594795 A7 --— ________B7____ 五、發明説明（i) ' ^ 【發明所屬之技術領域】 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關導體糊及其製造方法，該導體糊係使用 於積層陶瓷電谷器及其他陶瓷電子零件（包含各種電路元 件）内形成導體（内部電極等）之用途上者。又，本發明係與 使用該導體糊之陶瓷電子零件之製造有關。 【習知技藝】 隨著近年來電子機器之小型化、精密化，人們益加冀 望使用於前述電子機器上之積層陶瓷電容器（以下稱為 MLCC」）等陶究電子零件之小型化、高容量化及高性能 化。 作為實現前述事項之其一條件，係將形成於前述陶瓷 電子零件内之電極及佈線等膜狀導體（一般均指形成呈薄 層狀之導體。以下同〇)，於不損及電特性及機械特性之狀 態下’較習知更薄地形成於陶瓷基材（介電體層）上。且， 作為滿足此條件之一計策，係將用以形成此種膜狀導體之 材料’即導體糊本身之物性及組成加以改良、變更。 譬如，特開平6-290985號公報及特公平6-50702號公報 中’揭示有如下之導體糊，即，該導體糊係用於形或一將 鎳作為導體形成之主要成分的MLCC内部電極上，且，於 該鎳粉末中以特定之比率而添加各種金屬氧化物者。前述 公報中並記載有如下之情事，即，依此導體糊，可防止於 培燒後之陶瓷電子零件產生所謂的裂縫及脫層，即剝落破 又，特開平11-214242號公報中，揭示有如下之導體 本紙張尺度適用中國國家標準（哪）A4規格（21〇><297公爱） -4· 594795 A7 ---------B7_______ 五、發明説明（2 ) " -- 糊，即，該導體糊可防止業已形成於陶变基材上之薄膜導 體產生脫層及提高耐熱衝擊特性（即，於進行3⑽。C程产之 高溫處理（焊接等）後，仍不易於膜狀導體產生裂縫之= 特性），並於導體形成之主要成分，即鎳粉末中，添加Ti、 Zr、Ta、Hf、Nb或稀土類元素之金屬粉末，或由該等之碳 化物、氮化物、蝴化物、石夕化物等形成之粉末。 又，特開平10-144561號公報中，揭示有如下之導體 糊，即，該導體糊係用於形成一將鎳作為導體形成之主要 成分的MLCC外部電極（終端電極）上，且，於該鎳粉末中以 特定之比而率添加各種共生基體（即，由與陶瓷基材相同之 無機成分所形成之粉末）。前述公報中並記載有如下之俨 事，即，依此導體糊，不但可確保内部電極與外部電極之 良好導電性，並可製造一該外部電極與陶瓷基材之黏著性 優越的MLCC。 【發明欲解決之課題】 然’前述各公報中所載之導體糊，無一係著眼於膜狀 導體本身之薄層化而加以開發者。因此，藉該等公報中所 載之導體糊形成較習知更薄之膜狀導體時，與習知較厚之 膜狀導體同樣地’電特性及機械特性均無法受到保障。 即，雖然膜狀導體更進一步薄層化，但為使電特性（導 電性）及機械特性（黏合強度）於實用上保持在充分之等 級’即需提高用以形成膜狀導體之無機、金屬系粉末材料 (以下稱為「導體形成用粉末材料」）之充填率（密度p若未 具備充分之充填率，即緻密度，則膜狀導體之内部構造將 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） ................. ................裝..................訂..................線. (請先閲讀背面之注意事項再填寫本頁) 594795 A7 _____B7_ 五、發明説明（3 ) (請先閲讀背面之注意事項再塡寫本頁) 變的稀疏，而由該結果，因焙燒（烘乾）時之收縮便易於導 體内部產生成為電性斷線或導電率降低之原因之微小裂缝 及凹孔。進而，有一如下之疑慮，即，與陶£基材間之黏 著性（黏合強度）降低，且機械特性亦降低。且，有關此種 電特性及機械特性之問題，於所形成之膜狀導體厚度越薄 時便越明顯《然而，前述各公報中所載之發明，無一考慮 到有關提高此種導體形成用粉末材料之充填率。 因此，本發明係為解決有關前述習知之導體糊之問題 點而創作者，其目的係在於提供一種導體糊，該導體糊係 用以於陶瓷基材上形成導體，且，可於實用上維持充分等 級之電特性及/或機械特性之狀態下，形成較習知更薄且緻 密之膜狀導體者。又，本發明另一目的係在於提供一用以 製造此種導體糊之方法。又，本發明其他目的係在於提供 一種使用此種導體糊而製造陶瓷電子零件之方法。 【用以解決課題之手段】 本案發明人發現，藉由使用以構成糊之導體形成用粉 末材料之粒度分佈適當化，即，實現於調製導體形成用粉 末材料時為恰當之粒度，配合，可令前述充填率提高，因而 創作出本發明。 且，為達成前述目的，本發明係提供一種如下之導體 糊製造方法。 即，本發明所提供之方法係一種導體糊之製造方法， 係用以製造以導體形成用粉末材料為主要成分之導體糊 者包含有一調製刖述導體形成角粉末材料之步驟，及一 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -6- 五、發明説明（4 ) 字b杨末材料分散於載色劑之步驟。且，調製前述導體形 成用粉末材料時，對於用以構成該粉末材料之主體且具有 特疋之粒度分佈及平均粒徑之略呈球狀導電性金屬粉末， 以一將導體糊塗佈於陶瓷基材時之乾燥塗膜中的該粉末之 充填率較只由前述導電性金屬粉末形成時之導體形成用粉 末材料之充填率高之份量，添加一種或二種以上略呈球狀 之金屬粉末及/或陶瓷粉末，而該略呈球狀之金屬粉末及/ 或陶瓷粉末，係與前述導電性金屬粉末之粒度分佈不同， 且其平均粒徑小於該導電性金屬粉末之平均粒徑的略4分 之1者。 此外，有關本發明中所謂之「平均粒徑」，係指依據 用以構成粉末（粉體）之一次粒子的粒子徑而導出之估計 值。典型而言，係指依據SEM等電子顯微鏡觀察而估計之 平均粒徑。 又，本說明書中所謂之「略呈球狀之粉末」，係指用 以構成該粉末之粒子（一次粒子）的70wt%以上，具有呈球狀 或類似於球狀之形狀者。典型而言，係指用以構成該粉末 之粒子的70wt%以上’為長寬比(即，對於粒子長度之寬度 之比率）80〇/〇以上。又，本說明書中所謂之「粒度分佈不 同」，係指加以作比較之兩個粉末（二成分）間，用以構成 粒子之大崢为（典型而5，粉末之7〇wt%以上）粒子徑均相異 (不重複)。具體而言，前述兩個粉末各自之粒度分佈曲線 (一般而言，顯示於橫軸表示粒子徑、縱軸表示粒子存在比 率之座標平面上），係指實質上於橫轴方向不重疊或僅其中 本紙張尺度適用中國國家標準（CNS) A4規格（2ι〇χ297公楚） 594795 A7 _— B7_ 五、發明説明（5 ) 一端部重疊者而言。因此，混合本說明書中所定義之粒度 分佈不同的兩個粉末時，典型而言，可視為於該粒度分佈 曲線中.，兩個峰值相互分離之特定部位（典型而言，係對應 於混合前各粉末之平均粒徑的部位）^ 此種導體糊製造方法，於用以形成導體形成用粉末材 •料之主體且略呈球狀之導電性金屬粉末（以下稱為「主金屬 粉末」）中，藉由添加具有不同之粒度分佈且其平均粒徑小 於主金屬粉末之略4分之1的金屬粉末及/或陶瓷粉末（以 下，將前述細微粉末統稱為「充填補助細微粉末」），可提 南由導鱧形成用粉末材料形成之前述塗膜中之充填率。藉 此，依藉由本製造方法而得之導體糊，可於陶瓷基材上形 成充填性高之塗膜，即緻密構造之膜狀導體。因此，依本 製造方法而得之導體糊可實現於不損及電特性及/或.機械 特性之狀態下，形成較習知更薄狀之膜狀導體。 又’本發明之另一目的係提供如下之導體糊，以作為 前述製造方法之基礎。即，藉由本發明所提供之導體糊， 係以一導體形成用粉末材料為主要成分者，且，該導體糊 形成用粉末材料，係以具有特定之粒度分佈及平均粒徑且 略呈球狀之導電性金屬粉末為主體者。且，於作為該主體 之導電性金屬粉末中，以本導體糊塗佈於陶瓷基材而得之 乾燥塗膜中之該導體形成用粉末材料之充填率較只由前述 導電性金屬粉末形成之導體形成用粉末材料之充填率高之 份量，添加一種或兩種以上略呈球狀之金屬粉末及/或陶瓷 粉末而構成者，其中該略呈球狀之金屬粉末及/或陶瓷粉 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) ·、ΤΓ* 594795 A7 ______________B7___ 五、發明説明（6 ) --- 末，係與前述導電性金屬粉末之粒度分佈不同且其平均 粒經小於該導電性金屬粉末之平均粒㈣略4分之】者。 此種構成之本發明之導趙糊中，對主金屬粉末添加未 超過充填補助細微粉末有助於充填率提高之限度之量。藉 此，與只由習知之主金屬粉末或該粉末及其他金屬或陶^ 粉末（未如本發明施予粒度配合及平均粒徑之最適當化者） 之混合物所形成之膜狀導趙相較，可於維持電特性及機械 特性之狀態下，於m材上形成更薄之膜狀導艘。因此， 依本發明之導趙糊，可形成充分達到以高等級滿足mlcc 及其他陶变電子零件之小型化、高容量化及高性能化之要 求的薄膜狀導體。 又，藉本發明所提供之導體糊，係以一導體形成用粉 末材料為主要成分者，且，該導體形成用粉末材料，係以 具有特定之粒度分佈及平均粒徑之略呈球狀導電性金屬粉 末為主體者，且，藉於該導電性金屬粉末中，添加一種或 兩種以上略呈球狀之金屬粉末而構成者，其中該略呈球狀 之金屬粉末，係實質上與前述導電性金屬粉末為同一組 成’且，與該導電性金屬粉末之粒度分佈不同而其平均粒 小於该導電性金屬粉末之平均粒徑的略4分之1者。且， 前述導電性金屬粉末之含有率係佔導體形成用粉末材料全 體之75wt%以上，且，前述實質上為同一組成之略呈球狀 金屬粉末之含有率，係佔導體形成用粉末材料全體之 25wt%以下。 此種構成之導體糊中，實質上與主金屬粉末為同一組 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） ........................I:… f請先閲讀背面之注意事項再構寫本頁) -訂— :線· -9- 594795 A7 ________ B7_ 五、發明説明（7 ) 成（故’意即容許微量成分之有無及其質的差異等）之細微 金屬粉末’係作為充填補助細微粉末而適量地包含於其 中。藉此’依本構成之導體糊，可形成一具高電特性（導電 性）之薄膜狀導體。 又’藉本發明而提供之導體糊，係以一導體形成用粉 末材料為主要成分者，且，該導體形成用粉末材料，係以 具有特定之粒·度分佈及平均粒徑之略呈球狀鎳粉末為主體 者（以下稱為「Ni糊」）。且，本沁糊係於該鎳粉末中添加 一種或兩種以上略呈球狀之金屬粉末及/或陶瓷粉末，其中 該略呈球狀之金屬粉末及/或陶瓷粉末，係與前述鎳粉末之 粒度分佈不同，且其平均粒徑小於該鎳粉末之平均粒徑的 略4分之1者。且，對前述鎳粉末所添加之前述金屬粉末及/ 或陶瓷粉末之容積（份量），係以鈦酸鋇粉末換算作例示。 即’係規定為具有小於前述鎳粉末平均粒徑的略4分之1之 ，平均粒徑而相當於該鎳粉末之3〇wt%以下之重量的鈦酸鎖 粉末之容積。 前述構成之Ni糊中，以鈦酸鋇粉末換算而對作為主金 屬粉末之Ni粉末添加作為充填補助細微粉末之金屬粉末及 /或陶瓷粉末（即鈦酸鋇為其典型），俾可為前述份量。藉由 以此容積比為基準之粒度配合，可使以Ni粉末為主體之導 體形成用材料之充填率提高，更可進一步實現形成於陶瓷 基材上之Ni導體之緻密化。因此，依本發明之州糊，可以 成本方面優異之賤金屬（Ni)形成薄膜狀導體，而該薄膜狀 導體係可年分達到以高等級滿足MLCC及其他陶竞電子零 一 -- 本紙張尺度適用中國國家標準（CNS) A4規格（21〇X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂· -10 - 594795 五、發明説明（ 件之小型化、高容量化及高性能化之要求者。因此，可達 到陶瓷電子零件之小型（slim)t及低價格化。 又，宜作為本發明之Ni糊者中，用以形成前述導體形 成用粉末材料之主體且略呈球狀之鎳粉末的平均粒徑，係 於ΟΑη^.Ομπ^内，且，作為前述金屬粉末及陶究 籾末係3有導電性金屬粉末及鈦酸鋇系之介電體粉末， 而該導電性金屬粉末係具有前述鎳粉末之平均粒徑的略4 分之1以下之平均粒徑者。 依此種構成之Ni糊，可於陶瓷基材（尤其係含有鈦酸鋇 者）上形成黏合強度高且機械強度優越之薄膜狀％導體。 又，依本構成之Ni糊，藉Ni粉末與導電性金屬粉末（典型而 訂 言，係細微之Ni粉末）之組合，可形成導電性等電特性優越 之高密度薄膜狀Ni導體。 又，本發明之另一面，其特徵係在於使用藉前述糊製 造方法而得之導體糊（典型例係前述各導體糊），並提供 MLCC及其他陶瓷電子零件之製造方法。典型而言，本製 造方法係包含一將前述本發明之導體糊塗佈於陶瓷基材之 步驟，及一焙燒該業已進行塗佈之糊主要成分（即高充填之 導體形成用粉末材料）之步驟。依此製造方法，可製造並提 供MLCC及其他陶究電子零件，而該乂咖及其他陶泛電子 零件，係業已形成因應小型化、高容量化及高性能化之電 特性及機械特性優越之薄膜狀導體者。 又，本發明之另一面，係在於提供用以調製本發明導 體糊之導體形成用粉末材料及其叙造方法。其典型例，係 本紙張尺度適用中國國家標準（〇is) A4規格（210X297公爱） 11 - 594795 A7 B7 五、發明説明（ 特定成如各申請專利範圍之導體形成用粉末材料及其製造 方法者，其中該導體形成用粉末材料係使用於前述導體糊 製造方法上，進而，為前述各導體糊之主要構成要素者。 【簡單之圖示說明】 第1圖·係例示陶瓷添加材量與乾燥塗膜密度之關係之 圖表。 【發明之實施態樣】 以下，說明本發明之實施態樣。 作為本發明導體糊之主要成分之導體形成用粉末材 料’可藉網版印刷法及其他手法而使源自塗佈於陶瓷基材 (氧化鋁基板、玻璃基板等）上之糊的乾燥塗膜或其焙燒體 中之導體形成用粉末材料之充填率（最大充填率）提高，並 可對具有特定之粒度分佈及平均粒徑之主金屬粉末添加預 疋量略呈球狀之充填補助細微粉末，而該略呈球狀之充填 補助細微粉末係粒度分佈不同且平均粒徑小於該主金屬粉 末之4分之1(宜為4分之i〜8分之1，特別係6分之1〜8分之i 矛王度）者’且’主金屬粉末及充填補助細微粉末之種類及尺 寸（粒徑）並無特別限制。 譬如，具μιη順序（Order)(典型而言，為ι·0μιη〜ΙΟμιη) 之平均粒徑且略呈球狀之銀、金、白金、把，或由前述合 金所形成之導電性貴金屬粉末及鎳、銅等導電性賤金屬粉 末中，任一者均適宜作為本發明之導電性金屬粉末（主金屬 粉末）。就謀求所製造之MLCC等陶瓷電子零件之低成本化 方面而言，將本發明應用於以Ni耸賤金屬為主要成分之導 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) -訂· i丨 -12- 594795 A7 B7 五、發明説明（l〇 體糊及其調製上’意義極大。 又，於不損及電特性（導電性等）及機械特性（黏合強度 等）之狀態下，形成較習知更薄之膜狀導體之點來看，具亞 微型順序（宜為0·1μπι〜Ι.Ομπι)之平均粒徑的導電性金屬粉 末’尤其適於作為主金屬粉末。譬如，將本發明之Ni糊用 於MLCC之内部電極形成等用途上時，作為主金屬粉末之 Ni粉末的平均粒徑宜為〇 〇叫，尤以 〇.4μιη〜0·6μιη(譬如〇·5μπι)為佳。又，鎳粉末之比表面積（根 據BET)宜為 lm2/g〜l〇m2/g。 另一方面’作為添加於此種主金屬粉末之充填補助細 微粉末，宜為有助於所使用之主金屬粉末（導體形成用粉末 材料）之充填率提高且略呈球狀之細微粉末，而該略呈球狀 之細微粉末係與前述主金屬粉末之粒度分佈不同，且其平 均粒徑小於該主金屬粉末之平均粒徑的4分之丨（宜為 1/4〜1/8，尤以1/6〜1/8為佳）程度者。雖然依使用之用途而 將有所不同，但作為此種充填補助細微粉末，可使用譬如 各種介電體粉末及金屬氧化物之略呈球狀細微粉末。此 外作為此種充填細微粉末，宜為不會顯著損及本發明導 體糊之導電性（電阻率）、可焊性、耐焊熱、黏合強度等者。 s如，作為陶瓷粉末，可例舉玻璃粉末、無機氧化物（金屬 氧化物）等。