1245298 九、發明說明： 【發明所屬之技術領域】 本發明係關於電極糊、陶瓷電子零件及发制生 【先前技術】 ’ 〃μ方法者。 先前，於疊層陶莞電容器等之陶究電子零件之 採用以下之方法：形成疊層體，該疊層體係包含^成介泰 體層之陶瓷介電體之粉末之層與 "电 〇 I 3構成内部電極屉 4電極糊之層交互重疊複數層者曰 外部電極。 立層體後，没置 此處，於介電體層之形成中，係使用混合陶竟介電體於 末與有機固著劑以及有機溶劑等，藉由刀片到 ： 使漿化之介電體糊成為薄板狀， ，、/ 形體。又，用於内部電後製作之陶究成 全屬於H… 部電極糊係將鎳等 广末刀政於有機固著劑及有機溶劑等，使其成為糊狀 二:=體:常將内部電極糊網屏印刷於薄板狀之 體:面使包含於内部電極糊之有機溶劑乾燥 —重且稷數片此成形體，加壓成形後製成。 藉由將此疊層體晶Η π、，i 此陶菩1 亚加以培燒形成陶究元件。且於 找是70件之端面中於内部電極層露出之端面設置外部電 極。於此外部電極之飛 0 ^ ^ ^ ^ 少中，使用將銅等金屬粉末分散於 背及溶劑等’成為糊狀 件之端面塗佈此外部電極糊。即，於陶竞元 卩屯極糊後，焙燒塗佈有外部電極糊之 夕勺=件，藉由燒結外部電極糊内之金屬粉末，形成作為 夕孔貝之燒結體之外部電極。另，此種外部電極例如於下 96574.doc 1245298 述專利文獻1〜專利文獻5等中有揭示。 通常，向基板等焊錫安裝陶瓷電子零件前，為提高連接 可靠性或濕潤性，於外部電極之表面實施銅或鎳、錫等電 鍍處理。 專利文獻1 :曰本專利特開平5_275272號公報 專利文獻2 :曰本專利特開平8_3〇658〇號公報 專利文獻3:曰本專利特開2〇〇2-198253號公報 專利文獻4:曰本專利特開平7_335477號公報 專利文獻5 ·曰本專利特開平1〇_144559號公報 [發明所欲解決之問題] 然而，於上述之先前陶瓷電子零件中，存在如下問題。 即，存在外部電極之空隙中有電鍍中之水分滲入，由於此 滲入之水分，於陶莞電子零件安裝時產生「爆裂」之問題。 此「爆裂」係指於安裝時加熱外部電極時，滲入至外部電 極之空隙之水分蒸發，由於該蒸汽壓力焊錫彈出之現象。 當產生此種爆裂時，可能產生彈出之焊錫附著於陶究電子 零件或其他安裝零件、印刷配線之事態，造成產生短路不 良等之問題。 其目的在於提 子零件及其製 本發明係為解決上述問題而開發完成者， 供一種可控制爆裂之產生的電極糊、陶瓷電 造方法。 【發明内容】 本發明之陶瓷電子零 備介電體層與電極層交 件之製造方法之特徵為 互層疊之陶瓷元件 適用於具 以及形成於陶瓷 96574.doc 1245298 元件之電極層霖出夕山 作，包含於陶究;^ΛΛ 之陶究電子零件之製 是兀件之鈿面塗佈包含由Cu構成之第!粉末以 ^ u更卑之金屬構成之第2粉末的外部電極糊之步 驟，以及培燒塗佈有外部電極糊之陶竞元件之 粉末=於第冰末之重量比為〇.5〜1〇wt%，且第2粉末之弟平 均粒住為0.2〜l〇gm。 構=1 電子零件之製造方法中，外部電極糊中除以CU 1 ♦刀末外’亚包含由比Cu更卑之金屬構成之第2粉 。X明者等經過銳意研究後新發現，將僅含特；t量由比 a更卑之金屬構成之具有特定範圍粒徑之第2粉末 電極糊塗佈於陶宪元件製作陶£電子零件之情形時，在陶 瓦-子零件之外部電極保持足夠之強度之狀態1245298 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to electrode paste, ceramic electronic parts, and production [prior art] 者 〃μ method. Previously, the following methods were used to study electronic components in laminated ceramic capacitors, such as: forming a laminated body, the laminated system comprising a layer of powder of a ceramic dielectric body forming a dielectric body layer and "electricity" 3 The layers that constitute the internal electrode drawer 4 The layers of the electrode paste alternately overlap a plurality of layers and are called external electrodes. After the layered body, it is not placed here. In the formation of the dielectric layer, a mixed ceramic and an organic fixing agent and an organic solvent are used, and the blade is used to: The paste becomes a thin plate-like shape. In addition, the ceramics used in the production of internal electricity belong to H ... The electrode paste is made of nickel and other Hirosue knives on organic fixatives and organic solvents to make it a paste. Paste screen printing on a thin plate-shaped body: The organic solvent contained in the internal electrode paste is dried on the surface—heavier and several pieces of this formed body are formed after pressure forming. The ceramic element is formed by baking the laminated crystal Η, π, i, and the ceramic material. And among the 70 end faces, an external electrode was provided on the end face where the internal electrode layer was exposed. In the flying of this external electrode, the external electrode paste is applied by dispersing a metal powder such as copper on the back and a solvent and the like to form a paste-like member. That is, after Tao Jingyuan's paste was baked, the shovel coated with the external electrode paste was fired, and the metal powder in the external electrode paste was sintered to form an external electrode as a sintered body of the yuccon. Such external electrodes are disclosed, for example, in Patent Documents 1 to 5 described in 96574.doc 1245298. Generally, before mounting ceramic electronic components on solders such as substrates, in order to improve connection reliability or wettability, electroplating treatments such as copper, nickel, and tin are applied to the surface of external electrodes. Patent Literature 1: Japanese Patent Laid-Open No. 5_275272 Patent Literature 2: Japanese Patent Laid-Open No. 8_3065880 Patent Literature 3: Japanese Patent Laid-Open No. 2000-198253 Patent Literature 4: Japanese Patent Publication No. 7-335477 Patent Literature 5 · Japanese Patent Publication No. 10-144559 [Problems to be Solved by the Invention] However, the aforementioned conventional ceramic electronic components have the following problems. That is, there is a problem that moisture