JP2001274035A - Conductive paste for laminated ceramic capacitor and laminated ceramic capacitor using it - Google Patents
Conductive paste for laminated ceramic capacitor and laminated ceramic capacitor using itInfo
- Publication number
- JP2001274035A JP2001274035A JP2000089413A JP2000089413A JP2001274035A JP 2001274035 A JP2001274035 A JP 2001274035A JP 2000089413 A JP2000089413 A JP 2000089413A JP 2000089413 A JP2000089413 A JP 2000089413A JP 2001274035 A JP2001274035 A JP 2001274035A
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- Japan
- Prior art keywords
- glass frit
- component
- ceramic capacitor
- mol
- glass
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、積層セラミックコ
ンデンサの外部電極形成に好適な導電性ペーストならび
にこれを用いて外部電極を形成した積層セラミックコン
デンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste suitable for forming external electrodes of a multilayer ceramic capacitor and a multilayer ceramic capacitor using the same to form external electrodes.
【０００２】[0002]
【従来の技術】従来より積層セラミックコンデンサは、
複数のセラミック層が積層されてなるセラミック素体
と、それぞれの端縁が前記セラミック層の何れかの端面
に露出するように前記セラミック層間に形成された複数
の内部電極と、露出した前記内部電極に電気的に接続さ
れるように設けられた外部電極とを備えている。また、
上述の外部電極は、導電性ペーストをセラミック素体の
両端面に塗布し焼成して形成されている。また、このよ
うな外部電極上には、はんだ濡れ性やはんだ耐熱性の向
上を目的として、Ｎｉ，Ｓｎ，はんだ等のめっき処理が
施されているものがある。2. Description of the Related Art Conventionally, multilayer ceramic capacitors have been
A ceramic body in which a plurality of ceramic layers are stacked; a plurality of internal electrodes formed between the ceramic layers such that respective edges are exposed on any one end surface of the ceramic layer; and the exposed internal electrodes And an external electrode provided so as to be electrically connected to the external device. Also,
The above-mentioned external electrodes are formed by applying a conductive paste to both end surfaces of a ceramic body and firing the paste. Some of such external electrodes are plated with Ni, Sn, solder, or the like for the purpose of improving solder wettability and solder heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うな従来技術によれば、上述のめっき処理を施す場合に
めっき液が外部電極内に浸入し、セラミック素体のセラ
ミック層界面に達して内部欠陥を引き起こすという問題
がある。特に近年では、積層セラミックコンデンサの高
容量化に伴ってセラミック層の積層数の増加や内部電極
の薄層化が進み、めっき液の浸入による内部欠陥の不良
が顕著となってきている。このような、めっき液の浸入
による内部欠陥は、主に従来のガラスフリットの耐めっ
き性に起因し、具体的には、公知の３成分系ガラスであ
るＢ−Ｓｉ−Ｂａ−ＯガラスやＢ−Ｂａ−Ａｌ−Ｏガラ
ス、４成分系ガラスであるＢ−Ｓｉ−Ｂａ−Ｃｕ−Ｏガ
ラスやＢ−Ｓｉ−Ｂａ−Ｎｉ−Ｏガラス等のガラスフリ
ットが用いられていた。However, according to such prior art, when the above-described plating treatment is performed, the plating solution infiltrates into the external electrode, reaches the interface of the ceramic layer of the ceramic body, and causes internal defects. There is a problem that causes. In particular, in recent years, the number of stacked ceramic layers has been increased and the thickness of the internal electrodes has been reduced with the increase in the capacity of multilayer ceramic capacitors, and internal defects due to intrusion of a plating solution have become remarkable. Such internal defects due to the infiltration of the plating solution are mainly caused by the plating resistance of the conventional glass frit, and specifically, known B-Si-Ba-O glass or B-Si-Ba-O glass Glass frit such as -Ba-Al-O glass, quaternary glass such as B-Si-Ba-Cu-O glass or B-Si-Ba-Ni-O glass has been used.
【０００４】また、内部電極を構成する導電粉末の卑金
属化が進み、これに伴って外部電極を構成する導電粉末
もＣｕやＮｉ等の卑金属化が進み、従来のＡｇやＡｇ／
Ｐｄ等の貴金属を導電成分とする外部電極と比較して、
焼成後の外部電極の焼結密度が低下する傾向があり、め
っき液の浸入がより一層問題となっている。[0004] Further, the base metal of the conductive powder constituting the internal electrode is advanced, and the base metal of the conductive powder constituting the external electrode is also advanced to base metal such as Cu or Ni.
Compared to an external electrode using a noble metal such as Pd as a conductive component,
The sintered density of the external electrode after firing tends to decrease, and penetration of the plating solution has become even more problematic.
