JPH0282407A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JPH0282407A JPH0282407A JP23187488A JP23187488A JPH0282407A JP H0282407 A JPH0282407 A JP H0282407A JP 23187488 A JP23187488 A JP 23187488A JP 23187488 A JP23187488 A JP 23187488A JP H0282407 A JPH0282407 A JP H0282407A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- conductive paste
- surface electrode
- oxide
- metal powder
- 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
Links
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 27
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 26
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052709 silver Inorganic materials 0.000 abstract description 13
- 238000003878 thermal aging Methods 0.000 abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052763 palladium Inorganic materials 0.000 abstract description 12
- 239000004332 silver Substances 0.000 abstract description 12
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000005476 soldering Methods 0.000 abstract description 6
- 230000003679 aging effect Effects 0.000 abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 230000007423 decrease Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 hismuth oxide Chemical compound 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、低温焼成多層セラミック基板などに用いられ
る導電ペーストに関するものである。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a conductive paste used for low-temperature firing multilayer ceramic substrates and the like.
「従来の技術」
低温焼成多層セラミック基板を製造するときには、まず
セラミック生シートの上に導電ペーストを用いて電極回
路を形成し、これらのセラミック生シートを積層して真
空加熱圧着を行なうことによりセラミック生基板を形成
し、つづいてこの圧着成形されたセラミック生基板を脱
脂後、９５０℃で１５〜３０分間焼成していた。この焼
成後のセラミック基板が、低温焼成多層セラミック基板
である。この低温焼成多層セラミック基板の表面にチッ
プ部品等の電子部品素子を半田付けすることにより、電
子部品、ユニット部品が得られる。``Conventional technology'' When manufacturing a low-temperature fired multilayer ceramic substrate, first an electrode circuit is formed using a conductive paste on a raw ceramic sheet, and these raw ceramic sheets are laminated and bonded under vacuum heat and pressure. A green substrate was formed, and then the press-molded ceramic green substrate was degreased and fired at 950° C. for 15 to 30 minutes. This fired ceramic substrate is a low temperature fired multilayer ceramic substrate. By soldering electronic component elements such as chip components to the surface of this low-temperature fired multilayer ceramic substrate, electronic components and unit components can be obtained.
第１図は、この低温焼成多層セラミック基板の断面図で
ある。図中符号ｌはセラミック基板であり、２は表面電
極、３は内部電極で、４はバイア電極である。表面電極
２には、第２図に示すように、半田６によってチップ部
品等の端子７が半田付けされる。FIG. 1 is a cross-sectional view of this low-temperature fired multilayer ceramic substrate. In the figure, reference numeral 1 indicates a ceramic substrate, 2 is a surface electrode, 3 is an internal electrode, and 4 is a via electrode. Terminals 7 such as chip components are soldered to the surface electrode 2 with solder 6, as shown in FIG.
この表面電極２のような低温焼成多層セラミック基板の
電極を形成するには、従来より一般に、アルミナ基１仮
に用いられる厚膜ハイブリットＩＣ用導電ペーストを転
用していた。In order to form electrodes of a low-temperature fired multilayer ceramic substrate such as the surface electrode 2, a conductive paste for thick film hybrid ICs, which is used for the alumina base 1, has conventionally been generally used.
厚膜ハイブリットＩＣ用導電ペーストにおいては、現在
多くの種類のらのが市販されているが、一般に低温焼成
多層セラミック基板の表面電極用に転用されている導電
ペーストは、コスト等の関係から導電材料として銀−パ
ラジウムを用い、これにセラミック堰板との接着剤とし
て酸化ヒスマス、酸化銅、酸化マンガン等を添加した混
合金属粉を分散させてなる導電ペーストである。Currently, many types of conductive pastes for thick film hybrid ICs are commercially available, but conductive pastes that are generally used for surface electrodes on low-temperature fired multilayer ceramic substrates are made from conductive materials due to cost considerations. This is a conductive paste made by using silver-palladium as a conductive paste and dispersing mixed metal powder in which hismuth oxide, copper oxide, manganese oxide, etc. are added as an adhesive for ceramic dam plates.