in the plating penetrates into the gap between the external electrodes, and the moisture that has penetrated causes a problem of "burst" during the mounting of the ceramic parts. This "burst" refers to the phenomenon that when the external electrode is heated during installation, the moisture that has penetrated into the voids of the external electrode evaporates and the solder pops up due to the steam pressure. When such a burst occurs, there may be a problem that the popped solder adheres to the ceramic electronic parts or other mounting parts, and the printed wiring, causing problems such as short circuits. The purpose of the invention is to propose a part and a manufacturing method thereof. The present invention was developed to solve the above problems, and provides a method for producing electrode paste and ceramics which can control the occurrence of bursting. [Summary of the invention] The manufacturing method of the ceramic electronic spare dielectric layer and the electrode layer manufacturing method of the present invention is characterized in that the ceramic elements laminated on each other are suitable for the electrode layer formed on the ceramic 96574.doc 1245298 element. Included in ceramics; ^ ΛΛ of ceramics electronic parts is the step of coating the outer electrode paste containing the first powder made of Cu and the second powder made of ^ u more metal, And the powder of the ceramic element coated with the external electrode paste = the weight ratio at the end of the ice is 0.5 to 10 wt%, and the average particle size of the second powder is 0.2 to 10 gm. Structure = 1 In the manufacturing method of electronic parts, the external electrode paste is divided by CU 1 ♦ the blade end contains a second powder made of a metal that is humbler than Cu. X Mingzhe and others discovered after intensive research that they will only contain special; when the amount of t is a second powder electrode paste with a specific range of particle size made of a metal that is more inferior to a when it is applied to Taoxian components to make ceramics. , The external electrodes of the ceramic tile-sub-component maintain a sufficient strength
抑制爆裂之發生。 θ A 又’構成第2粉末之比Cu更卑之金屬較好的是錄、姑及欽 中之至少1種金屬。 本發明之陶瓷電子零件，其特徵在於··其係於 =極層交互層疊之陶竟元件之電極層露出之端面，塗； MCu構成之第i粉末與由比Cu差之金屬構成之第2粉 ，外部電極糊’焙燒塗佈有該外部電極糊之陶瓷元件而 者’第2粉末對於第冰末之重量比為〇5〜1〇心，且 弟2粉末之平均粒徑為0.2〜1〇 μηι。 :製作此陶瓷電子零件上使用之外部電極糊中，除以a 之第1粉末外，並包含由比Cu更卑之金屬構成之第2粉 。發明者等經過銳意研究後新發現，將僅含特定量由比 96574.doc 1245298Suppresses the occurrence of bursts. θ A is a metal that is more inferior to Cu that constitutes the second powder. At least one of the metals mentioned above is preferable. The ceramic electronic part of the present invention is characterized in that: it is coated on the exposed end surface of the electrode layer of the ceramic element that is alternately laminated on the pole layer, and is coated; the i-th powder made of MCu and the second powder made of a metal worse than Cu The external electrode paste 'fires a ceramic element coated with the external electrode paste while the' weight ratio of the second powder to the second ice powder is 0.05 to 10 cores, and the average particle size of the powder 2 is 0.2 to 1.0. μηι. : In addition to the first powder of a, the external electrode paste used in the manufacture of this ceramic electronic part contains a second powder composed of a metal that is humbler than Cu. After intensive research, the inventors discovered that they will only contain specific amounts from 96574.doc 1245298.
Cu更卑之金屬構成之具有特定 電極糊塗佈於陶究元件而製作 之二2私末之外部 極保持足夠之強戶之狀能下 …尽件’在外部電 強度之狀悲下’可有效抑制爆 又，構成第2粉末之比“更卑之金 中之至少傻金屬。 4好的疋録、銘及鈦 ::明之電極糊，其特徵在於··包含固著劑、以 =均粒徑小於2〇 _之第1粉末及以比Cu更皁之金屬構成 之㈣末，第2粉末料㈣末之重量比狀5〜1〇多 且第2粉末之平均粒徑為〇·2〜1〇 。 此電極糊中，除以c_成之第1粉末外，並包含由比Cu 更卑之金屬構成之第2粉末。發明者等經過銳意研究新發 現’將此種電極糊用作例如陶究電子零件之製作時使用的 卜電極糊’可製作出具有充分之強度’並可有效抑制爆 裂產生之外部電極。 又，構成第2粉末之&Cu更卑之金屬較好的是鎳、鈷及鈦 中之至少1種金屬。 [發明效果] 藉由本發明’可提供一種能夠控制爆裂之產生的電極 糊、陶瓷電子零件及其製造方法。 【實施方式】 以下，參照附圖，詳細說明本發明之電極糊、陶瓷電子 零件及實施其製造方法時之最佳形態。另，對於同一或同 等要素賦予相同符號，當說明重複時省略該說明。 圖1表示本發明之實施形態之陶瓷電容器之概略剖面 96574.doc 1245298 Θ如圖1所示’作為陶瓷電子焚丰 具備丄®髀π, 尤私子令件之一種之陶兗電容器10 外層之2声#思 體(陶“件)16,其包含作為最 曰、曰U，夾於表層11之大約300層之介電體； 12，以及介在於卜T人 ^增 ，14 上下配置之各介電體層12之間的内部電極 滑14。