譬如，作為金屬氧化物，可例舉Al、Zr、Ti、594795 A7 --- ________B7____ 5. Description of the Invention (i) '^ [Technical Field to which the Invention belongs] (Please read the precautions on the back before filling out this page) The present invention relates to conductor paste and its manufacturing method. It is used for forming a conductor (internal electrode, etc.) in a multilayer ceramic valley device and other ceramic electronic parts (including various circuit components). The present invention relates to the manufacture of ceramic electronic parts using the conductor paste. [Knowledge] With the miniaturization and precision of electronic equipment in recent years, people are looking forward to the miniaturization and high capacity of ceramic electronic components such as multilayer ceramic capacitors (hereinafter referred to as MLCC) used in the aforementioned electronic equipment. And high performance. As one of the conditions for realizing the foregoing, film-shaped conductors (such as electrodes formed in the form of thin layers) are generally formed in the aforementioned ceramic and electronic parts, such as electrodes and wiring. The same shall not affect the electrical characteristics and In the state of mechanical characteristics, it is formed thinner than on conventional ceramic substrates (dielectric layers). In addition, as one of measures to satisfy this condition, the physical properties and composition of the conductor paste itself, which is a material for forming such a film-like conductor, are improved and changed. For example, Japanese Unexamined Patent Publication No. 6-290985 and Japanese Unexamined Patent Publication No. 6-50702 'disclosed a conductor paste that is used for an MLCC internal electrode that is shaped or has nickel as a main component of the conductor. In addition, various metal oxides are added to the nickel powder at a specific ratio. In the aforementioned publication, it is described that the conductor paste can prevent the so-called cracks and delamination of ceramic electronic components after firing, that is, peeling and breaking. Japanese Unexamined Patent Publication No. 11-214242 discloses There are the following conductors: This paper size applies the Chinese National Standard (Which) A4 specification (21〇 > < 297 Public Love) -4 · 594795 A7 --------- B7_______ V. Description of the Invention (2) & quot --- Paste, that is, the conductor paste can prevent delamination and improve the thermal shock resistance of thin-film conductors already formed on the ceramic substrate (ie, after 3⑽. C process high temperature treatment (welding, etc.), It is still not easy to produce cracks in film-like conductors (characteristics), and the main component of the conductor formation, namely nickel powder, is added with Ti, Zr, Ta, Hf, Nb or rare earth metal powder, or carbonized by these Powder formed by metal compounds, nitrides, butterfly compounds, stone compounds, etc. Also, Japanese Patent Application Laid-Open No. 10-144561 discloses a conductor paste for forming an MLCC external electrode (terminal electrode) having nickel as a main component for forming a conductor. Various kinds of symbiotic substrates (that is, powders made of the same inorganic component as the ceramic substrate) are added to the nickel powder at a specific ratio. The foregoing publication also describes the following matters. According to this conductor paste, not only the good conductivity of the internal electrode and the external electrode can be ensured, but also an MLCC having excellent adhesion between the external electrode and the ceramic substrate can be manufactured. [Problems to be Solved by the Invention] Of course, none of the conductor pastes described in the aforementioned publications has been developed with a view to reducing the thickness of the film-like conductor itself. Therefore, when a thinner-than-known film-like conductor is formed by using the conductor paste contained in these bulletins, the same electrical characteristics and mechanical characteristics as the conventionally-thin-film-like conductor cannot be guaranteed. That is, although the film-shaped conductor is further thinned, in order to maintain the electrical characteristics (conductivity) and mechanical characteristics (adhesive strength) at a sufficient level in practical terms, it is necessary to increase the inorganic and metal used to form the film-shaped conductor. The filling rate of powdered materials (hereinafter referred to as "conductor-forming powder materials") (density p if the filling rate is not sufficient, that is, the density, the internal structure of the film-like conductor will apply this paper size to Chinese national standards (CNS ) A4 size (210X297mm) ........................................ .......... Order ........ line. (Please read the notes on the back before filling this page) 594795 A7 _____B7_ V. Invention Note (3) (Please read the precautions on the back before writing this page), and the result is that the shrinkage during firing (drying) will easily cause electrical disconnection or decrease in electrical conductivity due to shrinkage during baking. The reason is the small cracks and recessed holes. Furthermore, there is a concern that the adhesiveness (adhesive strength) with the ceramic substrate is reduced, and the mechanical characteristics are also reduced. Moreover, such electrical characteristics The problem of mechanical characteristics becomes more apparent as the thickness of the film-like conductor formed becomes thinner. "However, none of the inventions described in the aforementioned publications considers the improvement of the filling rate of powder materials for the formation of such conductors. Therefore, The present invention was created by the creator of the present invention to solve the problems of the conventional conductive paste, and the object is to provide a conductive paste which is used to form a conductor on a ceramic substrate, and can maintain a sufficient level in practical use. Forming a thinner and denser film-like conductor than conventional in the state of electrical and / or mechanical characteristics. Furthermore, another object of the present invention is to provide a method for manufacturing such a conductor paste. Another object of the present invention is to provide a method for manufacturing ceramic electronic parts using such a conductive paste. [Means to Solve the Problem] The inventors of the present case have found that the particle size distribution of a powder material for forming a conductor constituting a paste is appropriate by using the conductive paste. That is, it is realized that the particle size is appropriate when the powder material for modulation conductor formation is used. The combination can increase the aforementioned filling rate, so this invention was created. In addition, in order to achieve the foregoing object, the present invention provides a method for manufacturing a conductive paste as follows. That is, the method provided by the present invention is a method for manufacturing a conductive paste, which is used to manufacture a powder material for forming conductors as a main component. The conductor paste includes a step of modulating the conductor to form a corner powder material, and a paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -6- V. Description of the invention (4) Word b Yang material The step of dispersing in a vehicle. When preparing the aforementioned conductor-forming powder material, a slightly spherical conductive metal powder having a special particle size distribution and an average particle size, which constitutes the main body of the powder material, is The filling rate of the powder in the dry coating film when the conductor paste is applied to the ceramic substrate is higher than the filling rate of the powder material for conductor formation when the conductive metal powder is formed only, and one or two or more kinds are added. The slightly spherical metal powder and / or ceramic powder, and the slightly spherical metal powder and / or ceramic powder are the same particles as the aforementioned conductive metal powder. The degree distribution is different, and the average particle diameter is smaller than one-fourth of the average particle diameter of the conductive metal powder. The "average particle diameter" in the present invention refers to an estimated value derived from the particle diameter of the primary particles used to form a powder (powder). Typically, it refers to the average particle diameter estimated by observation with an electron microscope such as SEM. The "spherical powder" as used in this specification refers to those having 70% by weight or more of particles (primary particles) constituting the powder and having a spherical shape or a shape similar to a spherical shape. Typically, it means that 70% by weight or more of the particles used to constitute the powder is an aspect ratio (that is, the ratio of the width to the particle length) of 80/0 or more. The "different particle size distribution" in this specification refers to the particle size (typically 5, more than 70% by weight of the powder) between two powders (two components) to be compared for comparison. The diameters are all different (not repeated). Specifically, the particle size distribution curve of each of the two powders (in general, displayed on the coordinate plane where the horizontal axis represents the particle diameter and the vertical axis represents the particle existence ratio) means that the horizontal axis does not substantially overlap or only Among them, the paper size is in accordance with Chinese National Standard (CNS) A4 specification (2ι297 × 297). 