JP2002343671A - Ceramic electronic component - Google Patents
Ceramic electronic componentInfo
- Publication number
- JP2002343671A JP2002343671A JP2002002576A JP2002002576A JP2002343671A JP 2002343671 A JP2002343671 A JP 2002343671A JP 2002002576 A JP2002002576 A JP 2002002576A JP 2002002576 A JP2002002576 A JP 2002002576A JP 2002343671 A JP2002343671 A JP 2002343671A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- electronic component
- component
- glass
- conductive paste
- 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
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 95
- 239000011521 glass Substances 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 230000035515 penetration Effects 0.000 claims abstract description 9
- 239000003985 ceramic capacitor Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 6
- 230000002159 abnormal effect Effects 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract 2
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/14—Protection against electric or thermal overload
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Ceramic Capacitors (AREA)
Abstract
Description
【発明の属する技術分野】本発明は、中高電圧域で用い
られるセラミック電子部品に関するものであり、特に中
高電圧域で用いられる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 ceramic electronic component used in a middle and high voltage range, and more particularly to a ceramic capacitor used in a middle and high voltage range.
【従来の技術】従来よりセラミック電子部品は、誘電
体、半導体、圧電体等のセラミック材料からなるセラミ
ック素体を備える。これらのセラミック電子部品に付随
する電極や配線を構成する材料として導電性ペーストが
多く用いられている。セラミック電子部品の電極形成に
用いられる導電性ペーストの場合、ガラス粉末が添加さ
れる場合がある。導電性ペースト中にガラス粉末を添加
する効果としては、一般に電極焼成時に軟化流動して導
電成分の焼結を促進させること、端子電極の密着強度を
向上させること、セラミック素体をガラスでコートする
ことにより耐湿性を向上させること、さらにセラミック
電子部品がセラミックコンデンサの場合に、端子電極と
セラミック素体の界面部に生成するポアを埋めることに
より静電容量の低下を防ぐこと等が挙げられる。また、
従来よりセラミック電子部品の電極形成に用いられる導
電性ペーストは、Ｐｂ系ガラスが多く使用されてきた
が、近年では環境問題への配慮から非Ｐｂ系ガラスへの
置き換えが求められている。2. Description of the Related Art Conventionally, a ceramic electronic component has a ceramic body made of a ceramic material such as a dielectric, a semiconductor, and a piezoelectric. A conductive paste is often used as a material for forming electrodes and wirings attached to these ceramic electronic components. In the case of a conductive paste used for forming electrodes of ceramic electronic components, glass powder may be added. The effect of adding the glass powder to the conductive paste is generally to soften and flow during electrode baking to promote sintering of the conductive component, to improve the adhesion strength of the terminal electrode, and to coat the ceramic body with glass. In this case, when the ceramic electronic component is a ceramic capacitor, filling of pores formed at the interface between the terminal electrode and the ceramic body prevents a decrease in capacitance. Also,
Conventionally, Pb-based glass has been widely used as a conductive paste used for forming electrodes of ceramic electronic components. However, in recent years, replacement with non-Pb-based glass has been required in consideration of environmental issues.
【発明が解決しようとする課題】しかしながら従来の非
Ｐｂ系ガラス、例えばＢｉ系ガラスを添加した導電性ペ
ーストを用いて端子電極を形成した中高電圧域で用いら
れるセラミック電子部品、特に中高電圧域で用いられる
セラミックコンデンサは、Ｐｂ系ガラスを含有する従来
の導電性ペーストを用いて端子電極を形成した同様のセ
ラミック電子部品と比較して、セラミック素体の発熱温
度が高くなるという問題がある。これは、ガラス中のＢ
ｉ成分が、高電圧ならびに高周波負荷時にセラミック素
体に拡散し、セラミックが還元されて半導体化するため
に、セラミック素体のｔａｎδが上昇するためと考えら
れる。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、Ｐｂ成分を含有せずに、セラミック素体の
焼結促進、密着強度向上、耐湿性向上を実現しつつ、な
おかつセラミック素体の異常発熱を抑制し得る導電性ペ
ーストを用いて端子電極を形成した、セラミック電子部
品を提供することにある。However, ceramic electronic components used in a medium-high voltage range in which terminal electrodes are formed using a conventional non-Pb-based glass, for example, a conductive paste to which Bi-based glass is added, particularly in a medium-high voltage range. The ceramic capacitor used has a problem that the heat generation temperature of the ceramic body is higher than that of a similar ceramic electronic component in which terminal electrodes are formed using a conventional conductive paste containing Pb-based glass. This is B in glass
It is considered that the i component diffuses into the ceramic body at the time of high voltage and high frequency load, and the tan δ of the ceramic body increases because the ceramic is reduced to be a semiconductor. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and without promoting the sintering, improving the adhesion strength, and improving the moisture resistance of a ceramic body without containing a Pb component, and further improving the ceramic element. An object of the present invention is to provide a ceramic electronic component in which terminal electrodes are formed using a conductive paste capable of suppressing abnormal heat generation of a body.
