JPH0239411A - Conductive composed material for ceramic capacitor terminal electrode - Google Patents
Conductive composed material for ceramic capacitor terminal electrodeInfo
- Publication number
- JPH0239411A JPH0239411A JP18895888A JP18895888A JPH0239411A JP H0239411 A JPH0239411 A JP H0239411A JP 18895888 A JP18895888 A JP 18895888A JP 18895888 A JP18895888 A JP 18895888A JP H0239411 A JPH0239411 A JP H0239411A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- terminal electrode
- ceramic capacitor
- parts
- 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
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 28
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 31
- 239000011230 binding agent Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 13
- 238000007747 plating Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 238000005476 soldering Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- 101100473036 Mus musculus Hnrnpa1 gene Proteins 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 210000004013 groin Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
り鼠旦立丘里豆ヱ
本発明は、セラミックコンデンサの端子電極を形成する
ための導電性組成物であり、特にチタン酸バリウム系積
層コンデンサの端子電極付近に生じるクラックを防止し
た電極組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is a conductive composition for forming terminal electrodes of ceramic capacitors. The present invention relates to an electrode composition that prevents.
良米立韮韮
積層コンデンサ等、チップ状セラミックコンデンサの端
子電極は、銀、パラジウム、金、白金、銅、ニッケル又
はこれらの混合物などの導電性粉末と、ガラス質フリッ
ト等の無機結合剤とを有機ビヒクルに分散させたペース
ト状の組成物を、チップ素体の端子部に塗布し、焼付け
することによって形成される。The terminal electrodes of chip-shaped ceramic capacitors, such as Ryomaritsu Niranori multilayer capacitors, are made of conductive powder such as silver, palladium, gold, platinum, copper, nickel, or a mixture thereof, and an inorganic binder such as glass frit. It is formed by applying a paste-like composition dispersed in an organic vehicle to the terminal portion of the chip body and baking it.
コンデンサチップの回路基板への実装は、半田付けによ
って行うのが一般的であるが、電極中の導電成分が貴金
属のように半田に溶解し易い金属である場合は、耐半田
溶解性を高めるため電極表面に半田に溶解し難いニッケ
ル、銅などの金属の薄膜を電解メツキ等の手段によって
形成し、次いでその上に半田付性の良い錫や錫−鉛合金
などを被覆し、その後半田呼処理を行っている。Capacitor chips are generally mounted on circuit boards by soldering, but if the conductive component in the electrode is a metal that easily dissolves in solder, such as a noble metal, it may be necessary to use soldering to increase resistance to solder melting. A thin film of metal such as nickel or copper, which is difficult to dissolve in solder, is formed on the electrode surface by means such as electrolytic plating, and then tin or a tin-lead alloy, which has good solderability, is coated on top of it, followed by a soldering process. It is carried out.
ところが、従来この種の導電性組成物は無機結合剤に硼
珪酸鉛系や硼珪酸ビスマス系のガラス質フリットを用い
ているが、この組成物から形成された導電被膜に電解メ
ツキ処理を施したとき、端子とコンデンサ素体間の接合
強度が劣化する問題が生じ、このため電極材料、特に電
極に使用するガラス質フリットの改良がなされてきた。However, conventionally, this type of conductive composition uses a lead borosilicate-based or bismuth borosilicate-based glass frit as an inorganic binder; At this time, a problem arises in which the bonding strength between the terminal and the capacitor body deteriorates, and for this reason, improvements have been made to electrode materials, particularly the glass frit used in the electrodes.
例えば特公昭６０−３７５６２号は、鉛を含有しないＺ
ｎ０−Ｂ２０３−３ＬＯ２ガラスを使用したベーストで
酸処理、電解メツキの可能な導体膜を形成するものであ
る。又、特公昭６２−１６６２号には、アルカリ金属及
びアルカリ土類金属を含有する特定の組成の硼珪酸亜鉛
系ガラス質フリットを用いた導電塗料が記載されている
。しかしこれらのガラスを使用することによって、電解
メツキによる密着強度の劣化はある程度改善されるもの
の、電極表面にガラスが分布してメツキが一様に形成さ
れず、このため半田の付着性が不十分になる欠点かある
。For example, Special Publication No. 60-37562 is a lead-free Z
A conductor film that can be acid-treated and electrolytically plated is formed using a base using n0-B203-3LO2 glass. Further, Japanese Patent Publication No. 1662/1983 describes a conductive paint using a zinc borosilicate glass frit having a specific composition containing an alkali metal and an alkaline earth metal. However, although the use of these glasses improves the deterioration of adhesion strength due to electrolytic plating to some extent, the glass is distributed on the electrode surface and the plating is not formed uniformly, resulting in insufficient solder adhesion. There are some drawbacks to it.