594795 A7 _ — B7_ V. Description of the invention (5) For those with overlapping ends. Therefore, when mixing two powders with different particle size distributions as defined in this specification, typically, it can be regarded as the particle size distribution curve. The two peaks are separated from each other at a specific part (typically, it corresponds to before mixing Portion of the average particle size of each powder) ^ This method of manufacturing a conductive paste is a conductive metal powder (hereinafter referred to as "main metal powder") which is used to form the main body of a powder material for forming conductors and has a spherical shape. In addition, by adding a metal powder and / or a ceramic powder having a different particle size distribution and an average particle diameter of less than one-fourth of the main metal powder (hereinafter, the aforementioned fine powders are collectively referred to as "filling and assisting fine powders"), The filling rate in the aforementioned coating film formed of the powder material for guide formation can be improved. With this, the conductive paste obtained by this manufacturing method can form a highly filled coating film on a ceramic substrate, that is, a densely-structured film-like conductor. Therefore, the conductor paste obtained according to this manufacturing method can be realized to form a thinner film-like conductor than conventionally without compromising electrical and / or mechanical properties. Still another object of the present invention is to provide a conductor paste as a basis for the aforementioned manufacturing method. That is, the conductor paste provided by the present invention is a powder material for forming a conductor as a main component, and the powder material for forming a conductor paste has a specific particle size distribution and average particle diameter and is slightly spherical. The conductive metal powder is the main one. Moreover, in the conductive metal powder as the main body, the filling rate of the powder material for conductor formation in the dry coating film obtained by applying the conductor paste to a ceramic substrate is lower than that of a conductor formed only by the aforementioned conductive metal powder. The powder material for forming has a high filling rate, and is formed by adding one or two or more spherical metal powders and / or ceramic powders, wherein the slightly spherical metal powders and / or ceramic powders are on a paper scale. Applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), ΤΓ * 594795 A7 ______________B7___ 5. Description of the invention (6) --- At the end, it is conductive with the aforementioned The particle size distribution of the conductive metal powder is different and its average particle size is less than the average particle size of the conductive metal powder by a factor of 4]. In the present invention, the paste of the present invention is added to the main metal powder in an amount that does not exceed the limit that the filling fine powder helps the filling rate to increase. With this, a film-like guide phase formed with a mixture of only the conventional main metal powder or the powder and other metal or ceramic powder (which has not been optimized for particle size mixing and average particle size as in the present invention) Compared with that, it is possible to form a thinner film-shaped guide boat on the M material while maintaining the electrical and mechanical characteristics. Therefore, according to the present invention, it is possible to form a thin film conductor that satisfies the requirements for miniaturization, high capacity, and high performance of mlcc and other ceramic electronic components at a high level. In addition, the conductor paste provided by the present invention is composed of a powder material for conductor formation as a main component, and the powder material for conductor formation is a substantially spherical conductive material having a specific particle size distribution and average particle size. A metal powder is a main body, and one or two or more metal powders having a substantially spherical shape are added to the conductive metal powder, and the metal powder having a substantially spherical shape is substantially the same as the foregoing. The conductive metal powder has the same composition, and the particle size distribution of the conductive metal powder is different from that of the conductive metal powder, and its average particle size is smaller than one-fourth of the average particle diameter of the conductive metal powder. In addition, the content rate of the conductive metal powder accounts for 75% by weight or more of the powder material for conductor formation, and the content rate of the substantially spherical metal powder having substantially the same composition accounts for the entire powder material for conductor formation. 25% by weight or less. The conductor paste of this structure is essentially the same group as the main metal powder. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ...... ........ I:… f Please read the notes on the back before composing this page) -Order —: Line · -9- 594795 A7 ________ B7_ 5. Description of the invention (7) Success (intentionally That is, fine metal powders that allow the presence or absence of trace components and their qualitative differences, etc.) are included in a suitable amount as a supplementary fine powder. According to this, the conductive paste formed in this way can form a thin film conductor having high electrical characteristics (conductivity). Furthermore, the conductor paste provided by the present invention is a powder material for forming a conductor as a main component, and the powder material for forming a conductor is slightly spherical with a specific particle size distribution and average particle diameter. In the form of nickel powder (hereinafter referred to as "Ni paste"). In addition, the Benqin paste is one or two or more spherical metal powders and / or ceramic powders added to the nickel powder, and the slightly spherical metal powders and / or ceramic powders are the same as the foregoing nickel powders. The particle size distribution is different, and the average particle size is smaller than one-fourth of the average particle size of the nickel powder. The volume (parts) of the metal powder and / or ceramic powder added to the nickel powder is exemplified in terms of barium titanate powder conversion. That is, '' is defined as the volume of the titanate-locked powder having an average particle size which is slightly smaller than one-fourth of the average particle size of the aforementioned nickel powder and an average particle size equivalent to 30 wt% or less of the nickel powder. In the Ni paste of the foregoing composition, the metal powder and / or ceramic powder (that is, barium titanate is typical) is added to the Ni powder as the main metal powder in terms of barium titanate powder conversion to supplement the fine powder. Servings. With the particle size blending based on this volume ratio, the filling rate of the conductor-forming material mainly composed of Ni powder can be improved, and the density of the Ni conductor formed on the ceramic substrate can be further achieved. Therefore, according to the state paste of the present invention, a thin-film conductor can be formed from a base metal (Ni) that is excellent in cost, and the thin-film conductive system can meet the MLCC and other Taojing Electronics 1-1 at a high level every year-this paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (21 × 297 mm) (Please read the precautions on the back before filling out this page) Order · -10-594795 V. Description of the invention (miniaturization, high capacity and High performance requirements. Therefore, it is possible to achieve slim and low price of ceramic electronic parts. It is also suitable for forming the main body of the powder material for conductor formation in the Ni paste of the present invention. The average particle diameter of the spherical nickel powder is within 〇Αη ^ .