「発明が解決しようとする課題」
ところが、この一般に最も多く転用されている上記銀−
パラジウム系厚膜ハイブリットＩＣ用の導電ペーストは
、熱エージング特性に問題がある。"Problem to be Solved by the Invention" However, the above-mentioned silver, which is most commonly used for
Conductive pastes for palladium-based thick-film hybrid ICs have problems with thermal aging characteristics.
すなわち、従来の導電ペーストで作成された表面電極に
チップ部品等の電子部品索子を半田付けして電子部品と
した場合、これを熱雰囲気下に放置すると、セラミック
部と表面電極部との接着強度が時間と共に大きく低下し
てしまうので、信頼性の高い電子部品を得られない問題
があった。In other words, when an electronic component such as a chip component is soldered to a surface electrode made with a conventional conductive paste to form an electronic component, if it is left in a hot atmosphere, the adhesion between the ceramic part and the surface electrode part will occur. Since the strength significantly decreases over time, there is a problem that highly reliable electronic components cannot be obtained.
この導電ペーストの熱エージング特性の低下の機構につ
いては明らかではないが、予想されろ機構を第２図を用
いて説明する。Although the mechanism of this decrease in thermal aging characteristics of the conductive paste is not clear, the expected mechanism will be explained with reference to FIG.
電子部品が熱雰囲気中に放置された場合、図中矢印８て
示すように半田６中のスズが熱拡散して表面電極２中に
移行し、表面電極２内に存在する銀と銀−スズ金属間化
合物を形成する。ところがこの形成された銀−スズ金属
間化合物の体積膨張率が、導電ペーストに配合された接
着剤である酸化ヒスマスなどから焼成時に形成された接
合層５の膨張率と大きく異なっている。このため前記従
来の導伝性ベーストを用いて作成された電子部品が熱雰
囲気中におかれると、経時的に接合層５と表面電極２と
の間において接着力の低下らしくは剥離が起こる。これ
はつまり、表面電極とセラミック基板との接着力の低下
となる。When electronic components are left in a hot atmosphere, the tin in the solder 6 is thermally diffused and transferred into the surface electrode 2, as shown by arrow 8 in the figure, and the silver and silver-tin present in the surface electrode 2 are dissolved. Forms intermetallic compounds. However, the volumetric expansion coefficient of the formed silver-tin intermetallic compound is significantly different from that of the bonding layer 5 formed during firing from hismuth oxide, which is an adhesive blended in the conductive paste. Therefore, when an electronic component made using the conventional conductive base is placed in a hot atmosphere, peeling occurs between the bonding layer 5 and the surface electrode 2 over time, as if the adhesive force decreases. This means that the adhesive force between the surface electrode and the ceramic substrate decreases.
本発明は、熱エージング特性の良好な導電ペーストを提
供することを目的としている。An object of the present invention is to provide a conductive paste with good thermal aging properties.
「課題を解決するための手段」
本発明では、銀（Ａｇ）が８２７〜８８．７重量％、パ
ラジウム（Ｐｄ）が３．９〜６．０宙吊％、酸化ビスマ
ス（ＢＬＯ３）が１８〜２．８重量％、酸化銅（Ｃｕｏ
）が０．６〜０．９重量％、酸化マンガン（Ｍ１１０
２）が０．２〜０．３重量％、酸化鉄（ＦｅｔＯＪが３
．４〜８．１重量％からなる組成を有する混合金属粉体
を分散させた導電ペーストを用いることで、その解決手
段とした。"Means for Solving the Problems" In the present invention, silver (Ag) is 827 to 88.7% by weight, palladium (Pd) is 3.9 to 6.0% by weight, and bismuth oxide (BLO3) is 18 to 88.7% by weight. 2.8% by weight, copper oxide (Cuo
) is 0.6-0.9% by weight, manganese oxide (M110
2) is 0.2 to 0.3% by weight, iron oxide (FetOJ is 3% by weight)
．． The solution was to use a conductive paste in which mixed metal powder having a composition of 4 to 8.1% by weight was dispersed.