【課題を解決するための手段】上記目的を達成するため
に、本発明のセラミック電子部品は、セラミック素体
と、導電性ペーストを用いてセラミック素体上に形成さ
れた端子電極と、を備える、セラミック電子部品であっ
て、導電性ペーストは、導電成分とガラス粉末と有機ビ
ヒクルとを含有し、ガラス粉末は、結晶化ガラスを含有
し、結晶化ガラスは、Ｂ成分とＢｉ成分とＡｌ成分とア
ルカリ土類金属と不可避不純物とからなる酸化物であ
り、ガラス粉末は、端子電極の焼付け形成時に少なくと
も一部が溶融してセラミック素体内部に浸透し、浸透の
深さは、セラミック素体の表面から１５０μｍ以内であ
ることを特徴とする。なお、結晶化ガラス中の不可避不
純物とは、ガラス作製時に不可避的に混入する不純物の
ことである。具体的には、ガラス原料を溶融させるるつ
ぼからの不純物として、白金るつぼを用いた場合のＰ
ｔ、石英るつぼを用いた場合のＳｉが挙げられる。ま
た、得られたガラスの粉砕工程で混入する不純物とし
て、ＳＵＳロールで荒粉砕した場合のＦｅ、ジルコニア
ボールで微粉砕した場合のＺｒが挙げられる。また、本
発明のセラミック電子部品は、上述のセラミック電子部
品であって、導電性ペーストに含有するアルカリ土類金
属は、Ｃａ，ＳｒおよびＢａからなる群より選ばれる少
なくとも一種であることが好ましい。また、本発明のセ
ラミック電子部品は、上述のセラミック電子部品であっ
て、導電性ペーストに含有する結晶化ガラスの含有量
は、導電成分１００体積％に対して１〜２５体積％の範
囲内であることが好ましい。また、本発明のセラミック
電子部品は、上述のセラミック電子部品であって、中高
電圧域で用いられるセラミックコンデンサであることを
特徴とする。In order to achieve the above object, a ceramic electronic component according to the present invention comprises a ceramic body and terminal electrodes formed on the ceramic body using a conductive paste. A ceramic electronic component, wherein the conductive paste contains a conductive component, a glass powder, and an organic vehicle, the glass powder contains crystallized glass, and the crystallized glass has a B component, a Bi component, and an Al component. And an oxide composed of an alkaline earth metal and unavoidable impurities, and the glass powder at least partially melts and penetrates into the ceramic body at the time of baking of the terminal electrode. Characterized by being within 150 μm from the surface. Note that the unavoidable impurities in the crystallized glass are impurities that are unavoidably mixed during glass production. Specifically, Pt in the case of using a platinum crucible as an impurity from the crucible for melting the glass raw material
t, Si when a quartz crucible is used. Further, as impurities to be mixed in the obtained glass in the pulverizing step, there are Fe when coarsely pulverized with a SUS roll and Zr when finely pulverized with zirconia balls. Further, the ceramic electronic component of the present invention is the above-described ceramic electronic component, wherein the alkaline earth metal contained in the conductive paste is preferably at least one selected from the group consisting of Ca, Sr and Ba. The ceramic electronic component of the present invention is the above-described ceramic electronic component, wherein the content of the crystallized glass contained in the conductive paste is within a range of 1 to 25% by volume with respect to 100% by volume of the conductive component. Preferably, there is. Further, a ceramic electronic component of the present invention is the above-described ceramic electronic component, which is a ceramic capacitor used in a middle to high voltage range.