【０００５】本発明の目的は、上述の問題点を解消すべ
くなされたもので、めっき液の浸入を抑制し得る、積層
セラミックコンデンサの外部電極形成用導電性ペース
ト、ならびにめっき液の浸入の抑制された積層セラミッ
クコンデンサを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and a conductive paste for forming an external electrode of a multilayer ceramic capacitor capable of suppressing infiltration of a plating solution, and suppression of infiltration of a plating solution. To provide a laminated ceramic capacitor.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明の積層セラミックコンデンサ用導電性ペース
トは、Ｃｕまたは／およびＮｉ成分から主になる導電粉
末と、ガラスフリットと、有機ビヒクルを含有し、ガラ
スフリットは、Ｂ，Ｓｉ，Ｂａ，Ａｌ成分を含む主成分
と、Ｃｕまたは／およびＮｉ成分からなる副成分からな
る酸化物であって、実質的にＰｂ成分を含まず、Ｂａ成
分を酸化物ＢａＯに換算したときの酸化物モル比は、ガ
ラスフリット１００モル％に対して２０〜４５モル％で
あることを特徴とする。In order to achieve the above object, a conductive paste for a multilayer ceramic capacitor according to the present invention comprises a conductive powder mainly composed of Cu or / and Ni components, a glass frit, and an organic vehicle. The glass frit is an oxide composed of a main component including B, Si, Ba, and Al components and an auxiliary component including Cu and / or Ni components, and substantially does not include a Pb component, and includes a Ba component. Is converted to oxide BaO, the oxide molar ratio is 20 to 45 mol% with respect to 100 mol% of glass frit.
【０００７】また、ガラスフリットの含有量は、導電粉
末とガラスフリットの合計１００重量％のうち、５〜５
０重量％であることを特徴とする。The glass frit content is 5 to 5% of the total 100% by weight of the conductive powder and the glass frit.
0% by weight.
【０００８】また、本発明の積層セラミックコンデンサ
は、複数のセラミック層が積層されてなるセラミック素
体と、それぞれの端縁がセラミック層の何れかの端面に
露出するようにセラミック層間に形成された卑金属を導
電成分とする複数の内部電極と、露出した内部電極に電
気的に接続されるように設けられた外部電極とを備え、
外部電極は、本発明の導電性ペーストがセラミック素体
の両端面に塗布されて形成されていることを特徴とす
る。Further, the multilayer ceramic capacitor of the present invention is formed between a ceramic body in which a plurality of ceramic layers are laminated, and between the ceramic layers such that each edge is exposed at any one end face of the ceramic layer. A plurality of internal electrodes having a base metal as a conductive component, and an external electrode provided to be electrically connected to the exposed internal electrode,
The external electrode is characterized in that the conductive paste of the present invention is formed by applying to both end surfaces of the ceramic body.
【０００９】[0009]
【発明の実施の形態】本発明の導電性ペーストは、５成
分系または６成分系の硼珪酸バリウムアルミナ−卑金属
ガラス、すなわちＢ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｏガラ
ス、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｎｉ−Ｏガラス，ま
たはＢ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｎｉ−Ｏガラスを用
いることにより、ガラス構造の強化が図れて耐めっき性
が増し、同時に内部電極との接合安定性が増すことに特
徴がある。BEST MODE FOR CARRYING OUT THE INVENTION The conductive paste of the present invention comprises a five-component or six-component barium borosilicate alumina-base metal glass, that is, B-Si-Ba-Al-Cu-O glass, B-Si-Ba. By using -Al-Cu-Ni-O glass or B-Si-Ba-Al-Cu-Ni-O glass, the glass structure is strengthened and plating resistance is increased, and at the same time, the bonding stability with the internal electrode is stabilized. It is characterized by increased sex.
【００１０】ガラスフリットを構成する成分のうち、Ｂ
ａ成分はめっき液と安定な不溶性反応物を生成すること
により耐めっき性が増す効果が得られ、ガラスフリット
１００モル％中のＢａ成分の含有量は、酸化物ＢａＯ換
算で２０〜４５モル％の範囲内であることを要する。含
有量が２０モル％を下回ると、上述の添加効果が十分に
得られない。また、含有量が４５モル％を上回ると、ガ
ラスが低温から結晶化を引き起こし易くなるため、この
ようなガラスフリットを含有する導電性ペーストを用い
て形成される外部電極は、焼成中に焼結阻害を引き起こ
してめっき液の浸入が生じ易くなる。[0010] Among the components constituting the glass frit, B
The component a has an effect of increasing plating resistance by generating a stable insoluble reactant with the plating solution. The content of the Ba component in 100 mol% of the glass frit is 20 to 45 mol% in terms of oxide BaO. Must be within the range. If the content is less than 20 mol%, the above-mentioned addition effect cannot be sufficiently obtained. On the other hand, if the content exceeds 45 mol%, the glass tends to be crystallized from a low temperature, and thus the external electrode formed using the conductive paste containing such a glass frit is not sintered during firing. Inhibition causes the plating solution to easily penetrate.
【００１１】ガラスフリットを構成する成分のうち、Ａ
ｌ成分はガラス構造の強化を生じさせる目的で添加され
る。また、ＣｕやＮｉ成分は、同じ卑金属からなる内部
電極との接合安定性を図る目的で添加されている。Ｂａ
成分，Ａｌ成分，ＣｕもしくはＮｉ成分が、単独ではな
く全３成分がＢ−Ｓｉ−Ｏ系ガラスに含まれることで、
ガラス構造が強化され耐メッキ性が増す。なお、本発明
のガラスフリットは上述の５成分ないし６成分ガラスに
限定されることなく、さらにＬｉ，Ｎａ，Ｋ成分等のア
ルカリ金属酸化物や、Ｚｎ，Ｍｎ，Ｆｅ等の他の金属成
分を含有していても、同様に本発明の効果が得られる
が、アルカリ金属酸化物は、ガラスフリット中における
構成比率が増すと内部欠陥の発生率が高くなる傾向にあ
るため、ガラスフリット１００重量％中のアルカリ金属
酸化物は１０モル％以下であることが好ましい。Among the components constituting the glass frit, A
The l component is added for the purpose of causing the strengthening of the glass structure. Further, Cu and Ni components are added for the purpose of stabilizing the bonding with the internal electrode made of the same base metal. Ba
The component, Al component, Cu or Ni component is not alone, but all three components are contained in the B-Si-O-based glass,
The glass structure is strengthened and plating resistance is increased. In addition, the glass frit of the present invention is not limited to the above-described five-component or six-component glass, and further includes an alkali metal oxide such as a Li, Na, and K component, and another metal component such as Zn, Mn, and Fe. The effect of the present invention can be similarly obtained even if it is contained, but the alkali metal oxide tends to increase the incidence of internal defects when the composition ratio in the glass frit increases, so that 100% by weight of the glass frit It is preferable that the content of the alkali metal oxide therein is 10 mol% or less.
