JPH05174616A - Conductor paste - Google Patents
Conductor pasteInfo
- Publication number
- JPH05174616A JPH05174616A JP35443491A JP35443491A JPH05174616A JP H05174616 A JPH05174616 A JP H05174616A JP 35443491 A JP35443491 A JP 35443491A JP 35443491 A JP35443491 A JP 35443491A JP H05174616 A JPH05174616 A JP H05174616A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- weight
- glass
- parts
- conductor 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.)
- Pending
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- Ceramic Products (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半田付けした状態で熱履
歴を受けたときの接合強度の劣化の小さい電極を形成す
るための導体ペーストに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductor paste for forming an electrode having a small deterioration in bonding strength when subjected to heat history in a soldered state.
【０００２】[0002]
【従来の技術】厚膜電極材料として、銀とパラジウムを
含む複合粉末と、無機結合剤とをビヒクル中に分散した
Ａｇ−Ｐｄ系導体ペーストが用いられている。銀とパラ
ジウムを含む複合粉末としては、銀とパラジウムの混合
粉の外、銀パラジウム合金粉、銀パラジウム共沈粉また
はこれらと銀粉及び／又はパラジウム粉との混合粉が用
いられ通常Ａｇ／Ｐｄ比が１．５〜１９になる組成でペ
ースト固形分中に８５〜９５重量％含有される。2. Description of the Related Art As a thick film electrode material, an Ag--Pd based conductor paste in which a composite powder containing silver and palladium and an inorganic binder are dispersed in a vehicle is used. As the composite powder containing silver and palladium, a silver-palladium alloy powder, a silver-palladium co-precipitation powder, or a mixed powder of these and a silver powder and / or a palladium powder is used in addition to the mixed powder of silver and palladium, and the Ag / Pd ratio is usually used. Is contained in the paste solid content in an amount of 85 to 95% by weight.
【０００３】無機結合剤には、通常ガラスフリットと酸
化ビスマス粉末が用いられる。ガラス粉末は、ＰｂＯ−
Ｂ2 Ｏ3 −ＳｉＯ2 系ガラス、ＰｂＯ−Ｂ2 Ｏ3 −Ｚｎ
Ｏ系ガラス等が使用される場合が多い。導体ペースト
は、セラミック基板に印刷、焼成されるため、ガラスは
セラミック基板の熱膨張係数に近い値の熱膨張係数を持
つものが使われており、例えば、アルミナ基板に対して
は、７０〜７５×１０-6／℃程度の熱膨張係数をもつガ
ラスが用いられる。ガラス粉末はペースト固形分中に２
〜７重量％含有される。又酸化ビスマス粉末は、ペース
ト固形分中に３〜１３重量％含有される。Glass frit and bismuth oxide powder are usually used as the inorganic binder. Glass powder is PbO-
B 2 O 3 -SiO 2 -based glass, PbO-B 2 O 3 -Zn
O-based glass and the like are often used. Since the conductor paste is printed and fired on a ceramic substrate, glass having a coefficient of thermal expansion close to that of the ceramic substrate is used. For example, 70 to 75 for an alumina substrate. A glass having a coefficient of thermal expansion of approximately 10 −6 / ° C. is used. Glass powder is 2 in the paste solids
~ 7 wt% is contained. The bismuth oxide powder is contained in the paste solid content in an amount of 3 to 13% by weight.
【０００４】これらの固形物粉末を均一に混合してセラ
ミック基板上に印刷できるようにするために、固形分を
ビヒクルと混練してペースト状の組成物にする。このビ
ヒクルとして有機溶剤と樹脂の混合物が用いられてい
る。有機溶剤としてはターピネオール、ブチルカルビト
ール等が、又樹脂としてはエチルセルロース、ニトロセ
ルロース、ポリ酢酸ビニル等が用いられる。ターピネオ
ール中にエチルセルロースを２０重量％含有するものが
用いられる事が多い。また、印刷を円滑にするため、銀
とパラジウムを含む複合粉末、ガラス粉末及び酸化ビス
マス粉末は３２５メッシュより小さいものが用いられる
場合が多い。In order to uniformly mix these solid powders so that they can be printed on a ceramic substrate, the solids are kneaded with a vehicle to form a paste-like composition. A mixture of an organic solvent and a resin is used as this vehicle. As the organic solvent, terpineol, butyl carbitol, etc. are used, and as the resin, ethyl cellulose, nitrocellulose, polyvinyl acetate, etc. are used. Terpineol containing 20% by weight of ethyl cellulose is often used. Further, in order to facilitate printing, the composite powder containing silver and palladium, the glass powder, and the bismuth oxide powder are often smaller than 325 mesh.