「作用 」
銀、パラジウム、酸化ヒスマス、酸化銅、酸化マンガン
、酸化鉄を上記の組成で含む混合金属粉を分散した本発
明の導電ペーストで形成された表面電極には、一般に使
用されている銀−パラジウム系の導電ペーストを用いた
しのと比較して、下記■〜■の特徴がある。"Function" The surface electrode formed with the conductive paste of the present invention, in which mixed metal powder containing silver, palladium, hismuth oxide, copper oxide, manganese oxide, and iron oxide in the above composition is dispersed, does not contain commonly used silver. -Compared to the one using palladium-based conductive paste, it has the following characteristics (1) to (2).
■半田付は後の熱エージング時において、半田に含まれ
るスズの表面電極内べの拡散速度が低く、表面電極内で
の銀−スズ金属間化合物の形成をおさえることができる
。これは銀−スズ金属間化合物の形成に起因する表面電
極の熱膨張率の増加を防ぎ、表面電極と接合層との熱膨
張率の差を少なくする。■半田付は後の熱エージング時
において、導電ペースト内の接着剤により形成される接
合層の熱膨張率が、表面電極において形成される銀スズ
金属間化合物の熱膨張率に近くなる。■導電ペースト内
の接着剤により形成される接合層が強固である。(2) In soldering, during subsequent thermal aging, the diffusion rate of tin contained in the solder within the surface electrode is low, and the formation of silver-tin intermetallic compounds within the surface electrode can be suppressed. This prevents an increase in the coefficient of thermal expansion of the surface electrode due to the formation of a silver-tin intermetallic compound, and reduces the difference in coefficient of thermal expansion between the surface electrode and the bonding layer. (2) During soldering, during subsequent thermal aging, the coefficient of thermal expansion of the bonding layer formed by the adhesive in the conductive paste becomes close to the coefficient of thermal expansion of the silver-tin intermetallic compound formed in the surface electrode. ■The bonding layer formed by the adhesive in the conductive paste is strong.
そして、このような本発明の導電ペーストを表面電極に
用いることにより、表面電極の熱膨張率と接合層の熱膨
張率が近くなり、かつ接合層の強度ら大きくなるので、
熱エージング特性つまり半田付は後の熱エージング時に
おける表面電極と接合層と接着力の低下が防止される。By using such a conductive paste of the present invention for the surface electrode, the coefficient of thermal expansion of the surface electrode and the coefficient of thermal expansion of the bonding layer become close to each other, and the strength of the bonding layer becomes greater.
Thermal aging property, ie, soldering, prevents a decrease in adhesive strength between the surface electrode and the bonding layer during subsequent thermal aging.
以下、本発明の導電ペーストについて詳しく説明する。Hereinafter, the conductive paste of the present invention will be explained in detail.
本発明の導電ペーストは、！１１（Ａｇ）が８２．７〜
８８．７重量％、パラジウム（Ｐｄ）が３．９〜６０重
量％、酸化ビスマス（ＢｉｚＯ３）が１．８〜２８型組
％、酸化銅（Ｃｕｏ ）が０．６〜０゜９重量％、酸化
マンガン（ＭｎＯｔ）が０．２〜０゜３市川％、酸化鉄
（ｒ；’ ｅｔｏ ３）が３４〜８．１重！Ｕ％からな
る組成を有する混合金属粉体を分散させたしのである。The conductive paste of the present invention is! 11 (Ag) is 82.7~
88.7% by weight, palladium (Pd) 3.9 to 60% by weight, bismuth oxide (BizO3) 1.8 to 28% by weight, copper oxide (Cuo) 0.6 to 0.9% by weight, Manganese oxide (MnOt) is 0.2-0°3 Ichikawa%, iron oxide (r;' eto 3) is 34-8.1%! A mixed metal powder having a composition consisting of U% was dispersed.