【００１２】また、本発明の導電性ペーストにおける導
電成分とガラスフリットの混合比率は、特に限定するも
のではないが、好ましくは導電粉末５０〜９５体積％に
対してガラスフリットが５〜５０体積％である。ガラス
フリットの混合比率が５体積％を下回ると、めっき液の
浸入を抑制するという本発明の効果が得られにくく、他
方、混合比率が５０体積％を上回ると、外部電極の表面
に余剰のガラスが析出してめっき付き性が悪化する恐れ
がある。The mixing ratio of the conductive component and the glass frit in the conductive paste of the present invention is not particularly limited, but preferably the glass frit is 5 to 50% by volume based on 50 to 95% by volume of the conductive powder. It is. When the mixing ratio of the glass frit is less than 5% by volume, it is difficult to obtain the effect of the present invention that the intrusion of the plating solution is suppressed. On the other hand, when the mixing ratio is more than 50% by volume, surplus glass on the surface of the external electrode. May be deposited to deteriorate the plating ability.
【００１３】本発明の積層セラミックコンデンサを、図
１に基づいて詳細に説明する。すなわち、積層セラミッ
クコンデンサ１は、セラミック素体２と、内部電極３，
３と、外部電極４，４と、めっき膜５，５とからなる。The multilayer ceramic capacitor of the present invention will be described in detail with reference to FIG. That is, the multilayer ceramic capacitor 1 includes the ceramic body 2, the internal electrodes 3,
3, external electrodes 4 and 4, and plating films 5 and 5.
【００１４】セラミック素体２は、誘電体材料、例えば
ＢａＴｉＯ3を主成分とするセラミックグリーンシート
からなるセラミック層２ａが複数積層され、所定の温度
で焼成されてなる。The ceramic body 2 is formed by laminating a plurality of ceramic layers 2a composed of a ceramic green sheet containing a dielectric material, for example, BaTiO 3 as a main component, and firing at a predetermined temperature.
【００１５】内部電極３，３は、それぞれの端縁がセラ
ミック層２ａの何れかの端面に露出するようにセラミッ
ク層２ａ間に形成されており、Ｃｕまたは／およびＮｉ
成分を導電成分とする導電性ペーストが所定のセラミッ
ク層２ａ上に塗布され、セラミック層２ａと共に積層さ
れ、セラミック素体２と同時に焼成されてなる。The internal electrodes 3, 3 are formed between the ceramic layers 2a such that their respective edges are exposed on any one of the end faces of the ceramic layer 2a.
A conductive paste having a component as a conductive component is applied on a predetermined ceramic layer 2a, laminated with the ceramic layer 2a, and fired at the same time as the ceramic body 2.
【００１６】外部電極４，４は、セラミック素体２の両
端面に本発明の導電性ペーストが塗布され焼成されてな
り、セラミック素体２の端面に露出した内部電極３，３
の端縁の一方と電気的・機械的に接合されている。The external electrodes 4, 4 are formed by applying the conductive paste of the present invention to both end faces of the ceramic body 2 and sintering the inner electrodes 3, 3 exposed on the end faces of the ceramic body 2.
Is electrically and mechanically joined to one of the edges.
【００１７】めっき膜５，５は、例えば、ＳｎやＮｉ等
の無電解めっきや、はんだめっき等からなり、外部電極
上４，４上に少なくとも１層形成されてなる。The plating films 5 and 5 are made of, for example, electroless plating of Sn, Ni or the like, or solder plating, and are formed by forming at least one layer on the external electrodes 4 and 4.
【００１８】なお、本発明の積層セラミックコンデンサ
のセラミック素体２の材料は、上述の実施形態に限定さ
れることなく、例えばＰｂＴｉＯ3，ＰｂＺｒＯ3等その
他の誘電体材料からなっても構わない。The material of the ceramic body 2 of the multilayer ceramic capacitor of the present invention is not limited to the above embodiment, but may be made of other dielectric materials such as PbTiO 3 and PbZrO 3 .
【００１９】また、本発明の積層セラミックコンデンサ
の内部電極の枚数は、上述の実施形態に限定されること
なく、単数あるいは３枚以上の複数からなっても構わな
い。The number of internal electrodes of the multilayer ceramic capacitor of the present invention is not limited to the above-described embodiment, and may be a single or three or more.
