JP3915779B2 - Conductive resin composition and electronic component using the same - Google Patents

Description

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立に水素、低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、Ｘ^１は単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ_２−、−ＳＯ−、

を表し、ここでＲ^５およびＲ^６はそれぞれ独立に水素、低級アルキル基、トリフルオロメチル基、トリクロロメチル基またはフェニル基を表し、Ｙは、

を表し、ここで、Ａｒ^１は芳香族の２価の基を、Ａｒ^２は芳香族の３価の基を、Ａｒ^３は芳香族の４価の基を表す。）
一般式（ＩＩ）：

（式中、Ｒ^７、Ｒ^８およびＲ^９はそれぞれ独立に低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、ｓ，ｔおよびｕはそれぞれ独立に置換基数を示す０〜４の整数であり、Ｒ^７、Ｒ^８およびＲ^９はそれぞれが複数個結合しているときは、各々において同一でも異なってもよく、Ｘ^２およびＸ^３はそれぞれ独立に−Ｏ−または

を表し、ここでＲ^１０およびＲ^１１はそれぞれ独立に水素原子、低級アルキル基、トリフルオロメチル基、トリクロロメチル基またはフェニル基を示し、Ｙは、上記一般式（Ｉ）における定義と同じである。）
上記一般式（Ｉ）および（ＩＩ）において、低級アルキル基、低級アルコキシ基は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基であることが好ましい。上記一般式（Ｉ）および（ＩＩ）のＲ^５、Ｒ^６、Ｒ^１０、Ｒ^１１のフェニル基は、無置換であっても、メチル基、エチル基、スルホン基等の任意の置換基により置換されていてもよい。
上記一般式（Ｉ）で表される繰り返し単位は、下記一般式（ＩＩＩ）に示すように、互いに１，４−位でベンゼン環が結合したものであることが好ましい。

上記一般式（ＩＩ）で表される繰り返し単位も、同様に、下記一般式（ＩＶ）に示すように、互いに１，４−位でベンゼン環が結合したものであることが好ましい。

上記の繰り返し単位を有する熱可塑性樹脂（Ｂ１）は、以下に説明する酸成分（Ｓ）、すなわち芳香族ジカルボン酸、芳香族トリカルボン酸、芳香族テトラカルボン酸またはこれらの反応性酸誘導体と、以下に説明するジアミンとを反応させて製造することができる。酸成分およびジアミンは、それぞれ、複数種を組み合わせて使用してもよい。
上記の一般式（Ｉ）および（ＩＩＩ）で表される繰り返し単位は、ジアミンとしてたとえば、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３，５−ジメチル−４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３，５−ジブロモ−４−（４−アミノフェノキシ）フェニル］ブタン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］プロパン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］シクロヘキサン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］シクロペンタン、ビス［４−（４−アミノフェノキシ）フェニル］スルフォン、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（３−アミノフェノキシ）フェニル］スルフォン、４，４’−カルボニルビス（ｐ−フェニレンオキシ）ジアニリン、４，４’−ビス（４−アミノフェノキシ）ビフェニル等の１種以上を用いて形成することが好ましい。これらの中では、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパンが特に好ましい。
上記の一般式（ＩＩ）および（ＩＶ）で表される繰り返し単位は、ジアミンとしてたとえば、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−［１，３−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、３，３’−［１，３−フェニレンビス（１−メチルエチリデン）］ビスアニリン等の１種以上を用いて形成することが好ましい。
一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）、（ＩＶ）の繰り返し単位を形成するに当たり、例示の上記ジアミン以外にも、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノ−３，３’，５，５’−テトラメチルジフェニルエーテル、４，４’−ジアミノ−３，３’，５，５’−テトラメチルジフェニルメタン、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルエーテル、２，２’−［４，４’−ジアミノ−３，３’，５，５’−テトラメチルジフェニル］プロパン、メタフェニレンジアミン、パラフェニレンジアミン、３，３’−ジアミノジフェニルスルフォン、ピペラジン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、テトラメチレンジアミン、ｐ−キシレンジアミン、ｍ−キシレンジアミン、ｏ−キシレンジアミン、３−メチルヘプタメチレンジアミン、１，３−ビス（３−アミノプピル）テトラメチルジシロキサン等の１種以上を併用することができる。
芳香族ジカルボン酸は、芳香族環に２個のカルボキシル基が結合したカルボン酸である。芳香族トリカルボン酸は、芳香族環に３個のカルボキシル基が結合したカルボン酸であり、３個のカルボキシル基のうち２個は隣接炭素原子に結合しているものが好ましい。芳香族テトラカルボン酸は芳香族環に４個のカルボキシル基が結合したカルボン酸であり、４個のカルボキシル基のうち２個ずつは隣接炭素原子に結合しているものが好ましい。ここで、芳香族環はヘテロ原子が導入されたもの（芳香族複素環）でもよく、あるいは芳香族環同士がアルキレン基、酸素、単結合、カルボニル基等を介して結合されてもよい。さらに、これらの芳香族環は、アルコキシ基、アリルオキシ基、アルキルアミノ基、ハロゲン等の縮合反応に関与しない置換基を含んでいてもよい。
芳香族ジカルボン酸としては、たとえばテレフタル酸、イソフタル酸、４，４’−ジフェニルエーテルジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、４，４’−ジフェニルジカルボン酸、１，５−ナフタレンジカルボン酸等を挙げることができるが、テレフタル酸とイソフタル酸が入手容易で廉価であることから好ましい。芳香族ジカルボン酸の反応性誘導体とは、上記の芳香族ジカルボン酸のジハイドライドあるいはジブロマイド、ジエステル等を意味する。
芳香族トリカルボン酸としては、トリメリット酸、３，３’，４−ベンゾフェノントリカルボン酸、２，３，４’−ジフェニルトリカルボン酸、２，３，６−ピリジントリカルボン酸、３，４，４’−ベンズアニリドトリカルボン酸、１，４，５−ナフタリントリカルボン酸、２’−クロロ−３，４，４’−ベンズアニリドトリカルボン酸等が好ましい。芳香族トリカルボン酸の反応性誘導体とは、上記の芳香族トリカルボン酸の酸無水物、ハライド、エステル、アミド、アンモニウム塩などを意味する。具体的には、トリメリット酸無水物、トリメリット酸無水物モノクロライド、１，４−ジカルボキシ−３−Ｎ，Ｎ−ジメチルカルバモイルベンゼン、１，４−ジカルボメトキシ−３−カルボキシベンゼン、１，４−ジカルボキシ−３−カルボフェノキシベンゼン、２，６−ジカルボキシ−３−カルボメトキシピリジン、１，６−ジカルボキシ−５−カルバモイルナフタリン、上記芳香族トリカルボン酸塩類とアンモニア、ジメチルアミン、トリメチルアミン等からなるアンモニウム塩などが好適例として挙げられる。これらのうち、トリメリット酸無水物およびトリメリット酸無水物モノクロライドが、入手容易で廉価であるため好ましい。
芳香族テトラカルボン酸としては、たとえば、ピロメリット酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸、３，３’，４，４’−ビフェニルテトラカルボン酸、１，２，５，６−ナフタレンテトラカルボン酸、２，３，６，７−ナフタレンテトラカルボン酸、２，３，５，６−ピリジンテトラカルボン酸、１，４，５，８−ナフタレンテトラカルボン酸、３，４，９，１０−ペリレンテトラカルボン酸、４，４’−スルホニルジフタル酸、ｍ−ターフェニル−３，３”，４，４”−テトラカルボン酸、ｐ−ターフェニル−３，３”，４，４”−テトラカルボン酸、４，４’−オキシジフタル酸、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（２，３−ジカルボキシフェニル）プロパン、２，２−ビス（２，３−ジカルボキシフェニル）プロパン、２，２−ビス（３，４−ジカルボキシフェニル）プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２’−ビス［４−（２，３−ジカルボキシフェノキシ）フェニル］プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２’−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］プロパン等が好ましい。芳香族テトラカルボン酸の反応性誘導体とは、上記の芳香族テトラカルボン酸の酸二無水物、ハライド、エステル、アミド、アンモニウム塩などを意味する。
芳香族ジカルボン酸、芳香族トリカルボン酸、芳香族テトラカルボン酸またはこれらの反応性誘導体からなる酸成分（Ｓ）は、得られる重合体の分子量、機械強度、耐熱性などの観点から、ジアミンの総量１００モル％に対して総量で８０〜１２０モル％使用するのが好ましく、特に９５〜１０５モル％使用するのが好ましい。
組成物Ｍおよび組成物Ｎにおいては、バインダー樹脂として、形成される塗膜の耐熱性の向上および低弾性率化等の観点から、ポリアミドシリコーン樹脂、ポリアミドイミドシリコーン樹脂およびポリイミドシリコーン樹脂から選ばれた熱可塑性樹脂（Ｂ２）が用いられる。この熱可塑性樹脂（Ｂ２）は、複数種を組み合わせて用いることもできる。
これらの熱可塑性樹脂（Ｂ２）は、特に限定はされないが、たとえば、芳香族ジカルボン酸、芳香族トリカルボン酸、芳香族テトラカルボン酸またはそれらの反応性誘導体等の酸成分とジアミノシリコーンを必須成分とするジアミンとを重縮合させて得ることができる。
ジアミノシリコーンとしてはたとえば、下記一般式（Ｖ）：

（式中、Ｙ^１は二価の炭化水素基、Ｙ^２は一価の炭化水素基を表し、２個のＹ^１は互いに同一でも異なっていてもよく、複数個のＹ^２は互いに同一でも異なっていてもよく、ｍは１以上の整数である。）
で表されるものを使用することが好ましい。
Ｙ^１で示される二価の炭化水素基としては、たとえば炭素原子数が１〜１０のアルキレン基、置換または無置換のフェニレン基などが挙げられ、Ｙ^２で示される一価の炭化水素基としては、炭素原子数が１〜１０のアルキル基、置換または無置換のフェニル基などが挙げられ、ｍは１〜１００の整数であることが好ましい。これらのジアミノシリコーンは、単独で、または２種以上を組み合わせて用いられる。
上記ジアミノシリコーンと共に使用することができる、その他のジアミンとしては、特に制限はないが、樹脂の耐熱性、有機溶剤への溶解性および溶解粘度等の観点から芳香族ジアミンを用いることが好ましく、さらには、主鎖にフェニレンエーテルを含むポリフェニレンエーテルジアミンを用いることが好ましい。
具体的には、下記一般式（ＶＩ）で表される芳香族ジアミンを用いることがより好ましい。

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立に水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシル基またはハロゲン原子を表し、Ｘ^１は単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ_２−、−ＳＯ−、

を表し、ここで、Ｒ^５およびＲ^６はそれぞれ独立して水素、炭素数１〜４の低級アルキル基、トリフルオロメチル基、トリクロロメチル基、または、置換または無置換のフェニル基を表す）。
上記一般式（ＶＩ）のポリフェニレンエーテルジアミンは、好ましくは、下記一般式（ＶＩＩ）に示すように、互いに１，４−位でベンゼン環が結合したものであることが好ましい。

