JPH0721832A - Conductive paste and manufacture of multilayer ceramic electronic parts using the paste - Google Patents

Conductive paste and manufacture of multilayer ceramic electronic parts using the paste

Info

Publication number
JPH0721832A
JPH0721832A JP16557193A JP16557193A JPH0721832A JP H0721832 A JPH0721832 A JP H0721832A JP 16557193 A JP16557193 A JP 16557193A JP 16557193 A JP16557193 A JP 16557193A JP H0721832 A JPH0721832 A JP H0721832A
Authority
JP
Japan
Prior art keywords
conductive paste
paste
multilayer ceramic
ceramic green
green sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP16557193A
Other languages
Japanese (ja)
Other versions
JP3102454B2 (en
Inventor
Kiyomi Sasaki
清美 佐々木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to JP16557193A priority Critical patent/JP3102454B2/en
Publication of JPH0721832A publication Critical patent/JPH0721832A/en
Application granted granted Critical
Publication of JP3102454B2 publication Critical patent/JP3102454B2/en
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Links

Abstract

PURPOSE:To provide a conductive paste for thick layers which hardly causes delamination when sintered together with a ceramic green sheet and hardly causes deterioration of electric properties due to residual carbon when used for multilayer ceramic electronic parts and provide a manufacturing method of multilayer ceramic electronic parts using the paste. CONSTITUTION:Regarding a conductive paste which is applied to a ceramic green sheet and sintered together with the green sheet, hydrogen-added terpineol is contained in a solvent for the paste. After the conductive paste is printed on a ceramic green sheets, a plurality of the ceramic green sheets are layered and sintered.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、厚膜用の導電性ペース
トおよびこれを導電体として用いた積層セラミックコン
デンサ等の多層セラミック電子部品の製造方法に関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thick film conductive paste and a method for manufacturing a multilayer ceramic electronic component such as a multilayer ceramic capacitor using the conductive paste.

【0002】[0002]

【従来の技術】電子機器の小型化にともない、その電子
機器に使用される積層セラミックコンデンサ、多層セラ
ミック基板等のセラミックグリーンシートと導電性ペー
スト層を同時焼成して得られる多層セラミック電子部品
においても、薄層化、高密度化等により、小型化が進め
られている。
2. Description of the Related Art With the miniaturization of electronic equipment, multilayer ceramic electronic parts obtained by simultaneously firing a ceramic green sheet and a conductive paste layer such as a multilayer ceramic capacitor and a multilayer ceramic substrate used in the electronic equipment Miniaturization is being promoted by thinning layers and increasing the density.

【0003】これら多層セラミック電子部品は通常、ド
クターブレード法等で得たセラミックグリーンシートに
導電性ペーストをスクリーン印刷等により印刷し積層し
た後、この積層したセラミックグリーンシートと導電性
ペースト層を同時に焼成して得られる。また、このスク
リーン印刷用の導電性ペーストとしては、金属粉末等の
導電性材料をエチルセルロース樹脂やアルキッド樹脂等
のバインダーおよび溶剤を含有する有機ビヒクルに分散
させたものが用いられる。
In these multilayer ceramic electronic components, usually, a conductive green paste obtained by a doctor blade method or the like is printed with a conductive paste by screen printing or the like to be laminated, and then the laminated ceramic green sheet and the conductive paste layer are simultaneously fired. Obtained. As the conductive paste for screen printing, a conductive material such as metal powder dispersed in an organic vehicle containing a binder such as ethyl cellulose resin or alkyd resin and a solvent is used.

【0004】従来、この導電性ペーストの溶剤として
は、ブチルカルビトールアセテート、テルピネオール、
ケロシン等の溶剤が使用されていた(例えば、特開平2
−5591)。
Conventionally, as the solvent for this conductive paste, butyl carbitol acetate, terpineol,
Solvents such as kerosene were used (see, for example, Japanese Patent Laid-Open No. Hei 2
-5591).

【0005】[0005]

【発明が解決しようとする課題】このように、従来の厚
膜用の導電性ペーストにおいては、エチルセルロース樹
脂やアルキッド樹脂等のバインダー成分をブチルカルビ
トールアセテート、テルピネオールあるいはケロシン等
の溶剤に溶解した有機ビヒクル中に金属粉末等の一定量
の導電性材料を分散させている。また、この厚膜用の導
電性ペーストの粘度は、ペースト中のバインダー成分の
量等を増減させて、スクリーン印刷に適した粘度に調整
している。
As described above, in the conventional conductive paste for thick film, an organic compound prepared by dissolving a binder component such as ethyl cellulose resin or alkyd resin in a solvent such as butyl carbitol acetate, terpineol or kerosene is used. A certain amount of conductive material such as metal powder is dispersed in the vehicle. The viscosity of the conductive paste for thick film is adjusted to a viscosity suitable for screen printing by increasing or decreasing the amount of binder component in the paste.

