JP2004199941A - Conductive paste composition, and circuit board using the same - Google Patents
Conductive paste composition, and circuit board using the same Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は、Ｎ2 雰囲気中、７００℃よりも低温での焼成が可能なＰｂとＣｄを含有しない導電性ペースト組成物及びそのペースト組成物を用いた回路基板に関するものである。
【０００２】
【従来の技術】
従来、Ｎ2 雰囲気中、７００℃以下といった低温での焼成が可能な導電性ペースト（銅ペースト）組成物としては、例えば低温で軟化し、軟化した際の流動性が良好なＰｂＯを含有するガラスフリットを配合したり、低温でもアルミナ基板とケミカルボンドを形成するＣｄ化合物を配合することが一般的であった。ところが、近年、環境に対する配慮から、ＰｂやＣｄを含有しない導電性ペースト組成物が検討されている（例えば、特許文献１、特許文献２、特許文献３、特許文献４参照）。
【０００３】
特許文献１には、「Ｂｉ2Ｏ3とＳｉＯ2とＣｕＯとＺｎＯとＣｏＯとＦｅ2Ｏ3 とＭｎＯを含み、無鉛かつ無カドミウムであるガラス組成物ならびに係るガラス組成物と導電性粒子と有機媒質を含む厚膜ペースト組成物。」が記載されている。また、その段落番号〔００３６〕には、そのような配合のペースト組成物を印刷した基板を、通風されたベルトコンベヤ炉で、７００〜１０００℃の温度で焼成することが記載されている。
【０００４】
特許文献２には、「ルテニウム系導電性材料と、ＢｉＯ3とＳｉＯ2とＣｕＯとＺｎＯとＣｏＯとＦｅ2Ｏ3とＭｎＯを含み、鉛およびカドミウムを含まないガラス組成物と、有機媒体とを含有する厚膜ペースト組成物」が記載されている。また、その段落番号〔００６８〕には、そのような配合のペースト組成物を印刷した基板を、換気されたベルトコンベヤ炉で、７００〜１０００℃の温度で焼成することが記載されている。
【０００５】
特許文献３には、「７００〜８７０℃の範囲の結晶化温度を有する鉛を含まないガラスフリットと、導電性粉末と、酸化ビスマス、酸化亜鉛含有酸化物、酸化マンガン、酸化銅及び酸化モリブデンからなる無機添加剤と、有機媒体とを含有する導電性ペースト」が記載されている。また、その段落番号〔００４２〕には、そのような配合のペーストを印刷した基板を、空気中、８５０℃で焼成することが記載されている。
【０００６】
特許文献４には、「ＢａＯとＢ2Ｏ3とＺｎＯとＭｎＯ2とＡｌ2Ｏ3とＳｉＯ2とＬｉ2ＯとＮａ2ＯとＫ2ＯとＣｕ2ＯとＳｎＯ2とＦｅ2Ｏ3とＣｏ3Ｏ4とＴｉＯ2とＺｒＯ2 から選択され、鉛を含まないガラス組成物ならびに係るガラス組成物と無機フィラー粉末を含む厚膜ペースト」が記載されている。また、その段落番号〔０００７〕には、非酸化性雰囲気中７００〜８００℃で焼成することによって電極を形成する導体ペーストの無機バインダーとして適したガラス組成物を提供することが目的であると記載されている。
【０００７】
【特許文献１】
特開平８−６７５３３号公報
【特許文献２】
特開平８−２５３３４２号公報
【特許文献３】
特開平９−３０６２３６号公報
【特許文献４】
特開２００２−１６３９２８号公報
【０００８】
【発明が解決しようとする課題】
従来、７００℃よりも低温で焼成可能な導電性ペースト組成物（銅ペースト組成物）を基板上に印刷して電極を形成する場合、基板へのペースト組成物の接着強度を確保するために、Ｐｂ含有ガラスまたはＣｄのような有害な化合物の配合が不可欠であった。そこで、有害な化合物の配合を避けた導電性ペースト組成物が、特許文献１〜４に提案されている。
【０００９】