【発明の実施の形態】本発明のセラミック電子部品は、
端子電極中にＢ成分とＢｉ成分とＡｌ成分とアルカリ土
類金属とからなる結晶化ガラスを含有することを要す
る。すなわち、上述した結晶化ガラスを含有する導電性
ペーストを用いて端子電極が焼付け形成されていること
を要する。さらに、端子電極の焼付け形成時に、このよ
うな結晶化ガラスを溶融させ、セラミック素体の表面か
ら１５０μｍ以内まで浸透させることを要する。このよ
うな本発明のセラミック電子部品は、Ｐｂ成分を含有せ
ずに、セラミック素体の焼結促進、密着強度向上、耐湿
性向上を実現しつつ、なおかつセラミック素体の異常発
熱を抑制し、よってセラミック素体のｔａｎδが上昇す
ることを抑制し得る。なお、不可避不純物として、その
他の元素が微量含有することを妨げない。なお、本発明
における結晶化ガラスとは、ガラス作製時は、非晶質ガ
ラスであるが、ガラスを加熱していくと少なくとも一部
が結晶化するガラスを指す。また、結晶溶融温度とは、
ガラス加熱時に結晶化したガラスが溶融を開始する温度
を指す。また、焼付け温度とは、セラミック素体に導電
性ペーストを塗布した後、導電成分を焼結させるときの
温度を指し、セラミック電子部品の端子電極形成用導電
性ペーストの場合、一般に導電成分の融点より１００〜
２００℃前後低い温度で焼付けを行なう。また、本発明
のセラミック電子部品の端子電極形成に用いられる導電
性ペーストに含有するアルカリ土類金属成分としては、
Ｃａ，ＳｒおよびＢａから選ばれる１種以上を適宜用い
ることができるが、ガラス製造上の扱いやすさや環境へ
の負荷を考慮すると、ＣａまたはＳｒを用いることがよ
り好ましい。また、本発明のセラミック電子部品の端子
電極形成に用いられる導電性ペーストに含有する結晶化
ガラスの含有量は、導電成分１００体積％に対して１〜
２５体積％であることが好ましい。添加量が１体積％未
満では、結晶化ガラスを含有させた効果が小さく、端子
電極の密着強度を確保することが困難となる。他方、含
有量が２５体積％を超えると、セラミック素体へのガラ
スの浸透割合が増え、中高電圧域で用いるとセラミック
素体が異常発熱するとともに、ガラスが端子電極の表面
に偏析して、半田濡れ不良やめっき付き不良を生じるこ
とがある。なお、本発明のセラミック電子部品の端子電
極形成に用いられる導電性ペーストに含有する導電成分
としては、特に限定はしないが、例えばＡｇ，Ｐｄ等の
貴金属粉末ならびにこれらの合金粉末や、Ｎｉ，Ｃｕ等
の卑金属粉末ならびにこれらの合金粉末を適宜調整して
用いることができる。本発明のセラミック電子部品の一
つの実施形態としてセラミックコンデンサを例に挙げ、
図１に基づいて詳細に説明する。セラミックコンデンサ
１は、セラミック素体２と、セラミック素体２の両主面
に本発明の導電性ペーストを用いて形成された一対の端
子電極３，３と、端子電極３，３に電気的に接合された
リード線４，４と、端子電極３，３とリード線４，４を
電気的・機械的に接合させてなる半田５，５と、セラミ
ック素体２と端子電極３，３と半田５，５を完全に覆
い、リード線４，４の一端を覆うように形成されてなる
外装樹脂６とからなる。セラミック素体２は、例えば誘
電体，磁性体，圧電体，絶縁体等として機能する材料か
らなる、例えば単板型あるいは積層型の生のセラミック
素体が焼成されてなるが、本発明のセラミック電子部品
におけるセラミック素体は、特にこれらに限定されるも
のではない。端子電極３，３は上述した本発明の導電性
ペーストからなり、例えばセラミック素体２の両主面に
塗布され乾燥された後に焼付けられてなる。なお、端子
電極３，３は、焼成前の生のセラミック素体の両主面に
本発明の導電性ペーストが塗布され電極膜が形成された
後に、生のセラミック素体とともに同時に焼成されても
よく、形成方法について特に限定されるものではない。
また、本発明のセラミック電子部品は、図１に示したセ
ラミックコンデンサ１の形状に限定されることなく、例
えば、複数のセラミックグリーンシートが積層されたセ
ラミック素体を焼成してなるセラミック素体と、そのセ
ラミック素体の両主面に本発明の導電性ペーストを用い
て形成された一対の端子電極を備える積層セラミック電
子部品であっても構わない。また、リード線や外装樹脂
の材料は特に限定されることなく、またこれらを備えて
いなくても構わない。BEST MODE FOR CARRYING OUT THE INVENTION The ceramic electronic component of the present invention comprises:
It is necessary that the terminal electrode contains crystallized glass composed of the B component, the Bi component, the Al component, and the alkaline earth metal. That is, the terminal electrodes need to be formed by baking using the above-mentioned conductive paste containing crystallized glass. Further, at the time of baking formation of the terminal electrode, it is necessary that such crystallized glass is melted and penetrated to within 150 μm from the surface of the ceramic body. Such a ceramic electronic component of the present invention does not contain a Pb component, and promotes sintering of a ceramic body, improves adhesion strength, and improves moisture resistance, and suppresses abnormal heat generation of the ceramic body. Therefore, it is possible to suppress an increase in tan δ of the ceramic body. In addition, it does not prevent that trace amounts of other elements are contained as inevitable impurities. Note that the crystallized glass in the present invention refers to a glass that is an amorphous glass at the time of glass production, but at least partly crystallizes as the glass is heated. The crystal melting temperature is