【0006】ところが、ペースト中のバインダー成分が
多いと、例えば積層セラミックコンデンサの製造過程に
おいて、特に最近のように薄層化して積層枚数が多くな
ると、焼成時のバインダー成分の蒸発、熱分解、酸化分
解等が不十分となり、残留する炭素量が増加し、積層し
たセラミックグリーンシートと導電性ペースト層の間に
焼成時にデラミネーションが生じやすかった。また、デ
ラミネーションに至らないまでも、残留炭素により絶縁
抵抗等のコンデンサの電気的特性が劣化する原因にもな
った。
However, when the amount of the binder component in the paste is large, for example, in the manufacturing process of the monolithic ceramic capacitor, especially when the number of laminated layers is large due to thinning as recently, the evaporation, thermal decomposition and oxidation of the binder component during firing are caused. Decomposition and the like became insufficient, the amount of residual carbon increased, and delamination easily occurred between the laminated ceramic green sheet and the conductive paste layer during firing. Further, even if delamination does not occur, residual carbon may cause deterioration of electrical characteristics of the capacitor such as insulation resistance.

【0007】また、バインダー成分の多い導電性ペース
トは、チクソトロピー性が増すため、スクリーン印刷後
の印刷面のレベリンング性が悪く、印刷パターンの端部
が盛り上がり、厚みを薄く均一に形成できなくなり、厚
みの厚い部分で同様にデラミネーションが生じやすくな
るという問題点を有していた。
Further, the conductive paste containing a large amount of the binder component has an increased thixotropy property, so that the leveling property of the printing surface after screen printing is poor and the edge of the printed pattern rises to make it impossible to form a thin and uniform thickness. Similarly, there is a problem that delamination is likely to occur in a thick portion.

【0008】そこで、本発明の目的は、厚膜用の導電性
ペーストにおいて、セラミックグリーンシートと同時焼
成したときのデラミネーションや、多層セラミック電子
部品としたときの残留炭素による電気的特性の劣化のお
こりにくい厚膜用の導電性ペーストを提供すると共に、
その厚膜用の導電性ペーストを用いた多層セラミック電
子部品の製造方法を提供することにある。
Therefore, an object of the present invention is to prevent delamination of a thick film conductive paste when co-fired with a ceramic green sheet and deterioration of electric characteristics due to residual carbon when a multilayer ceramic electronic component is formed. In addition to providing a conductive paste for thick films that is unlikely to occur,
It is an object of the present invention to provide a method for manufacturing a multilayer ceramic electronic component using the thick film conductive paste.

【0009】[0009]

【課題を解決するための手段】上記目的を達成するた
め、本発明の導電性ペーストは、セラミックグリーンシ
ート上に印刷して同時焼成する導電性ペーストにおい
て、溶剤成分として水素添加テルピネオールを含有する
ことを特徴とする。
In order to achieve the above object, the conductive paste of the present invention contains hydrogenated terpineol as a solvent component in the conductive paste which is printed on a ceramic green sheet and simultaneously fired. Is characterized by.

【0010】また、本発明の多層セラミック電子部品の
製造方法は、セラミックグリーンシート上に、溶剤成分
として水素添加テルピネオールを含有する導電性ペース
トを印刷し、該セラミックグリーンシートを複数枚積層
し、焼成することを特徴とする。
In the method for producing a multilayer ceramic electronic component of the present invention, a conductive paste containing hydrogenated terpineol as a solvent component is printed on a ceramic green sheet, a plurality of the ceramic green sheets are laminated and fired. It is characterized by doing.