ごこて本発明の導電ペーストが従来の導電ぺ一ストと異
なる点は、接着剤として酸化鉄を添加したこと、および
銀、パラジウム、酸化ビスマス、酸化銅、酸化マンガン
、酸化鉄の各組成を上記範囲に限定したことである。Iron The conductive paste of the present invention is different from conventional conductive pastes in that iron oxide is added as an adhesive, and the composition of silver, palladium, bismuth oxide, copper oxide, manganese oxide, and iron oxide is This is limited to the above range.
酸化鉄を添加すると、表面電極の膨張率の値と接合層の
膨張率の値が近接し、また接合層の強度が向上する。こ
の酸化鉄の組成が３．４重量％未満であると上記効果が
発現せず、８１重量％を越えると半田の濡れが悪くなる
という不都合がある。When iron oxide is added, the value of the expansion coefficient of the surface electrode and the value of the expansion coefficient of the bonding layer become close to each other, and the strength of the bonding layer is improved. If the composition of this iron oxide is less than 3.4% by weight, the above-mentioned effects will not be achieved, and if it exceeds 81% by weight, there is a disadvantage that solder wetting becomes poor.
また酸化ビスマスの配合量が１．８重量％未満であると
接着強度が低下するという問題があり、２．８重量％を
越えるとセラミック基板を溶解するという問題がある。Furthermore, if the amount of bismuth oxide is less than 1.8% by weight, there is a problem that the adhesive strength decreases, and if it exceeds 2.8% by weight, there is a problem that the ceramic substrate is dissolved.
酸化銅の配合量が０．６重量％未満であると接着強度が
低下するという問題があり２Ｏ．９重ｉ？ｔ％を越える
と基板へ、拡散し、絶縁抵抗値か低下するという問題が
ある。If the content of copper oxide is less than 0.6% by weight, there is a problem that the adhesive strength decreases. Ninefold i? If it exceeds t%, there is a problem that it will diffuse into the substrate and the insulation resistance value will decrease.
酸化マンガンの配合量が０．２重量％未満であると接着
強度が低下するという問題があり２Ｏ３重量％を越える
と基板へ拡散し、絶縁抵抗値が低下するという問題があ
る。If the amount of manganese oxide is less than 0.2% by weight, there is a problem that the adhesive strength decreases, and if it exceeds 2O3% by weight, there is a problem that it diffuses into the substrate and the insulation resistance value decreases.
また導電材料である銀の配合量が８２．７重量％未満で
あると焼結性が悪くなるという問題があり、８８．７重
量％を越えると印刷性が悪くなるという問題がある。Furthermore, if the content of silver, which is a conductive material, is less than 82.7% by weight, there is a problem that sinterability deteriorates, and if it exceeds 88.7% by weight, there is a problem that printability deteriorates.
パラジウムの配合量が３．９重量％未満であると電極が
９５０℃で溶解してしまうという問題があり、６，０重
量％を越えるとコスト高となり不都合である。If the amount of palladium is less than 3.9% by weight, there is a problem that the electrode will melt at 950° C., and if it exceeds 6.0% by weight, the cost will increase, which is disadvantageous.
上記混合金属粉には、粒径が０５〜２．０μｍ程度のも
のが好適に使用される。The mixed metal powder having a particle size of about 05 to 2.0 μm is preferably used.
本発明の導電ペーストは、エチルセルロースなどを高沸
点溶剤に溶解してなるビヒクルに前記混合金属粉を分散
させて使用される。The conductive paste of the present invention is used by dispersing the mixed metal powder in a vehicle prepared by dissolving ethyl cellulose or the like in a high boiling point solvent.