【０００５】[0005]
【発明が解決しようとする課題】セラミック基板上に形
成された電極は、半田付けの工程を経た後ある時間の熱
履歴を受ける場合がある。例えば、前記電極を有する部
品を樹脂モールドする際に１５０℃程度の温度で数時間
の熱履歴を受けるし、完成部品を熱的雰囲気に曝される
自動車などに搭載した場合などには熱履歴を受ける。こ
のような熱履歴を受けると、半田中のＳｎが導体層へ徐
々に拡散して金属間化合物を多く生成し、これにより体
積膨張を起こしてセラミック基板との接合強度が低下す
る。甚だしい場合には、半田付け直後の接合強度の１０
％以下にまで低下し、その結果リード付け部分が取れて
しまうことがある。The electrode formed on the ceramic substrate may be subjected to a thermal history for a certain time after the soldering process. For example, when a component having the electrode is resin-molded, it is subjected to a heat history of several hours at a temperature of about 150 ° C., and when the finished component is mounted on a vehicle exposed to a thermal atmosphere, the heat history is receive. When subjected to such a thermal history, Sn in the solder gradually diffuses into the conductor layer to generate a large amount of intermetallic compounds, which causes volume expansion and decreases the bonding strength with the ceramic substrate. In extreme cases, the bonding strength immediately after soldering should be 10
% Or less, and as a result, the leaded part may be removed.
【０００６】この欠点は、金属成分を減らし、ガラス分
を多くすることにより、ある程度解消するが、そのよう
にすると今度は半田濡れ性が低下し、半田付けが困難に
なる。したがって、半田付け特性を維持しながらエージ
ング特性を高めるには無機結合剤に何らかの工夫が必要
である。This drawback can be solved to some extent by reducing the metal component and increasing the glass content, but if this is done, the solder wettability will decrease and soldering will become difficult. Therefore, in order to improve the aging characteristics while maintaining the soldering characteristics, it is necessary to devise an inorganic binder.
【０００７】本発明の目的は半田付け後のエージングに
よるセラミック基板との接合強度の劣化を抑制し、しか
も半田付けが容易な電極が形成できる導体ペーストを提
供することにある。An object of the present invention is to provide a conductor paste which can suppress deterioration of the bonding strength with a ceramic substrate due to aging after soldering and can form an electrode which can be easily soldered.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
本発明者等は種々研究の結果、ガラス粉末、酸化ビスマ
ス粉末のほかに添加剤としてコージェライト粉末及びア
ルミナ粉末を用いれば良いことを見いだして本発明に到
達した。さらに詳しくは、本発明のペーストは、銀とパ
ラジウムを含む混合粉末、ガラス粉末及び酸化ビスマス
粉末がビヒクル中に分散されているＡｇ−Ｐｄ系導体ペ
ーストであって、ペースト固形分中にガラス粉末を２〜
９重量％含有しかつ該ガラス粉末１０重量部当り酸化ビ
スマス粉末を５〜４５重量部、コージェライト（２Ｍｇ
Ｏ・２Ａｌ2 Ｏ3 ・５ＳｉＯ2 ）粉末を２〜５重量部及
びアルミナ粉末を１〜３重量部含有する点に特徴があ
る。[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted various studies and found that cordierite powder and alumina powder may be used as additives in addition to glass powder and bismuth oxide powder. And reached the present invention. More specifically, the paste of the present invention is an Ag-Pd-based conductor paste in which a mixed powder containing silver and palladium, a glass powder and a bismuth oxide powder are dispersed in a vehicle, and the glass powder is contained in the paste solid content. 2 to
9 wt% and 5 to 45 parts by weight of bismuth oxide powder per 10 parts by weight of the glass powder, cordierite (2Mg
It is characterized in that it contains 2 to 5 parts by weight of O.2Al 2 O 3 .5SiO 2 ) powder and 1 to 3 parts by weight of alumina powder.
【０００９】[0009]
【作用】ガラス量をペースト固形分中に２〜９重量％と
するのは、２重量％未満では半田濡れ性は良いが、セラ
ミック基板との接合力が不充分となり、又９重量％を超
えると、逆に、セラミック基板との接合力は向上する
が、半田濡れ性が低下し、実用上不都合を生じるからで
ある。When the amount of glass is 2 to 9% by weight in the solid content of the paste, the solder wettability is good when the amount is less than 2% by weight, but the bonding strength with the ceramic substrate becomes insufficient, and the amount exceeds 9% by weight. On the contrary, the bonding strength with the ceramic substrate is improved, but the solder wettability is reduced, which causes practical inconvenience.