即，雷穿您、主 弘u 體岸12盘由°—6具有大約600層之疊層構造，介電 ^ 電極層14交互#層。又，於電Μ =延伸於電容器素體16之厚度方向，並互相對向之一 _ & 16b ’以覆盍其端面16a、16b之全區域之方式 5又置有一對外部電極18、18 〇 進而，上下配置之内部電極層14之間藉由介電體層12互 相電性絕緣’又互相連接於相異之—方外部電㈣。因此， 當施加特定電壓至一對外部電極18、18間時，於上下對向 ^内部電極層14之間將積蓄電荷。另，此陶究電容器10之 靜電電容與上下對向之内部電極層14之對向面 比例。 取 表層11及介電體層12均係、以BaTiQ3為主成分之層，各表 層"之厚度大約為50㈣，各介電體層12之厚度為大約Η ㈣。此等表心及介電體層12培燒下述之生陶板（陶究成形 體）而形成。又，内部電極層14係含有州為主成分之金屬 層，其厚度為大約1，。各外部電極18係以金屬中具有高 導電性之Cu為主成分之多孔質體，其表面i8a之算術平均粗 度為大約1 /xm。 以下’關於製造上述之陶瓷電容器1〇之方法，參照圖2 及圖3加以說明。此處’圖2係表示生陶板之印刷圖案之部 96574.doc -10- 1245298 ::大圖，圖3係表示製作陶瓷電容器之步驟的圖。 入^陶時’如圖2所示，首先準備则〇3系之 ::體：陶板20。此生陶板2〇係藉由刀片刮抹法使混合 3'末與有機固著劑而漿化之介電體糊成為薄板狀 。又’準備2片厚度比生陶板2叫之作為表層11之生陶板 21° 屬而’於生陶板20之表面2Ga’藉由網屏印刷法塗佈特定 圖案之内部電極糊22並使其乾燥。即，於生陶板表面遍之 1應於1個％谷器之矩形區域24中3邊邊緣區域之外的區域 ::内部電極糊22(參照圖2)。此内部電極糊22係使鎳粉末 分散於有機固著劑及有機溶劑並使其成為漿狀者。有機固 著劑可使用眾所周知者，例如可使用纖維素系樹脂、環氧 树月曰、烯丙基樹脂、丙烯酸樹脂、酚醛樹脂、不飽和樹脂 树脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、醇酸 树月曰、松香樹脂等之固著劑。又，有機溶劑亦可使用眾所 周知者’可使用例如二甘醇一丁鱗、二甘醇丁驗醋酸酯、 松節油、α-松油醇、乙基乙二醇乙醚、丁基太酸酯等溶劑。 又’此内部電極糊22中添加有BaTi03粉末作為共材。 BaTi〇3粉末與作為介電體層12(及生陶板2〇)之主成分之 BaTi〇3相同，因此藉由向内部電極糊22添加BaTi〇3粉末， 可有效緩和内部電極糊22與生陶板20之間的收縮率及燒結 開始溫度之差異。 繼而，將塗佈有如上之内部電極糊22之生陶板20疊層於 生陶板21之上，使内部電極糊22於上方（參照圖3(a))。又， 96574.doc -11 - 1245298 將以同樣之方法製作之大約300片生陶板20以交互變換内 电極I月22之位置之方式依次疊層（參照圖冲））。繼而，於 疊層之线板2〇上被覆無任何塗佈之生陶板21，並自疊層 向知C使相鄰之生陶板21、生陶板別以及内部電極糊 2 2互相擠壓。如丨卜，制 衣作生陶板20與内部電極糊22交互疊 層之疊層體26。 1 ^ i而將此$層體26切斷為一個個對應於1個電容器之矩 形區域24實行晶片化（參照圖3⑷）。之後，以例如1200。〇左 右之溫度焙燒經晶片化之疊層體％，藉此生陶板2卜生陶 板20及内部電極糊22分別成為上述之表層U、介電體層12 以及内部電極層14，疊層體26成為介電體層Η與内部電極 層14交互疊層之電容器素㈣。進而，藉由於包含水及研 磨媒體之桶内處理電容器素體16，進行表面研磨。另，此 表面研磨亦可於疊層體26之階段進行。 取後’以覆盍電容器素體16之端面中延伸於疊層方向並 互相對向之一對端面16a、16b之方式形成外部電極Η，完 成陶瓷電容器10(參照圖3⑷)。以下，就外部電極18之形成 方法加以具體的說明。 首先’準備包含銅粉末（第1粉末）、鎳粉末（第2粉末）以及 有機固著劑之外部電㈣導電性_卜部電極糊）。於此處， 2粉末之平均粒徑為0.2 μιη，鎳粉末之相對於銅粉末之重 量比為2 wt%。繼而，塗佈此外部電極糊於電容器素體16 之端面16a、16b。之後，對塗佈有外部電極糊之電容器素 體16實施中性氣體環境中或還原氣體環境中議之熱處 96574.doc -12- 1245298 理，燒結外部電極糊，形成外部電極18。 :後&外邛電極18之表面18a’實施銅或鎳 '錫等之+ 鍍處理。藉由於外部帝 續寺之电 P私極18霄施此種電鍍處理， 陶瓷電容器10安裝於其L 士士 问將 連接可〜“ 、土 4使用之焊錫與外部電極18之 運接可罪性與濕潤性。 心 就如上製作之陶莞電容器10加以說明。 2上所述，於外部電極财不僅包含銅粉末，亦包含錄 :-。麥照圖4說明焙燒此種外部電極糊所獲得之外部電 虽。圖4⑷係㈣未添加鎳粉末之電極糊所獲得之外部電= :剖面照片，係梧燒添加有錄粉末之電極糊所獲得之外 :電極之剖面照片。由該圖4可知，於外部電極糊中未添加 鎳之情形時(參照圖4(a))，外部電極中未形成太多空障，而 形成之些微空隙被銅等之金屬成分包圍，幾乎㈣。另者， 於外部電極糊中添加有錄之情形時（參照圖4⑻），外部電極 中形成較多之空隙，多孔性提高，空隙幾乎未密閉。即， 精由添加錄於電極糊之處理，應可形成更加多孔質(多孔） 之外部電極。 &明者㈣於具有高多孔性之外部電極Η是否產生爆裂 進行„周查’發現此種外部電極可有效控制爆裂。又，替代 鎳，添加㈣鈦等比銅差（離子化傾向低）之金屬於外部電極 :寸亦可拴制爆裂。可認為其原因在於：添加比銅差之 金屬於外部電極糊時，藉由該金屬可控制銅之過剩燒結， 化成具有有效控制爆裂之多孔性之外部電極丨8，故而安裝 蚪塗佈於外部電極丨8之電鍍之水分容易蒸發於空氣中。 96574.doc -13- 1245298 另’依據發明者等進行者 裂之之貝，可知要獲得上述控制爆 ^效果’相對於⑽末之鎳粉末之重量比 : 平均粒徑係曹盘田各 B ’杲心末之 、重要口素。即，相對於Cu粉 比必需為0.M 螺私末之重$ …… 鎳粉末之平均粒徑必需為〇.2〜1〇 κ料末重^切〇.5 wt%時， 或鎳私末之平均粒徑大於10 法 τ鏢對於銅之燒結控制無 於C·末二 部電極之多孔性降低。另者，當相對 平均二，之重量比大於10wt%時，或者錄粉末之 =〇.2_時，錄對於銅之燒結控制過剩，因此 4外部電極之多孔性變得過高，對於外部電 生不良影響。 孤反座 [實施例] 以下，藉由實施例具體說明本發明之内容。 百先’就實施例1中使用之外部電極糊加以說明。本實施 例中使用之外部電極糊係混合作為主成分之c晴末、相^ 於Cu粉末重量比為2 wt%且平均粒徑為〇 2^^之沁粉末有 機固著劑、分散劑以及有機溶劑等，並以球磨機或滾筒混 煉機寻分散而成為糊狀者。繼而’使用此外部電極糊形成 陶竟電容器之外部電極。Cu端子電極之燒付於中性氣體環 境中，還原氣體環境巾以之溫度進行，獲得作為試料 之陶瓷電容器。繼而，對於此試料調查空隙程度、空隙率、 爆裂不良以及外部電極強度。又，改變添加之金屬種類或 相對於Cu粉末之重量比及平均粒徑，一共準備14種試料， 並對於各試料，調查空隙程度、空隙率、爆裂不良以及外 96574.doc •14- 1245298 部電極強度（參照圖5)。 此處「實施例2」試料係將「實施例丨」試料中使用之沁 粉末之平均粒徑換為2 之試料。「實施例3」試料係將「實 施例1」試料中使用之Nl粉末之平均粒徑換為1〇 一以之試 料。「實施例4」試料係將「實施例丨」試料中使用之见粉末 之平均粒徑換為2 μιη，並將相對mCu粉末之重量比改為〇·5 wt%之試料。「實施例5」試料係將「實施例丨」試料中使用 之Νι粉末之平均粒徑換為2 μιη，並將相對於Cu粉末之重量 比改為1 wt%之試料。「實施例6」試料係將「實施例i」試 料中使用之Ni粉末之平均粒徑換為2 ，並將相對於cu粉 末之重量比改為4 wt%之試料。「實施例7」試料係將「實施 例1」試料中使用之Ni粉末之平均粒徑換為2 ，並將相對 於Cu粉末之重量比改為1〇 wt%之試料。 「貫施例8」試料係取代「實施例1」試料中使用之见粉 末’使用平均粒徑為2 μιη且相對於Cu粉末之重量比為2 wt% 之Co粉末之試料。「實施例9」試料係取代「實施例1」試料 中使用之Ni粉末，使用平均粒徑為2 μπι且相對於Cu粉末之 重量比為2 wt%之Ti粉末之試料。 又，為加以比較，作為「比較例丨」試料，準備有未添加 Ni粉末之試料。「比較例2」試料係將「實施例1」試料中使 用之Ni粉末之平均粒徑換為〇.〇5 /xm，並將相對於Cu粉末之 重量比改為2 wt%之試料。「比較例3」試料係將「實施例1」 試料中使用之Ni粉末之平均粒徑換為20 μιη，並將相對於Cu 粉末之重量比改為2 wt%之試料。「比較例4」試料係將「實 96574.doc -15- 1245298 施例i」試料中使用之Nl粉末之平均粒徑換為2μιη,並將相· 對於Cu粉末之重量比改為oj wt%之試料。「比較例5」試料 · 係將「實施例1」試料中使用之Nl粉末之平均粒徑換為2 /xm，並將相對於Cu粉末之重量比改為2〇 wt%之試料。 此處，「空隙程度」係指表示端子電極中未有任何充填之 空間之程度的項目，藉由SEM之剖面觀察測定。又「空隙 率」係指使用基於端子電極之燒結樣本的體積與重量導出 之岔度（貫際密度）以及端子電極之構成成分之理論密度，由籲 下述算式（1)計算得出之值，係將上述空隙程度數值化之值。 0ί= (l-dr/dt)-l〇〇 ...(1) 此處以為空隙率，dr為實際密度，山為理論密度。 圖6係表示於本實施例中使用之用於強度測定之基板的 概略平面圖。即，於玻璃布基材環氧樹脂製之模擬性安裝 基板（l〇〇mmx4〇mm)30上，形成排列於一軸方向對向之一 對邢狀銅vg (I度10 mm)32A、32B，於此銅箔32A、32B之 上^/成有阻知膜34。