【0011】なお、導電性ペースト中の溶剤以外の成分
は、公知の材料を使用する。即ち、導電性材料として
は、同時焼成するセラミックグリーンシートの焼成温度
および雰囲気に耐えるものであれば良いが、積層セラミ
ックコンデンサ用としては、Pd,Ag,Au,Pt,
Ni,Cu等の単体あるいはこれらの混合物、合金の粉
末を用いることができる。また、多層セラミック基板用
としてはAg,Pd,Cu等の単体あるいはこれらの混
合物、合金の粉末を用いることができる。バインダーと
してはエチルセルロース樹脂、アルキド樹脂等に必要に
応じて可塑剤、分散剤等を添加して、単体あるいは混合
して用いることができる。
Known components are used for the components other than the solvent in the conductive paste. That is, any conductive material may be used as long as it can withstand the firing temperature and atmosphere of the ceramic green sheets that are fired at the same time, but for the laminated ceramic capacitor, Pd, Ag, Au, Pt,
A single substance such as Ni and Cu, a mixture thereof, or an alloy powder can be used. Further, for the multilayer ceramic substrate, it is possible to use powders of Ag, Pd, Cu and the like alone or a mixture thereof, or an alloy powder. As the binder, an ethyl cellulose resin, an alkyd resin and the like may be used alone or as a mixture by adding a plasticizer, a dispersant and the like as necessary.

【0012】そして、多層セラミック電子部品として
は、積層セラミックコンデンサ、積層セラミックインダ
クタ、積層セラミックLC部品、多層セラミック基板等
があり、これらは、本発明の導電性ペーストを用いて、
公知の製造方法で得ることができる。すなわち、例えば
ドクターブレード法等で得たセラミックグリーンシート
にスクリーン印刷法等により本発明の導電性ペーストを
塗布し導電性ペースト層を形成する。次に、所望の構造
になるように必要枚数積層して圧着し積層体とする。そ
の後、このこのセラミックグリーンシートと導電性ペー
スト層の積層体を同時焼成して積層セラミックを得た
後、外部電極を塗布し焼き付ける等の加工をして多層セ
ラミック電子部品を得る。
As the multilayer ceramic electronic component, there are a multilayer ceramic capacitor, a multilayer ceramic inductor, a multilayer ceramic LC component, a multilayer ceramic substrate and the like, which are produced by using the conductive paste of the present invention.
It can be obtained by a known production method. That is, for example, the conductive paste of the present invention is applied to a ceramic green sheet obtained by a doctor blade method or the like by a screen printing method or the like to form a conductive paste layer. Next, a required number of layers are laminated so as to obtain a desired structure and pressure-bonded to obtain a laminated body. After that, the laminated body of the ceramic green sheet and the conductive paste layer is simultaneously fired to obtain a laminated ceramic, and then the external electrodes are applied and baked to obtain a multilayer ceramic electronic component.

【0013】[0013]

【作用】本発明の導電性ペーストは、溶剤として水素添
加テルピネオールを用いる。これにより、従来ブチルカ
ルビトールアセテート、テルピネオールあるいはケロシ
ン等の溶剤を用いていた場合と比較して、少ないバイン
ダー量で均一な印刷膜厚が得られる導電性ペーストとす
ることができる。即ち、バインダー成分の比率の少ない
印刷特性の良好な導電性ペーストを得ることができる。
The conductive paste of the present invention uses hydrogenated terpineol as a solvent. As a result, a conductive paste can be obtained in which a uniform printed film thickness can be obtained with a small amount of binder, as compared with the case where a solvent such as butyl carbitol acetate, terpineol or kerosene is conventionally used. That is, it is possible to obtain a conductive paste having a small binder component ratio and good printing characteristics.

【0014】[0014]

【実施例】以下、本発明の実施例を、積層セラミックコ
ンデンサを製造する場合について説明する。まず、エチ
ルセルロース樹脂とアルキッド樹脂からなるバインダー
を、水素添加テルピネオールに1〜20重量%溶解し
て、導電性ペースト用の有機ビヒクルを用意した。同様
に、ブチルカルビトールアセテート、テルピネオールお
よびケロシンの各溶剤についても、エチルセルロースと
アルキッド樹脂からなる1〜20重量%のバインダーを
溶解して、導電性ペースト用の有機ビヒクルを用意し、
比較例とした。表1に用意した有機ビヒクルそれぞれの
組成を示す。次に、Pd粉末に先に用意した有機ビヒク
ルをそれぞれ40重量%添加し、三本ロールで混練して
それぞれPdペーストとした。
EXAMPLES Examples of the present invention will be described below for manufacturing a monolithic ceramic capacitor. First, a binder composed of an ethyl cellulose resin and an alkyd resin was dissolved in hydrogenated terpineol in an amount of 1 to 20% by weight to prepare an organic vehicle for a conductive paste. Similarly, for each solvent of butyl carbitol acetate, terpineol and kerosene, 1 to 20 wt% of a binder consisting of ethyl cellulose and alkyd resin is dissolved to prepare an organic vehicle for a conductive paste,
It was used as a comparative example. Table 1 shows the composition of each of the prepared organic vehicles. Next, 40% by weight of the previously prepared organic vehicle was added to each of the Pd powders, and they were kneaded with a three-roll mill to form Pd pastes.