Ομπ ^, and the metal powder and ceramic powder 3 have conductive metal powder and barium titanate-based dielectric powder, and The conductive metal powder has an average particle diameter of slightly less than one-fourth of the average particle diameter of the aforementioned nickel powder. The Ni paste having such a structure can be used on a ceramic substrate (especially a material containing barium titanate). High bonding strength and mechanical formation Film-like% conductor with excellent degree. In addition, according to the Ni paste of this composition, a combination of Ni powder and conductive metal powder (typically, a fine Ni powder) can form high electrical properties such as conductivity. Density thin film Ni conductor. Another aspect of the present invention is characterized in that it uses a conductor paste obtained by the aforementioned paste manufacturing method (typical examples are the aforementioned respective conductor pastes), and provides a method for manufacturing MLCC and other ceramic electronic parts. Typically, the manufacturing method includes a step of applying the aforementioned conductor paste of the present invention to a ceramic substrate, and firing the main component of the paste that has been applied (ie, a highly-filled conductor forming powder material). Step. According to this manufacturing method, MLCC and other ceramic electronic components can be manufactured and provided, and the coffee and other ceramic electronic components have already formed electrical and mechanical characteristics corresponding to miniaturization, high capacity and high performance. Excellent film-shaped conductor. Another aspect of the present invention is to provide a powder material for forming a conductor for preparing the conductor paste of the present invention and a method for making the same. The typical example is that this paper size applies the Chinese national standard (〇is) A4 specification (210X297 public love) 11-594795 A7 B7 V. Description of the invention (Specifically formed powder materials for conductor formation as in the scope of each patent application and their manufacture In the method, the powder material for conductor formation is used in the above-mentioned conductor paste manufacturing method, and is the main constituent element of each of the conductor pastes mentioned above. [Simple illustration] Figure 1 shows the amount of ceramic additive material The graph of the relationship with the density of the dry coating film. [Embodiments of the invention] The following describes the embodiments of the present invention. The conductor forming powder material, which is the main component of the conductor paste of the present invention, can be obtained by screen printing and other methods. The filling rate (maximum filling rate) of the powder material for conductor formation in a dried coating film or a fired body thereof derived from a paste applied on a ceramic substrate (alumina substrate, glass substrate, etc.) can be increased by a method, and The main metal powder with a specific particle size distribution and average particle size is added with a pre-filled amount of slightly spherical filling to help fine powder, and the slightly spherical filling Auxiliary fine powders are those whose particle size distribution is different and whose average particle size is less than one-fourth of the main metal powder (preferably one-fourth to one-eighth, especially one one-sixth to one-eighth. There is no particular limitation on the type and size (particle size) of the main metal powder and filling auxiliary fine powder. For example, silver, gold, platinum, handles, or conductive noble metal powders formed from the aforementioned alloys and having an average particle diameter of μιη order (typically, ι · 0μιη ~ ΙΟμιη) and a spherical shape, and Any of conductive base metal powders such as nickel and copper is suitable as the conductive metal powder (main metal powder) of the present invention. For the purpose of reducing the cost of ceramic electronic parts such as MLCC manufactured, the present invention is applied to a guide containing Ni base metal as the main component. The paper size is applicable to China National Standard (CNS) A4 (210 X 297). (%) (Please read the notes on the back before filling out this page) -Order · i 丨 -12- 594795 A7 B7 V. Description of the invention (10. Body paste and its modulation are of great significance. Also, it will not damage the electricity In the state of electrical properties (conductivity, etc.) and mechanical properties (adhesive strength, etc.), the point of forming a thinner film-like conductor than conventional, in terms of submicron order (preferably from 0.1 μm to 1.1 μm) The conductive metal powder having a particle size is particularly suitable as a main metal powder. For example, when the Ni paste of the present invention is used for the internal electrode formation of an MLCC, the average particle diameter of the Ni powder as the main metal powder is preferably 0. 〇 is called, especially from 0.4μm to 0.6μm (such as 0.5μm). Also, the specific surface area (according to the BET) of nickel powder should be lm2 / g ~ 10m2 / g. On the other hand, 'as an addition Filling and assisting fine powder in this main metal powder, It is preferably a fine powder having a slightly spherical shape that contributes to an increase in the filling rate of the main metal powder (powder material for conductor formation) used, and the fine powder having a slightly spherical shape is different from the particle size distribution of the main metal powder described above And whose average particle diameter is less than a quarter of the average particle diameter of the main metal powder (preferably 1/4 to 1/8, especially preferably 1/6 to 1/8). Although it depends on the use The application will be different, but as this filling auxiliary fine powder, various spherical powders such as various dielectric powders and metal oxides can be used. In addition, as the filling fine powder, it should not cause significant damage. And the conductivity (resistivity), solderability, solder heat resistance, adhesion strength, etc. of the conductor paste of the present invention. For example, as the ceramic powder, glass powder, inorganic oxide (metal oxide), etc. can be exemplified. As the metal oxide, Al, Zr, Ti,
Si、Pb、Fe、W、Mn、Bi、Nb、Ta、M〇、Ca、SrBa、Si, Pb, Fe, W, Mn, Bi, Nb, Ta, Mo, Ca, SrBa,