The temperature at which the crystallized glass starts melting when heated. The baking temperature refers to a temperature at which a conductive component is sintered after a conductive paste is applied to a ceramic body. In the case of a conductive paste for forming a terminal electrode of a ceramic electronic component, generally, the melting point of the conductive component is used. More than 100
Baking is performed at a low temperature of about 200 ° C. Further, as the alkaline earth metal component contained in the conductive paste used for forming the terminal electrode of the ceramic electronic component of the present invention,
One or more selected from Ca, Sr and Ba can be used as appropriate, but in view of ease of handling in glass production and environmental load, it is more preferable to use Ca or Sr. The content of the crystallized glass contained in the conductive paste used for forming the terminal electrode of the ceramic electronic component of the present invention is 1 to 100% by volume of the conductive component.
It is preferably 25% by volume. When the addition amount is less than 1% by volume, the effect of including the crystallized glass is small, and it is difficult to secure the adhesion strength of the terminal electrode. On the other hand, if the content exceeds 25% by volume, the rate of penetration of glass into the ceramic body increases, and when used in a medium to high voltage range, the ceramic body generates abnormal heat and the glass segregates on the surface of the terminal electrode, Poor solder wetting or poor plating may occur. The conductive component contained in the conductive paste used for forming the terminal electrodes of the ceramic electronic component of the present invention is not particularly limited. For example, noble metal powders such as Ag and Pd, alloy powders of these, Ni, Cu Base metal powders and alloy powders thereof can be appropriately adjusted and used. Taking a ceramic capacitor as an example of one embodiment of the ceramic electronic component of the present invention,
This will be described in detail with reference to FIG. The ceramic capacitor 1 includes a ceramic body 2, a pair of terminal electrodes 3, 3 formed on both main surfaces of the ceramic body 2 using the conductive paste of the present invention, and an electrical connection to the terminal electrodes 3, 3. The joined lead wires 4 and 4, the solders 5 and 5 formed by electrically and mechanically joining the terminal electrodes 3 and 3 with the lead wires 4 and 4, the soldering between the ceramic body 2 and the terminal electrodes 3 and 3 And an exterior resin formed so as to completely cover the ends of the lead wires. The ceramic body 2 is formed by firing, for example, a single-plate or laminated raw ceramic body made of a material that functions as a dielectric, a magnetic, a piezoelectric, an insulator, or the like. The ceramic body in the electronic component is not particularly limited to these. The terminal electrodes 3 and 3 are made of the above-described conductive paste of the present invention, and are baked, for example, applied to both main surfaces of the ceramic body 2 and dried. The terminal electrodes 3 and 3 may be simultaneously fired together with the raw ceramic body after the conductive paste of the present invention is applied to both main surfaces of the raw ceramic body before firing to form an electrode film. The formation method is not particularly limited.