【００２０】[0020]
【実施例】（実施例１）まず、表１に示すような組成比
率となるようなガラスフリットを作製した。すなわち、
まず、出発原料としてＢａＣＯ3，ＳｉＯ2，Ｈ3ＢＯ3，
Ａｌ（ＯＨ）3，ＺｎＯ，ＣｕＯ，ＮｉＯを所定量調合
し混合した後、アルミナるつぼで１０００〜１５００℃
の範囲で溶融させ、水中に投下して急冷してガラス化さ
せ、試料１〜２７のガラスカレットを得た。EXAMPLES (Example 1) First, a glass frit having a composition ratio as shown in Table 1 was produced. That is,
First, BaCO 3 , SiO 2 , H 3 BO 3 ,
After a predetermined amount of Al (OH) 3 , ZnO, CuO, and NiO are mixed and mixed, 1000 to 1500C in an alumina crucible.
Was melted, dropped into water, quenched and vitrified to obtain glass cullets of Samples 1 to 27.
【００２１】次いで、試料１〜２７のガラスカレットを
メノウ乳鉢で粗粉砕した後、ジルコニア球をメディアと
するボールミルを用いて微粉砕を行ない、試料１〜２７
のガラスフリットを得た。Next, the glass cullets of Samples 1 to 27 were roughly pulverized in an agate mortar, and then finely pulverized using a ball mill using zirconia spheres as media.
A glass frit was obtained.
【００２２】次いで、試料１〜２７のガラスフリットを
用いてＣｕを導電成分とする導電性ペーストを作製し
た。すなわち、Ｃｕ粉末と試料１〜２７のガラスフリッ
トを容積比率で８０：２０の割合で混合し、テルピネオ
ールにアクリル樹脂を２０重量％添加した有機ビヒクル
を適量加え、３本ロールで混合ならびに分散させて、試
料１〜２７の導電性ペーストを得た。Next, a conductive paste containing Cu as a conductive component was prepared using the glass frit of Samples 1 to 27. That is, the Cu powder and the glass frit of the samples 1 to 27 are mixed at a volume ratio of 80:20, an appropriate amount of an organic vehicle in which terpineol is added with 20% by weight of an acrylic resin is added, and mixed and dispersed with three rolls. Thus, conductive pastes of Samples 1 to 27 were obtained.
【００２３】次いで、ＢａＴｉＯ3を主成分とするセラ
ミック層を準備し、所定枚数のセラミック層の表面上に
一方の端縁がセラミック層の何れかの端面側に露出する
ように、内部電極となるべき電極膜を印刷し、これら複
数のセラミック層を所定枚数積層し圧着して、複数の生
のセラミック素体を準備した。Next, a ceramic layer containing BaTiO 3 as a main component is prepared, and an internal electrode is formed on a surface of a predetermined number of ceramic layers such that one edge is exposed to one of the end faces of the ceramic layer. An electrode film to be printed was printed, a predetermined number of these ceramic layers were laminated, and pressed to prepare a plurality of raw ceramic bodies.
【００２４】次に、生のセラミック素体の両端面に、試
料１〜２７の導電性ペーストを浸漬塗布し、１２０℃で
１０分間乾燥させた後、中性雰囲気中で８５０℃１０分
ピークの条件で焼成して、内部電極に電気的かつ機械的
に接合された一対の外部電極を形成した。次に、この一
対の外部電極上にＮｉめっき膜を電解めっき処理により
形成し、さらにＮｉめっき膜上にＳｎめっき膜を電解め
っき処理により形成して、試料１〜２７の積層セラミッ
クコンデンサを１００００個ずつ得た。Next, the conductive pastes of Samples 1 to 27 were dip-coated on both end surfaces of the raw ceramic body, dried at 120 ° C. for 10 minutes, and then peaked at 850 ° C. for 10 minutes in a neutral atmosphere. By firing under the conditions, a pair of external electrodes electrically and mechanically joined to the internal electrodes were formed. Next, a Ni plating film was formed on the pair of external electrodes by electrolytic plating, and a Sn plating film was formed on the Ni plating film by electrolytic plating to obtain 10,000 laminated ceramic capacitors of Samples 1 to 27. I got each.
【００２５】そこで、試料１〜２７の積層セラミックコ
ンデンサについて内部欠陥の発生率を測定し、これを表
１にまとめた。The occurrence rate of internal defects was measured for the multilayer ceramic capacitors of Samples 1 to 27, and the results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１から明らかであるように、導電性ペー
スト中に含有されるガラスフリットが、５成分のＢ−Ｓ
ｉ−Ｂａ−Ａｌ−Ｃｕ−ＯガラスまたはＢ−Ｓｉ−Ｂａ
−Ａｌ−Ｎｉ−Ｏガラスであって、Ｂａ成分を酸化物Ｂ
ａＯに換算したときの酸化物モル比が、ガラスフリット
１００モル％に対して２０〜４５モル％である試料７〜
１２，１７〜１９は、内部欠陥の発生率が０〜０．０９
％で低く優れ、本発明の範囲内となった。As is evident from Table 1, the glass frit contained in the conductive paste was a five-component BS
i-Ba-Al-Cu-O glass or B-Si-Ba
-Al-Ni-O glass, wherein Ba component is oxide B
Samples 7 to 10 in which the oxide molar ratio in terms of aO is 20 to 45 mol% with respect to 100 mol% of glass frit
12, 17 to 19 have an internal defect generation rate of 0 to 0.09.