上記一般式（ＶＩ）で表されるエーテル結合を有する芳香族ジアミン（ｅ１）としては、たとえば、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３，５−ジメチル−４−（４−アミノフェノキシ）フェニル］ブタン、２，２−ビス［３，５−ジブロモ−４−（４−アミノフェノキシ）フェニル］ブタン、１，１，１，３，３−ヘキサフルオロ−２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］プロパン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］シクロヘキサン、１，１−ビス［４−（４−アミノフェノキシ）フェニル］シクロペンタン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、４，４’−カルボニルビス（ｐ−フェニレンオキシ）ジアニリン、４，４’−ビス（４−アミノフェノキシ）ビフェニル等が挙げられ、これらは単独で、または組み合わせて用いられる。これらのうちでは、２，２−ビス［（４−アミノフェノキシ）フェニル］プロパンが好ましい。
上記（ｅ１）を除いた芳香族ジアミン（ｅ２）として、たとえば１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４−４’−［１，３−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、３，３’−［１，３−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−ジアミノフェニルエーテル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノ−３，３’、５，５’−テトラメチルジフェニルエーテル、４，４’−ジアミノ−３，３’，５，５’−テトラジメチルフェニルメタン、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルエーテル、２，２−［４，４’−ジアミノ−３，３’，５，５’−テトラメチルジフェニル］プロパン、メタフェニレンジアミン、パラフェニレンジアミン、３，３’−ジアミノジフェニルスルホン、ｏ−キシリレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン等が挙げられ、これらは単独で、または組合せて使用することができる。
上記（ｅ１）および（ｅ２）以外のジアミン、すなわち脂肪族または脂環式ジアミン（ｅ３）としては、たとえば、ピペラジン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、テトラメチレンジアミン、３−メチルヘプタメチレンジアミン等が挙げられ、これらは単独で、または組合せて使用することができる。
熱可塑性樹脂（Ｂ２）を合成するために上記ジアミノシリコーンを必須成分とするジアミンとさせる酸成分としては、上述の樹脂（Ｂ１）の合成において用いられる上記酸成分（Ｓ）を同様に好ましく使用することができる。これらの芳香族ジカルボン酸、芳香族トリカルボン酸、芳香族テトラカルボン酸またはこれらの反応性誘導体からなる酸成分（Ｓ）は、得られる重合体の分子量、機械強度、耐熱性などの観点から、ジアミンの総量１００モル％に対して総量で８０〜１２０モル％使用するのが好ましく、特に９５〜１０５モル％使用するのが好ましい。
組成物Ｋにおいて、導電性粉末（Ａ１）と熱可塑性樹脂（Ｂ１）の混合比率は得に限定されるものではないが、形成される塗膜の導電性等の観点から、（Ａ１）成分１００重量部に対して、（Ｂ１）成分が２〜２５重量部であることが好ましく、４〜１４重量部がより好ましい。
組成物Ｌにおいて、導電性粉末（Ａ２）と熱可塑性樹脂（Ｂ１）の混合比率は得に限定されるものではないが、形成される塗膜の導電性等の観点から、（Ａ２）成分１００重量部に対して、（Ｂ１）成分が２〜２５重量部であることが好ましく、４〜１４重量部がより好ましい。
組成物Ｍにおいて、導電性粉末（Ａ１）と熱可塑性樹脂（Ｂ２）の混合比率は得に限定されるものではないが、塗膜強度、靱性および導電性等の観点から、（Ａ１）成分１００重量部に対して、（Ｂ２）成分が２〜２５重量部であることが好ましく、４〜１４重量部がより好ましい。
組成物Ｎにおいて、導電性粉末（Ａ２）と熱可塑性樹脂（Ｂ２）の混合比率は得に限定されるものではないが、塗膜のフレキシブル性、導電性等の観点から（Ａ）成分１００重量部に対して、（Ｂ）成分が２〜２５重量部であることが好ましく、４〜１４重量部がより好ましい。
組成物Ｋ、Ｌ、Ｍ、Ｎに使用される有機溶剤（Ｃ）としては、ベンゼン、トルエン、キシレン等の芳香族溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル系溶剤；酢酸エチル、酢酸−ｎ−プロピル、酢酸イソプロピル、酢酸−ｎ−ブチル、エチレングリコールモノメチルエーテルアセタート、エチレングリコールモノエチルエーテルアセタート、エチレングリコールモノブチルエーテルアセタート、ジエチレングリコールモノメチルエーテルアセタート、ジエチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテルアセタート、プロピレングリコールモノエチルエーテルアセタート、γ−ブチロラクトン等のエステル系溶剤；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド系溶剤が挙げられる。これらの溶剤は、ペースト作製時の樹脂の溶解またはペーストの粘度調整に用いられ、単独でまたは２種以上組み合わせて用いられる。
有機溶剤（Ｃ）の添加量は、樹脂の溶解性、ペーストとした場合の粘度、導電性粉末の分散性および塗膜形成能等の観点から、熱可塑性樹脂１００重量部に対して、一般に７５〜４６００重量部の範囲で用いられ、好ましくは１２５〜３０６０重量部とされる。
以上のような配合成分を含む各組成物は、たとえば、各成分をらいかい機、３本ロール、ボールミル、ディスパー等で混練分散することにより製造することができる。導電性粉末（フィラー）の分散性および塗布性を向上させるために、分散剤やカップリング剤を添加してもよい。
分散剤としては、たとえば、炭素数１６〜２０のパルチミン酸、ステアリン酸等の飽和脂肪酸；炭素数１６〜１８のオレイン酸、リノレン酸等の不飽和脂肪酸；これらの飽和／不飽和脂肪酸のナトリウム、カリウム、カルシウム、亜鉛、銅等との金属塩、の１種以上を好ましく用いることができる。分散剤の配合量は、導電性粉末の分散性、塗膜の導電性、塗膜と基材との密着性の観点から、樹脂１００重量部に対して０．２〜２４０重量部であることが好ましく、２〜１２０重量部の範囲がより好ましい。
カップリング剤としては、たとえば、ビニルメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等のシランカップリング剤や、チタネート系カップリング剤、アルミネート系カップリング剤、ジルコアルミネート系カップリング剤等が使用でき、上記の熱可塑性樹脂１００重量部に対して３０重量部以下の添加量で添加することが好ましい。
本発明に係る組成物は、各種電子部品の導電体層、たとえば導電回路や電極材料として好適に使用することができる。
本発明に係る電子部品は、本発明に係る組成物を用いて形成された導電体層を有するものである。各種電子部品としては、電極材料としてこの組成物を用いたアルミ電解コンデンサ、タンタル固体電解コンデンサ、セラミックコンデンサ等；スクリーン印刷によって本発明の組成物からなる導電回路がその上に形成された各種基板；本発明の組成物からなる導電回路がアンテナ用回路として形成されたＩＣカード等が挙げられる。なかでも、陽極に弁作用金属を用いた固体電解コンデンサの陰極材料として、本発明の組成物を好適に用いることができる。
そこで、本発明の電子部品は、好ましくは、弁作用金属からなる陽極基体上に、誘電体酸化膜と、固体電解質層と、本発明の組成物を用いて形成された導電体層を含む陰極層とが形成された固体電解コンデンサである。
Ｆｉｇ．１にその一例が示されているように、固体電解コンデンサ１０は、陽極線１が埋め込まれた陽極基体２と、陽極基体２上に順次形成された誘電体酸化膜（陽極酸化被膜）３と、固体電解質層（半導体層）４と、カーボン層５１および導電体層５２とからなる陰極層５と、を含むコンデンサ素子を備えている。陽極基体２には、タンタル、アルミニウム、チタン、ニオブ等の弁作用金属を用いることが好ましい。陽極基体２の形状は、箔状、板状あるいは棒状であることが好ましい。この陽極基体２は、タンタルリード等の陽極線１を埋め込んだ形で、上記弁作用金属粉末を圧縮成型し、真空中、２０００℃程度の温度で数１０分間加熱して焼結体とすることで形成される。
次に、得られた焼結体（陽極基体２）を、硝酸やリン酸等の化成液中で、電圧を印加して化成し、陽極基体２の表面に、Ｔａ_２Ｏ_５等の誘電体酸化膜３を形成する。この酸化膜３は、陽極基体金属自体の酸化物からなる層であることが好ましいが、陽極基体とは別の誘電体酸化物の層であってもよい。誘電体酸化膜３を形成後、焼結体を硝酸マンガン溶液等の半導体母液中に浸漬して液を含浸させ、２００℃〜３５０℃の温度で焼成して、熱分解により焼結体内部（焼結体の表面）に二酸化マンガン層等を主とした固体電解質層４を形成する。熱分解後、再化成して焼結により損傷した誘電体酸化膜３を修復する。以上の浸漬、焼成および再化成の工程を必要に応じて５〜１０回繰り返して、所望の厚さの固体電解質層４を形成する。この固体電解質層は、有機半導体といわれるＴＣＮＱ（７，７，８，８−テトラシアノキノジメタン）錯体や導電性高分子であるポリピロール、ポリチオフェン、ポリアニリン等を用いて形成することもできる。
固体電解質層４を形成後、カーボンペーストを塗布し乾燥させて、陰極層５の一部としてのカーボン層５１を形成し、その上に、陰極層のさらに別な一部としての導電体層（銀層あるいは銀ペースト層）５２を、本発明の組成物を用いて形成する。得られた導電体層５２に、陰極取り出し用のリードフレーム７を、はんだまたは導電性接着剤６等を用いて接続し、一方、焼結体２から引き出した陽極線１をリードフレーム７等に溶接する。最後に全体を、樹脂ディップ法や樹脂モールド法等により外装樹脂８で封止外装する。このようにして得られる固体電解コンデンサは、一般的には、縦２〜７ｍｍ、横１．２５〜４．３ｍｍ、高さ１．２〜２．８ｍｍ程度の大きさのものである。
次に、本発明を実施例によりさらに詳しく説明する。以下の実施例における各種特性の測定および評価方法は、以下のとおりである。
［アスペクト比］
低粘度のエポキシ樹脂（ビューラー社製）の主剤（Ｎｏ．１０−８１３０）８ｇと硬化剤（Ｎｏ．１０−８１３２）２ｇを混合し、ここへ測定すべき粉体２ｇを混合して良く分散させ、そのまま３０℃で真空脱泡した後、１０時間３０℃で静置して粒子を沈降させ、樹脂を硬化させた。その後、得られた硬化物を垂直方向に切断し、切断面を電子顕微鏡で１０００倍に拡大して、切断面に現れた１５０個の粒子について長径／短径を求め、それらの平均値をもって、アスペクト比とした。
［平均粒径］
マスターサイザー（マルバン社製）を用いて、粉体の平均粒径を測定した。
［銅露出面積］
作製した鍍銀銅粉の粒子を無作為に５個取り出し、走査型オージェ電子分光分析装置で観察したオージェ像から貴金属（銀）および非貴金属（銅）の定量分析を行って銅占有比率を計算し、測定粒子５個の平均値を銅露出面積（％）とした。
［ペースト粘度］
東京計器製Ｅ型粘度計の３°コーンを用い、恒温層内の温度を２５℃に設定し、測定開始から１０分後の値をペーストの粘度とした。
［ペースト粘度の経時変化］
ペースト作製後、３０℃の恒温槽内に６ヶ月間放置し、その後粘度測定を行った。
［体積抵抗率］
ペーストを用いて得られた乾燥塗膜の体積抵抗率を、ダブルブリッジ式抵抗測定器（横河電気社製 ＴＹＰＥ２７６９）により測定した。
［マイグレーション特性］
体積抵抗率の測定に用いた乾燥塗膜を用い、乾燥塗膜の中央に間隔２ｍｍの電極を形成し、電極全体を覆うように純水を滴下した後、両端に７Ｖの電圧を印加し、銀が移行して電極間が短絡するまでの時間を測定することにより、マイグレーション特性を評価した。
［エッジカバーリング性］
１ｍｍ×１ｍｍ×１．５ｍｍの立方体状のタンタル焼結体を、測定すべきペースト中に浸漬し、乾燥した。得られた素子を透明なエポキシ樹脂で外装し、室温で１０時間放置して硬化させた。その後、ダイヤモンドカッターで立方体の長辺中央部を切断して、サンドペーパおよび研磨粒子を用いて研磨し、評価用素子とした。評価用素子における四隅のペーストのカバーリング状態を電子顕微鏡にて観察した。評価Ａ：良好、Ｂ：エッジ部の塗膜厚が１μｍ以下、Ｃ：エッジ部に欠損部あり
［塗膜強度］
テフロン板上にアプリケータを用いて、１８０℃、１時間乾燥後の膜厚が５０μｍになるように銀フィルムを作製した。フィルムをテフロン板から引き剥がし、幅５ｍｍ×４０ｍｍの短冊状の試験片を作製した。
その後、引張強度試験機（今田製作所製：引張圧縮試験器 ＳＬ−２００１）を用いて、塗膜強度を測定した。
［塗膜のフレキシブル性］
厚さ１２５μｍ、幅１ｃｍ、長さ１０ｃｍのＰＥＴフィルム上に２ミリ幅でペーストを塗布し、１８０℃、１時間乾燥した後、フィルムの端と端の表面同士を接触させ、次に裏面同士を接触させる操作を繰り返し行い、何回目に塗膜に亀裂が入るかを測定した。
［コンデンサ特性］
ＪＩＳ Ｃ ５１０２−１９９４（電子機器用固定コンデンサの試験方法）に従い、タンタルコンデンサの特性を測定した。等価直列抵抗（ＥＳＲ）はＬＣＲメータを用いて測定した。漏れ電流（ＬＣ）については、デジタル微少電流計（アドバンテスト；Ｒ８３４０Ａ）を用い、測定すべきペーストを導電体層に用いてタンタルコンデンサを作製し、８５℃８５％ＲＨ雰囲気下で１０００ｈおよび２０００ｈ放置した時の値を測定した。ｔａｎδ、インピーダンスは、ヒューレットパッカード社製ＬＣＲメータ（４２８４Ａ）を用いて測定した。Ｃａｐ（静電容量）は、ＬＣＲメータ（ヒューレットパッカード製 ４２８４Ａ）を用いて測定した。
［コンデンサの過電圧負荷特性］
タンタルコンデンサの定格電圧に対し、過電圧を印加し、その後のコンデンサ特性を測定し、コンデンサの破壊数を確認した。
［はんだ接着性］
幅１ｃｍ、長さ２ｃｍ、厚さ０．５ｍｍのアルミ板を、測定すべきペースト中に１ｃｍ浸漬させて引き上げ、オーブン乾燥機で１８０℃１時間乾燥し、評価用の試料を作成した。評価用試料をフラックスに浸漬させた後、各設定温度のはんだ浴に浸漬させ、はんだの接着状態を観察した。はんだのコーティング面積が８０％以上のものをＡ、５０％以上８０％未満のものをＢ、３０％以上５０％未満のものをＣ、３０％未満のものをＤとして評価した。