Further, the ceramic electronic component of the present invention is not limited to the shape of the ceramic capacitor 1 shown in FIG. 1, and may be, for example, a ceramic body obtained by firing a ceramic body in which a plurality of ceramic green sheets are laminated. Alternatively, a multilayer ceramic electronic component having a pair of terminal electrodes formed on both main surfaces of the ceramic body using the conductive paste of the present invention may be used. In addition, the materials of the lead wires and the exterior resin are not particularly limited, and they do not have to be provided.
【実施例】図１に示したセラミックコンデンサを作製し
て、発熱温度の測定を行なった。まず、表１に示すそれ
ぞれの組成となるように、出発原料であるアルカリ土類
金属の水酸化物，Ｂｉ2Ｏ3，Ｈ3ＢＯ3，Ａｌ（Ｏ
Ｈ）3，ＣａＣＯ3，ＳｒＣＯ3およびＢａＣＯ3を調合
し、白金製のるつぼに入れて９００〜１３００℃に１時
間保持した。次に、試料が完全に溶融したことを確認
し、炉から取り出して純水中に投入してガラス化させ
た。得られたビーズ状のガラスをボールミルで湿式粉砕
して、表１に示した組成割合からなる試料１〜９のガラ
ス粉末を得た。なお、試料１〜６のガラス粉末について
は、ＤＴＡ曲線ならびに高温Ｘ線回折法から、昇温して
いくと結晶化する結晶化ガラスであることを確認し、試
料７〜９のガラス粉末については、非晶質ガラスである
ことを確認した。EXAMPLE The ceramic capacitor shown in FIG. 1 was manufactured, and the heat generation temperature was measured. First, hydroxides of alkaline earth metals, Bi 2 O 3 , H 3 BO 3 , and Al (O 2) were used as starting materials so as to have the respective compositions shown in Table 1.
H) 3 , CaCO 3 , SrCO 3 and BaCO 3 were prepared and placed in a platinum crucible and kept at 900 to 1300 ° C. for 1 hour. Next, after confirming that the sample was completely melted, the sample was taken out of the furnace and put into pure water to vitrify. The obtained bead-shaped glass was wet-pulverized by a ball mill to obtain glass powders of Samples 1 to 9 having composition ratios shown in Table 1. The glass powders of Samples 1 to 6 were confirmed to be crystallized glass that crystallized as the temperature was increased from DTA curves and high-temperature X-ray diffraction. Was confirmed to be an amorphous glass.
【表１】 次いで、導電成分として粒径０．１〜５μｍのＡｇ粉末
３３体積％と、試料１〜９のガラス粉末６体積％と、ビ
ヒクル６１体積％を混合し、３本ロールミルで混練し
て、試料１〜９の導電性ペーストを得た。なおビヒクル
としては、ターピネオール８０重量％にエチルセルロー
スを２０重量％の割合で溶解させたものを用いた。次い
で、目標とする静電容量が１ｎＦとなるようなＢａＴｉ
Ｏ3からなるセラミック素体の両主面に試料１〜９の導
電性ペーストを３ｍｍφのパターンでスクリーン印刷
し、空気中８００℃で２時間焼成して端子電極を形成
し、それぞれ２００個ずつの試料１〜９の試験サンプル
を得た。そこで、それぞれ１００個ずつの試料１〜９の
試験サンプルについて、セラミック素体の表面からのガ
ラスの浸透深さを測定し、これらを表２にまとめた。な
お、ガラスの浸透深さは、Ｘ線マイクロアナライザを用
いて、加速電圧１５ｋＶ，照射電流１００ｎＡ，Ｄｗｅ
ｌｌ ｔｉｍｅ（１つの画素での取り込み時間）５０ｍ
ｓの条件で測定した。次いで、残りの１００個の試料１
〜９の試験サンプルの端子電極にリード線を半田で半田
付けし、外装樹脂を用いてセラミック素体と端子電極と
リード線の一端と半田を被覆して、試料１〜９のセラミ
ックコンデンサを得た。そこで、試料１〜９のセラミッ
クコンデンサに対してＡＣ電圧３ｋＶｐ−ｐを印加し、
熱電対を用いて外装樹脂表面の温度を測定し、室温２５
℃との差（ΔＴ）を求め、これを発熱温度として表２に
それぞれまとめた。評価は、発熱温度が３０℃以下であ
る試料を本発明の範囲内として○印で表し、３０℃を超
える試料を本発明の範囲外として×印で表した。[Table 1] Next, 33% by volume of an Ag powder having a particle size of 0.1 to 5 μm as a conductive component, 6% by volume of a glass powder of Samples 1 to 9 and 61% by volume of a vehicle were mixed, and kneaded with a three-roll mill to obtain Sample 1 ~ 9 conductive pastes were obtained. The vehicle used was a solution in which ethyl cellulose was dissolved at a ratio of 20% by weight in 80% by weight of terpineol. Next, BaTi such that the target capacitance becomes 1 nF
The conductive pastes of samples 1 to 9 were screen-printed on both main surfaces of the ceramic body made of O 3 in a pattern of 3 mmφ and baked in air at 800 ° C. for 2 hours to form terminal electrodes. Test samples of Samples 1 to 9 were obtained. The penetration depth of the glass from the surface of the ceramic body was measured for 100 test samples 1 to 9 each, and these are summarized in Table 2. The penetration depth of the glass was measured using an X-ray microanalyzer at an acceleration voltage of 15 kV, an irradiation current of 100 nA, and a Dwe.