Mg等氧化物，或高熔點之稀土類(即sc、γ、La、卜、 则 Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu) 本紙張尺度適财準（⑽）峨格（2歡297j^ ....................•:裝..................tr..................緣 (請先閲讀背面之注意事項再填容本頁) 13- W4795 A7 B7 11 五、發明説明（ 氧化物。又，作為介電體粉末，與所使用之陶瓷基材之共 通材料可例舉譬如鈦酸鋇系之氧化物、氮化矽、氮化鋁等 虱化物及碳化矽、碳化鈦等碳化物與前述之混合物。藉由 添加如前述之陶瓷粉末（包含前述金屬氧化物），可進而提 高由本發明導體糊形成之膜狀導體之耐熱性及黏合強度 等。 又’可作為充填補助細微粉末使用之金屬粉末，包含 貝質上與主金屬粉末為同一組成之金屬粉末（典型而言，係 由同一或類似之原料構成，比重與主金屬粉末相同或近似 之細微金屬粉末，且粒度分佈及平均粒徑與主金屬粉末不 同之略呈球狀粉末）。藉由組合（混合）此種平均粒徑及粒度 分佈不同而實質上為同一組成之金屬粉末，可不損及該金 屬粉末具有之電特性及其他物性，且，與只由主金屬粉末 單獨形成之粉末材料相較，可形成更緻密且機械強度及導 電性優越之膜狀導體。 此外’使用之充填補助細微粉末的粒度分佈及平均粒 徑’係依作為對象之主金屬粉末的粒度分佈及平均粒徑而 加以規定。譬如，將平均粒徑為〇邛111之金屬粉末作為主 金屬粉末時，可將小於O USpm之平均粒徑者作為充填補 助細微粉末而使用。 然而，由提高充填性之觀點來看，作為主金屬粉末及 充填補助細微粉末而使用之粉末材料，宜為粒度分佈狹窄 者°粒度分佛越狹窄（Sharp)，越可正確地進行適當之粒度 配合。雖無特別限定，但譬如將平均粒徑·為〇.5μιη程度之 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公楚) (請先閱讀背面之注意事項再填寫本頁) .、句· -14- 594795 A7 _____ B7_ 五、發明説明（12 ) 金屬粉末作為主金屬粉末時，宜為屬於如下範圍之狹窄粒 度分佈者，即，全體之略70%或70%以上之粒子係於該平 均粒徑之60%〜140%之粒徑範圍（以該平均粒徑之 80%〜120%之粒徑範圍為佳），具體而言，全體之略7〇%或 70X)以上之粒子係於粒徑〇 3μχη〜0·7μπι(以粒徑 0·4μιη〜0·6μπι為佳）之範圍内。又，將平均粒徑為〗〇μιη程 度之金屬粉末作為主金屬粉末時，宜為屬於如下範圍之狹 窄粒度分佈者，即，全體之略70%或70%以上之粒子係於 粒徑0·6μηι〜1·4μτη(以粒徑0·8μπι〜1·2μιη為佳）之範圍。 另一方面，作為使用前述平均粒徑為〇·5μιη程度之主 金屬粉末時之充填補助細微粉末，雖可使用平均粒徑小於 〇·125μτη(以 〇·125μιη 〜0·0625μιη 為佳，0·083μιη 〜0·062μπι 更 佳）者，但宜為屬於如下範圍之狹窄粒度分佈者，即，全體 之略70%或70%以上之粒子係於該平均粒徑之6〇%〜140% 程度之粒徑範圍（以80%〜120%程度之粒徑範圍為佳），具體 而言，全體之略70%或70%以上之粒子係於粒徑 0·075μιη〜0·15μιη(以粒徑Ο.ΐμπι〜0·15μιη為佳）之範圍。同樣 地’作為使用前述平均粒徑為ΙΟμ^程度之主金屬粉末時 之充填補助細微粉末，雖可使用平均粒徑小於〇·25μηι(以 〇·25μιη 〜0·125μπι為佳，〇·25μπι 〜0·167μηι 更佳）者，但宜為 屬於如下範圍之狹窄粒度分佈者，即，係於該平均粒徑之 60%〜140%程度之粒徑範圍（以該平均粒徑之80%〜120%程 度之粒徑範圍為佳），具體而言，全體之略7〇%或7〇%以上 之粒子係於粒徑0·75μm〜0·175μm(以粒徑0.1μm〜0·15μm為 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） .......................裝...............：：玎..................線. (請先閲讀背面之注意事項再填寫本頁) -15- 594795 A7 ___B7 五、發明説明（13 ) ， 佳）之範圍。 (請先閲讀背面之注意事項再填窝本頁) 此外，實施本發明時，只要主金屬粉末及充填補助細 微粉末中任一者略呈球狀，其製造方法便無限制。譬如， Ni及其他球狀金屬粉末及矽、氧化鋁等球狀陶究粉末，可 適宜地使用以習知方法製造者。譬如，製造球狀矽及其他 陶瓷微粒子之習知方法中，可例舉一喷霧乾燥法。又，犯 粉末專金屬粉末可藉喷霧熱分解法及所謂之Cvd·法進行製 造。實施本發明時，可適宜地使用（製造或購買）以習知方 法製造之球狀粉末。 其次，就有關調製本發明導鱧糊之主要成分，即導趙 形成用粉末材料而加以說明。此粉末材料係藉由於作為該 主要成分之主金屬粉末中’添加如前述性狀之充填補助細 微粉末而構成者〇且，有關此種充填補助細微粉末之添加 量，宜於可滿足如下條件之範圍内而加以設定。即，宜於 如下之範圍内設定添加量，即，將本發明之導體糊塗佈於 陶瓷基材時所得之乾燥塗膜中之該粉末材料之充填率（進 而係焙燒後之膜狀導體之緻密度），高於將只由主金屬粉末 形成之導體形成用粉末材料之糊塗佈於陶曼基材時所得之 乾無塗膜中之該粉末材料之充填率。概言之，使用之主金 屬粉末與充填補助細微粉末間，如前述之恰當•之平均粒徑 及粒度分佈不同時，於達到特定之添加量前，前述充填率 即因應該充填補助細微粉末之添加量而提高。因此，實施 本發明時之充填補助細微粉末之添加量（含有量），宜為達 到該特定添加量間之範圍内（當然·，即使為超過前述特定添 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -16 - 594795 A7 ------ -B7_ 五、發明説明（u ) 力量之添加i，如前述般，較使用只由主金屬粉末形成之 導體形成用粉末材料之糊，乾燥塗膜中之粉末材料之填充 率仍為較高之範圍），可不需太多實驗便加以決定。 雖無特別限定，作為充填補助細微粉末，使用實質上 與主金屬粉末為同一組成之略呈球狀金屬粉末時，其含有 率為導體形成用粉末材料全體之25wt%以下之量，而宜添 加導體形成用粉末材料全體之5 wt%〜2〇wt%(特別係1〇 wt%〜20wt%)之量。添加多於導體形成用粉末材料全體之 25wt%之量時，恐有添加超出主金屬粉末粒子間空隙之容 積量的充填補助細微粉末之疑慮，故不適宜。因存有無法 進入該空隙間之充填補助細微粉末，故有時充填率反倒降 低（參照後述之實施例）。 此外，前述適當之添加量之上限，係較粒徑互異之二 成分系之最大充填率的理論值高，而較該理論值多之添加 量係表示實施本發明時之理想數值。此外，此處二成分系 之最大充填率之理論值（理論添加量）係以下述方式求得。 即，於面心立方晶格之各晶格結點配置半徑q之球（一 -人球）之立方最在、充填構造中，充填率為74· 〇5%，且空隙比 為25.95%。另一方面，於用以構成該立方最密充填構造之 一次球之間隙（充填補助微粒子）配置連接於各一次球之直 徑之微粒子（填充補助微粒子）時，其充填率為81〇〇%，且 空隙率為19·00%，而刖述各一次球係指以可配置於該間隙 之最大級微粒子，即該重心位置為中心而相鄰接者。即， 由該充填率（81.00%)減去立方喪密充填構造之充填率 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公复）Oxides such as Mg, or high melting point rare earths (ie, sc, γ, La, Bu, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) This paper is suitable for financial standards (⑽) Ege (2 Huan 297j ^ .................. •: Installed ........ .tr ........ Famous (Please read the notes on the back before filling this page) 13- W4795 A7 B7 11 V. Description of the invention (oxides. As the dielectric powder, common materials used with the ceramic substrate used can be exemplified by barium titanate-based oxides, silicon nitride, aluminum nitride and other lice compounds, silicon carbide, titanium carbide and other carbides and the foregoing By adding the aforementioned ceramic powder (including the aforementioned metal oxide), the heat resistance and adhesive strength of the film-like conductor formed from the conductor paste of the present invention can be further improved. It is also a metal that can be used as a filler to supplement fine powder. Powder, including metal powder with the same composition as the main metal powder (typically, it is composed of the same or similar raw materials, fine metal powder with the same or similar specific gravity as the main metal powder, and the particle size distribution and average (Slightly spherical powder with a diameter different from that of the main metal powder). By combining (mixing) such metal powders with different average particle sizes and particle size distributions and having substantially the same composition, the electrical characteristics and Other physical properties, and compared with powder material formed only by the main metal powder, it can form a denser film-shaped conductor with superior mechanical strength and electrical conductivity. In addition, the filler used can help the fine particle size distribution and average particle size 'It is determined according to the particle size distribution and average particle size of the target main metal powder. For example, when a metal powder having an average particle size of 邛 111 is used as the main metal powder, an average particle size smaller than 0 USpm may be used as It is used for filling fine powder. However, from the viewpoint of improving filling properties, the powder material used as the main metal powder and filling fine powder is preferably one with a narrow particle size distribution. The narrower the particle size, the more sharp Proper particle size mixing can be performed correctly. Although not particularly limited, for example, a paper rule with an average particle size of about 0.5 μm Degree applies to Chinese National Standard (CNS) A4 specification (210X297). (Please read the precautions on the back before filling this page.) Sentence -14- 594795 A7 _____ B7_ V. Description of the invention (12) Metal powder as main In the case of metal powder, it is preferable to have a narrow particle size distribution, that is, a particle size of 70% or more of the entire particle size ranges from 60% to 140% of the average particle size (with the average particle size) The particle size range of 80% ~ 120% is better), specifically, the overall particle size is slightly more than 70% or 70X). The particle size is more than or equal to 0. 3μχη ~ 0. 7μπι (with a particle size of 0. 4μιη ~ 0. 6μπι is preferred). When a metal powder having an average particle size of about 0 μm is used as the main metal powder, it is preferable to have a narrow particle size distribution that falls within the range of 70% or more of the total particles with a particle size of 0 · The range is from 6 μηι to 1.4 μτη (preferably with a particle size of 0.8 μπι to 1.2 μιη). On the other hand, as the filling auxiliary fine powder when the above-mentioned main metal powder having an average particle size of about 0.5 μm is used, it is possible to use an average particle size of less than 0.25 μτη (preferably 0.25 μm to 0. 0625 μm, 0 · 083μιη ~ 0.062μπι), but it should be a narrow particle size distribution that falls within the range of 70% or more of the total particle size to 60% to 140% of the average particle size Particle size range (preferably a particle size range of about 80% to 120%), specifically, slightly more than 70% or more of the total particle size ranges from 0.075 μm to 0.15 μm (with a particle size of 0) .ΐμπι ~ 0 · 15μιη is preferred). Similarly, as the filling auxiliary fine powder when the main metal powder having an average particle diameter of about 10 μ ^ is used, an average particle diameter of less than 0.25 μηι (preferably 0.25 μιη to 0.125 μπι, 0.25 μπι to 0 · 167μηι is better), but it should be a narrow particle size distribution that falls within the range of 60% ~ 140% of the average particle size (80% ~ 120 of the average particle size) The particle size range of %% is better). Specifically, the particle size of 70% or more of 70% or more is based on the particle size of 0.75 μm to 0.175 μm (based on the particle size of 0.1 μm to 0.15 μm). Paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) .................... ..... :: 玎 ............ line. (Please read the notes on the back before filling out this page) -15- 594795 A7 ___B7 V. Invention Explain the scope of (13), good). (Please read the precautions on the back before filling this page.) In addition, in the practice of the present invention, as long as any one of the main metal powder and the filling auxiliary fine powder is slightly spherical, the manufacturing method is not limited. For example, Ni, other spherical metal powders, and spherical ceramic powders such as silicon and alumina can be suitably used by manufacturers using conventional methods. For example, among the conventional methods for manufacturing spherical silicon and other ceramic fine particles, a spray-drying method may be mentioned. In addition, the powder metal powder can be produced by a spray thermal decomposition method and a so-called Cvd · method. In the practice of the present invention, a spherical powder produced by a conventional method can be suitably used (manufactured or purchased). Next, the main component for preparing the paste of the present invention, that is, the powder material for forming the paste will be described. This powder material is constituted by adding the filling fine powder as the main component of the main metal powder as described above, and the amount of such filling fine powder is suitable for the range that can satisfy the following conditions. Set it inside. That is, it is appropriate to set the amount of addition within the range that the filling rate of the powder material in the dry coating film obtained when the conductor paste of the present invention is applied to a ceramic substrate (and further the denseness of the film-like conductor after firing) (Degree), which is higher than the filling rate of the powder material in the dry uncoated film obtained when the paste of the conductor-forming powder material formed of only the main metal powder is applied to the talman substrate. In summary, if the average particle size and particle size distribution of the main metal powder used and the filling auxiliary fine powder are appropriate as described above, before the specific addition amount is reached, the aforementioned filling rate should be used to fill the auxiliary fine powder. The amount is increased. Therefore, when the present invention is implemented, the amount of added fine powder (content) should be within the range of the specific addition amount (of course, even if the paper size exceeds the aforementioned specific addition, the Chinese National Standard (CNS) is applicable) A4 specification (210X297 mm) -16-594795 A7 ------ -B7_ V. Description of the invention (u) The addition of strength i, as mentioned above, uses a conductor forming powder material made of only the main metal powder. (The filling rate of the powder material in the dry coating film is still in a relatively high range), which can be determined without much experimentation. Although it is not particularly limited, when a slightly spherical metal powder having substantially the same composition as the main metal powder is used as the filling auxiliary fine powder, its content is 25 wt% or less of the entire powder material for conductor formation. An amount of 5 wt% to 20 wt% (particularly 10 wt% to 20 wt%) of the entire powder material for conductor formation. If it is added in an amount of more than 25% by weight of the entire powder material for conductor formation, there is a concern that a sufficient amount of the volume exceeding the space between the particles of the main metal powder may be used to supplement the fine powder, which is not suitable. Because there is a filling powder which cannot enter the space, the filling assisted fine powder may decrease the filling rate (see the example described later). In addition, the upper limit of the appropriate addition amount is higher than the theoretical value of the maximum filling rate of the two component systems with different particle sizes, and an addition amount greater than the theoretical value indicates an ideal value when the present invention is implemented. The theoretical value (theoretical addition amount) of the maximum filling rate of the two-component system is determined in the following manner. That is, the cube of the ball with a radius q (one-person sphere) is arranged in each lattice node of the face-centered cubic lattice. In the filling structure, the filling rate is 74 · 5% and the void ratio is 25.95%. On the other hand, when the particles (filling auxiliary particles) connected to the diameter of each primary ball (filling auxiliary particles) are arranged in the gap (filling auxiliary particles) of the primary ball constituting the cubic closest filling structure, the filling rate is 8100%. And the porosity is 19.0%, and each primary sphere refers to the largest particle that can be placed in the gap, that is, the center of gravity, and is adjacent to each other. That is, the filling rate of the cubic filling structure is subtracted from the filling rate (81.00%). The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public copy).
.......................裝…： (請先閲讀背面之注意事項再填窝本頁) :線丨 •訂丨 -17- 594795 A7 ____ B7 五、發明説明（15 ) (請先閲讀背面之注意事項再填寫本頁) (74.05%)之份（6·95%)為前述充填補助微粒子之容積。藉 此，對主金屬粉末（相當於前述一次球）1〇〇cm3之充填補助 細微粉末（相當於前述充填補助微粒子）之理論添加量，係 依據 74.05 : 6.95= 100 : 9.39而導出 9.39cm3。 /· 又，將本發明應用於Ni糊時，添加於作為主金屬粉末 之Νι粉末（宜為平均粒徑〇 2μπι〜丨〇^miNi粉末尤以平均 粒徑為略0·5μπι之Ni粉末為佳）中之充填補助細微粉末之 量，可以鈦酸鋇粉末換算時之容積而加以規定，前述鈦酸 鋇粉末宜具有小於該Ni粉末平均粒徑的略4分之寸之平 均粒徑。譬如，常溫常壓下，對平均粒徑為〇 5^m之⑷粉 末lOOgdcm3%8·%，因此100g%11二伽3)所添加之充填補 助微細粉末的適當添加量，可一般化為相當於該％粉末之 30wt%以下之重量（即30g以下）的鈦酸鋇粉末（lcm3与6 〇g) 所佔之容量（譬如以30g之鈦酸鋇粉末換算時為5 〇cm)。藉 由進行鈦酸鋇換算，用於本發明之犯糊之導體形成用粉末 材料，即可不限於充填補助細微粉末之種類（即不限於該粉 末比重之大小），且不需反覆進行過多之實驗便可決定適當 之添加量（容積）。 且’本發明之導體形成用粉末材料，係可藉混合特定 量之主金屬粉末與適當添加量之充填補助微細粉末而輕易 得之。此外，此種混合處理可單獨於將粉末材料分散於載 色劑前進行，或，亦可與將粉末材料分散於該載色劑之步 驟同時進行（卽，此時同時進行導體形成用粉末材料之調製 步驟及將該粉末材料分散於載色細之分散步驟）。 • ......... . 本紙張尺度適用中國國家標準（CNS) A4規格（210 X 297公楚） -18- 594795 A7 B7 16 五、發明說明（ ........................裝…… (請先閲讀背面之注意事項再填寫本頁) 此外，作為此種混合方法，可無特別限制地利用歷來 通韦使用之粉末混合手段。譬如，可使用各種混合器及滾 車匕機（Mill)(譬如行星滾軋機（Planetary Mill))授拌、混合前 述粉末。如此調製出之導體形成用粉末材料中，典型而言， 均5¾為於其粒度分佈曲線上有兩個或兩個以上之峰值。此 情況可作為一顯示本發明之導體形成用粉末混合材料粒度 刀佈互異之兩個或其以上粉末的多成分系材料之指標。 接著，說明有關用以構成本發明之導體糊之補助成 分。本發明之導體糊除有助於充填率提高之前述導體形成 用粉末材料外，並可將與習知之導體糊為同樣之物質作為 辅助成分而包含於其中。 •訂· :線丨 譬如’作為本發明之導體糊所需之輔助成分，可例舉 預先分散前述導體形成用粉末材料之有機媒質（載色劑）。 實施本發明時，此有機載色劑宜預先令導體形成用粉末材 料分散，且可無特別限制地使用用於習知之導體糊者。譬 如’可例舉乙基纖維素等纖維素系高分子、乙二醇及二甘 醇介電體、曱苯、二曱苯、礦油精、丁基卡必醇、蔥品醇 (Terpineol)等高沸點有機溶媒。 又’本發明之導體糊中，只要不損及該糊之導電性（低 電阻）、可焊性、耐焊熱、黏合強度等，便可將各種有機添 加劑作為輔助成分而内含。譬如，作為此種有機添加劑， 可例舉各種有機黏合劑（可與前述載色劑重複或添加另一 不同之黏合劑），及以提高與陶瓷基材之黏著性為目的之石夕 系、鈦酸酯系及鋁等各種偶合劑睿。 -19- ,594795 A7 ------ B7 ____ 五、發明説明（17 ) 作為有機黏合劑，可例舉譬如將丙烯酸酯樹脂、環氧 樹脂、酚醛樹脂、醇酸樹脂、纖維素系高分子、聚乙烯醇 等作為基底（Base)者。以可賦予本發明之導體糊良好黏性 及塗膜（基材上之附著膜）形成者為佳。又，欲賦予本發明 之導體糊光固化性（感光性）時，可適宜添地加各種光聚合 性化合物及光聚合開始劑。 此外’除前述者外，亦可依需求適宜地於本發明之導 體糊中添加界面活性劑、消泡劑、可塑劑、增稠劑、分散 劑、聚合抑制劑等。因前述等添加劑可於習知導體糊之調 製中得到，故省略詳細說明。 其次’說明有關本發明之導體糊之調製。本發明之導 體糊與習知之導體糊相同，典型而言，可藉混合前述導體 形成用粉末材料與有機媒質（載色劑）而輕易調製。此外， 主金屬粉末與充填補助細微粉末可個別添加於載色劑中， 或亦可於載色劑中添加預先混合前述粉末而得者。此時， 依需求可添加、混合如前述之添加劑。譬如，使用三個軋 制機（Roller Mill)及其他攪拌機（Kneading Machine)，以特 定之配合比將導體形成用粉末材料及各種添加劑直接混合 於有機載色劑，並藉相互冶煉（攪拌）而調製出本發明之導 體糊。 其次’說明有關使用本發明導體糊之膜狀導體形成（即 陶瓷電子零件之製造）的適宜例。