【００１０】酸化ビスマス粉末はセラミック基板と導体
との境界層付近でガラスと金属のマトリクスを強固に形
成するために必要である。酸化ビスマスがガラス１０重
量部当り５重量部未満では強固な層が形成されず、又半
田濡れ性が不充分となる。一方４５重量部を超えると焼
成中の導体粘性が低下し過ぎ、ペースト印刷時のパター
ンを維持できなくなる。The bismuth oxide powder is necessary for firmly forming a glass-metal matrix near the boundary layer between the ceramic substrate and the conductor. If the amount of bismuth oxide is less than 5 parts by weight per 10 parts by weight of glass, a strong layer will not be formed and solder wettability will be insufficient. On the other hand, if it exceeds 45 parts by weight, the viscosity of the conductor during firing becomes too low, and the pattern during paste printing cannot be maintained.
【００１１】コージェライトをガラス粉末１０重量部当
り２〜５重量部とするのは、２重量部未満ではセラミッ
ク基板と導体との境界に生じる熱応力を緩和する効果が
小さく、接合強度の向上にあまり寄与せず、５重量部を
超えると焼成時に無機結合剤の流動性が悪くなるため接
合強度が低下し、半田濡れ性も悪くなるからである。The cordierite content of 2 to 5 parts by weight per 10 parts by weight of glass powder is less than 2 parts by weight because the effect of relaxing the thermal stress generated at the boundary between the ceramic substrate and the conductor is small and the joint strength is improved. If the amount exceeds 5 parts by weight, the flowability of the inorganic binder becomes poor at the time of firing, so that the bonding strength decreases and the solder wettability also deteriorates.
【００１２】アルミナ粉末を添加する理由は、コージェ
ライトだけでは焼成膜内部にガラスが残存し、ガラス部
分の脆性破壊の原因となるので、ガラス部分を結晶化さ
せ靱性を付与するためである。アルミナ粉末をガラス粉
末１０重量部当り１重量部未満とするとこの結晶化の効
果が小さ過ぎ、又３重量部を超えると結晶化温度が低く
なり過ぎて金属粉末の焼結を阻害し、導体表面に無機結
合剤成分が残留し、半田濡れ性が悪化するので、１〜３
重量部とする必要がある。粉末はいずれも３２５メッシ
ュより小さいものが好ましい。The reason for adding the alumina powder is that the cordierite alone causes the glass to remain inside the fired film and causes brittle fracture of the glass portion, so that the glass portion is crystallized to impart toughness. If the amount of alumina powder is less than 1 part by weight per 10 parts by weight of glass powder, the effect of crystallization is too small, and if it exceeds 3 parts by weight, the crystallization temperature becomes too low and the sintering of metal powder is hindered. Since the inorganic binder component remains in the solder and the solder wettability deteriorates,
It must be part by weight. It is preferable that all the powders are smaller than 325 mesh.
【００１３】[0013]
【実施例】平均粒径１μｍの銀粉、平均粒径０．２μｍ
のパラジウム粉を用い、ガラス粉末、酸化ビスマス粉
末、コージェライト粉末及びアルミナ粉末を種々の割合
で配合したＡｇ−Ｐｄ系導体ペーストを調製し、試験に
供した。ペーストの組成を表１に示す。ガラスは重量比
でＰｂＯ：Ｂ2 Ｏ3 ：ＳｉＯ2 ：ＣａＯ：Ａｌ2 Ｏ3 ＝
５５：１０：１５：１０：１０からなる組成のものを用
いた。ビヒクルはターピネオール中にエチルセルロース
を２０重量％含有するものを用いた。Example: Silver powder having an average particle size of 1 μm, average particle size of 0.2 μm
The palladium powder was used to prepare an Ag-Pd-based conductor paste in which glass powder, bismuth oxide powder, cordierite powder and alumina powder were mixed at various ratios, and the paste was used for the test. The composition of the paste is shown in Table 1. Glass has a weight ratio of PbO: B 2 O 3 : SiO 2 : CaO: Al 2 O 3 =
A composition having a composition of 55: 10: 15: 10: 10 was used. The vehicle used was terpineol containing 20% by weight of ethyl cellulose.
【００１４】試験は下記の方法により行なった。 （１）接合強度 ２．５４ｃｍ角のアルミナ基板に導体ペーストを２ｍｍ
角のパターンで５個印刷し、８５０℃で焼成後、導体部
に０．６５ｍｍφの錫メッキ導線を鉛３７重量％、残部
錫のＰｂ−Ｓｎ半田で接合し、引張り試験を行なった。
半田接合直後の初期接合強度、１５０℃の炉に２４時間
放置した後の強度の２種類についてそれぞれ基板を１０
枚用意し測定を行なった。初期強度は平均値が４．５ｋ
ｇ、１５０℃で２４時間放置後の強度は平均値が１．５
ｋｇ以上を合格とする。The test was conducted by the following method. (1) Bonding strength 2mm of conductor paste on 2.54cm square alumina substrate
After printing five square patterns and firing at 850 ° C., a tin-plated lead wire having a diameter of 0.65 mm was joined to the conductor portion with Pb—Sn solder containing 37% by weight of lead and the remaining tin, and a tensile test was conducted.