又従来、電解メツキ処理したコンデンサを半田付する際
、半田浴の温度が高温で３００°Ｃ以上にも及ぶため、
半田浴にコンデンサチップを浸漬するときに急激な温度
変化が加わることになり、このため信頼性に問題を生ず
る６例えば積層セラミックコンデンサを製造する場合、
半田付時に加わるサーマルショックによりコンデンサ素
体にしばしばクラックが発生し、コンデンサとして使用
できなくなることがある。このクラックは、半田付時の
他、コンデンサ製造工程において大きな機械的応力が加
わったときなどにも生ずることがある。In addition, conventionally, when soldering electrolytically plated capacitors, the temperature of the solder bath was high and reached over 300°C.
When a capacitor chip is immersed in a solder bath, a sudden temperature change is applied, which causes reliability problems6. For example, when manufacturing multilayer ceramic capacitors,
Thermal shock applied during soldering often causes cracks in the capacitor body, making it unusable as a capacitor. These cracks may occur not only during soldering but also when large mechanical stress is applied during the capacitor manufacturing process.
このようなりラックの発生は、特に内部電極材料にパラ
ジウム系又は銀−パラジウム系の金属を使用し、端子電
極を銀−パラジウム又は銀系で形成したときに多く、又
機械的強度が比教的弱いＢａＴ ｉ Ｏ３系の積層コン
デンサで多発しており、大きな問題となっている。The occurrence of such racks is especially common when palladium-based or silver-palladium-based metals are used for the internal electrode material and the terminal electrodes are formed from silver-palladium or silver-based metals. This occurs frequently in weak BaT i O3 multilayer capacitors, and is a major problem.
が 決しようとする課題
本発明の目的は、セラミックコンデンサ端子電極のガラ
ス結合剤の改良により、端子とコンデンサ素体との接合
性及び半田付性を改善し、更に積層コンデンサの半田付
時の熱？Ｒ撃等によるクラックの発生を防止することに
ある。The purpose of the present invention is to improve the bondability and solderability between the terminal and the capacitor body by improving the glass bonding agent of the ceramic capacitor terminal electrode, and to improve the heat resistance during soldering of the multilayer capacitor. ? The purpose is to prevent the occurrence of cracks due to R strikes, etc.
課題を ゛ るための 段
本発明は、貴金属粉末１００重量部と、ガラスを構成す
る各元素の合計が酸化物換算でそれぞれＢ２Ｏ３
１５〜３５重量％Ｚｎ０ ３
５〜６０重量％Ｓｉｏ２ １〜１５重量
％Ａｌ２Ｏ３１−１５重厘％
ＰｂＯＯ，５〜１２重量％
の比率となるような１種又は２種以上のガラス質フリッ
ト０．２〜２０重１部とを有機ビヒクルに分散させてな
るセラミックコンデンサ端子ｔｉ用導電性組成物であり
、又第２の発明は貴金属粉末１００重凰部上、ガラスを
構成する各元素の合計が酸１ヒ物換算でそれぞれ
Ｂ２Ｏ３ １５〜３５ｆｆｉｊ１％Ｚｎ
０ ３５〜６０重呈％Ｓｉｏ２
１〜１５重坂％Ａｌ２Ｏ３１〜１５重量％
Ｐ ｂ ＯＯ，５〜１２重量％
ＢａＯ及びＣａＯから選
ばれる少なくとも１種 ２〜２８重量％の比率となるよ
うな１種又は２種以上のガラス質フリ、ト０．２〜２０
重量部とを有機ビヒクルに分散させてなるセラミックコ
ンデンサ端子電極用導電性組成物である。To solve the problem, the present invention provides 100 parts by weight of noble metal powder and a total of each element constituting the glass in terms of oxides of B2O3.