ll time (capture time for one pixel) 50m
The measurement was performed under the condition of s. Then, the remaining 100 samples 1
The lead wires were soldered to the terminal electrodes of the test samples of Nos. To 9 by soldering, and the ceramic body, the terminal electrodes, and one end of the lead wires were coated with the solder using an exterior resin to obtain the ceramic capacitors of Samples 1 to 9. Was. Therefore, an AC voltage of 3 kVp-p was applied to the ceramic capacitors of samples 1 to 9,
The temperature of the exterior resin surface was measured using a thermocouple, and the room temperature was measured.
The difference (.DELTA.T) from the temperature (.degree. C.) was obtained, and this was summarized in Table 2 as an exothermic temperature. In the evaluation, samples having an exothermic temperature of 30 ° C. or lower were indicated by “○” within the range of the present invention, and samples exceeding 30 ° C. were indicated by “X” outside the range of the present invention.
【表２】 表２から明らかであるように、結晶化ガラスであって、
Ｂ成分，Ｂｉ成分およびＡｌ成分と、アルカリ土類金属
であるＣａ，ＳｒおよびＢａからなる群より選ばれる少
なくとも一種とからなる、試料１〜６のガラス粉末を含
有する試料１〜６のセラミックコンデンサのうち、浸透
深さが１５０μｍ以下である試料１，３および５のセラ
ミックコンデンサは、発熱温度（ΔＴ）が２１．５〜２
４．５℃であり、本発明の範囲内となった。これに対し
て、浸透深さが１５０μｍを超えて１７３〜１８９μｍ
である試料２，４および６のセラミックコンデンサは、
発熱温度が３６．９〜３８．３℃であり、本発明の範囲
外となった。また、Ｂ成分，Ｂｉ成分およびＡｌ成分
と、アルカリ土類金属であるＣａ，ＳｒおよびＢａから
なる群より選ばれる少なくとも一種とからなるが、非晶
質ガラスである試料７〜９のガラス粉末を含有する試料
７〜９のセラミックコンデンサは、何れも浸透深さが１
５０μｍを超えて２０５〜２５０μｍであるため、発熱
温度は３８．５〜４０．５℃であり、本発明の範囲外と
なった。[Table 2] As is evident from Table 2, crystallized glass,
Ceramic capacitors of Samples 1 to 6 containing glass powders of Samples 1 to 6, comprising B component, Bi component and Al component and at least one selected from the group consisting of alkaline earth metals Ca, Sr and Ba Among them, the ceramic capacitors of Samples 1, 3 and 5 having a penetration depth of 150 μm or less have a heat generation temperature (ΔT) of 21.5 to 2
4.5 ° C., which was within the scope of the present invention. On the other hand, the penetration depth exceeds 173 to 189 μm
The ceramic capacitors of Samples 2, 4 and 6 are
The exothermic temperature was 36.9-38.3 ° C, which was outside the scope of the present invention. In addition, the glass powder of Samples 7 to 9, which is composed of B component, Bi component and Al component, and at least one selected from the group consisting of alkaline earth metals Ca, Sr and Ba, is an amorphous glass. Each of the contained ceramic capacitors of samples 7 to 9 has a penetration depth of 1
Since it is more than 50 μm and it is 205 to 250 μm, the heat generation temperature is 38.5 to 40.5 ° C., which is out of the range of the present invention.