［コンデンサのはんだ耐熱性］
タンタルコンデンサをはんだ浴に１０秒浸漬した後の容量変化率を測定した。はんだ浴温度：２３０℃、２６０℃、２９０℃
［コンデンサの耐熱衝撃性］
タンタルコンデンサを熱衝撃試験器に投入し、その１０００サイクルごとに取り出してコンデンサ特性の測定を行った。熱衝撃条件は−５０℃〜８０℃で行った。すなわち、−５０℃の槽で３０分間放置後、３分以内に８０℃の槽に移して３０分間放置し、その後３分以内に−５０℃の槽に移す。これを１サイクルとした。
＜熱可塑性樹脂（Ｂ１）の合成例１＞
ジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）１００ｇ（０．２４モル）を用い、これを、温度計、撹拌機、窒素導入管および冷却管を装着した１リットル四つ口フラスコ中、窒素ガス雰囲気下で、Ｎ−メチル−２−ピロリドン４００ｇに溶解した。得られた溶液を−１０℃に冷却し、溶液の温度が−５℃を超えないようにして、イソフタル酸ジクロライド４９．５ｇ（０．２４モル）を添加した、その後、プロピレンオキシド５６．６ｇを添加し、室温で３時間撹拌した。反応液を純水中に投入して重合体を単離し、乾燥した後、再びＮ−メチル−２−ピロリドンに溶解し、得られた溶液を純水中に投入して、ポリアミド重合体を精製した。
＜熱可塑性樹脂（Ｂ１）の合成例２＞
ジアミンとして２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン２０５ｇ（５００ミリモル）を用い、これを、温度計、攪拌機、窒素導入管および冷却管を装着した３リットルの四つ口フラスコ中、窒素ガス雰囲気化で、ジエチレングリコールジメチルエーテル１１１７７ｇに溶解した。得られた溶液を−１０℃に冷却し、溶液の温度が−５℃を超えないようにして、トリメリット酸無水物モノクロライド１０５．３ｇを添加した。その後、プロピレンオキシド８７ｇを添加し、室温で３時間撹拌し、反応液の粘度が上昇し液が透明になったところで、ジエチレングリコールジメチルエーテル８４１ｇを追加し、更に１時間撹拌した。その後、無水酢酸１２８ｇおよびピリジン６４ｇを加え、６０℃で１昼夜撹拌を続けた。得られた反応液をメタノール２５０ｇ中に投入してポリアミドイミド重合体を単離させた。これを乾燥した後、Ｎ，Ｎ−ジメチルホルムアミミドに再度溶解し、メタノール中に投入してポリアミドイミド重合体の生成物を得た。
＜熱可塑性樹脂（Ｂ２）の合成例１＞
温度計、攪拌機、窒素導入管および冷却管を装着した四つ口フラスコ中に、窒素ガス雰囲気下で、ジアミンとして２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン６５．６ｇ（１６０ミリモル）、および、前記一般式（Ｖ）で示されるジアミノシロキサン（信越化学工業（株）製、Ｘ−２２−１６１Ｂ；一般式（Ｖ）において、ｍ＝３８、Ｙ^１＝−Ｃ_３Ｈ_６−、Ｙ^２＝−ＣＨ_３）６４ｇ（４０ミリモル）（モル比で８０モル％／２０モル％）を入れ、ジエチレングリコールジメチルエーテル３３５ｇに溶解した。
得られた溶液を−１０℃に冷却し、溶液の温度が−５℃を越えないようにしてイソフタル酸ジクロライド４０．６ｇ（２００ミリモル）を添加した。その後、プロピレンオキシド２３．２ｇを添加し、ジエチレングリコールジメチルエーテル９６ｇを追加し、室温で３時間攪拌した。反応液をメタノール中に投入して重合体を単離し、これを乾燥した後、再びジメチルホルムアミドに溶解し、これをメタノール中に投入してポリアミドシリコーン共重合体を精製した。
＜熱可塑性樹脂（Ｂ２）の合成例２＞
温度計、攪拌機、窒素導入管および冷却管を装着した四つ口フラスコに、窒素ガス雰囲気下で、ジアミンとして２，２ビス［４−（４−アミノフェノキシ）フェニル］プロパン１７４．３ｇ（４２５ミリモル）、および、ジアミノプロピルテトラメチルジシロキサン１８．６ｇ（信越化学工業（株）製、ＬＰ７１００）（７５ミリモル）（モル比で８５モル％／１５モル％）を入れ、ジエチレングリコールジメチルエーテル１１７７ｇに溶解した。
得られた溶液を−１０℃に冷却し、溶液の温度が−５℃を超えないようにして、トリメリット酸無水物モノクロライド１０５．３ｇ（５００ミリモル）を添加した。その後、プロピレンオキシド８７ｇを添加し、室温で３時間攪拌して、反応液の粘度が上昇し、液が透明になったところでジエチレングリコールジメチルエーテル８４１ｇを追加し、さらに１時間攪拌した。その後、無水酢酸１２８ｇおよびピリジン６４ｇを加え、６０℃で１昼夜攪拌した。得られた反応液をｎ−ヘキサン／メタノール＝１／１（重量比）の大量の混合溶剤中に投入して、重合体を単離させ、これを乾燥した後、Ｎ，Ｎ−ジメチルホルムアミドに溶解し、メタノール中に投入してポリアミドイミドシリコーン共重合体を精製し、減圧乾燥した。
＜鍍銀銅粉（ａ１）の作製例＞
アトマイズ法で作製した平均粒径５．１μｍの球状銅粉（日本アトマイズ加工（株）製、商品名ＳＦＲ−Ｃｕ）を希塩酸および純水で洗浄した後、水１リットル当たりＡｇＣＮ ８０ｇおよびＮａＣＮ ７５ｇ含むめっき溶液で、球状銅粉に対して銀の量が１５重量％になるように置換めっきを行い、水洗、乾燥して鍍銀銅粉を得た。
２リットルのボールミル容器内に、得られた鍍銀銅粉７５０ｇおよび直径５ｍｍのジルコニアボール３ｋｇを投入し、４０分間回転させて、アスペクト比が平均１．３、長径の平均粒径が５．５μｍの鍍銀銅粉を得た。
＜鍍銀銅粉（ａ２）の作製例＞
アトマイズ法で作製した平均粒径５．１μｍの球状銅粉（日本アトマイズ加工（株）製、商品名ＳＦＲ−Ｃｕ）を希塩酸および純水で洗浄した後、水１リットルあたりＡｇＣＮ ８０ｇおよびＮａＣＮ ７５ｇ含むめっき溶液を用いて、球状銅粉に対して銀の量が２０重量％になるように置換めっきを行い、水洗、乾燥して鍍銀銅粉を得た。
２リットルのボールミル容器内に、得られた鍍銀銅粉７５０ｇおよび直径が５ｍｍのジルコニアボール３ｋｇを投入し、４０分間回転させて平均粒径８．１μｍの鍍銀銅粉を得た。
実施例Ｋ１
上記熱可塑性樹脂（Ｂ１）の合成例１で得られたポリアミド重合体２２．２重量部にジエチレングリコールジメチルエーテル２２２．２重量部を加えて溶解したワニスに、上記鍍銀銅粉（ａ１）の作製例で得られた鍍銀銅粉および銀粉（デグザ社製 ＳＦ＃７ 鱗片状 平均粒径６．８μｍ）を表１に示す割合で配合し、２０分間ディスパーで分散して組成物（ペースト）Ｋを得た。得られたペーストを脱泡した後、スクリーン印刷法にてその一定量をスライドガラス上に塗布し（塗布面積：１ｃｍ×７．５ｃｍ、塗布圧：４０±１０μｍ）、バッチ式乾燥炉で１８０℃、１時間乾燥させて乾燥塗膜を得た。得られた乾燥塗膜について、体積抵抗率、マイグレーション特性を測定した。このペーストを用いてタンタルコンデンサを作成し、等価直列抵抗と漏れ電流を測定し、エッジカバーリング性を評価した。
実施例Ｋ２
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍであり、鍍銀銅粉のアスペクト比が１．５、平均粒径が６．７μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ３
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍであり、ボールミルの回転時間が６０分であり、鍍銀銅粉のアスペクト比が２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ４
アトマイズ法で作製した球状銅粉の平均粒径が４．２μｍ、ボールミルの回転時間が１２０分で、鍍銀銅粉のアスペクト比１２、平均粒径７．２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ５
アトマイズ法で作製した球状銅粉の平均粒径が３．５μｍであり、ボールミルの回転時間が１８０分であり、鍍銀銅粉のアスペクト比２０、平均粒径６．２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ６
アトマイズ法で作製した球状銅粉の平均粒径が０．１μｍであり、鍍銀銅粉のアスペクト比３．２、平均粒径０．２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ７
アトマイズ法で作製した球状銅粉の平均粒径が０．６μｍであり、鍍銀銅粉のアスペクト比３、平均粒径１．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ８
アトマイズ法で作製した球状銅粉の平均粒径が１．０μｍ、鍍銀銅粉のアスペクト比３．１、平均粒径１．５μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ９
アトマイズ法で作製した球状銅粉の平均粒径が５．５μｍ、鍍銀銅粉のアスペクト比３．１、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１０
アトマイズ法で作製した球状銅粉の平均粒径が８．２μｍ、鍍銀銅粉のアスペクト比３．２、平均粒径１２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１１
アトマイズ法で作製した球状銅粉の平均粒径が１３．６μｍ、鍍銀銅粉のアスペクト比３．０、平均粒径２０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１２
アトマイズ法で作製した球状銅粉の平均粒径が４．６μｍ、球状銅粉に対して銀の置換めっき量が０．５重量％、鍍銀銅粉のアスペクト比３．５、平均粒径６．７μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１３
アトマイズ法で作製した球状銅粉の平均粒径が３．８μｍ、球状銅粉に対して銀の置換めっき量が１．０重量％、鍍銀銅粉のアスペクト比３．１、平均粒径５．３μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１４
アトマイズ法で作製した球状銅粉の平均粒径が３．６μｍ、球状銅粉に対して銀の置換めっき量が１．５重量％、鍍銀銅粉のアスペクト比３．５、平均粒径５．２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１５
アトマイズ法で作製した球状銅粉の平均粒径が４．３μｍ、球状銅粉に対して銀の置換めっき量が２５重量％、鍍銀銅粉のアスペクト比３．４、平均粒径６．２μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１６
アトマイズ法で作製した球状銅粉の平均粒径が５．０μｍ、球状銅粉に対して銀の置換めっき量が３５重量％、鍍銀銅粉のアスペクト比３．８、平均粒径７．５μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１７
アトマイズ法で作製した球状銅粉の平均粒径が４．７μｍ、球状銅粉に対して銀の置換めっき量が５０重量％、鍍銀銅粉のアスペクト比４．０、平均粒径７．１μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１８
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであり、銀粉（徳力化学 ＴＣＧ−１）の形状が球状で平均粒径が２．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ１９
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２０
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２１
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２２
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２３
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２４
アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が２０重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２５
上記熱可塑性樹脂（Ｂ１）の合成例２で得られたポリアミドイミド重合体を用い、アトマイズ法で作製した球状銅粉の平均粒径が５．９μｍ、球状銅粉に対して銀の置換めっき量が１５重量％、鍍銀銅粉のアスペクト比２．５、平均粒径８．０μｍであること以外は実施例Ｋ１と同様とした。
実施例Ｋ２６
上記熱可塑性樹脂（Ｂ１）の合成例２で得られたポリアミドイミド重合体を用い、アトマイズ法で作製した球状銅粉の平均粒径が４．４μｍ、球状銅粉に対して銀の置換めっき量が１５重量％、鍍銀銅粉のアスペクト比３．２、平均粒径６．５μｍであること以外は実施例Ｋ１と同様とした。
比較例Ｋ１
アトマイズ法で作製した球状銅粉の平均粒径が１３．８μｍで球状銅粉に対して銀の置換めっき量が１５重量％、ボールミルの回転時間が２４０分であり、アスペクト比２５、平均粒径２６μｍの鍍銀銅粉を使用したこと以外は実施例Ｋ１と同様とした。
比較例Ｋ２
上記熱可塑性樹脂（Ｂ１）の合成例２で得られたポリアミドイミド重合体を用い、アトマイズ法で作製した球状銅粉の平均粒径が１３．８μｍで球状銅粉に対して銀の置換めっき量が１５重量％、ボールミルの回転時間が２４０分であり、アスペクト比２５、平均粒径２６μｍの鍍銀銅粉を使用したこと以外は実施例Ｋ１と同様とした。
比較例Ｋ３
鍍銀銅粉の代わりに球状の銅粉（三井金属鉱山 ＭＦＰ１１１０ 平均粒径１．１μｍ）を用いたこと以外は実施例Ｋ１と同様とした。
比較例Ｋ４
銀粉を含まないこと以外は実施例Ｋ１と同様とした。
比較例Ｋ５
鍍銀銅粉を含まないこと以外は実施例Ｋ１と同様とした。
得られた結果を表Ｋ１および表Ｋ２に示す。
実施例Ｌ１
上記熱可塑性樹脂（Ｂ１）の合成例１で得られたポリアミド重合体２２．２重量部にジエチレングリコールジメチルエーテル２２２．２重量部を加えて溶解したワニスに、鍍銀銅粉（ａ２）作製例で得られた鍍銀銅粉（銅露出面積 ２０％）１１８．８重量部および銀粉（デグザ社製 ＳＦ＃７ 鱗片状 平均粒径６．８μｍ）７９．２重量部を配合し、２０分ディスパーで分散して、粘度２０００ｍＰａ・ｓの組成物（ペースト）Ｌを得た。得られたペーストを脱泡した後、スクリーン印刷法にて一定量スライドガラス上に塗布し（塗布面積：１ｃｍ×７．５ｃｍ 塗布圧：４０±１０μｍ）、バッチ式乾燥炉で１８０℃、１時間乾燥させて乾燥塗膜を得た。得られた乾燥塗膜の体積抵抗率を測定した。また、ペースト粘度の経時変化を測定するために、ペーストの一部を５０ｍｌのポリ容器に移し、３０℃の高温槽に放置し、６ヶ月後に再度粘度を測定して、その変化率を算出した。また、得られたペーストのはんだ接着性を評価した。さらに、このペーストを陰極に用いてタンタルコンデンサを作製し、はんだ耐熱性を試験した。
実施例Ｌ２
鍍銀銅粉作製時のボールミル回転時間が６０分で得られた鍍銀銅粉の銅露出面積が３０％であること以外は、実施例Ｌ１と同様とした。
実施例Ｌ３
鍍銀銅粉作製時の銀の置換めっき量が１５重量％であり、得られた鍍銀銅粉の銅露出面積が４０％であること以外は実施例Ｌ１と同様とした。
実施例Ｌ４
鍍銀銅粉作製時のボールミル回転時間が８０分であり、得られた鍍銀銅粉の銅露出面積が６０％であること以外は実施例Ｌ３と同様とした。
実施例Ｌ５
上記熱可塑性樹脂（Ｂ１）の合成例２で得られたポリアミドイミド重合体を用いたこと以外は実施例Ｌ２と同様とした。
比較例Ｌ１
鍍銀銅粉作製時の銀置換めっき量が３０重量部であり、ボールミルの回転時間が２０分であり、得られた鍍銀銅粉の銅露出面積が０％であること以外は、実施例Ｌ１と同様とした。
比較例Ｌ２
鍍銀銅粉を使用せず、銀粉を１９８重量部用いたこと以外は、実施例Ｌ１と同様とした。
比較例Ｌ３
鍍銀銅粉の代わりにアトマイズ法で作製した球状銅粉を用いたこと以外は、実施例Ｌ１と同様とした。
以上、得られた結果を表Ｌ１に示す。
実施例Ｍ１
上記熱可塑性樹脂（Ｂ２）の合成例１で得られたポリアミドシリコーン共重合体２２．２重量部にジエチレングリコールジメチルエーテル２２２．２重量部を加えて溶解したワニスに、鍍銀銅粉（ａ１）の作製例で得られた鍍銀銅粉１１８．８重量部および銀粉（デグザ社製 ＳＦ＃７ 鱗片状 平均粒径６．８μｍ）７９．２重量部を配合し、２０分ディスパーで分散し、粘度２０００ｍＰａ・ｓの組成物（ペースト）Ｍを得た。得られたペーストを脱泡した後、スクリーン印刷法にて一定量スライドガラス上に塗布し（塗布面積：１ｃｍ×７．５ｃｍ 塗布圧：４０±１０μｍ）、バッチ式乾燥炉で１８０℃、１時間乾燥させて乾燥塗膜を得た。得られた乾燥塗膜の体積抵抗率を測定した。また、得られたペーストを用いて、塗膜強度測定用の試料を作製し、塗膜強度を測定した。さらに、このペーストを陰極に用いてタンタルコンデンサを作製し（定格電圧４Ｖ）、インラッシュ試験を行った後のコンデンサ特性を測定し、コンデンサの破壊を確認した。
実施例Ｍ２
鍍銀銅粉の作製時のボールミル回転時間が８０分で、得られた鍍銀銅粉のアスペクト比が６．８であること以外は、実施例Ｍ１と同様とした。
実施例Ｍ３
鍍銀銅粉の作製時のボールミル回転時間が１２０分で、得られた鍍銀銅粉のアスペクト比が１２であること以外は、実施例Ｍ１と同様とした。
実施例Ｍ４
鍍銀銅粉の作製時のボールミル回転時間が１５０分で、得られた鍍銀銅粉のアスペクト比が１９．３であること以外は、実施例Ｍ１と同様とした。
実施例Ｍ５
上記熱可塑性樹脂（Ｂ２）の合成例２で得られたポリアミドイミドシリコーン共重合体を用いたこと以外は、実施例Ｍ２と同様とした。
比較例Ｍ１
鍍銀銅粉の作製時のボールミル回転時間が１８０分で、得られた鍍銀銅粉のアスペクト比が２３．０であること以外は、実施例Ｍ１と同様とした。
比較例Ｍ２
ポリアミドシリコーン共重合体の代わりに、上記熱可塑性樹脂（Ｂ１）の合成例１で得られたポリアミド重合体を用いたこと以外は、実施例Ｍ２と同様とした。
比較例Ｍ３
鍍銀銅粉の代わりに、アスペクト比３．５の銀粉を用いたこと以外は、実施例Ｍ１と同様とした。
比較例Ｍ４
鍍銀銅粉と銀粉の代わりにアスペクト比１の銅粉を用いたこと以外は、実施例Ｍ１と同様とした。
比較例Ｍ５
ポリアミドシリコーン共重合体の代わりにエポキシ樹脂（三井化学（株）製、商品名１４０Ｃ）６０重量部、脂肪族ジグリシジルエーテル（旭電化工業（株）製、商品名ＥＤ−５０３）４０重量部、２Ｐ４ＭＨＺ（四国化成（株）製、キュアゾール）３重量部およびジシアンジアミド（和光純薬工業（株））３重量部を加えた以外は実施例Ｍ２と同様とした。
得られた結果を表Ｍ１に示す。
実施例Ｎ１
熱可塑性樹脂（Ｂ２）の合成例１で得られたポリアミドシリコーン共重合体２２．２重量部にジエチレングリコールジメチルエーテル２２２．２重量部を加えて溶解したワニスに、鍍銀銅粉（ａ２）作製例で得られた鍍銀銅粉（銅露出面積 ３０％）１１８．８重量部および銀粉（デグザ社製 ＳＦ＃７ 鱗片状 平均粒径６．８μｍ）７９．２重量部を配合し、２０分ディスパーで分散し、粘度２０００ｍＰａ・ｓの組成物（ペースト）Ｎを得た。得られたペーストを脱泡した後、スクリーン印刷法にて一定量スライドガラス上に塗布し（塗布面積：１ｃｍ×７．５ｃｍ 塗布厚：４０±１０μｍ）、バッチ式乾燥炉で１８０℃、１時間乾燥させて乾燥塗膜を得た。得られた乾燥塗膜の体積抵抗率を測定した。また、得られたペーストのフレキシブル性を測定した。さらに、このペースト組成物を陰極に用いてタンタルコンデンサを作製し、熱衝撃性試験を行い、コンデンサの漏れ電流（ＬＣ）を測定した。
実施例Ｎ２
熱可塑性樹脂（Ｂ２）の合成例２で得られたポリアミドイミドシリコーン共重合体を用いたこと以外は、実施例Ｎ１と同様とした。
実施例Ｎ３
熱可塑性樹脂（Ｂ２）の合成例２で得られたポリアミドイミドシリコーン共重合体を用い、鍍銀銅粉作製時の銀の置換めっき量が１５重量％であり、ボールミル回転時間が８０分であり、得られた鍍銀銅粉の銅露出面積が５０％であること以外は、実施例Ｎ１と同様とした。
比較例Ｎ１
鍍銀銅粉作製時の銀置換めっき量が３０重量部であり、ボールミルの回転時間が２０分であり、得られた鍍銀銅粉の銅露出面積が０％であること以外は、実施例Ｎ１と同様とした。
比較例Ｎ２
ポリアミドシリコーン共重合体の代わりにエポキシ樹脂（三井化学（株）製、商品名１４０Ｃ）６０重量部、脂肪族ジグリシジルエーテル（旭電化工業（株）製、商品名ＥＤ−５０３）４０重量部、２Ｐ４ＭＨＺ（四国化成（株）製、キュアゾール）３重量部およびジシアンジアミド（和光純薬工業（株））３重量部を加えた以外は実施例Ｎ１と同様とした。
得られた結果を表Ｎ１に示す。
本願の開示は、２００１年１０月１９日に出願された特願２００１−３２２３２０号、２００１年１０月１９日に出願された特願２００１−３２２３２１号、２００１年１０月３１日に出願された特願２００１−３３３６４９号、および２００１年１０月３１日に出願された特願２００１−３３３６５０号に記載の主題と関連しており、それらのすべての開示内容は引用によりここに援用される。
既に述べられたもの以外に、本発明の新規かつ有利な特徴から外れることなく、上記の実施形態に様々な修正や変更を加えてもよいことに注意すべきである。従って、そのような全ての修正や変更は、添付の請求の範囲に含まれることが意図されている。