15-35 wt% Zn03
5 to 60% by weight Sio2 1 to 15% by weight Al2O3 1-15% by weight PbOO, 0.2 to 20% by weight and 1 part by weight of one or more types of vitreous frit such that the ratio is 5 to 12% by weight. The second invention is a conductive composition for ceramic capacitor terminals, which is dispersed in an organic vehicle. 15~35ffij1%Zn
0 35-60 weight%Sio2
1 to 15% by weight Al2O3 1 to 15% by weight P b OO, 5 to 12% by weight At least one type selected from BaO and CaO One or more types of vitreous material with a ratio of 2 to 28% by weight , 0.2-20
This is a conductive composition for ceramic capacitor terminal electrodes, which is prepared by dispersing parts by weight in an organic vehicle.
１■
本発明の特定組成の硼珪酸鉛−亜釦一アルミニウム系ガ
ラスを結合剤として使用した導電性組成物は、コンデン
サ素体に焼（−１けすることにより、コンデンサ素体と
の接合強度が強く、電解メツキを施しても接合強度の劣
化がない端子電極が形成される。又電極表面にガラスの
分布が少なく、従ってメツキの付着性及び半田の付着性
か優れている。又積層コンデンサの実装時の半田付に際
してのサーマルショックや、その他の機械的衝撃による
コンデンサ素体へのクラックの発生が著しく減少する。1. The conductive composition of the present invention using lead borosilicate-aluminum glass having a specific composition as a binder can be baked into a capacitor body to improve the bonding strength with the capacitor body. Terminal electrodes are formed that are strong and have no deterioration in bonding strength even when electrolytically plated.Also, there is little distribution of glass on the electrode surface, resulting in excellent plating and solder adhesion.Also, multilayer capacitors The occurrence of cracks in the capacitor body due to thermal shock during soldering during mounting and other mechanical shocks is significantly reduced.
積層コンデンサのクラックの発生ＩＲ椙については明確
には解っていないが、例えばパラジウム系の内部電極を
用いた積層セラミックコンデンサに、銀糸の端子電極組
成物を塗布し、焼成すると、パラジウムと銀の拡散速度
の違いから、端子中の銀が、端子に直接結合している内
部電極中に拡散し、端子近くの内部電極が体積膨張を起
こして周囲のセラミック誘電体層を圧迫する。このため
コンデンサ素体の内部電極が露出していない側面部に引
張り応力の集中が起こり、その結果セラミック誘電体層
に内部歪み、或いは極めて微細な亀裂を生じさせるもの
と考えられる。そして端子部に電解メツキを行なった後
、実装工程で高温の半田浴へ浸漬する際、急激な昇温に
よってこの歪み又は微細な亀裂が拡大され、特に機械的
強度があまり強くないＢａＴｉＯ３のようなセラミック
誘電体の場合、大きなりラックに至ると考えられる。The occurrence of cracks in multilayer capacitors is not clearly understood, but for example, when a terminal electrode composition of silver thread is applied to a multilayer ceramic capacitor using palladium-based internal electrodes and fired, the diffusion of palladium and silver occurs. Due to the difference in speed, the silver in the terminal diffuses into the internal electrode that is directly bonded to the terminal, causing volumetric expansion of the internal electrode near the terminal and compressing the surrounding ceramic dielectric layer. This is thought to cause tensile stress to concentrate on the side surfaces of the capacitor body where the internal electrodes are not exposed, resulting in internal distortion or very fine cracks in the ceramic dielectric layer. After electrolytically plating the terminals, when the terminals are immersed in a high-temperature solder bath during the mounting process, these distortions or minute cracks are enlarged due to the rapid temperature rise. In the case of ceramic dielectrics, this would lead to large racks.
本発明においてガラスを前記の組成とすると、端子電極
とコンデンサ素体との界面に強靭な結晶化ガラスの薄い
層が形成され、この層が形成されるとクラックが発生し
にくくなることか判明した。In the present invention, when the glass has the above composition, a thin layer of tough crystallized glass is formed at the interface between the terminal electrode and the capacitor body, and it has been found that the formation of this layer makes it difficult for cracks to occur. .