ところが、特許文献１、２、３に記載されてように、酸化雰囲気で、しかも７００℃以上の高温で焼成すると、銅のような卑金属は酸化しやすく、導体抵抗が増大するので電極としての適正を有しなくなる。
【００１０】
また、特許文献４に記載されたように、非酸化性雰囲気において７００℃以上の高温で焼成すると、誘電体セラミックの脱酸素現象が起こり、機械的強度が低下したり、酸素欠損を生じることによってコンデンサの誘電体特性を劣化させることがある。さらに、非酸化性の７００℃以上の高温雰囲気下は還元性が強いので、酸化物系の抵抗体層を形成することができない。
【００１１】
本発明は従来の技術の有するこのような問題点に鑑みてなされたものであって、その目的は、７００℃よりも低温で焼成した場合において、基板との十分な接着強度を有し、電気特性の優れた導体層や抵抗体層を形成することのできる、ＰｄとＣｄを含有しない、導電性ペースト組成物及びそのペースト組成物を用いた回路基板を提供することにある。
【００１２】
【課題を解決するための手段】
上記目的を達成するために本発明の導電性ペースト組成物は、適量のＣｕ粉末とＣｕ2Ｏ粉末とＣｕＯ 粉末と、軟化点が６５０℃以下でＰｂとＣｄを含有しない適量のガラスフリットと、Ｍｎ、ＮｉもしくはＢｉを含有する適量の化合物と、適量の有機ビヒクルとを含有しているので、７００℃よりも低温で焼成した場合においても、基板との十分な接着強度を有し、電気特性の優れた導体層や抵抗体層を形成することができる。
【００１３】
【発明の実施の形態】
すなわち、本発明の導電性ペースト組成物は、Ｃｕ粉末６５．０〜８０．０重量部、Ｃｕ2Ｏ粉末 １．０〜１５．０重量部、ＣｕＯ粉末１．０〜５．０重量部、軟化点が６５０℃以下でＰｂとＣｄを含有しないガラスフリット０．３〜５．０重量部、Ｍｎ、ＮｉもしくはＢｉを含有する化合物０．１〜５．０重量部および有機ビヒクル５．０〜２５．０重量部からなることを特徴としている。
【００１４】
Ｃｕ粉末は、平均粒径０．３〜５．０μｍで、還元法、電解法またはアトマイズ法で製造されたものが使用できる。
【００１５】
Ｃｕ粉末の平均粒径が０．３μｍ未満では、焼成膜が過焼結となり、焼成時の収縮による残留応力の影響で接着強度が低くなるからであり、一方、Ｃｕ粉末の平均粒径が５．０μｍを超えると、７００℃以下の温度での焼成では焼結が不十分で得られた焼成膜は疎となるため、半田付けしたものを高温で放置した場合、半田の浸透が速いため、接着強度の著しい低下が見られるからである。
【００１６】
このＣｕ粉末の配合量は、６５．０〜８０．０重量部の範囲が好ましい。
【００１７】
Ｃｕ粉末の配合量が６５．０重量部未満では、得られる導体の抵抗値が高く、一方、８０．０重量部を超えると、接着強度の低下が見られるからである。
【００１８】
Ｃｕ2Ｏ粉末は、有機バインダーの脱灰過程における酸素の供給源となり、自 身は活性なＣｕに還元され焼結に寄与するもので、平均粒径０．１〜１．０μｍのものを用いることが出来る。
【００１９】
平均粒径が０．１μｍ未満のＣｕ2Ｏ粉末を使用すると、作成されたペースト の流動性が著しく悪く、スクリーン印刷等に不向きとなるからであり、一方、Ｃｕ2Ｏ 粉末の平均粒径が１．０μｍを超えると比表面積が小さくなるため、有機バインダーの脱灰過程における酸素の放出が円滑に行なわれないため、脱灰不足に起因する焼結不良に伴う膜密度の低下が起こるからである。
【００２０】
このＣｕ2Ｏ 粉末の配合量は、１．０〜１５．０重量部の範囲が好ましい。
【００２１】
Ｃｕ2Ｏ 粉末の配合量が１．０重量部未満では、有機バインダーの脱灰過程における酸素の放出量が少ないため、脱灰不足に起因する焼結不良に伴う膜密度の低下が起こるからであり、一方、Ｃｕ2Ｏ 粉末の配合量が１５．０重量部を超えると、焼成後の導体膜の半田濡れ性が劣化するからである。
【００２２】
ＣｕＯ粉末は、平均粒径が０．３〜３．０μｍのものを用いることが出来る。
【００２３】