【図面の簡単な説明】
Ｆｉｇ．１は、本発明に係る電子部品の一実施形態である固体電解コンデンサの一例を模式的に示す断面図である。Technical field
The present invention relates to a conductive resin composition and an electronic component using the same.
Background art
In the field of electronic parts, it is a common practice to knead a conductive material such as metal into a resin to obtain a paste-like resin composition, which is used for forming an electric circuit or an electrode. Silver is the most typical conductive material, but when a voltage is applied under high humidity conditions, it is very easily ionized, and a silver migration phenomenon called migration is often observed. When migration occurs, a short circuit occurs between the electrodes, which causes a decrease in moisture resistance reliability of the electronic component.
It has been studied to add nickel powder, palladium powder or copper powder instead of silver powder or to add various additives, but in any case the resistance value as an electrode material becomes high, Improvements were sought.
Japanese Patent Application Laid-Open Nos. Hei 2-283010 and Hei 6-151261 disclose conventional techniques relating to migration prevention in a solid electrolytic capacitor.
Disclosure of the invention
According to the 1st side of this invention, it consists of a silver-silver-copper powder (a1) with an aspect ratio of 1-20, electroconductive powder (A1) containing silver powder, an amide group, an ester group, an imide group, and an ether group. A conductive resin composition (hereinafter referred to as “composition K”) comprising a thermoplastic resin (B1) having one or more functional groups selected from the group and an organic solvent (C) is provided.
According to the second aspect of the present invention, a silver-silver-copper powder (a2) having a copper exposed portion on a part of the surface, a conductive powder (A2) containing silver powder, an amide group, an ester group, an imide group, and A conductive resin composition (hereinafter referred to as “composition L”) comprising a thermoplastic resin (B1) having one or more functional groups selected from the group consisting of ether groups and an organic solvent (C). Provided.
According to the third aspect of the present invention, from the group consisting of silver copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, polyamide silicone, polyamideimide silicone and polyimide silicone. A conductive resin composition (hereinafter referred to as “composition M”) containing the selected thermoplastic resin (B2) and the organic solvent (C) is provided.
According to the fourth aspect of the present invention, silver-silver-copper powder (a2) having a copper exposed portion on a part of its surface, conductive powder (A2) containing silver powder, polyamide silicone, polyamideimide silicone, and polyimide silicone There is provided a conductive resin composition (hereinafter referred to as “composition N”) comprising a thermoplastic resin (B2) selected from the group consisting of: and an organic solvent (C).
According to the 5th side surface of this invention, the electronic component which has a conductor layer formed using the conductive resin composition (composition K, L, M, N) which concerns on the said invention is provided.
BEST MODE FOR CARRYING OUT THE INVENTION
The conductive resin composition according to the present invention is a paste-like resin composition, and is simply referred to as “composition” or “paste” in the following description.
Composition K is one or more selected from the group consisting of silver-silver-copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, an amide group, an ester group, an imide group, and an ether group It is a composition containing the thermoplastic resin (B1) which has a functional group, and the organic solvent (C). When scaly conductive powder is used, the edge coverage when applied to a complex shaped member (polyhedron) is not sufficient, resulting in increased electrical resistance and variations in inter-surface resistance. In addition, defects in the electrical characteristics of electronic components are likely to occur, which may lead to a decrease in dimensional accuracy even when packaged with resin. In particular, when used for forming a cathode of a solid electrolytic capacitor using a valve metal as an anode, there is a tendency that the leakage current (LC) of the product increases. In contrast, composition K has good coatability and good conductivity after drying, and the resulting coating film is stable at high temperatures and high humidity (migration resistance) and dimensional accuracy (edge) Excellent coverability. Therefore, by using the composition K, an electronic component excellent in moisture resistance reliability and dimensional accuracy can be provided. For example, when the composition K is used for forming a cathode, moisture resistance reliability is good and leakage current is improved. A small number of solid electrolytic capacitors can be provided.
Composition L is selected from the group consisting of silver-silver-copper powder (a2) having a copper exposed part on the surface and conductive powder (A2) containing silver powder, an amide group, an ester group, an imide group and an ether group A composition comprising the thermoplastic resin (B1) having one or more functional groups and the organic solvent (C). Currently, adding copper powder as a conductive powder is generally performed. In that case, the resistance value is better than when nickel powder or palladium powder is used, but there is a problem in the stability over time that the paste viscosity increases due to oxidation or aggregation of copper powder. In addition, when soldering to a conductive paste using silver powder, because the thermal decomposition of the binder resin is used as the soldering mechanism, a part of the coating film is lost, and it cannot be joined sufficiently There's a problem. Furthermore, conventional conductive paste using silver powder and copper powder reacts with oxygen and copper powder contained in the air and binder resin to form an oxide film on the surface, so soldering is applied. The problem of not being able to do it is also pointed out. On the other hand, the composition L is excellent in the past viscosity stability of the paste viscosity, and can form a coating film that can be soldered. Therefore, by using this composition L, an electronic component having excellent solder heat resistance, for example, by using the composition L for forming a cathode, it is excellent in solder adhesion to a cathode take-out member, and is excellent in solder heat resistance. A capacitor can be provided.
Composition M is a thermoplastic resin (A1) having an aspect ratio of 1 to 20 and a thermoplastic resin selected from the group consisting of conductive powder (A1) containing silver powder, polyamide silicone, polyamideimide silicone, and polyimide silicone ( B2) and an organic solvent (C). Conventionally, a paste using a thermosetting resin as a binder has been widely used, but the obtained coating film has a problem that it is inferior in coating film strength and toughness and inferior in impact resistance after circuit formation. Further, when this paste is used for an electrode of a solid electrolytic capacitor, there is a problem that the overvoltage load characteristic is not sufficient because the coating film strength and toughness are inferior. On the other hand, the composition M can form a dry coating film excellent in coating film strength and toughness, and provides an electronic component such as a solid electrolytic capacitor excellent in overvoltage load characteristics using the composition M. be able to.
Composition N was selected from the group consisting of silver-silver-copper powder (a2) having a copper exposed part on the surface and conductive powder (A2) containing silver powder, polyamide silicone, polyamideimide silicone, and polyimide silicone. It is a composition containing a thermoplastic resin (B2) and an organic solvent (C). In the case of a paste using a thermosetting resin as a binder, the resulting coating film is inferior in flexibility, and when forming a circuit on a flexible substrate, if the bending rate is large, the coating film will crack and the circuit will break. There is a problem that. On the other hand, the composition N can form a dry coating film excellent in flexibility, and can be used to provide an electronic component such as a solid electrolytic capacitor particularly excellent in thermal shock. .
In the composition K and the composition M, the silver chloride copper powder (a1) having an aspect ratio of 1 to 20 and the conductive powder (A1) containing silver powder are used. This aspect ratio refers to the ratio of the major axis to the minor axis (major axis / minor axis) of the silver bronze copper powder particles. In the present invention, the silver-copper powder particles are mixed well in the low-viscosity curable resin, and the particles are allowed to settle, and the resin is cured, and the resulting cured product is cut in the vertical direction. The shape of the particles appearing on the cut surface is observed by magnifying with a microscope, the major axis / minor axis of each particle is determined for at least 100 particles, and the average value thereof is used as the aspect ratio. Here, the minor axis is a particle that appears on the cut surface, and a combination of two parallel lines in contact with the outside of the particle is selected so as to sandwich the particle. The distance of parallel lines. On the other hand, the major axis is two parallel lines perpendicular to the parallel line that determines the minor axis, and the two parallel lines that are the longest interval among the combination of two parallel lines in contact with the outside of the particle Is the distance. The rectangle formed by these four lines is sized to fit the particles just inside it. Specific methods performed in the present invention will be described later.
The silver-silver-copper powder (a1) is a conductive powder in which a part or all of the surface of the copper powder is coated with silver. This is obtained, for example, by coating the atomized copper powder with silver by a method such as displacement plating, electroplating or electroless plating. It is preferable to coat with a displacement plating method because of high adhesion between copper powder and silver and low running costs.
In composition K, the silver coating amount of the silver-plated copper powder (a1) is not particularly limited, but considering conductivity and migration resistance, 0.5 to 50 parts by weight with respect to 100 parts by weight of copper. Parts by weight are preferred, 1.0 to 35 parts by weight are more preferred, and 1.5 to 25 parts by weight are even more preferred. As the aspect ratio of the silver-silver-copper powder (a1), 1 to 20 is selected from the viewpoint of the coating property of the paste. When this aspect ratio exceeds 20, the paste coating property deteriorates, and particularly when used for the cathode of a solid electrolytic capacitor, the edge cover property of the device is low, which may lead to an increase in leakage current. Considering the conductivity of the coating film, the aspect ratio is preferably 1.5 to 18, and more preferably 2.5 to 12. The average particle diameter of the silver-plated copper powder (a1) is preferably 0.2 μm to 20 μm, more preferably 1 μm to 12 μm, in consideration of the dispersibility of the paste, leveling properties, edge cover properties, and film conductivity. 5 μm to 8 μm is more preferable. When the average particle size is less than 0.2 μm, the paste tends to aggregate, and when it exceeds 20 μm, the edge cover property and the resistance tend to decrease. This average particle diameter can be measured by a laser scattering type flow distribution measuring device.
In the composition M, 1 to 20 is selected as the aspect ratio of the silver chloride copper powder (a1). If this aspect ratio exceeds 20, the paste applicability, the strength and toughness of the conductive coating film are reduced, and particularly when used for the cathode of a solid electrolytic capacitor, the overvoltage load characteristics deteriorate and the cause of impedance reduction There is a fear. Considering the conductivity of the coating film, the aspect ratio is preferably 1.5 to 18, and more preferably 2.5 to 12. The silver coating amount of the silver-silver-copper powder (a1) is not particularly limited, but is preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of copper in consideration of conductivity and migration resistance. 0.0 to 35 parts by weight is more preferable, and 1.5 to 25 parts by weight is even more preferable. When the silver coating amount is less than 1 part by weight, the conductivity tends to be low, and when it exceeds 30 parts by weight, the overvoltage load characteristic of the capacitor tends to be lowered. The average particle diameter of the silver-plated copper powder (a1) is preferably 0.2 μm to 20 μm, more preferably 1 μm to 12 μm, and more preferably 1.5 μm to 1.5 μm, considering the dispersibility, viscosity, workability, and film conductivity of the paste. 8 μm is more preferable. When the average particle size is less than 0.2 μm, the paste tends to aggregate, and when it exceeds 20 μm, the coating property and the resistance tend to decrease. The average particle diameter can be measured by a laser scattering type flow distribution measuring device.
The silver powder contained in the conductive powder (A1) is not particularly limited, and commonly used shapes such as scales, spheres, and lumps can be used. In consideration of conductivity, coating properties and edge cover properties, scaly and spherical particles having a particle size of 0.2 μm to 12 μm are preferable, and those of 1 μm to 8 μm are more preferable.
The ratio (weight ratio) of silver silver copper powder (a1) to silver powder in the conductive powder (A1) is not particularly limited, but the ratio of silver powder to 100 parts by weight of silver silver copper powder (a1) is It is preferably 25 parts by weight or more from the viewpoint of membrane conductivity, preferably 400 parts by weight or less from the viewpoint of leakage current or capacitor overvoltage load characteristics, more preferably 42.8 to 233.3 parts by weight, and 66. 6-150 weight part is still more preferable.
In composition L and composition N, silver-silver-copper powder (a2) having a copper exposed portion on a part of the surface and conductive powder (A2) containing silver powder are used. This silver-silver-copper powder (a2) is one in which a part of the copper alloy powder (that is, silver-silver-copper powder) is exposed and the surface is covered with approximately silver. If silver is coated on the entire surface of the silver copper powder without exposing a part of the copper, the composition L has poor solderability and the composition N has poor thermal shock. Moreover, silver powder is used in order to improve electroconductivity, and the composition which does not contain silver powder is not suitable for use as a conductor layer.
As the copper powder of the silver-plated copper powder (a2), those having any shape such as a spherical shape, a scale shape, a lump shape, and a crushed shape can be used, and preferably an atomized copper powder is used. The exposed area of copper in the silver-plated copper powder (a2) is preferably 10 to 70% from the viewpoints of aging stability of paste viscosity, solderability, oxidation of exposed portions, conductivity, thermal shock resistance, etc. The range of 10 to 50% is more preferable, and the range of 10 to 30% is more preferable. The exposed area of copper can be determined from the difference between the surface area of the copper powder measured by measuring the area covered with silver.
The silver-silver-copper powder (a2) can be obtained by covering the atomized copper powder with silver by a method such as displacement plating, electroplating or electroless plating. It is preferable to coat with a displacement plating method because of high adhesion between copper powder and silver and low running costs.
The coating amount of silver on the surface of the copper powder is preferably in the range of 5 to 25% by weight with respect to 100 parts by weight of the copper powder from the viewpoint of stability of paste viscosity over time, solder adhesiveness, cost, conductivity improvement, etc. The range of 10 to 23% by weight is more preferable.
The silver powder contained in the conductive powder (A2) is not particularly limited, and generally used powders such as scales, spheres, and lumps can be used. In consideration of conductivity, coating properties and edge cover properties, scaly and spherical particles having a particle size of 0.2 μm to 12 μm are preferable, and those of 1 μm to 8 μm are more preferable.
The mixing ratio of the silver-silver-copper powder (a2) and the silver powder is not particularly limited, but considering the conductivity, the ratio of the silver powder is 25 parts by weight to 100 parts by weight of the silver-silver-copper powder (a2). It is preferably 266 parts by weight, more preferably 66 parts by weight to 150 parts by weight.
The silver-silver-copper powder (a2) tends to increase the resistance of the coating film obtained when the number of contact points between the powders is small. In order to increase the contact area between the silver-silver-copper powders and obtain high conductivity, it is preferable that the silver-silver-copper powder (a2) is impacted to deform the shape of the particles into a flat shape. The average particle diameter of the silver-plated copper powder (a2) is not particularly limited, but is preferably 1 to 20 μm and more preferably 1 to 10 μm in view of paste applicability and dispersion stability. The average particle diameter can be measured by a laser scattering type flow distribution measuring device.
In the composition K and the composition L, the binder resin is selected from the group consisting of an amide group, an ester group, an imide group, and an ether group from the viewpoints of adhesion, filler dispersibility, solubility in an organic solvent, and the like. Further, a thermoplastic resin (B1) having one or more functional groups is used. This thermoplastic resin (B1) can also be used in combination of multiple types.
Although it does not specifically limit as a thermoplastic resin (B1), From a viewpoint of heat resistance etc., it is preferable that it has an aromatic ring. From the viewpoint of solubility in the organic solvent (C), it is preferable to have an ether bond. For example, polyphenylene ether amide with phenylene ether (phenylene oxide) bond and amide bond in the main chain, polyphenylene ether imide with phenylene ether bond and imide bond in the main chain, phenylene ether bond, amide bond and imide bond in the main chain Polyphenylene ether amide imide, polyphenylene amide having phenylene bond and amide bond in the main chain, polyphenylene imide having phenylene bond and imide bond in the main chain, polyphenylene amide imide having phenylene bond, amide bond and imide bond in the main chain, main chain Polyxylylene amide having a xylylene bond and an amide bond, polyxylylene imide having a xylylene bond and an imide bond in the main chain, and a polyxylylene imide having a xylylene bond, an amide bond and an imide bond in the main chain. Xylylene amide imide, and the like, can be preferably used one or more of any of these. These may further contain an ester bond, a sulfide bond or the like, and the benzene ring may be substituted with an arbitrary substituent.
More specifically, the thermoplastic resin (B1) is more preferably a resin having a repeating unit represented by the following general formula (I) or (II). A resin having both the repeating unit (I) and the repeating unit (II) is also preferred.
Formula (I):