この層は分析の結果、亜鉛系の結晶化ガラス中にＺｎＯ
とＴｉＯ２を主成分とする結晶が析出したものであるが
、これは端子電極の焼成時、軟化したガラスをフラック
スとしてコンデンサ素体の一部が分解され、端子電極の
ガラスの構成成分であるＺｎＯと反応したものではない
かと推定される。As a result of analysis, this layer was found to contain ZnO in zinc-based crystallized glass.
Crystals mainly composed of TiO2 were precipitated, but this is because when the terminal electrodes were fired, part of the capacitor body was decomposed using softened glass as a flux, and ZnO, which is a component of the glass of the terminal electrodes, was decomposed. It is presumed that this was a reaction.
この素体の分解と反応層が生成する現象に伴って、前述
の内部’Ｅ ｆＩの膨脹に起因するセラミックの内部歪
み、及び半田付時の急激な温度変化による歪みが緩和さ
れ、加えてクラック発生箇所の機械的強度が増大するた
め、種々の熱衝撃や機械的衝撃を受けてもクラックの発
生が抑制されると考えられる。Along with this phenomenon of decomposition of the element and the formation of a reaction layer, the internal distortion of the ceramic caused by the expansion of the internal 'E fI mentioned above and the distortion caused by the rapid temperature change during soldering are alleviated, and in addition, cracks are reduced. It is thought that since the mechanical strength of the crack generation site increases, the generation of cracks is suppressed even when subjected to various thermal shocks and mechanical shocks.
更にガラス質フリットとコンデンサ素体とが反応して接
着しているため、端子とコンデンサ素体間の接合強度ら
著しく改善され、電解メツキ後も強度の劣化が起こらな
いと考えられる。Furthermore, since the glassy frit and the capacitor body react and adhere to each other, the bonding strength between the terminal and the capacitor body is significantly improved, and it is thought that no deterioration in strength will occur even after electrolytic plating.
第二の発明においては、第一の発明の硼珪酸鉛−亜鉛−
アルミニウムガラスにＢａＯ及び／又はＣａＯを特定量
添加するか、この添加により素体との接合強度が更に大
きくなり、又膜の緻密性が改善される。焼成膜の膜密度
が向上すると、メツキ工程でメツキ液の浸入が防止され
、従ってメツキ液の滲込みに起因する絶縁抵抗の低下や
、メツキ後の高温加熱時閉込められた水分が膨脹、破裂
するいわゆるポツプコーン現象が防止されるので、信顆
性が向上する。In the second invention, the lead-zinc borosilicate of the first invention
By adding a specific amount of BaO and/or CaO to aluminum glass, the bonding strength with the element body is further increased and the denseness of the film is improved. When the film density of the fired film is improved, the infiltration of the plating liquid during the plating process is prevented, and therefore the insulation resistance decreases due to seepage of the plating liquid, and the trapped moisture expands and ruptures during high temperature heating after plating. Since the so-called popcorn phenomenon that occurs is prevented, reliability is improved.
ガラスの組成を限定した理由は次の通りである。The reason for limiting the composition of the glass is as follows.
Ｂ２０３は１０重量％未満ではガラス化か困難であり、
３５重量％を越えると軟化温度が高くなり、又失透する
ので望よしくない。If B203 is less than 10% by weight, it is difficult to vitrify it.
If it exceeds 35% by weight, the softening temperature becomes high and devitrification occurs, which is not desirable.
ＺｎＯはコンデンサ成分と反応して、素体との密着強度
を改善するとともにクラックを防止すると考えられるが
、３５重１％より少ないと反応層の形成か不十分で効果
がなく、ス６０重量％を越えるとガラス１ヒが困難にな
る。It is thought that ZnO reacts with the capacitor components to improve the adhesion strength with the element body and prevent cracks, but if it is less than 1% by weight, the formation of a reaction layer is insufficient and there is no effect; If you exceed this, glass 1hi becomes difficult.
ＳｉＯ２は、１重量％未満では耐酸性が低く、１５重量
％より多いと軟化温度が高くなりすぎるので望ましくな
い。If SiO2 is less than 1% by weight, the acid resistance is low, and if it is more than 15% by weight, the softening temperature becomes too high, which is not desirable.