%, Which was low and excellent, and was within the range of the present invention.
【００２８】また、上述の５成分に加えてアルカリ金属
酸化物をガラスフリット１００モル％に対して５〜１０
モル％含有してなるガラスフリットを用いた試料２１〜
２７は、内部欠陥の発生率が０．０１〜０．０９％で低
く優れ、本発明の範囲内となった。Further, in addition to the above five components, an alkali metal oxide is added in an amount of 5 to 10 with respect to 100 mol% of the glass frit.
Sample 21 using a glass frit containing mol%
In No. 27, the rate of occurrence of internal defects was as low as 0.01 to 0.09%, which was excellent and fell within the range of the present invention.
【００２９】これに対して、Ｂ成分、Ｓｉ成分、Ａｌ成
分の何れかを含有しないガラスフリットを用いた試料１
〜４は、内部欠陥の発生率が４．４２〜１０．２３％と
高く劣り、本発明の範囲外となった。On the other hand, Sample 1 using a glass frit containing no B component, Si component or Al component
In Nos. To 4, the incidence of internal defects was as high as 4.42 to 10.23%, which was out of the range of the present invention.
【００３０】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｏガ
ラスであっても、Ｂａ成分を酸化物ＢａＯに換算したと
きの酸化物モル比が、ガラスフリット１００モル％に対
して２０モル％を下回る試料５，６は、内部欠陥の発生
率がそれぞれ２．３０％，０．７６％で高く劣り、本発
明の範囲外となった。Also, even in the case of B-Si-Ba-Al-Cu-O glass, when the Ba component is converted to oxide BaO, the oxide molar ratio is 20 mol% with respect to 100 mol% of glass frit. Samples 5 and 6, which were lower than the above, had an internal defect generation rate of 2.30% and 0.76%, respectively, which were inferior and were out of the range of the present invention.
【００３１】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｏガ
ラスであって、Ｂａ成分を酸化物ＢａＯに換算したとき
の酸化物モル比が、ガラスフリット１００モル％に対し
て４５モル％を上回る試料１３は、内部欠陥の発生率が
０．２９％で高く劣り、本発明の範囲外となった。同様
に、試料１４，１５は、外部電極の焼成時にガラスフリ
ットが溶融しなかったため、積層セラミックコンデンサ
の外部電極形成用の導電性ペーストに用いるガラスフリ
ットとしては不適確であり、本発明の範囲外となった。In the case of B-Si-Ba-Al-Cu-O glass, when the Ba component is converted to oxide BaO, the oxide molar ratio is 45 mol% with respect to 100 mol% of glass frit. Sample 13 which was higher than the sample 13 had an internal defect generation rate of 0.29%, which was inferior and was out of the range of the present invention. Similarly, in Samples 14 and 15, the glass frit was not melted during firing of the external electrode, and thus was unsuitable as a glass frit used as a conductive paste for forming an external electrode of a multilayer ceramic capacitor, and was outside the scope of the present invention. It became.
【００３２】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｎｉ−Ｏガ
ラスであって、Ｂａ成分を酸化物ＢａＯに換算したとき
の酸化物モル比が、ガラスフリット１００モル％に対し
て２０モル％を下回る試料１６と、４５モル％を上回る
試料２０は、内部欠陥の発生率がそれぞれ０．９２％，
０．１８％で高く劣り、本発明の範囲外となった。 （実施例２）実施例１における試料１〜２７のガラスフ
リットと同じ組成のガラスフリットを試料２８〜５４の
ガラスフリットとして作製し、この試料２８〜５４のガ
ラスフリットを用いてＮｉを導電成分とする導電性ペー
ストを作製した。すなわち、Ｎｉ粉末と試料２８〜５４
のガラスフリットを容積比率で８０：２０の割合で混合
し、テルピネオールにアクリル樹脂を２０重量％添加し
た有機ビヒクルを適量加え、３本ロールで混合ならびに
分散させて、試料２８〜５４の導電性ペーストを得た。Further, in the case of B-Si-Ba-Al-Ni-O glass, when the Ba component is converted to oxide BaO, the oxide molar ratio is 20 mol% with respect to 100 mol% of glass frit. Sample 16 which was lower than that and Sample 20 which was more than 45 mol% had an internal defect occurrence rate of 0.92%,
0.18% was inferior and high, and was out of the range of the present invention. (Example 2) A glass frit having the same composition as the glass frit of Samples 1 to 27 in Example 1 was prepared as glass frit of Samples 28 to 54, and Ni was used as a conductive component by using the glass frit of Samples 28 to 54. A conductive paste was prepared. That is, Ni powder and samples 28 to 54
Are mixed in a volume ratio of 80:20, an appropriate amount of an organic vehicle in which terpineol is added with 20% by weight of an acrylic resin is added and mixed and dispersed with three rolls, and the conductive pastes of Samples 28 to 54 are prepared. I got
【００３３】次いで、実施例１で作製した生のセラミッ
ク素体の両端面に、試料２８〜５４の導電性ペーストを
浸漬塗布し、１２０℃で１０分間乾燥させた後、中性雰
囲気中で９００℃１０分ピークの条件で焼成して、内部
電極に電気的かつ機械的に接合された一対の外部電極を
形成した。次に、この一対の外部電極上にＮｉめっき膜
を電解めっき処理により形成し、さらにＮｉめっき膜上
にＳｎめっき膜を電解めっき処理により形成して、試料
２８〜５４の積層セラミックコンデンサを１００００個
ずつ得た。Next, the conductive pastes of Samples 28 to 54 were dip-coated on both end surfaces of the raw ceramic body prepared in Example 1 and dried at 120 ° C. for 10 minutes. Baking was performed at a peak temperature of 10 ° C. for 10 minutes to form a pair of external electrodes electrically and mechanically joined to the internal electrodes. Next, a Ni plating film was formed on the pair of external electrodes by electrolytic plating, and a Sn plating film was formed on the Ni plating film by electrolytic plating to obtain 10,000 laminated ceramic capacitors of Samples 28 to 54. I got each.