另，各銅箔32A、32B之兩端部露出有 _ 3 6a 3 6b、3 8a、3 8b。繼而，以外部電極位於兩銅箔32a、 32B之對向之端部36a、38a上之方式，於安裝基板上設置 試料（未圖示）。另，兩銅箔32A、32B之間隔距離（圖中之符 號幻"式料之没置寬度（圖中之符號b)以及兩銅箔32A、32B 之對向之i而部36a、3 8a之寬度（圖中之符號c)於JIS得以規格 化例如右為C3225型之試料，則a= 2·2 mm，b = 5.0 mm， c = 2.9 mm。 另者，藉由金屬罩（厚度：〇·25 mm)塗佈焊錫膏於用於強 96574.doc -16- 1245298 =u料之外部電極。繼而，藉由軟熔焊錫法方式（最 所:240 C) ’安裝試料於基板30上。繼而，使用圖7 力=大之按壓頭4〇,於變位速度3〇麵/她之條件下，施 倉口會於試料42之大致中央部。、繼而，判斷施加5N以内之 貞重不會損壞之試料為良 展之捕為不良。另，所謂 剝離之情= 部電極44之部分或全部自試料本體 料中斤月不於「霄施例h試料〜「實施例9」試 另者/ 「外部電極強度」均顯示良好結果。 例4」試料產生爆裂不;/I用 例5」試料時外部_度未達到基= 試料及「竇絲点以u κ知例2」 又，二：峰」試料之空隙率分別為卿一5%。 乂例1」之空隙率為25 98 %。由此 可認為，佶用办姐、參4 守工丨承手之貝# 裂。用4率為大約34〜39%之外部電極不易產生爆 本發明並非僅限於上述實施形態者… 例如，陶瓷電子零件並非僅限 ^又形 為厣帝曰Η雨Μ 、 j ^私合為，例如，亦可 、土电日日令件或片式壓敏電阻零件等久藉雷工+ 【圖式簡單說明】 ，件$各種電子零件。 二St:”施形態之陶究電容器之概略剖面圖。 圖2係表不生陶板之印刷圖案的部分放大圖。 圖3(a)’係表示製作陶莞電容器之步驟的圖。 圖4⑷係梧燒未添加錄粉末之電極糊所獲得之外部電極 96574.doc 17 1245298 之剖面照片，圖4(b)係焙燒添加有鎳粉末之電極糊所獲得之 外部電極之剖面照片。 圖5係表示本發明之實施例之實驗結果的表。 圖6係表示實施例之強度測定中所使用之基板的概略平 面圖。 圖7係表示實施例中之強度測定之方法的圖。 【主要元件符號說明】 10 陶瓷電容器 11 表層 12 介電體層 14 内部電極層 16 電容器素體 18 外部電極 18a 外部電極表面 20, 21 生陶板 20a 表面 22 内部電極糊 26 疊層體Cu is made of a more humble metal and has a specific electrode paste coated on ceramic components. 2 The external pole of the private body is kept strong enough to be able to do it ... all things 'under the condition of external electrical strength' can be effective Suppression of explosion, the second powder constitutes at least a stupid metal in "more humble gold. 4 good transcripts, inscriptions and titanium :: Mingzhi electrode paste, characterized by ... The first powder having a diameter of less than 20 mm and the powder made of a metal more soapy than Cu, the weight ratio of the powder powder of the second powder is more than 5 to 10 and the average particle diameter of the second powder is 0.2 to 2 10. This electrode paste contains a second powder composed of a metal that is humbler than Cu, in addition to the first powder of c_. The inventors and other researchers have discovered through intensive research that the electrode paste is used as, for example, The electrode paste used in the study of the manufacture of electronic parts "can produce an external electrode with sufficient strength" and can effectively suppress the occurrence of bursts. In addition, the & Cu more inferior metal constituting the second powder is preferably nickel. At least one metal among cobalt, cobalt, and titanium. [Inventive effect] According to the present invention, one can provide Electrode paste, ceramic electronic parts, and manufacturing method thereof capable of controlling the occurrence of burst. [Embodiment] Hereinafter, referring to the drawings, the electrode paste, ceramic electronic parts of the present invention, and the best form when implementing the manufacturing method will be described in detail. The same symbols are assigned to the same or equivalent elements, and the description is omitted when the description is repeated. Fig. 1 shows a schematic cross section of a ceramic capacitor according to an embodiment of the present invention. 96574.doc 1245298 Θ As shown in Fig. 1 ® 髀 π, a ceramic pottery capacitor made by Yousuizi 10, 2 sounds in the outer layer # 思 体 (陶 "件) 16, which contains about 300 layers of dielectric sandwiched between the top layer 11 and the U layer. 12; and an internal electrode slide 14 between the dielectric layers 12 disposed above and below the substrate 14. That is to say, Lei Chuanyou, the main body of the 12-bank body consists of a layered structure with about 600 layers, and the dielectric ^ electrode layer 14 interacts with # layers. In addition, at the electrode M = extending in the thickness direction of the capacitor element body 16 and facing each other _ & 16b 'in a manner 5 covering the entire area of its end faces 16a, 16b 5 and a pair of external electrodes 18, 18 〇 Further, the internal electrode layers 14 arranged above and below are electrically insulated from each other by the dielectric layer 12 and are connected to each other in a different external electric field. Therefore, when a specific voltage is applied between the pair of external electrodes 18 and 18, electric charges are accumulated between the upper and