【発明の効果】以上のように本発明のセラミック電子部
品は、セラミック素体と、導電性ペーストを用いてセラ
ミック素体上に形成された端子電極と、を備える、セラ
ミック電子部品であって、導電性ペーストは、導電成分
とガラス粉末と有機ビヒクルとを含有し、ガラス粉末
は、結晶化ガラスを含有し、結晶化ガラスは、Ｂ成分と
Ｂｉ成分とＡｌ成分とアルカリ土類金属と不可避不純物
とからなる酸化物であり、ガラス粉末は、端子電極の焼
付け形成時に少なくとも一部が溶融してセラミック素体
内部に浸透し、浸透の深さは、セラミック素体の表面か
ら１５０μｍ以内であることを特徴とすることで、中高
電圧域で用いた場合であっても、セラミック素体の焼結
促進、密着強度向上、耐湿性向上を実現しつつ、かつセ
ラミック素体の異常発熱を抑制し得、なおかつ端子電極
中にＰｂ成分を含有しないセラミック電子部品を提供す
ることができる。また、本発明のセラミック電子部品の
端子電極焼付け形成に用いられる導電性ペーストに含有
する結晶化ガラスの含有量が、導電成分１００体積％に
対して１〜２５体積％であれば、セラミック素体の焼結
促進、密着強度向上、耐湿性向上を実現しつつ、かつセ
ラミック素体の異常発熱を抑制し得るとともに、この導
電性ペーストを用いて端子電極を形成した場合にガラス
が端子電極の表面に偏析すること、ならびに半田濡れ不
良やめっき付き不良を抑制する効果が高まる。As described above, the ceramic electronic component of the present invention is a ceramic electronic component comprising a ceramic body and terminal electrodes formed on the ceramic body using a conductive paste. The conductive paste contains a conductive component, a glass powder, and an organic vehicle, the glass powder contains a crystallized glass, and the crystallized glass has a B component, a Bi component, an Al component, an alkaline earth metal, and inevitable impurities. At least part of the glass powder melts and penetrates into the ceramic body when the terminal electrodes are formed by baking, and the penetration depth is within 150 μm from the surface of the ceramic body. The feature is that, even when used in the middle and high voltage range, the ceramic body promotes sintering, improves adhesion strength, improves moisture resistance, and has abnormalities in the ceramic body. It is possible to provide a suppressing heat obtained, yet the ceramic electronic component which does not contain Pb component in the terminal electrode. Further, if the content of the crystallized glass contained in the conductive paste used for the baking of the terminal electrode of the ceramic electronic component of the present invention is 1 to 25% by volume with respect to 100% by volume of the conductive component, While promoting the sintering, improving the adhesion strength, and improving the moisture resistance of the ceramic body, and suppressing the abnormal heating of the ceramic body, when the terminal electrode is formed using this conductive paste, the glass becomes the surface of the terminal electrode. And the effect of suppressing poor solder wetting and poor plating is enhanced.
【図１】本発明に係る一つの実施の形態のセラミック電
子部品の断面図である。FIG. 1 is a cross-sectional view of a ceramic electronic component according to one embodiment of the present invention.
１ セラミック電子部品 ２ セラミック素体 ３ 端子電極 DESCRIPTION OF SYMBOLS 1 Ceramic electronic component 2 Ceramic body 3 Terminal electrode
Claims (4)
いて前記セラミック素体上に形成された端子電極と、を
備える、セラミック電子部品であって、 前記導電性ペーストは、導電成分とガラス粉末と有機ビ
ヒクルとを含有し、 前記ガラス粉末は、結晶化ガラスを含有し、 前記結晶化ガラスは、Ｂ成分とＢｉ成分とＡｌ成分とア
ルカリ土類金属と不可避不純物とからなる酸化物であ
り、 前記ガラス粉末は、前記端子電極の焼付け形成時に少な
くとも一部が溶融して前記セラミック素体内部に浸透
し、 前記浸透の深さは、前記セラミック素体の表面から１５
０μｍ以内であることを特徴とする、セラミック電子部
品。1. A ceramic electronic component comprising: a ceramic body; and terminal electrodes formed on the ceramic body using a conductive paste, wherein the conductive paste comprises a conductive component and glass powder. And an organic vehicle, wherein the glass powder contains crystallized glass, and the crystallized glass is an oxide comprising a B component, a Bi component, an Al component, an alkaline earth metal, and an unavoidable impurity, The glass powder at least partially melts and penetrates into the ceramic body at the time of baking of the terminal electrode, and the penetration depth is 15 μm from the surface of the ceramic body.