ビヒクルには、樹脂粘結体としてエチルセルロース、ニ
トロセルロース、アクリル樹脂、ブチラール樹脂の内少
なくとも１種類以上の樹脂を、溶剤としてブチルカルピ
トール、ターピネオール、ブチルカルピトールアセテー
ト等の内少なくとらＩｌｌ類以上の高沸点溶剤を用いる
のが好適である。The vehicle contains at least one resin selected from the group consisting of ethyl cellulose, nitrocellulose, acrylic resin, and butyral resin as a resin caking body, and at least one type Ill or higher resin selected from among butyl calpitol, terpineol, butyl calpitol acetate, etc. as a solvent. Preference is given to using high-boiling solvents.
さらにこのビヒクルには、必要に応じてパラフィンワッ
クス、マイクロワックス等のワックス類、ジオクチルフ
タレート等の可塑剤、ソルビタン酸モノステアレート等
の界面活性剤などを適宜添加してらよい。面記樹脂粘結
体の配合量は、混合金属粉１００重量部に対して０５〜
３．０重量部用いるのが好適であり、溶剤の配合量は、
混合金属粉１００重量部に対して９〜２９重徹部用いる
のか好適である。Furthermore, waxes such as paraffin wax and microwax, plasticizers such as dioctyl phthalate, surfactants such as sorbitan acid monostearate, etc. may be added to this vehicle as appropriate. The blending amount of the cylindrical resin caking body is 05 to 100 parts by weight of mixed metal powder.
It is preferable to use 3.0 parts by weight, and the amount of the solvent is:
It is preferable to use 9 to 29 parts by weight per 100 parts by weight of the mixed metal powder.
次に、本発明の導電ペーストの作製方法の一例を以下に
示す。Next, an example of a method for producing the conductive paste of the present invention will be shown below.
まず、銀、パラジウム、酸化ビスマス、酸化銅、酸化マ
ンガン、酸化鉄の各々の粉体の重量が上記範囲になるよ
うに各粉体を配合する。次にこの混合金属粉を、Ｖ型混
合機等の粉体混合装置にて十分に混合する。そして、こ
の混合金属粉を上記ビヒクルに分散させて本発明の導電
ペーストとする。First, each powder of silver, palladium, bismuth oxide, copper oxide, manganese oxide, and iron oxide is blended so that the weight of each powder falls within the above range. Next, this mixed metal powder is thoroughly mixed using a powder mixing device such as a V-type mixer. This mixed metal powder is then dispersed in the vehicle to form the conductive paste of the present invention.
ビヒクルと上記混合金属粉との混合は、少量ならば乳鉢
等、多量ならば万能混合撹拌機あるいはライカイ機等の
混合機で良く祖練りをし、さらに三本ロールで良く混練
し粉体の粒径を整えた後、導電ペーストとして使用に供
される。When mixing the vehicle and the above-mentioned mixed metal powder, if the amount is small, use a mortar or the like, or if the amount is large, use a mixer such as an all-purpose mixer or a Raikai mixer, and then knead thoroughly with three rolls to form powder particles. After adjusting the diameter, it is used as a conductive paste.
［実施例」
銀、パラジウム、酸化ビスマス、酸化銅、酸化マンガン
、酸化鉄を、第１表に示す割合で配合してビヒクル中に
分散し実施例１〜１７の導電ペース１−を作成した。[Example] Conductive pastes 1- of Examples 1 to 17 were prepared by blending silver, palladium, bismuth oxide, copper oxide, manganese oxide, and iron oxide in the proportions shown in Table 1 and dispersing them in a vehicle.
ビヒクルには、樹脂粘結体としてのニトロセルロース樹
脂を混合金属粉１００重量部に対して２８重里部、溶剤
としてのブチルカルピトール、ターピネオールを混合金
属粉１００重量部に対してそれぞれ！２重量部配合した
ものを用いた。この池にこのビヒクルには、ソルビタン
酸モノステアレートを０，２重量部を配合した。The vehicle contains 28 parts by weight of nitrocellulose resin as a resin caking body per 100 parts by weight of mixed metal powder, and butyl calpitol and terpineol as solvents per 100 parts by weight of mixed metal powder! A mixture containing 2 parts by weight was used. The vehicle was mixed with 0.2 parts by weight of sorbitan monostearate.