lower opposed internal electrode layers 14. In addition, the electrostatic capacitance of the ceramic capacitor 10 is proportional to the facing surface of the internal electrode layer 14 facing up and down. The surface layer 11 and the dielectric layer 12 are both layers with BaTiQ3 as the main component. The thickness of each surface layer is about 50 ㈣, and the thickness of each dielectric layer 12 is about Η ㈣. These surface cores and dielectric layers 12 are formed by firing the following ceramic plates (ceramics). The internal electrode layer 14 is a metal layer containing a state as a main component, and has a thickness of about 1 Å. Each external electrode 18 is a porous body mainly composed of Cu having high conductivity in metal, and the arithmetic average thickness of the surface i8a is about 1 / xm. Hereinafter, a method for manufacturing the ceramic capacitor 10 will be described with reference to FIGS. 2 and 3. Here 'FIG. 2 is a diagram showing a printed pattern portion of a green ceramic plate 96574.doc -10- 1245298 :: large image, and FIG. 3 is a diagram showing a step of manufacturing a ceramic capacitor. When entering the pottery, as shown in FIG. 2, first prepare the :: body: pottery board 20 of the 03 series. This raw ceramic plate 20 is made into a thin plate-like dielectric paste by a blade scraping method, which mixes the 3 'powder and the organic fixing agent to make a slurry. Also, "preparing 2 pieces of green ceramic plate 2 thicker than the green ceramic plate 2 as the surface layer 11" is prepared, and the surface 2Ga of the green ceramic plate 20 is coated with a specific pattern of the internal electrode paste 22 and dried by screen printing. . In other words, the area on the surface of the green ceramic slab should be outside the three-sided edge area of the rectangular area 24 of the 1% trough :: the internal electrode paste 22 (see FIG. 2). The internal electrode paste 22 is a paste in which nickel powder is dispersed in an organic fixing agent and an organic solvent. As the organic fixing agent, a known one can be used. For example, a cellulose resin, an epoxy resin, an allyl resin, an acrylic resin, a phenol resin, an unsaturated resin resin, a polycarbonate resin, a polyamide resin, and a polymer can be used.醯 imine resin, alkyd resin, rosin resin and other fixing agents. As the organic solvent, well-known ones can be used. For example, solvents such as diethylene glycol monobutyl scale, diethylene glycol butyl acetate, turpentine, α-terpineol, ethyl ethylene glycol ether, and butyl teraester can be used. . In addition, BaTi03 powder is added to the internal electrode paste 22 as a common material. The BaTi〇3 powder is the same as BaTi〇3 as the main component of the dielectric layer 12 (and the green ceramic plate 20). Therefore, by adding the BaTi0 3 powder to the internal electrode paste 22, the internal electrode paste 22 and the green ceramic plate can be effectively alleviated Difference between shrinkage and sintering start temperature between 20%. Next, the green ceramic plate 20 coated with the internal electrode paste 22 as described above is laminated on the green ceramic plate 21 so that the internal electrode paste 22 is above (see FIG. 3 (a)). In addition, 96574.doc -11-1245298, approximately 300 green ceramic plates 20 produced in the same manner are sequentially stacked in such a manner as to alternately change the positions of the internal electrodes 22 (see the figure). Then, the laminated ceramic wire plate 20 is covered with the uncoated green ceramic plate 21, and the adjacent green ceramic plate 21, the green ceramic plate and the internal electrode paste 22 are squeezed from each other from the laminated layer C. For example, the garment is made as a laminated body 26 in which the green ceramic plate 20 and the internal electrode paste 22 are alternately laminated. 