The initial bonding strength immediately after solder bonding and the strength after being left in a furnace at 150 ° C. for 24 hours were 10
One sheet was prepared and measured. 4.5k average initial strength
g, the average value of strength after standing at 150 ° C. for 24 hours is 1.5
Pass more than kg.
【００１５】（２）半田濡れ性 ２．５４ｃｍ角のアルミナ基板に導体ペーストを１０ｍ
ｍ角パターンで印刷し、８５０℃で焼成後導体部にフラ
ックスを滴下し、直径４ｍｍ、高さ２．８５ｍｍの円柱
状に成形された鉛３７重量％、残部錫のＳｎ−Ｐｂ半田
をのせ、該基板を２３０℃の半田浴上に浮かべ、１０秒
後に取り出し、溶融固化した半田の広がり直径を測定し
た。直径５．６ｍｍ以上を合格とした。(2) Solder wettability: 10 m of conductor paste is applied to a 2.54 cm square alumina substrate.
After printing with an m-square pattern and firing at 850 ° C., flux is dropped onto the conductor part, and 37 wt% of lead shaped into a cylinder having a diameter of 4 mm and a height of 2.85 mm and Sn-Pb solder of the remaining tin are placed, The substrate was floated on a solder bath at 230 ° C., taken out after 10 seconds, and the spread diameter of the melted and solidified solder was measured. A diameter of 5.6 mm or more was accepted.
【００１６】試験結果を表１にまとめて示す。The test results are summarized in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】表１からガラス１０重量部当り酸化ビスマ
スを５〜４５重量部、コージェライト粉末を２〜５重量
部及びアルミナ粉末１〜３重量部で良好な結果が得られ
ていることが分る。It can be seen from Table 1 that good results are obtained with 5 to 45 parts by weight of bismuth oxide, 2 to 5 parts by weight of cordierite powder and 1 to 3 parts by weight of alumina powder per 10 parts by weight of glass. ..
【００１９】[0019]
【発明の効果】本発明の導体ペーストにより、半田付け
後のエージングによるセラミック基板との接合強度の劣
化を抑制し、しかも半田付けが容易な電極を形成できる
ようになった。EFFECTS OF THE INVENTION The conductor paste of the present invention makes it possible to suppress the deterioration of the bonding strength with a ceramic substrate due to aging after soldering, and to form an electrode which can be easily soldered.
Claims (1)
粉末及び酸化ビスマス粉末がビヒクル中に分散されてい
る導体ペーストにおいて、ペースト固形分中にガラス粉
末を２〜９重量％含有しかつ該ガラス粉末１０重量部当
り酸化ビスマス粉末を５〜４５重量部、コージェライト
（２ＭｇＯ・２Ａｌ2 Ｏ3 ・５ＳｉＯ2 ）粉末を２〜５
重量部及びアルミナ粉末を１〜３重量部含有することを
特徴とする導体ペースト。1. A conductor paste in which a composite powder containing silver and palladium, a glass powder and a bismuth oxide powder are dispersed in a vehicle, wherein the paste solid content contains 2 to 9% by weight of the glass powder and the glass powder. 5 to 45 parts by weight 10 parts by weight per bismuth oxide powder, cordierite (2MgO · 2Al 2 O 3 · 5SiO 2) powder 2-5
A conductor paste containing 1 part by weight and 1 to 3 parts by weight of alumina powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35443491A JPH05174616A (en) | 1991-12-20 | 1991-12-20 | Conductor paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35443491A JPH05174616A (en) | 1991-12-20 | 1991-12-20 | Conductor paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05174616A true JPH05174616A (en) | 1993-07-13 |
Family
ID=18437543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35443491A Pending JPH05174616A (en) | 1991-12-20 | 1991-12-20 | Conductor paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05174616A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267713B2 (en) | 2003-04-28 | 2007-09-11 | Murata Manufacturing Co., Ltd. | Conductive paste and glass circuit structure |
| JP2008117790A (en) * | 2008-01-16 | 2008-05-22 | Murata Mfg Co Ltd | Conductive paste, and glass circuit structure |
| JP2018098327A (en) * | 2016-12-13 | 2018-06-21 | 太陽誘電株式会社 | Multilayer ceramic capacitor and manufacturing method thereof |
-
1991
- 1991-12-20 JP JP35443491A patent/JPH05174616A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267713B2 (en) | 2003-04-28 | 2007-09-11 | Murata Manufacturing Co., Ltd. | Conductive paste and glass circuit structure |
| JP2008117790A (en) * | 2008-01-16 | 2008-05-22 | Murata Mfg Co Ltd | Conductive paste, and glass circuit structure |
| JP2018098327A (en) * | 2016-12-13 | 2018-06-21 | 太陽誘電株式会社 | Multilayer ceramic capacitor and manufacturing method thereof |
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