本發明之導體糊於陶瓷製 之基材（基板)形成佈線、電極等膜狀導體上，可採取與歷 來使用之導體糊同樣的方式，亦可無特別限制地採用習知 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐）............. Install ...: (Please read the precautions on the back before filling in this page): Line 丨 • Order 丨 -17- 594795 A7 ____ B7 V. Description of the invention (15) (Please read the notes on the back before filling out this page) (74.05%) The portion (6.95%) is the volume of the aforesaid filler particles. Based on this, the theoretical amount of filling supplementary fine powder (equivalent to the aforementioned filling assisting fine particles) of 100 cm3 for the main metal powder (equivalent to the aforementioned primary sphere) is derived from 74.05: 6.95 = 100: 9.39 and 9.39 cm3. / · In addition, when the present invention is applied to a Ni paste, the Ni powder (preferably an average particle size of 0 2 μm to 5 μm) is added to the Ni powder as the main metal powder, and the Ni powder having an average particle size of approximately 0.5 μm is particularly The amount of the fine powder in the filling method can be specified in terms of the volume when the barium titanate powder is converted. The foregoing barium titanate powder preferably has an average particle size that is slightly smaller than the average particle size of the Ni powder by a quarter of an inch. For example, at room temperature and pressure, 100 gdcm3% 8 ·% of osmium powder with an average particle size of 0 5 ^ m, so 100g% 11 digal 3) The appropriate amount of filler to supplement the fine powder can be generalized to equivalent The capacity occupied by the barium titanate powder (1 cm3 and 60 g) with a weight of 30% by weight or less (that is, 30 g or less) of the% powder (for example, 50 cm in terms of 30 g of barium titanate powder). By performing barium titanate conversion, the powdered material for conductor formation used in the present invention is not limited to the type of filling fine powder (that is, not limited to the specific gravity of the powder), and it is not necessary to perform too many experiments repeatedly. Can determine the appropriate amount (volume). Furthermore, the powder material for conductor formation of the present invention can be easily obtained by mixing a specific amount of the main metal powder with an appropriate amount of filling and filling fine powder. In addition, such a mixing treatment may be performed separately before dispersing the powder material in the vehicle, or may be performed simultaneously with the step of dispersing the powder material in the vehicle (该, at this time, the powder material for conductor formation is simultaneously performed). The preparation step and the dispersion step of dispersing the powder material in a fine color carrier). • .......... This paper size applies to China National Standard (CNS) A4 (210 X 297 Gongchu) -18- 594795 A7 B7 16 V. Description of the invention (........ ... install ... (Please read the notes on the back before filling out this page) In addition, as this mixing method, you can use the traditional Tongwei without any restrictions Powder mixing means. For example, various mixers and Mills (such as Planetary Mill) can be used to mix and mix the aforementioned powders. Among the powder materials for conductor formation prepared in this way, typically In other words, the average of 5¾ is that there are two or more peaks on the particle size distribution curve. This case can be used as a display of two or more powders having different particle size cloths for the powder-mixing material for conductor formation of the present invention. The index of the composition material is explained. Next, the supplementary ingredients for constituting the conductor paste of the present invention will be described. The conductor paste of the present invention can be used in addition to the conventional conductor forming powder material that contributes to the improvement of the filling rate. The paste is contained in the same substance as an auxiliary component. • Order ·: Line 丨 For example, as an auxiliary component required for the conductor paste of the present invention, an organic medium (coloring agent) in which the aforementioned powder material for conductor formation is dispersed in advance may be mentioned. In the practice of the present invention, the organic coloring agent It is desirable to disperse the powder material for conductor formation in advance, and it is possible to use conventional conductor pastes without any particular restrictions. For example, a cellulose-based polymer such as ethyl cellulose, a dielectric of ethylene glycol, and diethylene glycol may be mentioned. High-boiling organic solvents such as toluene, xylene, xylene, mineral spirits, butylcarbitol, terpineol, etc. Also, in the conductive paste of the present invention, as long as the conductivity of the paste is not impaired ( Low resistance), solderability, soldering heat resistance, adhesive strength, etc., and various organic additives can be included as auxiliary components. For example, as such organic additives, various organic adhesives can be exemplified (comparable with the aforementioned color-loading) Repeat or add another different adhesive), and various coupling agents such as Shixi series, titanate series, and aluminum, which are used to improve the adhesion to ceramic substrates. -19-, 594795 A7 --- --- B7 ____ V. Description of the invention (17 ) As the organic binder, for example, an acrylic resin, an epoxy resin, a phenol resin, an alkyd resin, a cellulose polymer, a polyvinyl alcohol, etc. can be used as a base (Base). The conductor that can be given to the present invention Those with good adhesiveness and the formation of a coating film (adhesive film on a substrate) are preferred. In addition, in order to impart photocurability (photosensitivity) to the conductor paste of the present invention, various photopolymerizable compounds and light may be appropriately added. Polymerization initiator. In addition to the foregoing, in addition to the foregoing, a surfactant, an antifoaming agent, a plasticizer, a thickener, a dispersant, a polymerization inhibitor, etc. may be appropriately added to the conductor paste of the present invention as required. Other additives can be obtained in the preparation of conventional conductor pastes, so detailed descriptions are omitted. Next, the modulation of the conductor paste of the present invention will be described. The conductor paste of the present invention is the same as the conventional conductor paste. Typically, the conductor paste can be easily prepared by mixing the aforementioned powder material for conductor formation with an organic medium (a vehicle). In addition, the main metal powder and the filling auxiliary fine powder may be individually added to the vehicle, or may be obtained by adding the aforementioned powder to the vehicle beforehand. At this time, the aforementioned additives can be added and mixed as required. For example, using three rolling mills (Roller Mill) and other mixers (Kneading Machine), the powder material for conductor formation and various additives are directly mixed with the organic vehicle at a specific mixing ratio, and are smelted (stirred) to each other. The conductive paste of the present invention is prepared. Next, a suitable example of film-like conductor formation (i.e., manufacture of ceramic electronic parts) using the conductor paste of the present invention will be described. The conductor paste of the present invention is formed on ceramic substrates (substrates) to form wirings, electrodes and other film-like conductors. The same method can be used as conventional conductor pastes. It can also be used without special restrictions. National Standard (CNS) A4 specification (210X297 mm)