1 ^ i, this $ layer body 26 is cut into rectangular regions 24 corresponding to one capacitor, and waferization is performed (see FIG. 3 (a)). After that, for example, 1200. The wafer-like laminated body% is fired at a temperature of about 0 °, whereby the green ceramic plate 2, the ceramic plate 20 and the internal electrode paste 22 become the surface layer U, the dielectric layer 12 and the internal electrode layer 14 respectively, and the laminated body 26 becomes a dielectric. Capacitor element 叠层 laminated with electric body layer Η and internal electrode layer 14 alternately. Furthermore, the surface of the capacitor element body 16 is polished by processing the capacitor element body 16 in a tank containing water and a grinding medium. This surface polishing may be performed at the stage of the laminated body 26. After removal ', an external electrode Η is formed so as to cover the end face of the capacitor element body 16 in the stacking direction and face one pair of end faces 16a, 16b to complete the ceramic capacitor 10 (see Fig. 3). The method of forming the external electrode 18 will be specifically described below. First, an external electroconductivity (electrode conductivity_bu part electrode paste) containing copper powder (first powder), nickel powder (second powder), and an organic fixing agent is prepared. Here, the average particle diameter of the 2 powders was 0.2 μm, and the weight ratio of the nickel powder to the copper powder was 2 wt%. Then, the external electrode paste is applied to the end faces 16 a and 16 b of the capacitor element body 16. After that, the capacitor element 16 coated with the external electrode paste is subjected to a heat treatment in a neutral gas environment or a reducing gas environment 96574.doc -12-1245298, and the external electrode paste is sintered to form the external electrode 18. : The surface 18a 'of the rear & outer electrode 18 is plated with copper or nickel' tin and the like. By applying this type of plating treatment to the electric power of the private temple 18 of the external temple, the ceramic capacitor 10 is mounted on its L. The connection between the solder and the external electrode 18 is guilty. And wettability. The heart is described by the ceramic capacitor 10 made as above. 2 As mentioned above, the external electrode contains not only copper powder, but also records:-. External electricity though. Figure 4: External electricity obtained from electrode paste without added nickel powder =: cross-section photo, except for electrode paste obtained by adding fired powder: cross-section photograph of electrode. From this figure 4 In the case where nickel is not added to the external electrode paste (see FIG. 4 (a)), there are not many voids formed in the external electrode, and some micro-voids formed are surrounded by metal components such as copper, which is almost rampant. In addition, When recording is added to the external electrode paste (refer to Figure 4⑻), a large number of voids are formed in the external electrode, the porosity is improved, and the voids are hardly closed. That is, the treatment added to the electrode paste should be able to form More porous (porous) The external electrode & The one who knows whether the external electrode with high porosity will cause a burst or not. Conduct a "weekly inspection" and find out that this type of external electrode can effectively control the burst. In addition, instead of nickel, palladium-titanium and other metals that are inferior to copper (lower ionization tendency) are added to the external electrode: it can also be used for bursting. The reason is believed to be that when adding a metal that is inferior to copper to the external electrode paste, the metal can control the excessive sintering of copper to form an external electrode with porosity that effectively controls bursting. Therefore, it is installed and applied to the outside. The moisture in the plating of the electrode 8 is easily evaporated in the air. 96574.doc -13- 1245298 In addition, according to the inventor's cracked shell, we can know that to achieve the above-mentioned control effect ^ 'weight ratio to nickel powder at the end: the average particle size is Cao Pantian's B' heart In the end, important voxels. That is, the ratio of Cu powder to Cu powder must be 0. M. The weight of snail powder must be 0.2% ~ 1〇κ When the weight of the powder is cut to 0.5 wt%, or nickel powder The average