平均粒径が０．３μｍ未満のＣｕＯ粉末を使用すると、作成されたペーストの流動性が著しく悪く、スクリーン印刷等に不向きとなるからであり、一方、ＣｕＯ粉末の平均粒径が３．０μｍを超えると、期待される接着強度への寄与が低下するからである。
【００２４】
このＣｕＯ粉末の配合量は、１．０〜５．０重量部の範囲が好ましい。
【００２５】
ＣｕＯ粉末の配合量が１．０重量部未満では、十分な接着強度が得られず、一方、５．０重量部を超えると、焼成後の導体膜の半田濡れ性が劣化するからである。
【００２６】
軟化点が６５０℃以下で、ＰｂとＣｄを含有しないガラスフリットとしては、例えば、Ｌｉ2Ｏ・Ｂ2Ｏ3・ＳｉＯ2、Ｋ2Ｏ・Ｂ2Ｏ3・ＳｉＯ2、Ｎａ2Ｏ・Ｂ2Ｏ3・ＳｉＯ2、Ｎａ2Ｏ・Ｂ2Ｏ3・ＺｎＯ、Ｌｉ2Ｏ・ＺｎＯ、Ｌｉ2Ｏ・Ｂ2 Ｏ3・ＺｎＯ、Ｋ2Ｏ・Ｂ2Ｏ3・ＺｎＯ、Ｂｉ2Ｏ3・Ｂ2Ｏ３・ＺｎＯ、ＺｎＯ・ Ｂ2Ｏ3・ＳｉＯ2、Ｂｉ2Ｏ3・ＺｎＯ・Ｂ2Ｏ3・ＳｉＯ2，Ｌｉ2Ｏ・ＺｎＯ・Ｂ2Ｏ3・ＳｉＯ2、ＮａＯ・ＺｎＯ・Ｂ2Ｏ3・ＳｉＯ2、Ｋ2Ｏ・ＺｎＯ・Ｂ2Ｏ3・ＳｉＯ2 、Ｌｉ2Ｏ・Ｋ2Ｏ・Ｂ2Ｏ3・ＳｉＯ2、Ｂｉ2Ｏ3・Ｂ2Ｏ3・ＳｉＯ2 なる組成で示されるガラスフリットを挙げることがき、示差熱分析（ＤＴＡ）測定による軟化点が６５０℃以下のものであり、平均粒径が０．５〜１０μｍのものを単独もしくは２種以上併用して使用できる。
【００２７】
平均粒径が０．５μｍ未満のガラスフリットを使用すると、作成されたペーストの流動性が著しく悪く、スクリーン印刷等に不向きとなるからであり、一方、ガラスフリットの平均粒径が１０μｍを超えると、７００℃以下の温度での焼成では焼結が不十分で得られた焼成膜は疎となるため、半田付けしたものを高温で放置した場合、半田の浸透が速いため、接着強度の著しい低下が見られるからである。
【００２８】
このガラスフリットの配合量は、０．３〜５．０重量部の範囲が好ましい。
【００２９】
ガラスフリットの配合量が０．３重量部未満では、導体膜の基板への接着に不足しており、十分な接着強度が得られず、一方、５．０重量部を超えると、導体抵抗が上昇するのみならず、導体表面へのガラスの浮き出しに伴う、半田濡れ性の劣化が見られるからである。
【００３０】
Ｍｎ、ＮｉもしくはＢｉを含有する無機化合物としては、酸化物、ホウ化物、硅化物、ホウ酸塩および炭酸塩の中から選択された無機化合物を用いることができる。また、Ｍｎ、ＮｉもしくはＢｉを含有する有機金属化合物としては、酢酸塩、オクチル酸塩，ナフテン酸塩等の有機カルボン酸塩およびアセチルアセトン錯塩の中から選択された有機金属化合物を用いることができる。
【００３１】
これらの化合物の配合量は０．１〜５．０重量部の範囲が好ましい。０．１重量部未満の配合では、配合されることにより期待される接着強度の向上が見られないからであり、一方、その配合量が５．０重量部を超えると、焼成後の導体膜の半田濡れ性が劣化するからである。
【００３２】
有機ビヒクルとしては、通常、厚膜ペースト用に使用されるものを用いることができ、例えば、エチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロースをはじめとするセルロース誘導体やブチラール樹脂，ポリメタクリル酸エステルのようなアクリル系樹脂を有機溶媒に溶解したものが使用できる。
【００３３】
この有機ビヒクルは、以上の配合の導電性材料、ガラスフリット、無機もしくは有機添加剤に対して、５．０〜２５．０重量部配合するのが好ましい。５重量部未満ではペースト化が困難で、２５重量部を超えると、膜の緻密性が悪化し、電極としての特性を維持できないという不都合な点があるからである。
【００３４】
【実施例】
以下に本発明の好ましい実施例を説明するが、本発明は下記実施例に限定されるものではなく、本発明の技術的範囲を逸脱しない範囲において適宜の修正と変更が可能である。
（ペーストの作製）