(Wherein R ¹ , R ² , R ³ And R ⁴ Each independently represents hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom; ¹ Is a single bond, -O-, -S-, -CO-, -SO ₂ -, -SO-,

Where R ⁵ And R ⁶ Each independently represents hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y is

Where Ar is ¹ Is an aromatic divalent group, Ar ² Is an aromatic trivalent group, Ar ³ Represents an aromatic tetravalent group. )
General formula (II):

(Wherein R ⁷ , R ⁸ And R ⁹ Each independently represents a lower alkyl group, a lower alkoxy group or a halogen atom, s, t and u are each independently an integer of 0 to 4 representing the number of substituents; ⁷ , R ⁸ And R ⁹ Each may be the same or different when X ² And X ³ Are each independently -O- or

Where R ¹⁰ And R ¹¹ Each independently represents a hydrogen atom, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y has the same definition as in the general formula (I). )
In the general formulas (I) and (II), the lower alkyl group and the lower alkoxy group are preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. R in the above general formulas (I) and (II) ⁵ , R ⁶ , R ¹⁰ , R ¹¹ The phenyl group may be unsubstituted or substituted with an arbitrary substituent such as a methyl group, an ethyl group, or a sulfone group.
As shown in the following general formula (III), the repeating unit represented by the general formula (I) is preferably one in which a benzene ring is bonded to each other at the 1,4-position.

Similarly, the repeating unit represented by the general formula (II) is also preferably one in which benzene rings are bonded to each other at the 1,4-positions as shown in the following general formula (IV).

The thermoplastic resin (B1) having the above repeating unit includes an acid component (S) described below, that is, an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, an aromatic tetracarboxylic acid, or a reactive acid derivative thereof, and It can manufacture by making the diamine demonstrated to react. You may use an acid component and diamine, combining multiple types, respectively.
The repeating units represented by the above general formulas (I) and (III) are, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl as diamines. -4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl ] Butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-amino) Phenoxy) Nyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether Bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4-aminophenoxy) biphenyl, etc. It is preferable to form them. Among these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable.
The repeating units represented by the above general formulas (II) and (IV) are diamines such as 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-Bis (4-aminophenoxy) benzene, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene) )] Bisaniline, 3,3 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline and the like are preferably used.
In forming the repeating units of the general formulas (I), (II), (III) and (IV), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, , 4′-diamino-3,3 ′, 5,5′-tetramethyldiphenyl ether, 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-diamino-3, 3 ′, 5,5′-tetraethyldiphenyl ether, 2,2 ′-[4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenyl] propane, metaphenylenediamine, paraphenylenediamine, 3, 3′-diaminodiphenylsulfone, piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylenediamine, m-xylenedi One or more of amine, o-xylenediamine, 3-methylheptamethylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and the like can be used in combination.
An aromatic dicarboxylic acid is a carboxylic acid having two carboxyl groups bonded to an aromatic ring. The aromatic tricarboxylic acid is a carboxylic acid in which three carboxyl groups are bonded to an aromatic ring, and two of the three carboxyl groups are preferably bonded to adjacent carbon atoms. The aromatic tetracarboxylic acid is a carboxylic acid having four carboxyl groups bonded to an aromatic ring, and two of the four carboxyl groups are preferably bonded to adjacent carbon atoms. Here, the aromatic ring may be one in which a hetero atom is introduced (aromatic heterocyclic ring), or the aromatic rings may be bonded to each other via an alkylene group, oxygen, a single bond, a carbonyl group, or the like. Furthermore, these aromatic rings may contain a substituent that does not participate in the condensation reaction, such as an alkoxy group, an allyloxy group, an alkylamino group, or a halogen.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like. Among them, terephthalic acid and isophthalic acid are preferable because they are easily available and inexpensive. The reactive derivative of aromatic dicarboxylic acid means dihydride, dibromide, diester or the like of the above aromatic dicarboxylic acid.
As aromatic tricarboxylic acid, trimellitic acid, 3,3 ′, 4-benzophenone tricarboxylic acid, 2,3,4′-diphenyltricarboxylic acid, 2,3,6-pyridinetricarboxylic acid, 3,4,4′- Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2′-chloro-3,4,4′-benzanilide tricarboxylic acid and the like are preferable. The reactive derivative of aromatic tricarboxylic acid means an acid anhydride, halide, ester, amide, ammonium salt or the like of the above aromatic tricarboxylic acid. Specifically, trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,4-dicarbomethoxy-3-carboxybenzene, 1 , 4-Dicarboxy-3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6-dicarboxy-5-carbamoylnaphthalene, the above aromatic tricarboxylates and ammonia, dimethylamine, trimethylamine Preferred examples include ammonium salts consisting of the above. Of these, trimellitic anhydride and trimellitic anhydride monochloride are preferred because they are readily available and inexpensive.
Examples of the aromatic tetracarboxylic acid include pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 1,2,5, 6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,4, 9,10-perylenetetracarboxylic acid, 4,4′-sulfonyldiphthalic acid, m-terphenyl-3,3 ″, 4,4 ″ -tetracarboxylic acid, p-terphenyl-3,3 ″, 4 4 "-tetracarboxylic acid, 4,4'-oxydiphthalic acid, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane, 2,2- Bis (2,3-dicarbox Phenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2′-bis [4- (2,3-di Carboxyphenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2′-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane and the like are preferable. The reactive derivative of aromatic tetracarboxylic acid means acid dianhydride, halide, ester, amide, ammonium salt and the like of the above aromatic tetracarboxylic acid.
The acid component (S) comprising an aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid or a reactive derivative thereof is the total amount of diamine from the viewpoint of the molecular weight, mechanical strength, heat resistance, etc. of the resulting polymer. The total amount is preferably 80 to 120 mol%, more preferably 95 to 105 mol%, based on 100 mol%.
In the composition M and the composition N, the binder resin was selected from a polyamide silicone resin, a polyamideimide silicone resin, and a polyimide silicone resin from the viewpoint of improving the heat resistance of the coating film to be formed and lowering the elastic modulus. A thermoplastic resin (B2) is used. This thermoplastic resin (B2) can also be used in combination of multiple types.
These thermoplastic resins (B2) are not particularly limited. For example, an acid component such as aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid, or a reactive derivative thereof, and diaminosilicone are essential components. It can be obtained by polycondensation with diamine.
Examples of the diamino silicone include the following general formula (V):