particle diameter of the terminal is greater than 10 darts. The sintering control of copper is not lower than the porosity of the two electrodes. In addition, when the relative average weight ratio is greater than 10wt%, or when the powder is equal to 0.22, the sintering control of copper is excessive, so the porosity of the 4 external electrodes becomes too high, and Adverse effects. Solitary seat [Example] Hereinafter, the content of the present invention will be specifically described by way of examples. Baixian 'will explain the external electrode paste used in Example 1. The external electrode paste used in this example is a mixture of c powder as a main component, a powder organic fixing agent, a dispersant, and a powder powder having a weight ratio of 2 wt% to Cu powder and an average particle size of 0 2 ^. Organic solvents and the like are dispersed in a ball mill or a roll kneader to form a paste. This external electrode paste is then used to form the external electrode of a ceramic capacitor. The Cu terminal electrode was burned in a neutral gas environment, and the reducing gas environment was performed at a temperature to obtain a ceramic capacitor as a sample. Then, the degree of voids, void ratio, burst failure, and external electrode strength were investigated for this sample. In addition, a total of 14 samples were prepared by changing the type of metal added or the weight ratio and average particle size with respect to Cu powder. For each sample, investigate the degree of voids, porosity, burst failure, and outer 96574.doc • 14-1245298 Electrode strength (see Figure 5). Here, the "Example 2" sample is a sample in which the average particle size of the Qin powder used in the "Example 丨" sample is changed to 2. The "Example 3" sample was a sample in which the average particle size of the Nl powder used in the "Example 1" sample was changed to 101 or more. The sample of "Example 4" was a sample in which the average particle diameter of the powder used in the sample of "Example 丨" was changed to 2 µm, and the weight ratio to the mCu powder was changed to 0.5 wt%. The "Example 5" sample was a sample in which the average particle size of the Ni powder used in the "Example 丨" sample was changed to 2 µm, and the weight ratio to the Cu powder was changed to 1 wt%. The "Example 6" sample was a sample in which the average particle size of the Ni powder used in the "Example i" sample was changed to 2 and the weight ratio to the Cu powder was changed to 4 wt%. The "Example 7" sample is a sample in which the average particle diameter of the Ni powder used in the "Example 1" sample is changed to 2 and the weight ratio to the Cu powder is changed to 10 wt%. The sample of "Persistent Example 8" is a sample of Co powder having an average particle diameter of 2 µm and a weight ratio to Cu powder of 2 wt% instead of the powder used in the sample of "Example 1." The sample of "Example 9" is a sample of Ti powder having an average particle diameter of 2 µm and a weight ratio of 2 wt% to the Cu powder, instead of the Ni powder used in the sample of "Example 1." For comparison, a sample of "Comparative Example 丨" was prepared without adding Ni powder. The "Comparative Example 2" sample was a sample in which the average particle size of the Ni powder used in the "Example 1" sample was 0.05 / xm, and the weight ratio to the Cu powder was changed to 2 wt%. The "Comparative Example 3" sample was a sample in which the average particle diameter of the Ni powder used in the "Example 1" sample was 20 μm, and the weight ratio to the Cu powder was changed to 2 wt%. The "Comparative Example 4" sample was obtained by changing the average particle size of the Nl powder used in the sample "Act 96574.doc -15-1245298 Example i" to 2 µm, and changing the weight ratio of phase to Cu powder to oj wt%. Of the sample. Sample of "Comparative Example 5" A sample in which the average particle size of Nl powder used in the sample of "Example 1" was changed to 2 / xm, and the weight ratio to Cu powder was changed to 20 wt%. Here, the "degree of voids" refers to an item indicating the extent of the space in the terminal electrode without any