以下の表１に示す組成のガラスフリットを用い、表２に示す配合（重量部）の実施例１〜１０と比較例１〜１０の各試料を遊星式撹拌機に仕込み、３０分間撹拌混合した。得られた混合物を３本ロールミルで粉砕・混練して配合成分を均一に分散したペーストを得た。さらに、このペーストをスクリーン印刷に適した粘性とするために、α−テルピネオール等の有機溶媒にて、１００〜４００Ｐａ・ｓ程度の絶対粘度に調整した。
（試験片の作製）
作製したペースト試料を、９６％Ａｌ2Ｏ3基板上に、ステンレス製の＃２５０メッシュのスクリーンを用いてスクリーン印刷した。そして、ペーストを印刷したＡｌ2Ｏ3基板を、循環式熱風乾燥機にて１２０℃で１０分間乾燥した後、ベルト式連続焼成炉にて、Ｏ2濃度５ppm以下のＮ2雰囲気中、ピーク温度６００〜６８０℃、ピーク温度保持時間１０分間の条件にて焼成し、試験片を得た。
（評価試験）
以上のようにして作製した試験片について、初期接着強度と高温放置後の接着強度と半田濡れ性を評価した。その評価方法は下記のとおりであり、その結果を表３に示す
(1) 初期接着強度
上記試験片の２mm×２mmの正方形パターンの電極に、Ｓｎ／Ａｇ／Ｃｕ系で融点が２１８℃の半田を用いて０．８mmの直径の錫メッキ銅線を接着した後、その錫メッキ銅線の引き剥がし強度を測定することにより初期の接着強度を評価した。
(2) 高温放置後の接着強度
上記試験片の２mm×２mmの正方形パターンの電極に、Ｓｎ／Ａｇ／Ｃｕ系で融点が２１８℃の半田を用いて０．８mmの直径の錫メッキ銅線を接着した後、１５０℃で１００Ｈｒ高温に晒して放置後、その錫メッキ銅線の引き剥がし強度を測定することにより高温放置後の接着強度を評価した。
(3) 半田濡れ性
Ｓｎ／Ａｇ／Ｃｕ系で融点が２１８℃の０．１mm径の半田ボールを上記試験片の１０mm×１０mmの正方形パターンの電極上にて２３０℃に加熱溶融し、加熱前後の半田ボールの直径を測定し、以下の式にて半田拡がり率を算出した。
【００３５】
半田拡がり率（％）＝（溶融後直径−初期直径）×１００／（初期直径）
この半田拡がり率の数値が大きいほど、半田濡れ性は良好である。
【００３６】
【表１】
【表２】
【表３】
表３に明らかなように、本発明の実施例１〜１０は、本発明の範囲内の適正な配合のＣｕ粉末と、Ｃｕ2Ｏ 粉末と、ＣｕＯ粉末と、軟化点が６５０℃以下でＰｂとＣｄを含有しないガラスフリットと、Ｍｎ、ＮｉもしくはＢｉを含有する化合物と、有機ビヒクルとを含んでいるので、初期接着強度、高温放置後の接着強度が比較例１〜１０に比べて高く、半田濡れ性が良好である。
【００４０】
しかし、比較例１、２、３、４、９には、Ｍｎ、ＮｉもしくはＢｉを含有する化合物が全く添加されておらず、比較例５と６はこれらの化合物の添加量が少な過ぎるので、初期接着強度および高温放置後の接着強度のいずれもが実施例１〜１０に比べてかなり低い。また、比較例７と８は、上記化合物の添加量が多過ぎ、比較例１０は、ガラスフリットの添加量が多過ぎるので、半田拡がり率の数値が極めて低い。
【００４１】
【発明の効果】
本発明は上記のとおり構成されているので、７００℃以下の低温で焼成した場合において、基板との十分な接着強度を有し、電気特性の優れた導体層や抵抗体層を形成することのできる、ＰｄとＣｄを含有しない、導電性ペースト組成物とそのペースト組成物を用いた回路基板を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a conductive paste composition containing no Pb and Cd, which can be fired at a temperature lower than 700 ° C. in an N 2 atmosphere, and a circuit board using the paste composition.