(Where Y ¹ Is a divalent hydrocarbon group, Y ² Represents a monovalent hydrocarbon group and two Y ¹ May be the same or different from each other, and a plurality of Y ² May be the same as or different from each other, and m is an integer of 1 or more. )
It is preferable to use what is represented by these.
Y ¹ Examples of the divalent hydrocarbon group represented by the formula include an alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted phenylene group, and the like. ² Examples of the monovalent hydrocarbon group represented by the formula include an alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted phenyl group, and m is preferably an integer of 1 to 100. These diamino silicones are used alone or in combination of two or more.
Other diamines that can be used together with the diaminosilicone are not particularly limited, but aromatic diamines are preferably used from the viewpoints of heat resistance of the resin, solubility in organic solvents, and dissolution viscosity. It is preferable to use polyphenylene ether diamine containing phenylene ether in the main chain.
Specifically, it is more preferable to use an aromatic diamine represented by the following general formula (VI).

(Wherein R ¹ , R ² , R ³ And R ⁴ Each independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms or a halogen atom; ¹ Is a single bond, -O-, -S-, -CO-, -SO ₂ -, -SO-,

Where R ⁵ And R ⁶ Each independently represents hydrogen, a lower alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a trichloromethyl group, or a substituted or unsubstituted phenyl group).
The polyphenylene ether diamine of the above general formula (VI) is preferably one in which benzene rings are bonded to each other at the 1,4-positions as shown in the following general formula (VII).

Examples of the aromatic diamine (e1) having an ether bond represented by the general formula (VI) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3 -Methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) ) Phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl ] Butane, 1,1,1,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-amino) Phenoxy) Enyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether Bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4-aminophenoxy) biphenyl, and the like. Used alone or in combination. Of these, 2,2-bis [(4-aminophenoxy) phenyl] propane is preferred.
As the aromatic diamine (e2) excluding the above (e1), for example, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 4-4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3', 5,5 '-Tetramethyldiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetradimethylphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraethyl Phenyl ether, 2,2- [4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenyl] propane, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, o- Examples include xylylenediamine, m-xylylenediamine, p-xylylenediamine and the like, and these can be used alone or in combination.
Examples of diamines other than the above (e1) and (e2), that is, aliphatic or alicyclic diamines (e3) include piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, 3-methylheptamethylenediamine, and the like. These can be used alone or in combination.
In order to synthesize the thermoplastic resin (B2), the acid component (S) used in the synthesis of the resin (B1) is preferably used as the acid component to be the diamine containing the diaminosilicone as an essential component. be able to. The acid component (S) composed of these aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids or reactive derivatives thereof is a diamine from the viewpoint of the molecular weight, mechanical strength, heat resistance, etc. of the resulting polymer. The total amount is preferably 80 to 120 mol%, more preferably 95 to 105 mol%, based on 100 mol%.
In the composition K, the mixing ratio of the conductive powder (A1) and the thermoplastic resin (B1) is not limited to obtaining, but from the viewpoint of the conductivity of the coating film to be formed, the component (A1) 100 The component (B1) is preferably 2 to 25 parts by weight and more preferably 4 to 14 parts by weight with respect to parts by weight.
In the composition L, the mixing ratio of the conductive powder (A2) and the thermoplastic resin (B1) is not limited, but from the viewpoint of the conductivity of the coating film to be formed, the component (A2) 100 The component (B1) is preferably 2 to 25 parts by weight and more preferably 4 to 14 parts by weight with respect to parts by weight.
In the composition M, the mixing ratio of the conductive powder (A1) and the thermoplastic resin (B2) is not limited, but from the viewpoint of coating film strength, toughness, conductivity, etc., the component (A1) 100 The component (B2) is preferably 2 to 25 parts by weight and more preferably 4 to 14 parts by weight with respect to parts by weight.
In the composition N, the mixing ratio of the conductive powder (A2) and the thermoplastic resin (B2) is not limited to obtaining, but from the viewpoint of the flexibility and conductivity of the coating film, the component (A) is 100 weights. It is preferable that (B) component is 2-25 weight part with respect to part, and 4-14 weight part is more preferable.
Examples of the organic solvent (C) used in the compositions K, L, M, and N include aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, Ether solvents such as isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl Ester solvents such as ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone; dimethylformamide, dimethylacetamide, N-methyl Examples include amide solvents such as pyrrolidone. These solvents are used for dissolving the resin during paste preparation or adjusting the viscosity of the paste, and are used alone or in combination of two or more.
The addition amount of the organic solvent (C) is generally 75 with respect to 100 parts by weight of the thermoplastic resin from the viewpoints of the solubility of the resin, the viscosity when made into a paste, the dispersibility of the conductive powder, the coating film forming ability, and the like. It is used in the range of ˜4600 parts by weight, preferably 125 to 3060 parts by weight.
Each composition containing the compounding components as described above can be produced, for example, by kneading and dispersing each component with a rake machine, three rolls, ball mill, disper or the like. In order to improve the dispersibility and coatability of the conductive powder (filler), a dispersant or a coupling agent may be added.
Examples of the dispersant include saturated fatty acids such as palmitic acid and stearic acid having 16 to 20 carbon atoms; unsaturated fatty acids such as oleic acid and linolenic acid having 16 to 18 carbon atoms; sodium of these saturated / unsaturated fatty acids, One or more metal salts with potassium, calcium, zinc, copper and the like can be preferably used. The blending amount of the dispersing agent is 0.2 to 240 parts by weight with respect to 100 parts by weight of the resin from the viewpoint of dispersibility of the conductive powder, conductivity of the coating film, and adhesion between the coating film and the substrate. Is preferable, and the range of 2 to 120 parts by weight is more preferable.
As the coupling agent, for example, vinyl methoxysilane, vinyl triethoxysilane, vinyl tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ -A silane coupling agent such as mercaptopropyltrimethoxysilane, titanate coupling agent, aluminate coupling agent, zircoaluminate coupling agent, etc. can be used, with respect to 100 parts by weight of the above thermoplastic resin. Addition of 30 parts by weight or less In is preferably added.
The composition according to the present invention can be suitably used as a conductor layer of various electronic components, for example, a conductive circuit or an electrode material.
The electronic component according to the present invention has a conductor layer formed using the composition according to the present invention. As various electronic components, an aluminum electrolytic capacitor, a tantalum solid electrolytic capacitor, a ceramic capacitor and the like using this composition as an electrode material; various substrates on which conductive circuits made of the composition of the present invention are formed by screen printing; Examples include an IC card in which a conductive circuit made of the composition of the present invention is formed as an antenna circuit. Especially, the composition of this invention can be used suitably as a cathode material of the solid electrolytic capacitor which used the valve action metal for the anode.
Therefore, the electronic component of the present invention is preferably a cathode including a dielectric oxide film, a solid electrolyte layer, and a conductor layer formed using the composition of the present invention on an anode substrate made of a valve metal. A solid electrolytic capacitor in which a layer is formed.
FIG. As shown in FIG. 1, the solid electrolytic capacitor 10 includes an anode substrate 2 in which an anode wire 1 is embedded, a dielectric oxide film (anodized film) 3 formed on the anode substrate 2 in sequence, and A capacitor element including a solid electrolyte layer (semiconductor layer) 4 and a cathode layer 5 composed of a carbon layer 51 and a conductor layer 52 is provided. The anode substrate 2 is preferably made of a valve action metal such as tantalum, aluminum, titanium, niobium or the like. The shape of the anode substrate 2 is preferably a foil shape, a plate shape, or a rod shape. The anode substrate 2 is formed by embedding the anode wire 1 such as a tantalum lead, compression-molding the valve action metal powder, and heating it in a vacuum at a temperature of about 2000 ° C. for several tens of minutes to obtain a sintered body. Formed with.
Next, the obtained sintered body (anode base 2) is formed by applying voltage in a chemical conversion liquid such as nitric acid or phosphoric acid, and Ta surface is formed on the surface of the anode base 2. ₂ O ₅ A dielectric oxide film 3 is formed. The oxide film 3 is preferably a layer made of an oxide of the anode base metal itself, but may be a dielectric oxide layer different from the anode base. After the dielectric oxide film 3 is formed, the sintered body is immersed in a semiconductor mother liquor such as a manganese nitrate solution, impregnated with the liquid, fired at a temperature of 200 ° C. to 350 ° C., and thermally decomposed inside the sintered body ( A solid electrolyte layer 4 mainly including a manganese dioxide layer is formed on the surface of the sintered body. After thermal decomposition, re-forming and repairing the dielectric oxide film 3 damaged by sintering is performed. The above immersion, firing and re-chemical conversion steps are repeated 5 to 10 times as necessary to form the solid electrolyte layer 4 having a desired thickness. This solid electrolyte layer can also be formed using a TCNQ (7,7,8,8-tetracyanoquinodimethane) complex called an organic semiconductor, or a conductive polymer such as polypyrrole, polythiophene, or polyaniline.
After forming the solid electrolyte layer 4, a carbon paste is applied and dried to form a carbon layer 51 as a part of the cathode layer 5, and a conductor layer (a further part of the cathode layer ( A silver layer or silver paste layer) 52 is formed using the composition of the present invention. A lead frame 7 for removing a cathode is connected to the obtained conductor layer 52 using solder or a conductive adhesive 6 or the like, while the anode wire 1 drawn out from the sintered body 2 is connected to the lead frame 7 or the like. Weld. Finally, the whole is sealed and packaged with the exterior resin 8 by a resin dipping method, a resin molding method, or the like. The solid electrolytic capacitor thus obtained is generally about 2 to 7 mm in length, 1.25 to 4.3 mm in width, and about 1.2 to 2.8 mm in height.
Next, the present invention will be described in more detail with reference to examples. The measurement and evaluation methods for various characteristics in the following examples are as follows.
[aspect ratio]
8 g of the main agent (No. 10-8130) of low viscosity epoxy resin (Buhler) and 2 g of the curing agent (No. 10-8132) are mixed, and 2 g of the powder to be measured is mixed and dispersed well. Then, after vacuum deaeration at 30 ° C. as it was, the particles were allowed to settle for 10 hours at 30 ° C. to cure the resin. Thereafter, the obtained cured product was cut in the vertical direction, the cut surface was magnified 1000 times with an electron microscope, and the major axis / minor axis were obtained for 150 particles appearing on the cut surface, and the average value thereof was obtained. The aspect ratio was used.
[Average particle size]
The average particle diameter of the powder was measured using a master sizer (manufactured by Malvern).
[Copper exposed area]
Randomly remove 5 particles of the silver-silver copper powder produced, and calculate the copper occupation ratio by quantitative analysis of noble metal (silver) and non-noble metal (copper) from the Auger image observed with a scanning Auger electron spectrometer The average value of the five measurement particles was defined as the copper exposed area (%).
[Paste viscosity]
Using a 3 ° cone of an E-type viscometer manufactured by Tokyo Keiki Co., Ltd., the temperature in the thermostatic layer was set to 25 ° C., and the value 10 minutes after the start of measurement was taken as the viscosity of the paste.
[Change in paste viscosity over time]
After preparing the paste, it was left in a thermostatic bath at 30 ° C. for 6 months, and then the viscosity was measured.
[Volume resistivity]
The volume resistivity of the dried coating film obtained using the paste was measured with a double bridge type resistance measuring instrument (TYPE 2769 manufactured by Yokogawa Electric Corporation).
[Migration characteristics]
Using the dry coating film used for measuring the volume resistivity, forming an electrode with an interval of 2 mm at the center of the dry coating film, dropping pure water so as to cover the entire electrode, and then applying a voltage of 7 V to both ends, The migration characteristics were evaluated by measuring the time from when silver transferred to when the electrodes were short-circuited.
[Edge coverability]
A 1 mm × 1 mm × 1.5 mm cubic tantalum sintered body was immersed in the paste to be measured and dried. The obtained element was covered with a transparent epoxy resin and allowed to stand at room temperature for 10 hours to be cured. Then, the long side center part of the cube was cut | disconnected with the diamond cutter, and it grind | polished using the sand paper and the abrasive particle, and was set as the element for evaluation. The covering state of the paste at the four corners of the evaluation element was observed with an electron microscope. Evaluation A: Good, B: Coating thickness of edge portion is 1 μm or less, C: Defect in edge portion
[Coating strength]
Using an applicator on a Teflon plate, a silver film was prepared so that the film thickness after drying at 180 ° C. for 1 hour was 50 μm. The film was peeled off from the Teflon plate to produce a strip-shaped test piece having a width of 5 mm × 40 mm.
Thereafter, the coating strength was measured using a tensile strength tester (manufactured by Imada Seisakusho: tensile compression tester SL-2001).
[Flexibility of coating film]
After applying a paste of 2 mm width on a PET film having a thickness of 125 μm, a width of 1 cm, and a length of 10 cm, drying at 180 ° C. for 1 hour, the ends of the film are brought into contact with each other, and then the back surfaces are joined together. The contact operation was repeated and the number of times the coating film cracked was measured.
[Capacitor characteristics]
The characteristics of the tantalum capacitor were measured in accordance with JIS C 5102-1994 (Testing method for fixed capacitors for electronic equipment). Equivalent series resistance (ESR) was measured using an LCR meter. For the leakage current (LC), a digital microammeter (Advantest; R8340A) was used, and a tantalum capacitor was prepared using the paste to be measured for the conductor layer, and left for 1000 h and 2000 h in an 85 ° C. and 85% RH atmosphere. The hour value was measured. Tan δ and impedance were measured using an LCR meter (4284A) manufactured by Hewlett-Packard Company. Cap (capacitance) was measured using an LCR meter (manufactured by Hewlett-Packard 4284A).
[Capacitor overvoltage load characteristics]
Overvoltage was applied to the rated voltage of the tantalum capacitor, and the subsequent capacitor characteristics were measured to confirm the number of capacitor breakdowns.
[Solder adhesion]
An aluminum plate having a width of 1 cm, a length of 2 cm, and a thickness of 0.5 mm was dipped in the paste to be measured by 1 cm, pulled up, and dried in an oven dryer at 180 ° C. for 1 hour to prepare a sample for evaluation. After the sample for evaluation was immersed in the flux, the sample was immersed in a solder bath at each set temperature, and the adhesion state of the solder was observed. A solder coating area of 80% or more was evaluated as A, 50% or more and less than 80% as B, 30% or more and less than 50% as C, and less than 30% as D.