filling, and is measured by cross-sectional observation of SEM. Also, "void ratio" refers to the value obtained by calculating the bifurcation (transmission density) based on the volume and weight of the sintered sample of the terminal electrode and the theoretical density of the constituent components of the terminal electrode, calculated from the following formula (1) , Is the value of the above-mentioned degree of void. 0ί = (l-dr / dt)-l00 (1) Here is the porosity, dr is the actual density, and mountain is the theoretical density. Fig. 6 is a schematic plan view showing a substrate for strength measurement used in this embodiment. That is, a pair of Xing-shaped copper vg (I degree 10 mm) 32A, 32B are formed on a glass substrate-based epoxy mounting substrate (100 mm x 4 mm) 30 arranged in a direction opposite to one axis. A resist film 34 is formed on the copper foils 32A and 32B. In addition, _ 3 6a 3 6b, 3 8a, and 3 8b are exposed at both end portions of each of the copper foils 32A and 32B. Then, a sample (not shown) is provided on the mounting substrate so that the external electrodes are located on the opposite ends 36a, 38a of the two copper foils 32a, 32B. In addition, the separation distance between the two copper foils 32A, 32B (the symbol width in the figure is "not placed width of the material (symbol b in the figure)", and the opposite sides of the two copper foils 32A, 32B are i and 36a, 38a. The width (symbol c in the figure) is standardized in JIS. For example, the sample on the right is C3225, then a = 2.2 mm, b = 5.0 mm, and c = 2.9 mm. In addition, a metal cover (thickness: 〇 · 25 mm) Apply solder paste to the external electrode used to strengthen 96574.doc -16-1245298 = u material. Then, use the soldering method (maximum: 240 C) 'install the sample on the substrate 30 . Then, using Figure 7 force = big pressing head 40, under the condition of displacement speed 30 face / her, Shicangkou will be in the approximate center of sample 42. Then, it is judged that the weight within 5N The sample that will not be damaged is good and the catch is bad. In addition, the so-called peeling condition = part or all of the electrode 44 is not in the sample material. / "External electrode strength" both showed good results. Example 4 "The sample burst did not occur; / I Use case 5" When the sample was outside the degree did not reach the base = sample and "sinus wire Take u κ for Example 2 and the second: the peaks. The porosity of the samples is 5%. The porosity of Example 1 is 25 98%. From this, it can be considered that the use of sisters and reference 4 guards.丨 承 手 的 贝 # cracking. It is not easy to explode with external electrodes with a ratio of about 34 ~ 39%. The present invention is not limited to those described above ... For example, ceramic electronic parts are not limited to ^ and are also called 厣 帝 厣 Η 雨Μ, j ^ are privately-owned, for example, it can also be used for a long time, such as earth, electricity, daily use parts or chip varistor parts, etc. [Simplified illustration of the diagram], $$ various electronic parts. Two St: ”施A schematic cross-sectional view of a ceramic capacitor in the form. Figure 2 is an enlarged view of a part of a printed pattern showing a raw ceramic plate. Figure 3 (a) 'is a diagram showing the steps of manufacturing a ceramic capacitor. Figure 4 A cross-sectional photograph of an external electrode 96574.doc 17 1245298 obtained from a powdered electrode paste, and Fig. 4 (b) is a cross-sectional photograph of an external electrode obtained by firing an electrode paste added with nickel powder. Fig. 5 shows an embodiment of the present invention. Table of experimental results. Figure 6 shows the substrate used in the strength measurement of the example. 7 is a schematic plan view showing a method for measuring the strength in the embodiment. [Description of main component symbols] 10 Ceramic capacitor 11 Surface layer 12 Dielectric layer 14 Internal electrode layer 16 Capacitor body 18 External electrode 18a External electrode surface 20, 21 Ceramic surface 20a Surface 22 Internal electrode paste 26 Laminate
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