【００３４】そこで、試料２８〜５４の積層セラミック
コンデンサについて内部欠陥の発生率を測定し、これを
表２にまとめた。The occurrence rate of internal defects was measured for the multilayer ceramic capacitors of Samples 28 to 54, and the results are shown in Table 2.
【００３５】[0035]
【表２】 [Table 2]
【００３６】表２から明らかであるように、導電性ペー
スト中に含有されるガラスフリットが、５成分のＢ−Ｓ
ｉ−Ｂａ−Ａｌ−Ｃｕ−ＯガラスまたはＢ−Ｓｉ−Ｂａ
−Ａｌ−Ｎｉ−Ｏガラスであって、Ｂａ成分を酸化物Ｂ
ａＯに換算したときの酸化物モル比が、ガラスフリット
１００モル％に対して２０〜４５モル％である試料３４
〜３９，４４〜４６は、内部欠陥の発生率が０〜０．０
７％で低く優れ、本発明の範囲内となった。As is evident from Table 2, the glass frit contained in the conductive paste was a five-component BS
i-Ba-Al-Cu-O glass or B-Si-Ba
-Al-Ni-O glass, wherein Ba component is oxide B
Sample 34 in which the oxide molar ratio in terms of aO is 20 to 45 mol% with respect to 100 mol% of glass frit.
-39,44-46, the incidence of internal defects is 0-0.0
7% was low and excellent, and was within the range of the present invention.
【００３７】また、上述の５成分に加えてアルカリ金属
酸化物をガラスフリット１００モル％に対して５〜１０
モル％含有してなるガラスフリットを用いた試料４８〜
５４は、内部欠陥の発生率が０〜０．０５％で低く優
れ、本発明の範囲内となった。Further, in addition to the above five components, an alkali metal oxide is added in an amount of 5 to 10 with respect to 100 mol% of the glass frit.
Sample 48 using a glass frit containing mol%
In No. 54, the incidence of internal defects was as low as 0 to 0.05%, which was within the scope of the present invention.
【００３８】これに対して、Ｂ成分、Ｓｉ成分、Ａｌ成
分の何れかを含有しないガラスフリットを用いた試料２
８〜３１は、内部欠陥の発生率が１．９８〜５．６６％
と高く劣り、本発明の範囲外となった。On the other hand, Sample 2 using a glass frit containing no B component, Si component or Al component was used.
8 to 31, the internal defect occurrence rate is 1.98 to 5.66%.
And it was out of the range of the present invention.
【００３９】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｏガ
ラスであっても、Ｂａ成分を酸化物ＢａＯに換算したと
きの酸化物モル比が、ガラスフリット１００モル％に対
して２０モル％を下回る試料３２，３３は、内部欠陥の
発生率がそれぞれ１．０５％，０．５５％で高く劣り、
本発明の範囲外となった。Even in the case of B-Si-Ba-Al-Cu-O glass, when the Ba component is converted to BaO, the molar ratio of oxide is 20 mol% with respect to 100 mol% of glass frit. Samples 32 and 33, which are lower than the above, have an internal defect generation rate of 1.05% and 0.55%, respectively, which are high and inferior.
It is outside the scope of the present invention.
【００４０】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｃｕ−Ｏガ
ラスであって、Ｂａ成分を酸化物ＢａＯに換算したとき
の酸化物モル比が、ガラスフリット１００モル％に対し
て４５モル％を上回る試料４０は、内部欠陥の発生率が
０．１９％で高く劣り、本発明の範囲外となった。同様
に、試料４１，４２は、外部電極の焼成時にガラスフリ
ットが溶融しなかったため、積層セラミックコンデンサ
の外部電極形成用の導電性ペーストに用いるガラスフリ
ットとしては不適確であり、本発明の範囲外となった。In the case of B-Si-Ba-Al-Cu-O glass, when the Ba component is converted to oxide BaO, the oxide molar ratio is 45 mol% with respect to 100 mol% of glass frit. Sample 40, which exceeded, had an internal defect generation rate of 0.19%, which was inferior and was out of the range of the present invention. Similarly, since the glass frit did not melt when the external electrodes were fired, the samples 41 and 42 were unsuitable as the glass frit used as the conductive paste for forming the external electrodes of the multilayer ceramic capacitor, and were outside the scope of the present invention. It became.