A ceramic electronic component having a thickness of 0 μm or less.
土類金属は、Ｃａ，ＳｒおよびＢａからなる群より選ば
れる少なくとも一種であることを特徴とする、請求項１
に記載のセラミック電子部品2. The method according to claim 1, wherein the alkaline earth metal contained in the conductive paste is at least one selected from the group consisting of Ca, Sr and Ba.
Ceramic electronic components described in
化ガラスの含有量は、導電成分１００体積％に対して１
〜２５体積％の範囲内であることを特徴とする、請求項
１または２に記載のセラミック電子部品。3. The content of the crystallized glass contained in the conductive paste is 1 to 100% by volume of the conductive component.
The ceramic electronic component according to claim 1, wherein the content is within a range of from about 25% by volume to about 25% by volume.
デンサであることを特徴とする、請求項１〜３の何れか
に記載のセラミック電子部品。4. The ceramic electronic component according to claim 1, wherein the ceramic electronic component is a ceramic capacitor used in a medium-high voltage range.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002002576A JP3780945B2 (en) | 2001-03-14 | 2002-01-09 | Ceramic electronic components |
| TW091101126A TW527607B (en) | 2001-03-14 | 2002-01-24 | Ceramic electronic element |
| KR10-2002-0008423A KR100438126B1 (en) | 2001-03-14 | 2002-02-18 | Ceramic electronic component |
| CNB021073376A CN1181496C (en) | 2001-03-14 | 2002-03-13 | Ceramic electronic element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-72029 | 2001-03-14 | ||
| JP2001072029 | 2001-03-14 | ||
| JP2002002576A JP3780945B2 (en) | 2001-03-14 | 2002-01-09 | Ceramic electronic components |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002343671A true JP2002343671A (en) | 2002-11-29 |
| JP3780945B2 JP3780945B2 (en) | 2006-05-31 |
Family
ID=26611235
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002002576A Expired - Lifetime JP3780945B2 (en) | 2001-03-14 | 2002-01-09 | Ceramic electronic components |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3780945B2 (en) |
| KR (1) | KR100438126B1 (en) |
| CN (1) | CN1181496C (en) |
| TW (1) | TW527607B (en) |
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|---|---|---|---|---|
| US7384577B2 (en) * | 2005-03-09 | 2008-06-10 | E.I. Du Pont De Nemours And Company | Black conductive thick film compositions, black electrodes, and methods of forming thereof |
| JP4650794B2 (en) * | 2005-07-01 | 2011-03-16 | 昭栄化学工業株式会社 | Conductive paste for multilayer electronic component and multilayer electronic component using the same |
| KR101015259B1 (en) * | 2010-08-19 | 2011-02-16 | 주식회사 튜풀테크놀러지 | Device for improvement of voltaic energy and method of making the same |
| KR102435641B1 (en) | 2016-10-05 | 2022-08-23 | 밀워키 일렉트릭 툴 코포레이션 | Tape measure with compact retraction system |
| EP3601943A4 (en) | 2017-03-22 | 2020-12-30 | Milwaukee Electric Tool Corporation | Tape measure with epicyclic gear drive for tape retraction |
-
2002
- 2002-01-09 JP JP2002002576A patent/JP3780945B2/en not_active Expired - Lifetime
- 2002-01-24 TW TW091101126A patent/TW527607B/en not_active IP Right Cessation
- 2002-02-18 KR KR10-2002-0008423A patent/KR100438126B1/en active IP Right Grant
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|---|---|
| JP3780945B2 (en) | 2006-05-31 |
| KR20020073089A (en) | 2002-09-19 |
| CN1375834A (en) | 2002-10-23 |
| CN1181496C (en) | 2004-12-22 |
| TW527607B (en) | 2003-04-11 |
| KR100438126B1 (en) | 2004-07-01 |
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