 |
Family
ID=18112648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31964892A Pending JPH06157876A (en) | 1992-11-30 | 1992-11-30 | Conductive one-pack epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06157876A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1114852A3 (en) * | 2000-01-07 | 2001-11-07 | Matsushita Electric Industrial Co., Ltd. | Conductive adhesive and connection structure using the same |
| EP1275674A4 (en) * | 2000-04-21 | 2003-08-06 | Mitsubishi Rayon Co | Epoxy resin composition and prepreg made with the epoxy resin composition |
| WO2006028205A1 (en) * | 2004-09-10 | 2006-03-16 | Mitsui Mining & Smelting Co., Ltd. | Conductive paste and flexible printed wiring board obtained by using the conductive paste |
| WO2006090794A1 (en) * | 2005-02-23 | 2006-08-31 | Asahi Kasei Chemicals Corporation | Latent hardener for epoxy resin and epoxy resin composition |
| WO2013010492A1 (en) * | 2011-07-20 | 2013-01-24 | Henkel (China) Company Limited | Conductive adhesive for capacitor and the corresponding capacitors |
| JP2014510803A (en) * | 2011-02-11 | 2014-05-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Conductive adhesive comprising at least one metal precursor |
| WO2014192839A1 (en) * | 2013-05-28 | 2014-12-04 | 株式会社ダイセル | Curable composition for sealing optical semiconductor |
| WO2023112667A1 (en) * | 2021-12-13 | 2023-06-22 | パナソニックＩｐマネジメント株式会社 | Electronic component |
-
1992
- 1992-11-30 JP JP31964892A patent/JPH06157876A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1114852A3 (en) * | 2000-01-07 | 2001-11-07 | Matsushita Electric Industrial Co., Ltd. | Conductive adhesive and connection structure using the same |
| EP1275674A4 (en) * | 2000-04-21 | 2003-08-06 | Mitsubishi Rayon Co | Epoxy resin composition and prepreg made with the epoxy resin composition |
| WO2006028205A1 (en) * | 2004-09-10 | 2006-03-16 | Mitsui Mining & Smelting Co., Ltd. | Conductive paste and flexible printed wiring board obtained by using the conductive paste |
| JP2006080013A (en) * | 2004-09-10 | 2006-03-23 | Mitsui Mining & Smelting Co Ltd | Conductive paste and flexible printed wiring board formed by using it |
| WO2006090794A1 (en) * | 2005-02-23 | 2006-08-31 | Asahi Kasei Chemicals Corporation | Latent hardener for epoxy resin and epoxy resin composition |
| JP2014510803A (en) * | 2011-02-11 | 2014-05-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Conductive adhesive comprising at least one metal precursor |
| US10000671B2 (en) | 2011-02-11 | 2018-06-19 | Henkel Ag & Co. Kgaa | Electrically conductive adhesives comprising at least one metal precursor |
| WO2013010492A1 (en) * | 2011-07-20 | 2013-01-24 | Henkel (China) Company Limited | Conductive adhesive for capacitor and the corresponding capacitors |
| WO2014192839A1 (en) * | 2013-05-28 | 2014-12-04 | 株式会社ダイセル | Curable composition for sealing optical semiconductor |
| US9685597B2 (en) | 2013-05-28 | 2017-06-20 | Daicel Corporation | Curable composition for sealing optical semiconductor |
| WO2023112667A1 (en) * | 2021-12-13 | 2023-06-22 | パナソニックＩｐマネジメント株式会社 | Electronic component |
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