【００４１】また、Ｂ−Ｓｉ−Ｂａ−Ａｌ−Ｎｉ−Ｏガ
ラスであって、Ｂａ成分を酸化物ＢａＯに換算したとき
の酸化物モル比が、ガラスフリット１００モル％に対し
て２０モル％を下回る試料４３と、４５モル％を上回る
試料４７は、内部欠陥の発生率がそれぞれ０．８８％，
０．１５％で高く劣り、本発明の範囲外となった。 （実施例３）Ｃｕを導電粉末として、１４Ｂ−３３Ｓｉ
−３３Ｂａ−７Ａｌ−８Ｃｕ−５ＮＡ−Ｏガラスからな
るガラスフリットを添加した試料２２について、導電粉
末とガラスフリットの構成比率を変化させた試料５７〜
６２の導電性ペーストを作製した。すなわち、導電性粉
末とガラスフリットの構成比率を表３に示す割合とし
て、実施例１と同様の作製方法によって実施例５７〜６
２の導電性ペーストを作製し、実施例１と同様の作製方
法によって実施例５７〜６２の積層セラミックコンデン
サを作製した。In the case of B-Si-Ba-Al-Ni-O glass, when the Ba component is converted to oxide BaO, the oxide molar ratio is 20 mol% with respect to 100 mol% of glass frit. Sample 43, which is less than 45%, and Sample 47, which exceeds 45 mol%, have an internal defect occurrence rate of 0.88%, respectively.
At 0.15%, it was inferior and was out of the range of the present invention. (Example 3) 14B-33Si using Cu as a conductive powder
With respect to the sample 22 to which the glass frit made of -33Ba-7Al-8Cu-5NA-O glass was added, the samples 57 to 57 in which the constituent ratio between the conductive powder and the glass frit was changed.
62 conductive pastes were produced. That is, the composition ratios of the conductive powder and the glass frit were set to the ratios shown in Table 3 by the same manufacturing method as that of the first embodiment.
2 was prepared, and the multilayer ceramic capacitors of Examples 57 to 62 were manufactured by the same manufacturing method as that of Example 1.
【００４２】そこで、試料５７〜６２の積層セラミック
コンデンサについて内部欠陥の発生率を測定し、これを
表３にまとめた。The occurrence rate of internal defects was measured for the multilayer ceramic capacitors of Samples 57 to 62, and the results are shown in Table 3.
【００４３】[0043]
【表３】 [Table 3]
【００４４】表３から明らかであるように、ガラスフリ
ットの構成比率が、導電粉末とガラスフリットの合計１
００重量％のうち５〜５０重量％である試料５８〜６１
は、内部欠陥の発生率が０〜０．０９％で低く優れ、本
発明の範囲内となり、かつめっき付き性も優れた。As is clear from Table 3, the composition ratio of the glass frit is 1 in total of the conductive powder and the glass frit.
Samples 58 to 61 which are 5 to 50% by weight of 00% by weight
Has a low internal defect rate of 0 to 0.09%, which is within the range of the present invention, and also has excellent plating ability.
【００４５】[0045]
【発明の効果】以上のように本発明の導電性ペースト
は、Ｃｕまたは／およびＮｉ成分から主になる導電粉末
と、ガラスフリットと、有機ビヒクルを含有し、ガラス
フリットは、Ｂ，Ｓｉ，Ｂａ，Ａｌ成分を含む主成分
と、Ｃｕまたは／およびＮｉ成分からなる副成分からな
る酸化物であって、実質的にＰｂ成分を含まず、Ｂａ成
分を酸化物ＢａＯに換算したときの酸化物モル比は、ガ
ラスフリット１００モル％に対して２０〜４５モル％で
あることを特徴とすることで、耐メッキ性が向上する結
果、積層セラミックコンデンサの内部欠陥不良を改善で
きる。As described above, the conductive paste of the present invention contains a conductive powder mainly composed of Cu or / and Ni components, a glass frit, and an organic vehicle, and the glass frit is composed of B, Si, and Ba. , An oxide composed of a main component containing an Al component and an auxiliary component consisting of a Cu or / and Ni component, which does not substantially contain a Pb component, and which has a Ba component converted to an oxide BaO. Since the ratio is 20 to 45 mol% with respect to 100 mol% of the glass frit, the plating resistance is improved, and the internal defect of the multilayer ceramic capacitor can be improved.
【００４６】また、上述のガラスフリットの含有量は、
導電粉末とガラスフリットの合計１００重量％のうち、
５〜５０重量％であることを特徴とすることで、本発明
のガラスフリットの効果が十分に発揮されて、積層セラ
ミックコンデンサの内部欠陥不良を改善でき、かつ、十
分なはんだ濡れ性を備える外部電極を形成し得る。The content of the above glass frit is
Of the total 100% by weight of the conductive powder and the glass frit,
By being characterized in that the content is 5 to 50% by weight, the effect of the glass frit of the present invention is sufficiently exerted, the internal defect failure of the multilayer ceramic capacitor can be improved, and the outside having sufficient solder wettability can be obtained. An electrode may be formed.
【００４７】また、本発明の積層セラミックコンデンサ
は、複数のセラミック層が積層されてなるセラミック素
体と、それぞれの端縁がセラミック層の何れかの端面に
露出するようにセラミック層間に形成された卑金属を導
電成分とする複数の内部電極と、露出した内部電極に電
気的に接続されるように設けられた外部電極とを備え、
外部電極は本発明の導電性ペーストがセラミック素体の
両端面に塗布されて形成されていることを特徴とするこ
とで、外部電極の耐メッキ性が向上する結果、内部欠陥
不良が改善されるという効果が得られる。Further, the multilayer ceramic capacitor of the present invention is formed between a ceramic body in which a plurality of ceramic layers are laminated, and between the ceramic layers such that each edge is exposed at any one end face of the ceramic layer. A plurality of internal electrodes having a base metal as a conductive component, and an external electrode provided to be electrically connected to the exposed internal electrode,
Since the external electrode is formed by applying the conductive paste of the present invention to both end surfaces of the ceramic body, plating resistance of the external electrode is improved, and internal defect defects are improved. The effect is obtained.