【0015】一方、BaTiO3 系セラミック原料粉末
にポリビニールブチラールの有機バインダーおよびトル
エンの有機溶剤を加え混練してスラリーを得た。続い
て、このスラリーをドクターブレード法によりシート状
に成形して、厚さ30μmのセラミックグリーンシート
を作製した。
On the other hand, an organic binder of polyvinyl butyral and an organic solvent of toluene were added to the BaTiO 3 -based ceramic raw material powder and kneaded to obtain a slurry. Subsequently, this slurry was formed into a sheet by a doctor blade method to produce a ceramic green sheet having a thickness of 30 μm.

【0016】その後、グリーンシートの一面に先に準備
した各Pdペーストをスクリーン印刷法にて印刷し、乾
燥させ導電性ペースト層を形成した。ここで、この導電
性ペースト層の厚み形状を、接触式表面あらさ計で測定
して確認した。次に、導電性ペースト層を有する所定枚
数のセラミックグリーンシートを容量電極を形成するよ
うに積み重ねた後、導電性ペースト層を有しないセラミ
ックグリーンシートに挟んで圧着して、積層体とした。
その後、この積層体のセラミックグリーンシートおよび
導電性ペースト中のバインダー成分を熱処理して除去し
た後、さらに昇温して積層誘電体セラミックの焼結体を
得た。そして最後に、この積層誘電体セラミックの内部
の容量電極が露出している焼結体の端面にAgペースト
を塗布し、焼き付けて外部電極を形成して、積層セラミ
ックコンデンサを完成させた。
Thereafter, each Pd paste prepared previously was printed on one surface of the green sheet by a screen printing method and dried to form a conductive paste layer. Here, the thickness shape of the conductive paste layer was measured and confirmed by a contact type surface roughness meter. Next, a predetermined number of ceramic green sheets having a conductive paste layer were stacked so as to form a capacitor electrode, and then sandwiched between the ceramic green sheets having no conductive paste layer and pressure-bonded to obtain a laminated body.
Then, the ceramic green sheet of this laminate and the binder component in the conductive paste were removed by heat treatment, and the temperature was further raised to obtain a sintered body of the laminated dielectric ceramic. Finally, Ag paste was applied to the end surface of the sintered body where the capacitive electrode inside the laminated dielectric ceramic was exposed, and baked to form external electrodes, thus completing the laminated ceramic capacitor.

【0017】次に、これらの積層セラミックコンデンサ
を内部の容量電極に垂直な面で切断・研磨して、内部の
容量電極とセラミック誘電体層との間のデラミネーショ
ンの有無を実体顕微鏡で確認した。
Next, these monolithic ceramic capacitors were cut and polished along a plane perpendicular to the internal capacitance electrode, and the presence or absence of delamination between the internal capacitance electrode and the ceramic dielectric layer was confirmed by a stereoscopic microscope. .

【0018】表1に有機ビヒクルの組成とともに、その
結果を示す。表1において、導電性ペースト層の形状の
欄の○印は、導電性ペーストのレベリング性が良く、印
刷された導電性ペースト層の厚み形状が印刷パターン内
の一縁端部から他の縁端部まで直線状をしており、ほぼ
均一な膜厚であったものを示す。×印は、導電性ペース
トの粘度が高くチクソトロピー性が増して印刷面のレベ
リンング性が悪いため、導電性ペースト層の厚み形状が
印刷パターン内の縁端部で盛り上がり、不均一な膜厚で
あったものを示す。△印は、導電性ペーストの粘度が低
く、滲んでスクリーン印刷できなかったものを示す。ま
た、デラミネーションの欄の数字は[デラミネーション
が認められた試料数/総供試数]を示し、△印は、電極
形状の欄の△印と同一である。
Table 1 shows the composition of the organic vehicle and the results. In Table 1, the mark ○ in the column of the shape of the conductive paste layer indicates that the leveling property of the conductive paste is good, and the thickness shape of the printed conductive paste layer is from one edge part to another edge part in the print pattern. The part has a linear shape up to the part, and shows that the film thickness is almost uniform. The mark x indicates that the conductive paste has high viscosity and thixotropy, and the leveling property of the printed surface is poor. Shows The mark Δ indicates that the conductive paste had a low viscosity and could not be screen-printed due to bleeding. The number in the column of delamination indicates [the number of samples in which delamination was recognized / the total number of samples], and the symbol Δ is the same as the symbol Δ in the electrode shape column.