[Capacitor solder heat resistance]
The capacity change rate after the tantalum capacitor was immersed in the solder bath for 10 seconds was measured. Solder bath temperature: 230 ° C, 260 ° C, 290 ° C
[Thermal shock resistance of capacitors]
A tantalum capacitor was put into a thermal shock tester and taken out every 1000 cycles to measure the capacitor characteristics. Thermal shock conditions were -50 ° C to 80 ° C. That is, after being left in a -50 ° C bath for 30 minutes, it is transferred to an 80 ° C bath within 3 minutes, left for 30 minutes, and then transferred to a -50 ° C bath within 3 minutes. This was one cycle.
<Synthesis example 1 of thermoplastic resin (B1)>
100 g (0.24 mol) of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) was used as a diamine, and this was equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube. It melt | dissolved in 400 g of N-methyl- 2-pyrrolidone in nitrogen gas atmosphere in 1 liter four necked flask. The resulting solution was cooled to −10 ° C. and 49.5 g (0.24 mol) of isophthalic acid dichloride was added so that the temperature of the solution did not exceed −5 ° C., and then 56.6 g of propylene oxide was added. Add and stir at room temperature for 3 hours. The reaction solution is poured into pure water, the polymer is isolated, dried, then dissolved again in N-methyl-2-pyrrolidone, and the resulting solution is poured into pure water to purify the polyamide polymer. did.
<Synthesis example 2 of thermoplastic resin (B1)>
205 g (500 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used as the diamine, and this was added to a 3 liter four-neck equipped with a thermometer, stirrer, nitrogen inlet tube and condenser tube. The flask was dissolved in 11177 g of diethylene glycol dimethyl ether in a nitrogen gas atmosphere. The resulting solution was cooled to −10 ° C., and 105.3 g of trimellitic anhydride monochloride was added so that the temperature of the solution did not exceed −5 ° C. Thereafter, 87 g of propylene oxide was added, and the mixture was stirred at room temperature for 3 hours. When the viscosity of the reaction solution increased and the solution became transparent, 841 g of diethylene glycol dimethyl ether was added, and the mixture was further stirred for 1 hour. Thereafter, 128 g of acetic anhydride and 64 g of pyridine were added, and stirring was continued for one day at 60 ° C. The obtained reaction solution was poured into 250 g of methanol to isolate the polyamideimide polymer. After drying this, it was dissolved again in N, N-dimethylformamimide and poured into methanol to obtain a polyamideimide polymer product.
<Synthesis example 1 of thermoplastic resin (B2)>
In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, 65.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine under a nitrogen gas atmosphere ( 160 mmol), and diaminosiloxane represented by the general formula (V) (Shin-Etsu Chemical Co., Ltd., X-22-161B; in the general formula (V), m = 38, Y ¹ = -C ₃ H ₆ -, Y ² = -CH ₃ ) 64 g (40 mmol) (80 mol% / 20 mol% in molar ratio) was added and dissolved in 335 g of diethylene glycol dimethyl ether.
The resulting solution was cooled to −10 ° C., and 40.6 g (200 mmol) of isophthalic acid dichloride was added so that the temperature of the solution did not exceed −5 ° C. Thereafter, 23.2 g of propylene oxide was added, 96 g of diethylene glycol dimethyl ether was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was put into methanol to isolate the polymer, dried, and then dissolved again in dimethylformamide. The solution was put into methanol to purify the polyamide silicone copolymer.
<Synthesis example 2 of thermoplastic resin (B2)>
174.3 g (425 mmol) of 2,2bis [4- (4-aminophenoxy) phenyl] propane as a diamine under a nitrogen gas atmosphere in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser tube And 18.6 g of diaminopropyltetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., LP7100) (75 mmol) (85 mol% / 15 mol% in molar ratio) were dissolved in 1177 g of diethylene glycol dimethyl ether.
The resulting solution was cooled to −10 ° C., and 105.3 g (500 mmol) of trimellitic anhydride monochloride was added so that the temperature of the solution did not exceed −5 ° C. Thereafter, 87 g of propylene oxide was added, and the mixture was stirred at room temperature for 3 hours. When the viscosity of the reaction liquid increased and the liquid became transparent, 841 g of diethylene glycol dimethyl ether was added, and the mixture was further stirred for 1 hour. Thereafter, 128 g of acetic anhydride and 64 g of pyridine were added and stirred at 60 ° C. for one day. The obtained reaction solution was put into a large amount of a mixed solvent of n-hexane / methanol = 1/1 (weight ratio) to isolate the polymer, dried, and then converted into N, N-dimethylformamide. It melt | dissolved and thrown into methanol, the polyamidoimide silicone copolymer was refine | purified, and it dried under reduced pressure.
<Preparation example of agate silver copper powder (a1)>
A spherical copper powder having an average particle size of 5.1 μm produced by the atomizing method (trade name SFR-Cu, manufactured by Nippon Atomizing Co., Ltd.) is washed with dilute hydrochloric acid and pure water, and then contains 80 g of AgCN and 75 g of NaCN per liter of water. With the plating solution, substitution plating was performed so that the amount of silver was 15% by weight with respect to the spherical copper powder, followed by washing with water and drying to obtain a silver-silver-copper powder.
Into a 2 liter ball mill container, 750 g of the obtained silver bronze powder and 3 kg of zirconia balls having a diameter of 5 mm are charged and rotated for 40 minutes. The average aspect ratio is 1.3 and the average diameter of the major axis is 5.5 μm. Of silver bronze powder was obtained.
<Preparation example of agate silver copper powder (a2)>
A spherical copper powder having an average particle diameter of 5.1 μm produced by the atomizing method (trade name SFR-Cu, manufactured by Nippon Atomizing Co., Ltd.) is washed with dilute hydrochloric acid and pure water, and then 80 g of AgCN and 75 g of NaCN are contained per liter of water Using the plating solution, substitution plating was performed so that the amount of silver was 20% by weight with respect to the spherical copper powder, followed by washing with water and drying to obtain a silver-silver-copper powder.
In a 2-liter ball mill container, 750 g of the obtained silver-silver-copper powder and 3 kg of zirconia balls having a diameter of 5 mm were charged and rotated for 40 minutes to obtain a silver-silver-copper powder having an average particle size of 8.1 μm.
Example K1
Preparation example of the above silver-silver-copper powder (a1) in a varnish obtained by adding 222.2 parts by weight of diethylene glycol dimethyl ether to 22.2 parts by weight of the polyamide polymer obtained in Synthesis Example 1 of the thermoplastic resin (B1) The silver chloride copper powder and silver powder (SF # 7 scale-like average particle size 6.8 μm, manufactured by Degusa) obtained in step 1 are blended in the proportions shown in Table 1, and dispersed with a disper for 20 minutes to obtain the composition (paste) K. Obtained. After defoaming the obtained paste, a certain amount thereof was applied on a slide glass by a screen printing method (application area: 1 cm × 7.5 cm, application pressure: 40 ± 10 μm), and 180 ° C. in a batch drying oven. It was dried for 1 hour to obtain a dry coating film. About the obtained dry coating film, the volume resistivity and the migration characteristic were measured. A tantalum capacitor was prepared using this paste, and the equivalent series resistance and leakage current were measured to evaluate the edge covering property.
Example K2
The spherical copper powder produced by the atomization method had an average particle size of 5.9 μm, the aspect ratio of the silver-plated copper powder was 1.5, and the average particle size was 6.7 μm. .
Example K3
The average particle size of the spherical copper powder produced by the atomization method is 5.9 μm, the rotation time of the ball mill is 60 minutes, the aspect ratio of the silver chloride copper powder is 2.5, and the average particle size is 8.0 μm. Other than that was the same as Example K1.
Example K4
Example K1 except that the average particle size of the spherical copper powder produced by the atomizing method is 4.2 μm, the rotation time of the ball mill is 120 minutes, the aspect ratio of the silver chloride copper powder is 12, and the average particle size is 7.2 μm. Same as above.
Example K5
Implemented except that the spherical copper powder produced by the atomization method has an average particle size of 3.5 μm, the rotation time of the ball mill is 180 minutes, the aspect ratio is 20 and the average particle size is 6.2 μm. Same as Example K1.
Example K6
The spherical copper powder produced by the atomization method had the same average particle diameter as 0.1 μm, the same as Example K1 except that the silver silver copper powder had an aspect ratio of 3.2 and an average particle diameter of 0.2 μm.
Example K7
The spherical copper powder produced by the atomization method had an average particle diameter of 0.6 μm, and the same as Example K1, except that the silver silver copper powder had an aspect ratio of 3 and an average particle diameter of 1.0 μm.
Example K8
Example K1 was the same as that of Example K1 except that the spherical copper powder produced by the atomization method had an average particle diameter of 1.0 μm, an aspect ratio of 3.1%, and an average particle diameter of 1.5 μm.
Example K9
The same procedure as in Example K1 was conducted, except that the spherical copper powder produced by the atomization method had an average particle diameter of 5.5 μm, an aspect ratio of 3.1%, and an average particle diameter of 8.0 μm.
Example K10
The same procedure as in Example K1 was conducted except that the spherical copper powder produced by the atomization method had an average particle diameter of 8.2 μm, an aspect ratio of the silver chloride copper powder of 3.2, and an average particle diameter of 12 μm.
Example K11
The same procedure as in Example K1 was conducted except that the spherical copper powder produced by the atomization method had an average particle diameter of 13.6 μm, an aspect ratio of galvanized copper powder of 3.0, and an average particle diameter of 20 μm.
Example K12
The average particle diameter of the spherical copper powder produced by the atomization method is 4.6 μm, the amount of silver substitution plating is 0.5% by weight with respect to the spherical copper powder, the aspect ratio of glazed silver copper powder is 3.5, and the average particle diameter is 6 The same as Example K1 except that the thickness was 0.7 μm.
Example K13
The average particle diameter of the spherical copper powder produced by the atomizing method is 3.8 μm, the amount of silver substitution plating is 1.0% by weight with respect to the spherical copper powder, the aspect ratio 3.1 of the silver copper powder, and the average particle diameter 5 The same as Example K1 except that the thickness was 3 μm.
Example K14
The average particle diameter of the spherical copper powder produced by the atomization method is 3.6 μm, the amount of silver substitution plating is 1.5% by weight with respect to the spherical copper powder, the aspect ratio is 3.5, and the average particle diameter is 5 The same as Example K1 except that the thickness was 2 μm.
Example K15
The average particle diameter of the spherical copper powder produced by the atomizing method is 4.3 μm, the amount of silver substitution plating is 25 wt% with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 3.4, and the average particle diameter is 6.2 μm. Except that, it was the same as Example K1.
Example K16
The average particle diameter of the spherical copper powder produced by the atomization method is 5.0 μm, the amount of silver substitution plating is 35% by weight with respect to the spherical copper powder, the aspect ratio of 鍍 silver copper powder is 3.8, and the average particle diameter is 7.5 μm. Except that, it was the same as Example K1.
Example K17
The average particle diameter of the spherical copper powder produced by the atomization method is 4.7 μm, the amount of silver substitution plating is 50% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 4.0, and the average particle diameter is 7.1 μm. Except that, it was the same as Example K1.
Example K18
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. It was the same as Example K1 except that the shape of the silver powder (Tokuri Chemical TCG-1) was spherical and the average particle size was 2.0 μm.
Example K19
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K20
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K21
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K22
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K23
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K24
The average particle diameter of the spherical copper powder produced by the atomization method is 5.9 μm, the amount of silver substitution plating is 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver copper powder is 2.5, and the average particle diameter is 8.0 μm. Except that, it was the same as Example K1.
Example K25
Using the polyamide-imide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1), the spherical copper powder produced by the atomization method has an average particle diameter of 5.9 μm, and the amount of silver substituted plating with respect to the spherical copper powder Was 15% by weight, the aspect ratio of silver bronze powder was 2.5, and the average particle size was 8.0 μm.
Example K26
Using the polyamideimide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1), the average particle size of the spherical copper powder produced by the atomization method is 4.4 μm, and the amount of silver substituted plating with respect to the spherical copper powder Is 15% by weight, the aspect ratio of the silver bronze powder is 3.2, and the average particle size is 6.5 μm.
Comparative Example K1
The average particle diameter of the spherical copper powder produced by the atomization method is 13.8 μm, the amount of silver substitution plating is 15 wt% with respect to the spherical copper powder, the rotation time of the ball mill is 240 minutes, the aspect ratio is 25, the average particle diameter The same procedure as in Example K1 was conducted except that 26 μm silver bronze powder was used.
Comparative Example K2
Using the polyamideimide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1), the spherical copper powder produced by the atomization method has an average particle diameter of 13.8 μm, and the amount of silver substituted plating with respect to the spherical copper powder 15% by weight, the rotation time of the ball mill was 240 minutes, and the same procedure as in Example K1 was used except that a silver bronze powder having an aspect ratio of 25 and an average particle size of 26 μm was used.
Comparative Example K3
It was the same as Example K1 except that spherical copper powder (Mitsui Metal Mining MFP1110 average particle size 1.1 μm) was used instead of the silver chloride copper powder.
Comparative Example K4
Except not containing silver powder, it was the same as Example K1.
Comparative Example K5
It was the same as Example K1 except that it did not contain agate silver copper powder.
The obtained results are shown in Table K1 and Table K2.
Example L1
In the varnish obtained by adding 222.2 parts by weight of diethylene glycol dimethyl ether to 22.2 parts by weight of the polyamide polymer obtained in Synthesis Example 1 of the thermoplastic resin (B1), and obtained in the example of preparation of silver bronze powder (a2) 118.8 parts by weight of the obtained silver-silver-copper powder (copper exposed area 20%) and 79.2 parts by weight of silver powder (SF # 7 scale-like average particle size 6.8 μm, manufactured by Degussa) were mixed and dispersed with a disper for 20 minutes. Thus, a composition (paste) L having a viscosity of 2000 mPa · s was obtained. After defoaming the obtained paste, a fixed amount was applied on a slide glass by a screen printing method (application area: 1 cm × 7.5 cm, application pressure: 40 ± 10 μm), and 180 ° C. for 1 hour in a batch drying oven. A dried coating film was obtained by drying. The volume resistivity of the obtained dried coating film was measured. In order to measure the change in paste viscosity over time, a part of the paste was transferred to a 50 ml plastic container, left in a high temperature bath at 30 ° C., and the viscosity was measured again after 6 months to calculate the rate of change. . Moreover, the solder adhesiveness of the obtained paste was evaluated. Further, a tantalum capacitor was produced using this paste as a cathode, and the solder heat resistance was tested.
Example L2
It was the same as Example L1 except that the copper exposed area of the silver-silver-copper powder obtained in 60 minutes for the ball mill rotation time when the silver-silver-copper powder was produced was 30%.
Example L3
It was the same as Example L1 except that the amount of silver substitution plating during the production of the silver silver copper powder was 15% by weight and the copper exposed area of the obtained silver silver copper powder was 40%.
Example L4
It was the same as Example L3 except that the ball mill rotation time during the production of the silver silver copper powder was 80 minutes and the copper exposed area of the obtained silver silver copper powder was 60%.
Example L5
Example L2 was the same as Example L2 except that the polyamideimide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1) was used.
Comparative Example L1
Example: Except that the amount of silver-displaced plating at the time of producing the silver-silver-copper powder is 30 parts by weight, the rotation time of the ball mill is 20 minutes, and the copper-exposed area of the obtained silver-silver-copper powder is 0% Same as L1.
Comparative Example L2
The same procedure as in Example L1 except that 198 parts by weight of silver powder was used without using silver bronze powder.
Comparative Example L3
Except having used the spherical copper powder produced by the atomizing method instead of the silver-silver copper powder, it was the same as that of Example L1.
The results obtained above are shown in Table L1.
Example M1
Preparation of silver-silver-copper powder (a1) in a varnish obtained by adding 222.2 parts by weight of diethylene glycol dimethyl ether to 22.2 parts by weight of the polyamide silicone copolymer obtained in Synthesis Example 1 of the thermoplastic resin (B2) 118.8 parts by weight of the silver bronze powder obtained in Examples and 79.2 parts by weight of silver powder (SF # 7 scale-like average particle size 6.8 μm, manufactured by Degusa) were blended, dispersed with a disper for 20 minutes, and a viscosity of 2000 mPa -Composition (paste) M of s was obtained. After defoaming the obtained paste, a fixed amount was applied on a slide glass by a screen printing method (application area: 1 cm × 7.5 cm, application pressure: 40 ± 10 μm), and 180 ° C. for 1 hour in a batch drying oven. A dried coating film was obtained by drying. The volume resistivity of the obtained dried coating film was measured. Moreover, the sample for coating-film strength measurement was produced using the obtained paste, and coating-film strength was measured. Further, a tantalum capacitor was produced using this paste as a cathode (rated voltage 4 V), and the capacitor characteristics after an in-rush test were measured to confirm the destruction of the capacitor.
Example M2
It was the same as Example M1 except that the ball mill rotation time during the production of the silver bronze powder was 80 minutes and the aspect ratio of the obtained silver silver copper powder was 6.8.
Example M3
It was the same as Example M1 except that the ball mill rotation time during the production of the silver silver copper powder was 120 minutes and the aspect ratio of the silver silver copper powder obtained was 12.
Example M4
It was the same as Example M1 except that the ball mill rotation time during the production of the silver silver copper powder was 150 minutes and the aspect ratio of the silver silver copper powder obtained was 19.3.
Example M5
Example 2 was the same as Example M2 except that the polyamideimide silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2) was used.
Comparative Example M1
It was the same as Example M1 except that the ball mill rotation time during the production of the silver silver copper powder was 180 minutes and the aspect ratio of the obtained silver silver copper powder was 23.0.
Comparative Example M2
The same procedure as in Example M2 was conducted except that the polyamide polymer obtained in Synthesis Example 1 of the thermoplastic resin (B1) was used instead of the polyamide silicone copolymer.
Comparative Example M3
Example 3 was the same as Example M1 except that silver powder having an aspect ratio of 3.5 was used instead of silver copper powder.
Comparative Example M4
It was the same as Example M1 except that copper powder having an aspect ratio of 1 was used instead of silver-copper powder and silver powder.
Comparative Example M5
60 parts by weight of an epoxy resin (trade name 140C, manufactured by Mitsui Chemicals, Inc.) instead of polyamide silicone copolymer, 40 parts by weight of aliphatic diglycidyl ether (trade name ED-503, manufactured by Asahi Denka Kogyo Co., Ltd.) Example 2 was repeated except that 3 parts by weight of 2P4MHZ (manufactured by Shikoku Kasei Co., Ltd., Curazole) and 3 parts by weight of dicyandiamide (Wako Pure Chemical Industries, Ltd.) were added.
The results obtained are shown in Table M1.
Example N1
In a varnish prepared by adding 222.2 parts by weight of diethylene glycol dimethyl ether to 22.2 parts by weight of the polyamide-silicone copolymer obtained in Synthesis Example 1 of the thermoplastic resin (B2), a silver-silver-copper powder (a2) was prepared. The obtained silver-silver-copper powder (copper exposed area 30%) 118.8 parts by weight and silver powder (Degusa SF # 7 scale-like average particle size 6.8 μm) 79.2 parts by weight were blended, and 20 minutes by disper Dispersion was performed to obtain a composition (paste) N having a viscosity of 2000 mPa · s. After defoaming the obtained paste, a certain amount was applied on a slide glass by a screen printing method (application area: 1 cm × 7.5 cm, application thickness: 40 ± 10 μm), and 180 ° C. for 1 hour in a batch drying oven. A dried coating film was obtained by drying. The volume resistivity of the obtained dried coating film was measured. Moreover, the flexibility of the obtained paste was measured. Further, a tantalum capacitor was prepared using the paste composition as a cathode, a thermal shock test was performed, and a leakage current (LC) of the capacitor was measured.
Example N2
Example N1 was the same as Example N1 except that the polyamideimide silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2) was used.
Example N3
Using the polyamide-imide silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2), the silver substitution plating amount at the time of producing the silver-silver-copper powder is 15% by weight, and the ball mill rotation time is 80 minutes The obtained silver-silver-copper powder was the same as Example N1 except that the exposed copper area was 50%.
Comparative Example N1
Example: Except that the amount of silver-displaced plating at the time of producing the silver-silver-copper powder is 30 parts by weight, the rotation time of the ball mill is 20 minutes, and the copper-exposed area of the obtained silver-silver-copper powder is 0% The same as N1.
Comparative Example N2
60 parts by weight of an epoxy resin (trade name 140C, manufactured by Mitsui Chemicals, Inc.) instead of polyamide silicone copolymer, 40 parts by weight of aliphatic diglycidyl ether (trade name ED-503, manufactured by Asahi Denka Kogyo Co., Ltd.) Example 2 was the same as Example N1 except that 3 parts by weight of 2P4MHZ (manufactured by Shikoku Kasei Co., Ltd., Curazole) and 3 parts by weight of dicyandiamide (Wako Pure Chemical Industries, Ltd.) were added.
The results obtained are shown in Table N1.
The disclosure of the present application is disclosed in Japanese Patent Application No. 2001-322320 filed on October 19, 2001, Japanese Patent Application No. 2001-322321 filed on October 19, 2001, and Japanese Patent Application No. 2001-322321 filed on October 31, 2001. This is related to the subject matter described in Japanese Patent Application No. 2001-333649 and Japanese Patent Application No. 2001-333650 filed on Oct. 31, 2001, the entire disclosures of which are incorporated herein by reference.
It should be noted that various modifications and changes may be made to the above-described embodiments without departing from the novel and advantageous features of the present invention other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an example of a solid electrolytic capacitor which is an embodiment of an electronic component according to the present invention.