Ａｌ２Ｏ３はガラスを安定化させるために配合する。配
合量が１重量％未満では失透か起こり易く、素体とガラ
スとの反応が均一に起こりにくくなって強度等が低下す
る。１５重量％を越えるとガラスの流動性が損なわれる
。Al2O3 is added to stabilize the glass. If the blending amount is less than 1% by weight, devitrification is likely to occur, making it difficult for the reaction between the element body and the glass to occur uniformly, resulting in a decrease in strength, etc. If it exceeds 15% by weight, the fluidity of the glass will be impaired.
ＰｂＯは０．５重量％より少ないとガラス化が困難であ
り、又１２重量％を越えると軟化温度が低下し、流動性
が大きくなりすぎて使用に適さない。When PbO is less than 0.5% by weight, vitrification is difficult, and when it exceeds 12% by weight, the softening temperature decreases and fluidity becomes too high, making it unsuitable for use.
特にガラス成分にＢａｄ、ＣａＯが含まれない場合は０
．５〜９重量％の範囲か好適である。Especially if the glass component does not contain Bad or CaO, 0
．． A range of 5 to 9% by weight is suitable.
Ｂａｄ、ＣａＯは必すしも配合されなくてもよいが、上
記の硼珪酸鉛−亜鉛−アルミニウムガラスガラスに添加
することによって接合強度が更に改善されるとともに、
膜密度か大きくなるので膜へのメツキ液の滲込みが防止
され、信頼性が向上する。ＢａＯ１ＣａＯの合計量か２
重量％より少ないとこれらの特性改善にあまり効果がな
く、２８重量％を越えると前述の反応層の形成が困難に
なり、クラックの発生が多くなる。Bad and CaO do not necessarily have to be added, but by adding them to the lead borosilicate-zinc-aluminum glass, the bonding strength is further improved, and
Since the film density is increased, plating solution is prevented from seeping into the film, improving reliability. Total amount of BaO1CaO2
If it is less than 28% by weight, it will not be very effective in improving these properties, and if it exceeds 28% by weight, it will be difficult to form the above-mentioned reaction layer and cracks will occur more often.
ガラス質フリットとしては単一のガラス質フリｙトを使
用してもよいが、２種以上のフリ・ｙｌ−の混合物で、
各成分酸化物の合計が前記の比率となるものを用いても
よい。A single glassy frit may be used as the glassy frit, but a mixture of two or more types of glassy frits,
You may use the one in which the total of each component oxide has the above-mentioned ratio.
本発明にはガラス質フリットの曲に、無機結合剤として
通常使用される酸化ビスマス、酸化銅、酸化亜鉛等の添
加剤を併用してもよい。In the present invention, additives such as bismuth oxide, copper oxide, and zinc oxide, which are commonly used as inorganic binders, may be used in combination with the vitreous frit.
導電性粉末としては銀、パラジウム、白金、金などの貴
金属や、これらの合金或いは混合物が使用される。As the conductive powder, noble metals such as silver, palladium, platinum, and gold, and alloys or mixtures thereof are used.
有機ビヒクルは特に制限はなく、通常この種の導電性組
成物に使用されるものでよい。The organic vehicle is not particularly limited, and may be one that is normally used in this type of conductive composition.
導電性粉末とガラス質フリットの比率は、導電性粉末１
００重量部に対してガラス質フリット０．２〜２０重量
部の範囲で使用される。これより少ないと電極の接合強
度が充分でなく、多ずぎると電極の表層部に存在するガ
ラスが多くなるために、均一なメツキ膜の形成が困難に
なるので望ましくない。又有機ビヒクルは導電性粉末１
００重量部に対し１０〜４０重１部程度か適当である。The ratio of conductive powder to vitreous frit is conductive powder 1
The glassy frit is used in an amount of 0.2 to 20 parts by weight per 0.00 parts by weight of the glass frit. If the amount is less than this, the bonding strength of the electrodes will not be sufficient, and if it is too much, the amount of glass present on the surface layer of the electrode will increase, making it difficult to form a uniform plating film, which is not desirable. Also, the organic vehicle is conductive powder 1
Approximately 1 part by weight of 10 to 40 parts per 00 parts by weight is appropriate.