[0002]
[Prior art]
Conventionally, as a conductive paste (copper paste) composition that can be fired at a low temperature of 700 ° C. or less in an N 2 atmosphere, for example, PbO-containing glass that softens at a low temperature and has good fluidity when softened is used. It is common to mix a frit or a Cd compound that forms a chemical bond with an alumina substrate even at low temperatures. However, in recent years, conductive paste compositions that do not contain Pb or Cd have been studied in consideration of the environment (for example, see Patent Literature 1, Patent Literature 2, Patent Literature 3, and Patent Literature 4).
[0003]
Patent Document 1 discloses a glass composition containing Bi 2 O 3 , SiO 2 , CuO, ZnO, CoO, Fe 2 O 3, and MnO, which is lead-free and cadmium-free, and the glass composition, conductive particles, and organic material. Thick film paste composition comprising a medium. " The paragraph number [0036] describes that the substrate on which the paste composition having such a composition is printed is fired in a ventilated belt conveyor furnace at a temperature of 700 to 1000 ° C.
[0004]
Patent Document 2 discloses that “a ruthenium-based conductive material, a glass composition containing BiO 3 , SiO 2 , CuO, ZnO, CoO, Fe 2 O 3, and MnO, free of lead and cadmium, and an organic medium. Containing thick film paste composition ". The paragraph [0068] describes that a substrate on which a paste composition having such a composition is printed is fired at a temperature of 700 to 1000 ° C. in a ventilated belt conveyor furnace.
[0005]
Patent Literature 3 discloses “from a lead-free glass frit having a crystallization temperature in the range of 700 to 870 ° C., a conductive powder, bismuth oxide, zinc oxide-containing oxide, manganese oxide, copper oxide, and molybdenum oxide. Conductive paste containing an inorganic additive and an organic medium ". Further, paragraph [0042] describes that a substrate on which a paste having such a composition is printed is fired at 850 ° C. in air.
[0006]
Patent Document 4 discloses “BaO, B 2 O 3 , ZnO, MnO 2 , Al 2 O 3 , SiO 2 , Li 2 O, Na 2 O, K 2 O, Cu 2 O, SnO 2, and Fe 2 O 3. Co 3 O 4 and is selected from TiO 2 and ZrO 2, have been described thick film paste "containing glass compositions and according glass composition and an inorganic filler powder does not contain lead and. The paragraph [0007] states that the object is to provide a glass composition suitable as an inorganic binder of a conductive paste for forming an electrode by firing at 700 to 800 ° C. in a non-oxidizing atmosphere. Have been.
[0007]
[Patent Document 1]
JP-A-8-67533 [Patent Document 2]
JP-A-8-253342 [Patent Document 3]
Japanese Patent Application Laid-Open No. 9-306236 [Patent Document 4]
JP-A-2002-163928
[Problems to be solved by the invention]
Conventionally, when an electrode is formed by printing a conductive paste composition (copper paste composition) that can be fired at a temperature lower than 700 ° C. on a substrate, in order to secure the adhesive strength of the paste composition to the substrate, The incorporation of harmful compounds such as Pb-containing glass or Cd was essential. Therefore, conductive paste compositions that avoid the incorporation of harmful compounds have been proposed in Patent Documents 1 to 4.
[0009]
However, as described in Patent Documents 1, 2, and 3, when fired in an oxidizing atmosphere and at a high temperature of 700 ° C. or more, a base metal such as copper is easily oxidized, and the conductor resistance increases. Will be lost.
[0010]
Further, as described in Patent Document 4, when firing is performed at a high temperature of 700 ° C. or more in a non-oxidizing atmosphere, the dielectric ceramic deoxidizes, causing a decrease in mechanical strength and oxygen deficiency. The dielectric characteristics of the capacitor may be deteriorated. Further, in a non-oxidizing high-temperature atmosphere of 700 ° C. or more, since the reducing property is strong, an oxide-based resistor layer cannot be formed.
[0011]
The present invention has been made in view of the above problems of the prior art, and has an object to have a sufficient adhesive strength with a substrate when fired at a temperature lower than 700 ° C. An object of the present invention is to provide a conductive paste composition which does not contain Pd and Cd and can form a conductor layer or a resistor layer having excellent characteristics, and a circuit board using the paste composition.