【0019】表1より明らかな通り、本発明の水素添加
テルピネオールを有機ビヒクルの溶剤として用いた導電
性ペーストは、従来のブチルカルビトールアセテート、
テルピネオールあるいはケロシンの溶剤を用いていた場
合と比較して、少ないバインダー量で均一な印刷厚み形
状が得られている。即ち均一な印刷厚み形状を得るため
には、従来のブチルカルビトールアセテート、テルピネ
オールあるいはケロシンを溶剤とした場合には、5〜1
0%のバインダーを添加する必要があったのに対し、水
素添加テルピネオールの場合には、1〜5%のバインダ
ー量で十分である。このため、得られた積層誘電体セラ
ミックのデラミネーションの発生率が、(10〜20)
/20から(0〜2)/20へと大幅に減少している。
As is clear from Table 1, the conductive paste using the hydrogenated terpineol of the present invention as the solvent of the organic vehicle is the conventional butyl carbitol acetate,
Compared with the case where a solvent of terpineol or kerosene was used, a uniform print thickness shape was obtained with a small amount of binder. That is, in order to obtain a uniform print thickness shape, when conventional butyl carbitol acetate, terpineol or kerosene is used as a solvent, it is 5 to 1
Whereas it was necessary to add 0% binder, in the case of hydrogenated terpineol, a binder amount of 1-5% is sufficient. Therefore, the occurrence rate of delamination of the obtained laminated dielectric ceramic is (10 to 20).
It is greatly reduced from / 20 to (0-2) / 20.

【0020】なお、以上実施例において、積層セラミッ
クコンデンサを製造する場合について説明したが、他の
積層セラミックインダクタ、積層セラミックLC部品、
多層セラミック基板等の同様の積層構造を取る多層セラ
ミック電子部品を製造する場合にも、同様の効果が得ら
れることは言うまでもない。
In the above embodiments, the case of manufacturing a monolithic ceramic capacitor has been described, but other monolithic ceramic inductors, monolithic ceramic LC parts,
It goes without saying that similar effects can be obtained when manufacturing a multilayer ceramic electronic component having a similar laminated structure such as a multilayer ceramic substrate.

【0021】[0021]

【発明の効果】以上の説明で明らかなように、本発明の
導電性ペーストは、従来より少ないバインダー量で均一
な印刷膜厚が得られる。従って、積層セラミックコンデ
ンサ等のセラミックグリーンシートと導電性ペースト層
を同時焼成して得られる多層セラミック電子部品のデラ
ミネーションを防止することができる。
As is apparent from the above description, the conductive paste of the present invention can obtain a uniform printed film thickness with a smaller amount of binder than before. Therefore, it is possible to prevent delamination of a multilayer ceramic electronic component obtained by simultaneously firing a ceramic green sheet such as a laminated ceramic capacitor and a conductive paste layer.

【0022】また、導電性ペースト中のバインダー量が
少ない分、同時焼成して得られる多層セラミック電子部
品に残留する炭素量が少なくなり、電気的特性の劣化を
防止することができる。
Further, as the amount of the binder in the conductive paste is smaller, the amount of carbon remaining in the multilayer ceramic electronic component obtained by co-firing becomes smaller, and the deterioration of the electrical characteristics can be prevented.

【0023】[0023]

【表1】 [Table 1]

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 セラミックグリーンシート上に印刷して
同時焼成する導電性ペーストにおいて、溶剤成分として
水素添加テルピネオールを含有することを特徴とする導
電性ペースト。
1. A conductive paste which is printed on a ceramic green sheet and co-fired, wherein the conductive paste contains hydrogenated terpineol as a solvent component.
【請求項2】 セラミックグリーンシート上に、溶剤成
分として水素添加テルピネオールを含有する導電性ペー
ストを印刷し、該セラミックグリーンシートを複数枚積
層し、焼成することを特徴とする多層セラミック電子部
品の製造方法。
2. A multilayer ceramic electronic component, comprising: printing a conductive paste containing hydrogenated terpineol as a solvent component on a ceramic green sheet, laminating a plurality of the ceramic green sheets, and firing. Method.
JP16557193A 1993-07-05 1993-07-05 Conductive paste and method for manufacturing multilayer ceramic electronic component using the same Expired - Lifetime JP3102454B2 (en)

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