本発明の導電性組成物は、特にＢ ａ Ｔ ｉ ＯＢ系
の積層コンデンサに対して特に効果か大きいが、Ｔ ｉ
Ｏ２系その他の積層コンデンサや、単板形のコンデン
サの端子電極形成用にも用いることかできるのはもちろ
んである。更にメツキを行わず直接半田付けするタイプ
の端子電極にもｆ重用することができる。The conductive composition of the present invention is particularly effective for B a T i OB type multilayer capacitors;
Of course, it can also be used for forming terminal electrodes of O2-based and other multilayer capacitors and single-plate capacitors. Furthermore, it can also be used for terminal electrodes that are directly soldered without plating.
実施例
実施例１
銀粉末１００重量部に対して下記組成のガラス質フリッ
ト６重量部と、有機ビヒクルとしてエチルセルロースの
テルピネオール溶液３０重量部を混会し、ペースト状の
導電性組成物を得た。Examples Example 1 100 parts by weight of silver powder were mixed with 6 parts by weight of a vitreous frit having the following composition and 30 parts by weight of a terpineol solution of ethyl cellulose as an organic vehicle to obtain a paste-like conductive composition.
Ｂ２Ｏ３ ２９重量％
Ｚｎ０ ４９重量％
ＳｉＯ２８重量％
Ａｌ２Ｏ３２重量％
ＰｂＯ１２重量％
このベーストを、内部ｔ ％にパラジウムを用いたＢａ
Ｔｉ０ｑ系積層セラミックコンデンサ（層数３０層）の
端子部即ち内部電極端部の露出した側面に塗布し、１５
０°Ｃで１０分間乾燥した後、最高温度８００℃で焼成
し、端子電極被膜を形成した。B2O3 29% by weight Zn0 49% by weight SiO28% by weight Al2O32% by weight PbO 12% by weight
Coat it on the exposed side surface of the terminal part, that is, the end of the internal electrode, of a Ti0q-based multilayer ceramic capacitor (30 layers).
After drying at 0°C for 10 minutes, it was fired at a maximum temperature of 800°C to form a terminal electrode coating.
次いで端子部にニッケル及び錫を順次電解メツキした。Next, the terminal portions were sequentially electrolytically plated with nickel and tin.
メツキ処理の前後で電極とセラミンク索体間の接合強度
を測定したところ、それぞれ４１ｋｇ、 ３．９ｋｇで
あった。When the bonding strength between the electrode and the ceramink cord was measured before and after the plating treatment, it was 41 kg and 3.9 kg, respectively.
又メツキ処理したコンデンサを３００°Ｃの錫／釦共晶
半田浴に１秒間浸漬し、その後、光学顕微鏡でセラミッ
ク素体を観察したところ、クラックの発生は見られなか
った。半田の付着性は極めて良好であった。Furthermore, when the plated capacitor was immersed in a tin/button eutectic solder bath at 300° C. for 1 second and the ceramic body was then observed with an optical microscope, no cracks were observed. Solder adhesion was extremely good.
実施例２〜７
表１に示したガラス質フリｙトを使用する以外は実施例
１と同様にして、端子電極を形成した。Examples 2 to 7 Terminal electrodes were formed in the same manner as in Example 1 except that the vitreous frit shown in Table 1 was used.
同様にメツキ前後の接合強度及びクラｙりの発生状況、
半田付性、膜密度を調べ、結果を表１に併せて示した。Similarly, the joint strength before and after plating and the occurrence of cracking,
The solderability and film density were investigated, and the results are also shown in Table 1.
尚、表１において半田付性は、試料１０個中、半田がは
じかれ均一に付着しなかったものの個数で示した。膜密
度は顕微鏡写真により判定し、実施例１の焼成膜を基準
にして、はぼ同等のものは○、より緻密なものは◎とし
た。In Table 1, the solderability is shown by the number of samples out of 10 samples in which the solder was repelled and did not adhere uniformly. The film density was determined by a microscopic photograph, and based on the fired film of Example 1, the film density was rated ◯ if it was equivalent to that of Example 1, and ◎ if it was denser.