[0012]
[Means for Solving the Problems]
In order to achieve the above object, the conductive paste composition of the present invention comprises an appropriate amount of Cu powder, Cu 2 O powder and CuO powder, and an appropriate amount of glass frit having a softening point of 650 ° C. or less and containing no Pb and Cd, Since it contains an appropriate amount of a compound containing Mn, Ni or Bi and an appropriate amount of an organic vehicle, it has sufficient adhesive strength to a substrate even when fired at a temperature lower than 700 ° C. A conductor layer and a resistor layer having excellent characteristics can be formed.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
That is, the conductive paste composition of the present invention comprises 65.0 to 80.0 parts by weight of Cu powder, 1.0 to 15.0 parts by weight of Cu 2 O powder, 1.0 to 5.0 parts by weight of CuO powder, 0.3 to 5.0 parts by weight of a glass frit having a softening point of 650 ° C. or less and containing no Pb and Cd, 0.1 to 5.0 parts by weight of a compound containing Mn, Ni or Bi, and 5.0 to 5.0 parts of an organic vehicle. It is characterized by comprising 25.0 parts by weight.
[0014]
As the Cu powder, those having an average particle diameter of 0.3 to 5.0 μm and manufactured by a reduction method, an electrolytic method, or an atomizing method can be used.
[0015]
If the average particle size of the Cu powder is less than 0.3 μm, the fired film is over-sintered, and the adhesive strength is reduced due to the influence of residual stress due to shrinkage during firing, while the average particle size of the Cu powder is 5 μm. If the thickness exceeds 0.0 μm, sintering at a temperature of 700 ° C. or less is insufficient and sintering is insufficient, resulting in a sparse film. This is because a remarkable decrease in the adhesive strength is observed.
[0016]
The amount of the Cu powder is preferably in the range of 65.0 to 80.0 parts by weight.
[0017]
If the amount of the Cu powder is less than 65.0 parts by weight, the resulting conductor has a high resistance value, while if it exceeds 80.0 parts by weight, the adhesive strength is reduced.
[0018]
Cu 2 O powder is a source of oxygen in the process of deashing the organic binder, and is itself reduced to active Cu and contributes to sintering, and has an average particle size of 0.1 to 1.0 μm. I can do it.
[0019]
If Cu 2 O powder having an average particle size of less than 0.1 μm is used, the fluidity of the produced paste is extremely poor, and the paste is not suitable for screen printing or the like. On the other hand, the average particle size of the Cu 2 O powder is If the thickness exceeds 1.0 μm, the specific surface area becomes small, so that oxygen is not released smoothly in the process of decalcification of the organic binder, and the film density decreases due to poor sintering due to insufficient decalcification. is there.
[0020]
The amount of the Cu 2 O powder is preferably in the range of 1.0 to 15.0 parts by weight.
[0021]
If the amount of the Cu 2 O powder is less than 1.0 part by weight, the amount of oxygen released during the decalcification process of the organic binder is small, and the film density is reduced due to poor sintering due to insufficient decalcification. On the other hand, if the blending amount of the Cu 2 O powder exceeds 15.0 parts by weight, the solder wettability of the conductor film after firing deteriorates.
[0022]
CuO powder having an average particle diameter of 0.3 to 3.0 μm can be used.
[0023]
If CuO powder having an average particle size of less than 0.3 μm is used, the fluidity of the prepared paste is extremely poor, and the paste is not suitable for screen printing or the like. On the other hand, the average particle size of the CuO powder is 3.0 μm. If it exceeds, the expected contribution to the adhesive strength decreases.
[0024]
The amount of the CuO powder is preferably in the range of 1.0 to 5.0 parts by weight.
[0025]
If the amount of the CuO powder is less than 1.0 part by weight, sufficient adhesive strength cannot be obtained, while if it exceeds 5.0 parts by weight, the solder wettability of the conductor film after firing deteriorates.