【図１】本発明に係る一つの実施の形態の積層セラミッ
クコンデンサの断面図である。FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to one embodiment of the present invention.
１ 積層セラミックコンデンサ ２ セラミック素体 ３ 内部電極 ４ 外部電極 ５，６ めっき膜 DESCRIPTION OF SYMBOLS 1 Multilayer ceramic capacitor 2 Ceramic body 3 Internal electrode 4 External electrode 5, 6 Plating film
Claims (3)
る導電粉末と、ガラスフリットと、有機ビヒクルを含有
し、 前記ガラスフリットは、Ｂ，Ｓｉ，Ｂａ，Ａｌ成分を含
む主成分と、Ｃｕまたは／およびＮｉ成分からなる副成
分からなる酸化物であって、実質的にＰｂ成分を含ま
ず、 前記Ｂａ成分を酸化物ＢａＯに換算したときの酸化物モ
ル比は、前記ガラスフリット１００モル％に対して２０
〜４５モル％であることを特徴とする、積層セラミック
コンデンサ用導電性ペースト。1. A glass frit comprising a conductive powder mainly composed of Cu and / or Ni components, a glass frit, and an organic vehicle, wherein the glass frit contains a main component containing B, Si, Ba, and Al components, Cu or And / or an oxide composed of subcomponents composed of a Ni component, which substantially does not contain a Pb component, and the oxide molar ratio when the Ba component is converted into oxide BaO is 100 mol% of the glass frit. 20 for
A conductive paste for a multilayer ceramic capacitor, characterized by being in an amount of about 45 mol%.
電粉末と前記ガラスフリットの合計１００重量％のう
ち、５〜５０重量％であることを特徴とする、請求項１
に記載の積層セラミックコンデンサ用導電性ペースト。2. The method according to claim 1, wherein the content of the glass frit is 5 to 50% by weight based on a total of 100% by weight of the conductive powder and the glass frit.
4. The conductive paste for a multilayer ceramic capacitor according to 1.).
ラミック素体と、それぞれの端縁が前記セラミック層の
何れかの端面に露出するように前記セラミック層間に形
成された卑金属を導電成分とする複数の内部電極と、露
出した前記内部電極に電気的に接続されるように設けら
れた外部電極とを備え、 前記外部電極は、請求項１または２に記載の導電性ペー
ストが前記セラミック素体の両端面に塗布されて形成さ
れていることを特徴とする、積層セラミックコンデン
サ。3. A conductive element comprising: a ceramic body formed by laminating a plurality of ceramic layers; and a base metal formed between the ceramic layers such that each edge is exposed on any one end surface of the ceramic layer. 3. A plurality of internal electrodes, and external electrodes provided so as to be electrically connected to the exposed internal electrodes. 3. The external electrode, wherein the conductive paste according to claim 1 or 2 is formed of the ceramic body. 4. Characterized in that the multilayer ceramic capacitor is formed by being applied to both end surfaces of the multilayer ceramic capacitor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000089413A JP4576660B2 (en) | 2000-03-28 | 2000-03-28 | Conductive paste for multilayer ceramic capacitor and multilayer ceramic capacitor using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000089413A JP4576660B2 (en) | 2000-03-28 | 2000-03-28 | Conductive paste for multilayer ceramic capacitor and multilayer ceramic capacitor using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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ID=18605180
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013106035A (en) * | 2011-11-11 | 2013-05-30 | Samsung Electro-Mechanics Co Ltd | Multilayer ceramic electronic component |
| WO2013108533A1 (en) * | 2012-01-19 | 2013-07-25 | 株式会社村田製作所 | Ceramic electronic component |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
| KR20170135665A (en) | 2016-05-31 | 2017-12-08 | 다이요 유덴 가부시키가이샤 | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013106035A (en) * | 2011-11-11 | 2013-05-30 | Samsung Electro-Mechanics Co Ltd | Multilayer ceramic electronic component |
| US8941972B2 (en) | 2011-11-11 | 2015-01-27 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic electronic component |
| KR101532114B1 (en) * | 2011-11-11 | 2015-06-29 | 삼성전기주식회사 | Multi-layered ceramic electronic parts |
| WO2013108533A1 (en) * | 2012-01-19 | 2013-07-25 | 株式会社村田製作所 | Ceramic electronic component |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
| JP5904305B2 (en) * | 2013-04-25 | 2016-04-13 | 株式会社村田製作所 | Multilayer ceramic capacitor and manufacturing method thereof |
| JPWO2014175034A1 (en) * | 2013-04-25 | 2017-02-23 | 株式会社村田製作所 | Multilayer ceramic capacitor and manufacturing method thereof |
| US9842698B2 (en) | 2013-04-25 | 2017-12-12 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and manufacturing method therefor |
| KR20170135665A (en) | 2016-05-31 | 2017-12-08 | 다이요 유덴 가부시키가이샤 | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor |
| US10522291B2 (en) | 2016-05-31 | 2019-12-31 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor |
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