Claims (9)

One or more functional groups selected from the group consisting of glazed silver copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, and an amide group, ester group, imide group and ether group The conductive resin composition containing the thermoplastic resin (B1) which has, and an organic solvent (C). One or more selected from the group consisting of silver-silver-copper powder (a2) having a copper exposed part on the surface, conductive powder (A2) containing silver powder, amide group, ester group, imide group and ether group The conductive resin composition containing the thermoplastic resin (B1) which has a functional group, and the organic solvent (C). The thermoplastic resin (B1) is a group consisting of polyphenylene ether amide, polyphenylene ether imide, polyphenylene ether amide imide, polyphenylene amide, polyphenylene imide, polyphenylene amide imide, polyxylylene amide, polyxylylene imide, polyxylylene amide imide. The conductive resin composition according to claim 1 or 2, wherein the conductive resin composition is selected from. The thermoplastic resin (B1) is represented by the following general formula (I):

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, and X ¹ represents a single bond, —O—, —S—, —CO; _{-, - SO 2 -, -} SO-,

Wherein R ⁵ and R ⁶ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y represents

Here, Ar ¹ represents an aromatic divalent group, Ar ² represents an aromatic trivalent group, and Ar ³ represents an aromatic tetravalent group. )
And a repeating unit represented by the following general formula (II):

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represents a lower alkyl group, a lower alkoxy group or a halogen atom, s, t and u are each independently an integer of 0 to 4 representing the number of substituents; R ⁷ , R ⁸ and R ⁹ may be the same as or different from each other when a plurality of R ⁷ , R ⁸ and R ⁹ are bonded to each other, and X ² and X ³ are each independently —O— or

Wherein R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y is the same as defined in the general formula (I). . )
The conductive resin composition according to any one of claims 1 to 3, which is a resin having at least one of repeating units represented by formula (1). Thermoplastic resin (B2) selected from the group consisting of silver silver copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, polyamide silicone resin, polyamideimide silicone resin and polyimide silicone resin ) And an organic solvent (C). Heat selected from the group consisting of silver-silver-copper powder (a2) having a copper exposed part on the surface, conductive powder (A2) containing silver powder, polyamide silicone resin, polyamideimide silicone resin, and polyimide silicone resin A conductive resin composition comprising a plastic resin (B2) and an organic solvent (C). The conductive resin composition according to any one of claims 2, 3, 4, and 6, wherein an exposed area of copper in the silver-plated copper powder (a2) is 10 to 70%. The electronic component which has the conductor layer formed using the conductive resin composition of any one of Claims 1-7. A cathode comprising a dielectric oxide film, a solid electrolyte layer, and a conductive layer formed using the conductive resin composition according to any one of claims 1 to 7 on an anode substrate made of a valve metal. 9. The electronic component according to claim 8, wherein the electronic component is a solid electrolytic capacitor having a layer formed thereon.

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