また比較例１として酸化鉄を含まない導電ペーストを作
成した。さらにその他の比較例として、市販の銀〜パラ
ジウム系導電ペースト２種類を準備した。Further, as Comparative Example 1, a conductive paste containing no iron oxide was prepared. Furthermore, as other comparative examples, two types of commercially available silver-palladium conductive pastes were prepared.
本発明の実施例、比較例を第１表に示す。Examples and comparative examples of the present invention are shown in Table 1.
これらの導電ペーストを用いて、２ ｍｍＸ ２ ｍｍ
の電極をセラミック生シートに印刷し、脱脂の後９５０
°Ｃにて焼成を行なった。このように形成されたＴｉ極
にさらにスズ６２重里％、鉛３６重量％、銀２重量％か
らなる半田にて半田付けを行ない、これを１５０℃の恒
温層にて熱エージングを行なった後、それぞれセラミッ
ク基板との接着強度を測定した。結県を第３図に示す。Using these conductive pastes, 2 mm x 2 mm
electrodes were printed on a ceramic raw sheet, and after degreasing, 950
Firing was performed at °C. The thus formed Ti electrode was further soldered with a solder consisting of 62% tin, 36% lead, and 2% silver, and after heat aging in a constant temperature bath at 150°C, The adhesive strength with the ceramic substrate was measured for each. The prefectures are shown in Figure 3.
第３図中符号Δにて示す曲線は、実施例１５の混合金属
粉を用いた導電ペーストによる表面電極と接合層との熱
エージング後の接着強度の変化を示す曲線である。池の
実施例についてもほぼ同じ曲線を示すので図中において
は省略する。曲線Ｂは比較例１の混合金属粉を用いた導
電ペーストによろ表面電極のらのである。曲線Ｃは市販
の導電ペーストである比較例２（商品名 Ｄ−４６８９
製造メーカー：昭栄化学）のらので、曲線りも同様に比
較例３（商品名・＃１７０２．製造メーカー ＤＥ Ｍ
Ｅ Ｔ ＲＯＮ ）のしのである。The curve indicated by the symbol Δ in FIG. 3 is a curve showing the change in adhesive strength between the surface electrode and the bonding layer after thermal aging using the conductive paste using the mixed metal powder of Example 15. Since the pond example also shows almost the same curve, it is omitted in the figure. Curve B is the surface electrode formed by the conductive paste using the mixed metal powder of Comparative Example 1. Curve C represents Comparative Example 2 (trade name D-4689), which is a commercially available conductive paste.
Manufacturer: Shoei Chemical) Norano, the curve is similar to Comparative Example 3 (Product name #1702. Manufacturer DE M
This is Shino (ET RON).
第３図より明らかであるように、実施例は比較例と比べ
て熱エージング中の接着強度の低下率が小さい。As is clear from FIG. 3, the rate of decrease in adhesive strength during heat aging is smaller in the example than in the comparative example.