[0026]
Examples of the glass frit having a softening point of 650 ° C. or less and containing no Pb and Cd include, for example, Li 2 O.B 2 O 3 .SiO 2 , K 2 O.B 2 O 3 .SiO 2 , and Na 2 O.B 2 O 3 · SiO 2, Na 2 O · B 2 O 3 · ZnO, Li 2 O · ZnO, Li 2 O · B 2 O 3 · ZnO, K 2 O · B 2 O 3 · ZnO, Bi 2 O 3 · B 2 O3 · ZnO, ZnO · B 2 O 3 · SiO 2, Bi 2 O 3 · ZnO · B 2 O 3 · SiO 2, Li 2 O · ZnO · B 2 O 3 · SiO 2, NaO · ZnO · B 2 O 3 · SiO 2, K 2 O · ZnO · B 2 O 3 · SiO 2, Li 2 O · K 2 O · B 2 O 3 · SiO 2, Bi 2 O 3 · B 2 O 3 · SiO 2 Glass frit having a softening point of 650 ° C. or less as measured by differential thermal analysis (DTA), and an average particle size of 0.5 to 1 In combination can be used alone or two or more types of μm.
[0027]
When a glass frit having an average particle size of less than 0.5 μm is used, the fluidity of the prepared paste is extremely poor, and the paste is not suitable for screen printing or the like. On the other hand, when the average particle size of the glass frit exceeds 10 μm, When sintering at a temperature of 700 ° C. or less, sintering is insufficient and the obtained sintering film becomes sparse, and when the soldered one is left at a high temperature, the penetration of the solder is fast, so that the adhesive strength is significantly reduced. Is seen.
[0028]
The amount of the glass frit is preferably in the range of 0.3 to 5.0 parts by weight.
[0029]
If the amount of the glass frit is less than 0.3 parts by weight, the adhesion of the conductor film to the substrate is insufficient, and a sufficient adhesive strength cannot be obtained. This is because not only the rise but also the deterioration of solder wettability due to the protrusion of the glass on the conductor surface is observed.
[0030]
As the inorganic compound containing Mn, Ni or Bi, an inorganic compound selected from oxides, borides, silicides, borates and carbonates can be used. Further, as the organometallic compound containing Mn, Ni or Bi, an organometallic compound selected from organic carboxylate such as acetate, octylate, naphthenate and acetylacetone complex salt can be used.
[0031]
The compounding amount of these compounds is preferably in the range of 0.1 to 5.0 parts by weight. If the amount is less than 0.1 part by weight, the expected improvement in adhesive strength due to the incorporation will not be observed. On the other hand, if the amount exceeds 5.0 parts by weight, the conductor film after firing will not be obtained. The reason for this is that the solder wettability is deteriorated.
[0032]
As the organic vehicle, those usually used for thick film pastes can be used. For example, cellulose derivatives such as ethylcellulose, hydroxypropylcellulose and nitrocellulose, butyral resins and acrylics such as polymethacrylic acid esters can be used. What dissolved the system resin in the organic solvent can be used.
[0033]
It is preferable that the organic vehicle is blended in an amount of 5.0 to 25.0 parts by weight with respect to the conductive material, glass frit, inorganic or organic additive having the above composition. If the amount is less than 5 parts by weight, it is difficult to form a paste, and if the amount exceeds 25 parts by weight, there is an inconvenience that the denseness of the film deteriorates and characteristics as an electrode cannot be maintained.
[0034]
【Example】
Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and appropriate modifications and changes can be made without departing from the technical scope of the present invention.
(Preparation of paste)
Using a glass frit having the composition shown in Table 1 below, each sample of Examples 1 to 10 and Comparative Examples 1 to 10 having the composition (parts by weight) shown in Table 2 was charged into a planetary stirrer and stirred and mixed for 30 minutes. . The obtained mixture was pulverized and kneaded with a three-roll mill to obtain a paste in which the components were uniformly dispersed. Furthermore, in order to make the paste suitable for screen printing, the paste was adjusted to an absolute viscosity of about 100 to 400 Pa · s with an organic solvent such as α-terpineol.
(Preparation of test pieces)
The prepared paste sample was screen-printed on a 96% Al 2 O 3 substrate using a stainless steel # 250 mesh screen. Then, the Al 2 O 3 substrate on which the paste is printed is dried at 120 ° C. for 10 minutes by a circulating hot air dryer, and then, in a belt type continuous firing furnace, in an N 2 atmosphere having an O 2 concentration of 5 ppm or less, the peak temperature is reduced. The specimen was fired under the conditions of 600 to 680 ° C and a peak temperature holding time of 10 minutes to obtain a test piece.
(Evaluation test)
With respect to the test pieces prepared as described above, the initial adhesive strength, the adhesive strength after leaving at high temperature, and the solder wettability were evaluated. The evaluation method is as follows, and the results are shown in Table 3.