比較例１〜５
表１に示した組成のガラス質フリットを使用する以外は
実施例と同様にして、端子電極を形成し、接合強度、ク
ラックの発生、半田付性及び膜密度を調べた。結果を表
１に併せて示した。Comparative Examples 1 to 5 Terminal electrodes were formed in the same manner as in the example except that a glassy frit having the composition shown in Table 1 was used, and the bonding strength, occurrence of cracks, solderability, and film density were examined. The results are also shown in Table 1.
表１から明らかなように、本発明の組成物ではクラック
か全く発生せず、接合強度、半ＩＩＩ吋性及び膜密度と
もに優れているか、本発明外の組成のガラスを用いるも
のでは、比較例１−３．５では多数のクラックか発生し
た。比較例４．５では、半ＩＪＩ濡れ性が悪いか、これ
は電極１摸にガラスか多く存在し、ニノゲルメッキが均
一に１４着しないためと考えられる。また比較例１．３
・〜５では強度も弱い。尚、ガラスにＢａＯ１ＣａＯを
含む実施例５〜７では１模密度が非常に優れていた。As is clear from Table 1, the composition of the present invention does not generate any cracks and is excellent in bonding strength, half-III toughness, and film density. 1-3.5, many cracks occurred. In Comparative Example 4.5, the semi-IJI wettability was poor, and this is thought to be because a large amount of glass was present in each electrode, and the Ninogel plating was not applied uniformly. Also, Comparative Example 1.3
・At ~5, the strength is weak. In addition, in Examples 5 to 7 in which the glass contained BaO1CaO, the 1 simulcast density was very excellent.
実施例８
銀粉末１００１扛量部、実施例６と同−釘■成のガラス
質フリット３市鼠部及びｆｌｉ２’３扮木５重量部をエ
チルセル１ｍ？−スのデルビイ・オール溶１１ｔ３０車
鼠部に混合分散し、ペースｉ・状の導電性組成物を得た
。このペーストを、ＢａＴｉ○３系績層セラミ７クコン
デンサの端子部に塗布し、乾燥後、最高温度７５０°Ｃ
で焼成し、端子電極被膜を形成した。Example 8 1001 parts of silver powder, 3 parts by weight of the same vitreous frit as in Example 6, and 5 parts by weight of fli2'3 were placed in 1 m of ethyl cell. The mixture was mixed and dispersed in the groin area of a Delby All solution 11t30 vehicle to obtain a conductive composition in the form of a paste. This paste was applied to the terminals of a BaTi○3-layer ceramic 7-layer capacitor, and after drying, the maximum temperature was 750°C.
A terminal electrode coating was formed by firing the terminal electrode.
メツキ処理を行わない端子の接合強度は！ｉ、２ｋｇで
あり、陵れた密着性を示した。又半Ｉ１１１寸性は良好
であった。What is the bonding strength of terminals that are not plated? i, 2 kg, and showed good adhesion. In addition, the semi-I111 dimensional properties were good.
発明の効果
本発明の特定組成のガラスを前桟結合剤として便用する
電極用組成物により、コンデンサ素体との接合強度か強
く、電解メツＡにも耐える（憂れな”Ａ’＋ ”Ｉ′−
電極が形成され、かつ実装時の半ｕｌ ｌ・ｊに際して
のサーマルショックやその曲の機械的衝撃によるクラッ
クの発生のない、信頼性か極めて高いセラミックコンデ
ンサを得ることができる。Effects of the Invention The electrode composition that uses the glass of the specific composition of the present invention as a front beam bonding agent has strong bonding strength with the capacitor body and can withstand electrolytic metal A (the unfortunate "A'+"). I'-
It is possible to obtain a highly reliable ceramic capacitor in which electrodes are formed and which does not generate cracks due to thermal shock or mechanical impact during half-ul l·j during mounting.