「発明の効果」
以」二説明したように、本発明の導電ペーストは、銀（
Ａｇ）が８２７〜８８．７重量％、パラジウム（Ｐｄ）
が３．９〜６．０重量％、酸化ビスマス（ＢＬＯ：＋）
が１．８〜２．８重量％、酸化銅（Ｃｕｏ ）が０６〜
０９重量％、酸化マンガン（ＭｎＯ７）か０．２〜０．
３重ｆｆｌ ９／、酸化鉄（ＦｅｔＯｉ）が３４〜８．
１重量％からなる組成を何するｉ’［Ｚ合金属粉体を分
散させたしのであるので、この導電ペーストをセラミッ
ク基板等の表面電極に用いると、半田付けされた状態で
の熱エージング時において、表面電極の膨張率の値と接
合層の熱膨張率の値が近接し、さらに表面電極とセラミ
ック基板との接合層自体ら強化できる。その結果、接合
層と表面電極との接着強度の低下が抑制され、熱エージ
ング特性が改良される。従って、本発明の導電ペースト
を表面電極に用いろことにより、電子；１−品の熱雰囲
気下における信頼性が向」ニし、さらには溶融樹脂によ
る実装樹脂封止時などにおける実装部品の信頼性、歩ど
まりが向上する。また本発明の導電ペーストを用いるこ
とにより、自動車用基板部品等の高温にて使用される基
板部品への低温焼成セラミック基板の応用が可能になる
などの効果ら打る。"Effects of the Invention" As explained below, the conductive paste of the present invention has silver (
Ag) is 827-88.7% by weight, palladium (Pd)
is 3.9 to 6.0% by weight, bismuth oxide (BLO:+)
is 1.8 to 2.8% by weight, and copper oxide (Cuo) is 06 to 2.8% by weight.
09% by weight, manganese oxide (MnO7) or 0.2-0.
Triple ffl 9/, iron oxide (FetOi) 34-8.
What is the composition of 1% by weight i' In this case, the coefficient of expansion of the surface electrode and the coefficient of thermal expansion of the bonding layer are close to each other, and the bonding layer itself between the surface electrode and the ceramic substrate can be strengthened. As a result, a decrease in adhesive strength between the bonding layer and the surface electrode is suppressed, and thermal aging characteristics are improved. Therefore, by using the conductive paste of the present invention for surface electrodes, the reliability of electronic components in a hot atmosphere is improved, and furthermore, the reliability of mounted components when sealed with molten resin is improved. Improves productivity and yield. Further, by using the conductive paste of the present invention, effects such as the application of low-temperature fired ceramic substrates to substrate parts used at high temperatures, such as automotive board parts, are achieved.
第１図は低温焼成多層セラミック基板を示す概略断面図
、第２図は表面電極での半田付けの状態を示す概略断面
図、第３図は実施例における表面電極と接着層との熱エ
ージング時間に対する接着強度の変化を示すグラフであ
る。Fig. 1 is a schematic cross-sectional view showing a low-temperature fired multilayer ceramic substrate, Fig. 2 is a schematic cross-sectional view showing the soldering state of the surface electrode, and Fig. 3 is the thermal aging time of the surface electrode and adhesive layer in the example. 2 is a graph showing changes in adhesive strength with respect to
Claims (1)
特徴とする導電ペースト。[Claims] Ag82.7-88.7% by weight Pd3.9-6.0% by weight Bi_2O_31.8-2.8% by weight CuO0.6-0.9% by weight MnO_20.2-0.3% by weight % Fe_2O_ 33.4 to 8.1% by weight of a mixed metal powder is dispersed therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23187488A JPH0282407A (en) | 1988-09-16 | 1988-09-16 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23187488A JPH0282407A (en) | 1988-09-16 | 1988-09-16 | Conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0282407A true JPH0282407A (en) | 1990-03-23 |
Family
ID=16930377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23187488A Pending JPH0282407A (en) | 1988-09-16 | 1988-09-16 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0282407A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07500952A (en) * | 1992-08-28 | 1995-01-26 | トムソン コンシューマ エレクトロニクス インコーポレイテッド | Printed circuit board shield assembly for tuners etc. |
| US6839955B2 (en) * | 1999-08-06 | 2005-01-11 | Tdk Corporation | Method of making a multilayer inductor |
-
1988
- 1988-09-16 JP JP23187488A patent/JPH0282407A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07500952A (en) * | 1992-08-28 | 1995-01-26 | トムソン コンシューマ エレクトロニクス インコーポレイテッド | Printed circuit board shield assembly for tuners etc. |
| US6839955B2 (en) * | 1999-08-06 | 2005-01-11 | Tdk Corporation | Method of making a multilayer inductor |
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