(1) Initial bonding strength After bonding a tin-plated copper wire of 0.8 mm diameter to a 2 mm × 2 mm square pattern electrode of the test piece using a Sn / Ag / Cu based solder having a melting point of 218 ° C. The initial adhesive strength was evaluated by measuring the peel strength of the tin-plated copper wire.
(2) Adhesive strength after standing at high temperature A tin-plated copper wire with a diameter of 0.8 mm using a Sn / Ag / Cu-based solder having a melting point of 218 ° C. was applied to the electrode of the test piece having a square pattern of 2 mm × 2 mm. After bonding, the substrate was exposed to a high temperature of 100 hours at 150 ° C. and allowed to stand. Then, the peeling strength of the tin-plated copper wire was measured to evaluate the adhesive strength after standing at high temperature.
(3) Solder wettability A Sn / Ag / Cu based solder ball having a melting point of 218 ° C. and a diameter of 0.1 mm was heated and melted at 230 ° C. on a 10 mm × 10 mm square pattern electrode of the test piece, and before and after heating. Was measured, and the solder spread rate was calculated by the following equation.
[0035]
Solder spread rate (%) = (diameter after melting−initial diameter) × 100 / (initial diameter)
The larger the numerical value of the solder spread rate, the better the solder wettability.
[0036]
[Table 1]
[Table 2]
[Table 3]
As is evident from Table 3, Examples 1 to 10 of the present invention were prepared by properly mixing Cu powder, Cu 2 O powder, CuO powder, and Pb at a softening point of 650 ° C. or less within the scope of the present invention. And a glass frit containing no Cd, a compound containing Mn, Ni or Bi, and an organic vehicle, so that the initial adhesive strength and the adhesive strength after standing at high temperature are higher than those of Comparative Examples 1 to 10, Good solder wettability.
[0040]
However, in Comparative Examples 1, 2, 3, 4, and 9, no compound containing Mn, Ni or Bi was added at all, and in Comparative Examples 5 and 6, the amounts of these compounds added were too small. Both the initial adhesive strength and the adhesive strength after standing at high temperature are considerably lower than those of Examples 1 to 10. Further, Comparative Examples 7 and 8 have too large amounts of the above compound, and Comparative Example 10 has too small an amount of glass frit, so that the value of the solder spread rate is extremely low.
[0041]
【The invention's effect】
Since the present invention is configured as described above, when fired at a low temperature of 700 ° C. or less, it is possible to form a conductive layer or a resistor layer having sufficient adhesive strength to a substrate and excellent electric characteristics. A conductive paste composition containing no Pd and Cd and a circuit board using the paste composition can be provided.
Claims (4)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012054113A (en) * | 2010-09-01 | 2012-03-15 | Kyocera Corp | Copper paste composition and ceramic structure |
| JP2012226837A (en) * | 2011-04-14 | 2012-11-15 | Hitachi Chem Co Ltd | Paste composition for electrode, solar cell element, and solar cell |
| EP2275503A3 (en) * | 2008-01-30 | 2014-01-08 | Basf Se | Conductive inks with metallo-organic modifiers |
| WO2016186185A1 (en) * | 2015-05-20 | 2016-11-24 | 住友金属鉱山株式会社 | Cu paste composition for forming thick film conductor, and thick film conductor |
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- 2002-12-17 JP JP2002365338A patent/JP4064226B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2275503A3 (en) * | 2008-01-30 | 2014-01-08 | Basf Se | Conductive inks with metallo-organic modifiers |
| JP2012054113A (en) * | 2010-09-01 | 2012-03-15 | Kyocera Corp | Copper paste composition and ceramic structure |
| JP2012226837A (en) * | 2011-04-14 | 2012-11-15 | Hitachi Chem Co Ltd | Paste composition for electrode, solar cell element, and solar cell |
| WO2016186185A1 (en) * | 2015-05-20 | 2016-11-24 | 住友金属鉱山株式会社 | Cu paste composition for forming thick film conductor, and thick film conductor |
| JP2016219256A (en) * | 2015-05-20 | 2016-12-22 | 住友金属鉱山株式会社 | Cu paste composition and thick film conductor |
| CN107533877A (en) * | 2015-05-20 | 2018-01-02 | 住友金属矿山株式会社 | Thick film conductor forms and uses Cu composite creams and thick film conductor |
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