Claims (1)
素の合計が酸化物換算でそれぞれ下記比率となるような
１種又は２種以上のガラス質フリット０．２〜２０重量
部とを、有機ビヒクルに分散させてなるセラミックコン
デンサ端子電極用導電性組成物。 Ｂ＿２Ｏ＿３ １５〜３５重量％ ＺｎＯ ３５〜６０重量％ ＳｉＯ＿２ １〜１５重量％ Ａｌ＿２Ｏ＿３ １〜１５重量％ ＰｂＯ ０．５〜１２重量％ ２ 貴金属粉末１００重量部と、ガラスを構成する各元
素の合計が酸化物換算でそれぞれ下記比率となるような
１種又は２種以上のガラス質フリット０．２〜２０重量
部とを、有機ビヒクルに分散させてなるセラミックコン
デンサ端子電極用導電性組成物。 Ｂ＿２Ｏ＿３ １５〜３５重量％ ＺｎＯ ３５〜６０重量％ ＳｉＯ＿２ １〜１５重量％ Ａｌ＿２Ｏ＿３ １〜１５重量％ ＰｂＯ ０．５〜１２重量％ ＢａＯ及びＣａＯから選 ばれる少なくとも１種 ２〜２８重量％ ３ 更に酸化ビスマス粉末を添加した請求項１又は２記
載のセラミックコンデンサ端子電極用導電性組成物。[Scope of Claims] 1. 100 parts by weight of noble metal powder and 0.2 to 20 parts by weight of one or more types of vitreous frit such that the total of each element constituting the glass is in the following ratio in terms of oxide. 1. A conductive composition for a ceramic capacitor terminal electrode, which is prepared by dispersing the above components in an organic vehicle. B_2O_3 15-35% by weight ZnO 35-60% by weight SiO_2 1-15% by weight Al_2O_3 1-15% by weight PbO 0.5-12% by weight 2 100 parts by weight of noble metal powder and the total of each element constituting the glass are oxidized A conductive composition for a ceramic capacitor terminal electrode, comprising 0.2 to 20 parts by weight of one or more glassy frits having the following ratios, respectively, dispersed in an organic vehicle. B_2O_3 15-35% by weight ZnO 35-60% by weight SiO_2 1-15% by weight Al_2O_3 1-15% by weight PbO 0.5-12% by weight At least one selected from BaO and CaO 2-28% by weight 3 Furthermore, bismuth oxide The conductive composition for ceramic capacitor terminal electrodes according to claim 1 or 2, further comprising powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18895888A JPH0817141B2 (en) | 1988-07-28 | 1988-07-28 | Conductive composition for ceramic capacitor terminal electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18895888A JPH0817141B2 (en) | 1988-07-28 | 1988-07-28 | Conductive composition for ceramic capacitor terminal electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0239411A true JPH0239411A (en) | 1990-02-08 |
| JPH0817141B2 JPH0817141B2 (en) | 1996-02-21 |
Family
ID=16232905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18895888A Expired - Lifetime JPH0817141B2 (en) | 1988-07-28 | 1988-07-28 | Conductive composition for ceramic capacitor terminal electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0817141B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561587A (en) * | 1993-12-10 | 1996-10-01 | Murata Manufacturing Co., Ltd. | Conductive paste and multilayer ceramic capacitor |
| US5623389A (en) * | 1994-06-20 | 1997-04-22 | Murata Manufacturing Co., Ltd. | Conductive paste and multilayered ceramic capacitor employing the same |
| US5707555A (en) * | 1994-11-24 | 1998-01-13 | Murata Manufacturing Co., Ltd. | Conductive paste and external electrodes for electronic product formed using same |
| WO2001048762A1 (en) * | 1999-12-24 | 2001-07-05 | Ngk Insulators, Ltd. | Ceramic capacitor electrode-forming paste |
-
1988
- 1988-07-28 JP JP18895888A patent/JPH0817141B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561587A (en) * | 1993-12-10 | 1996-10-01 | Murata Manufacturing Co., Ltd. | Conductive paste and multilayer ceramic capacitor |
| US5623389A (en) * | 1994-06-20 | 1997-04-22 | Murata Manufacturing Co., Ltd. | Conductive paste and multilayered ceramic capacitor employing the same |
| US5707555A (en) * | 1994-11-24 | 1998-01-13 | Murata Manufacturing Co., Ltd. | Conductive paste and external electrodes for electronic product formed using same |
| WO2001048762A1 (en) * | 1999-12-24 | 2001-07-05 | Ngk Insulators, Ltd. | Ceramic capacitor electrode-forming paste |
| US6565774B2 (en) | 1999-12-24 | 2003-05-20 | Ngk Insulators, Ltd. | Paste for formation of ceramic capacitor electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0817141B2 (en) | 1996-02-21 |
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