、可| (請先閲讀背面之注意事項再填寫本頁) -20- 594795 A7 一_ —____B7_ 五、發明説明（18 ) 之方法。典型而言，藉網版印刷法及計量分配塗佈法等， 可使導體糊以預定之形狀、厚度而塗覆於陶瓷基材（基 板）。接著，宜於乾燥後，於加熱器中以適當之加熱條件（最 高培燒溫度約為600°C〜1300°C，典型上雖為700°C〜1000 °C，但Ni糊宜為llOOt〜1300t：)加熱預定時間，藉此，焙 燒（烘乾）、固化該業已進行塗覆之糊成分。藉此一連串之 處理，可得業已形成目標之薄膜狀導體（佈線、電極等）之 陶瓷電子零件（譬如MLCC之電極及混合集成電路、多片模 件（Multichip Module)之構築用陶瓷佈線基板）。且，藉由 將該陶瓷電子零件作為裝配材料使用，並應用習知之構築 方法，可進而得高度之陶瓷電子零件（譬如混合集成電路及 多片模件）。此外，因此構築方法本身並無賦予本發明特別 之特徵，故省略詳細之說明。 此外，無限定用途之意，但如前述，依本發明之導艘 糊可形成較習知者之緻密性更優越之膜狀導體。因此，本 發明之導體糊不僅適於形成膜厚為ΙΟμηι〜30μηι程度之導 體，亦適於形成ΙΟμπι以下膜厚較薄之導體。譬如，作為 MLCC用Ni内部電極，可形成1·5μτη〜3μπι厚之敏密性優越 之膜狀導體。 【實施例】 以下，說明幾個有關本發明之實施例，但並無將本發 明限於以下實施例所例示者之意圖。 〈實施例1〉 實施例1係調製將鈦酸鋇粉末作為充填補助細微粉末 本紙張尺度適用中國國家標準（CNS) Α4規格（210X297公釐） .......................裝..................訂..................線. (請先閲讀背面之注意事項再塀寫本頁) -21 - 594795 A7 __________B7_ 五、發明説明（19 ) 之Νι糊。即’於平均粒徑約為〇4|[1111之犯粉末100g中，添 加相當於該Ni粉末之1〇wt%之量（1〇g)之平均粒徑約為 0·1 μηι之鈦酸鋇粉末，並藉攪拌、混合而調製本實施例之 導體形成用粉末材料。 其次’使用前述所得之導體形成用粉末材料調製Ni 糊。即，秤量前述材料，俾使最後之糊濃度（重量比）為導 體形成用粉末材料之55wt%(Ni粉末5〇wt%、鈦酸鋇粉末 5wt%)及殘部為溶劑（42wt%)與黏合劑（樹脂：3wt%)，並使 用二根滾札機進行攪拌。藉此，調製本實施例之Ni糊。 〈比較例1〉 除使用之鈦酸頷粉末之平均粒徑約為0·2μιη外，並進 行與前述實施例1同樣之處理，以調製本比較例之Ni糊。 〈比較例2〉 不添加鈦酸鋇粉末而將前述沁粉末直接作為導體形成 用粉末材料使用，以調製本比較例之Ni糊。此外，最後之 糊固形份濃度與實施例1相同。 〈試驗例1 :塗膜密度之評價（其U〉 接著，使用實施例1、比較例1及2之Ni糊，分別於玻璃 基材上形成塗膜，並測定該塗膜密度（g/cm3)。即，於玻璃 基材（厚度約1.3mm之鹼石灰製基板）之表面，以一般之網版 印刷法塗佈各導體糊，形成預定膜厚之塗膜。其次，使用 遠紅外線乾燥機，以1 〇〇°C施行15分鐘之乾燥處理。藉此乾 燥處理，溶剤由塗膜揮發而得一由導體形成用粉末材料形 成之乾燥塗膜。接著，測定所得乾燥塗膜之塗膜重量與塗 ________ 本紙張尺度適财國國家標準（⑽）A4規格（2獻撕公爱） ............，象----- (請先閲讀背面之注意事項再填寫本頁) •、^τ·， 可 | (Please read the precautions on the back before filling this page) -20- 594795 A7 I _ —____ B7_ V. Method of Invention Description (18). Typically, the conductor paste can be applied to a ceramic substrate (substrate) in a predetermined shape and thickness by a screen printing method or a metering and dispensing method. Next, after drying, it is suitable to use a suitable heating condition in a heater (the highest baking temperature is about 600 ° C ~ 1300 ° C, although it is typically 700 ° C ~ 1000 ° C, but the Ni paste is preferably 100t ~ 1300t :) It is heated for a predetermined time, thereby baking (drying) and curing the paste component which has been coated. Through this series of processing, ceramic electronic parts (such as MLCC electrodes and hybrid integrated circuits, and multichip modules) for the construction of ceramic electronic components that have formed target film-like conductors (wiring, electrodes, etc.) can be obtained. . Furthermore, by using this ceramic electronic component as an assembly material and applying a known construction method, a highly advanced ceramic electronic component (such as a hybrid integrated circuit and a multi-chip module) can be obtained. In addition, since the construction method itself does not give special features to the present invention, detailed descriptions are omitted. In addition, it is not intended to be limited in use, but as mentioned above, the guide paste according to the present invention can form a film-like conductor having a higher density than a conventional one. Therefore, the conductor paste of the present invention is not only suitable for forming a conductor having a film thickness of about 10 μm to 30 μm, but also suitable for forming a thin film having a thickness of less than 10 μm. For example, as the Ni internal electrode for MLCC, it is possible to form a film-shaped conductor having a thickness of 1.5 μτη to 3 μπι and having excellent sensitivity. [Examples] Hereinafter, several examples of the present invention will be described, but it is not intended to limit the present invention to those illustrated in the following examples. 〈Example 1〉 Example 1 is prepared by using barium titanate powder as a filler to help fill the fine powder. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ......... ........................................... Order ........ line. (Please read the precautions on the back before copying this page) -21-594795 A7 __________B7_ V. The paste of invention description (19). That is, to 100 g of the guilty powder having an average particle diameter of about 0 4 | [1111, a titanic acid having an average particle diameter of about 0.1 μm is added in an amount equivalent to 10 wt% (10 g) of the Ni powder. The barium powder is prepared by stirring and mixing the powder material for conductor formation in this embodiment. Next, Ni paste is prepared using the powder material for conductor formation obtained above. That is, the foregoing materials are weighed so that the final paste concentration (weight ratio) is 55 wt% (50 wt% of Ni powder, 5 wt% of barium titanate powder) of the powder material for conductor formation, and the remainder is a solvent (42 wt%). Agent (resin: 3wt%), and stirred using two rollers. Thereby, the Ni paste of this embodiment is prepared. <Comparative Example 1> Except that the average particle diameter of the rhenium titanate powder used was about 0.2 µm, the same treatment as in Example 1 was performed to prepare the Ni paste of this comparative example. <Comparative example 2> The barium titanate powder was not added, and the aforementioned Qin powder was directly used as a powder material for conductor formation to prepare the Ni paste of this comparative example. The final paste concentration was the same as in Example 1. <Test Example 1: Evaluation of Coating Film Density (No. U) Next, the Ni paste of Example 1, Comparative Examples 1 and 2 was used to form a coating film on a glass substrate, and the coating film density (g / cm3) was measured. ). That is, on the surface of a glass substrate (a soda-lime substrate with a thickness of about 1.3 mm), each conductor paste is coated by a general screen printing method to form a coating film of a predetermined thickness. Next, a far-infrared dryer is used. A drying treatment was performed at 100 ° C. for 15 minutes. With this drying treatment, the coating was evaporated from the coating film to obtain a dry coating film made of a powder material for conductor formation. Next, the coating film weight of the obtained dry coating film was measured. With Tu ________ This paper is suitable for the national standard of the country of wealth (⑽) A4 size (2 for public love) ............, like ----- (Please read the note on the back first (Please fill in this page for more details) •, ^ τ ·
V -22- 594795 A7 ~---------B7_ 五、發明説明（2〇 ) 膜厚度’以算出塗膜密度。於第1表顯示該結果。 【第1表】 一導體糊 實施例1 比較例1 比較例2 N i粉末平均粒 _—_ 徑（μηι) 鈦酸鋇添加 (g/100gNi) 一平均粒徑（um) 0.5 0.5 0.5 10.0 0.1 10.0 0.2 不添加 送膜密度（g/cm3) 5.05 4.65 4.75 由第1表可知，由實施例1之導體糊所得之乾燥塗膜之 ........................裝…… (請先閲讀背面之注意事項再填寫本頁) 饮度’大幅超出由比較例1及比較例2之各導體糊所得之乾 燥塗膜之役度。由該結果，藉由於作為主金屬粉末之犯粉 末中添加、混合適量之平均粒徑小於該粉末之4分之〗之鈦 酸鋇粉末，即可提高用以構成乾燥塗膜之導體形成用粉末 材料之充填率，並可進一步使膜狀導鱧之構造緻密化。相 對於此，添加、混合平均粒徑超過前述Ni粉末之4分之1， 即粒徑較大的鈦酸鋇粉末而得之導體糊（比較例〗），不僅無 法提高充填率，即無法實現乾燥塗膜之高密度化，且較未 •線丨 添加鈦酸鋇粉末（比較例2)者，充填率反倒更加減少（參照 第1表）。 〈實施例2〉 實施例2係調製將實質上為同一組成之州粉末作為充 填補助細微粉末之Ni糊。即，對平均粒徑約為〇邛顶之州 糊（以下稱為「主Ni粉末」）1()〇g,添加平均粒#约為〇如 之Ni粉末（以下稱為「副Ni粉末」）94g，並藉櫈拌、混合 而調製本實施例之導體形成用粉末材料。即，本實施例之 導體形成用粉末材料之副Ni粉末.（即相當於前述充填補助 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公爱） -23- 594795 A7 — ____B7_ 五、發明説明（21 ) 細微粉末之金屬粉末）的含有率，為導體形成用粉末材料全 體之8.6wt%。其次，使用此導體形成用粉末材料，進行與 前述實施例1同樣的攪拌處理，以調製本實施例之Ni糊。 〈實施例3〉 對主Ni粉末l〇〇g添加副Ni粉末14』g，单藉攪拌、混合 而調製本實施例之導體形成用粉末材料。即，本實施例之 V體形成用粉末材料之副Ni粉末的含有率，為導體形成用 粉末材料全體之12.9wt%。接著，使用此導體形成用粉末 材料，進行與前述實施例1相同之攪拌處理，以調製本實施 例之Ni糊。 · 〈實施例4〉 對主Ni粉末l〇〇g添加副Ni粉末20.8g，並藉授拌、混合 而調製本實施例之導體形成用粉末材料。即，本實施例之 導體形成用粉末材料之副Ni粉末的含有率，為導體形成用 粉末材料全體之17.2wt%。其次，俵用此導體形成用粉末 材料，進行與前述實施例1相同之攪拌處理，以調製本實施 例之Ni糊。 〈比較例3〉 · 對主Ni粉末l〇〇g添加副Ni粉末l〇〇g，並藉授拌、混合 而調製本比較例之導體形成用粉末材料。即，本比較例之 導體形成用粉末材料之副Ni粉末的含有率，為導體形成用 粉末材料全體之50wt%。其次，使用此導體形成用粉末材 料’進行與前述實施例1相同之攪拌處理，以調製本比較例 之Ni糊。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂丨 -24- 594795 【第2表】 A7 _____B7__ 五、發明説明（22 ) 〈比較例4〉 不添加副Ni粉末，將主Ni粉末（與比較例2使用者不同） 直接作為導體形成用粉末材料而加以使用，進行與前述實 施例1相同之攪拌處理，以調製本比較例之Ni糊。 〈試驗例2:塗膜密度之評價（其2)〉 其次，使用實施例2〜4及比較例3、4之Ni糊，並以與 前述試驗例1相同之條件進行塗膜密度評價試驗。於第2表 顯示該結果。 導體糊 主Ni粉末平 均粒徑(μπι) 含有率(wt%) 副Ni粉末平 均粒徑 含有率(wt%) 實施例2 實施例3 實施例4 比較例3 比較例4 0.5 91.4 0.5 87.1 0.5 82.8 0.5 50.0 0.5 100.0 0.1 8.6 0.1 12.9 0.1 17.2 0.1 50.0 0 塗膜密度 (g/cm 3) 5.67 5.73 5.69 5.41 5.61 由第2表可知，由實施例2〜4之各個犯糊所得之各乾燥 塗膜之密度’任一者皆超過由比較例3及比較例4之各犯糊 所得之乾燥塗膜之密度。由該結果，藉由對主Ni粉末添加、 混合適量之平均粒徑小於該粉末之4分之1之副Ni粉末，即 可提1¾用以構成乾燥塗膜之導體形成用粉末材料（即％粉 末）之充填率，且可進一步使膜狀Ni導體之構造緻密化。相 對於此，對主Ni粉末添加、混合過量之副沁粉末而得之Ni 糊（比較3)，不僅無法提高充填率，即無法實現乾燥塗膜之 同抢度化，且未添加副Ni粉末者（比較例句，充填率反倒減 少（參照第2表）。 ^紙張尺度適用中關家標準_ A4規格（2iqx297公爱) (請先閲讀背面之注意事項再填寫本頁) .裝· 訂丨 -25- 594795 五、發明説明（23 ) 〈試驗例3:塗膜密度之評價（其3)〉 將鈦酸鋇粉末（平均粒徑約〇·1μιη)作為陶瓷添加材（即 本發明之充填補助細微粉末）而加以使用，以調製幾種該添 加量互異之Ni糊，並檢查該添加量與塗膜密度之關係。即， 對平均粒徑約為〇.4μιη之Ni粉末l〇〇g，添加Og、7.5g、10g、 12-5g、15g、17.5g、20g或30g之前述鈦酸鋇粉末，並藉攪 拌、混合，以調製8種鈦酸鋇粉末添加量不同之導體形成用 粉末材料。其次，進行與前述實施例1相同之攪拌處.理，以 由前述導體形成用粉末材料分別調製Ni糊。接著，以與前 述試驗例1相同之條件進行各Ni糊之塗膜密度評價試驗。於 第3表及第1圖顯示該結果。 【第3表】 陶瓷添加材 添加量 (g/100gNi) 0 7.5 10 12.5 15 17.5 . 20 30 乾燥塗膜密 度(g/cm3) 5.38 5.74 5.76 5.77 5.79 5.8 5.79 5.63 如第3表及第1圖所示，由本試驗例中作成之添加有陶 竟添加材之Ni糊形成之乾燥塗膜，密度高於由完全不添加 陶瓷添加材（鈦酸鋇粉末）之Ni糊形成之乾燥塗膜'尤其， 對NilOOg添加陶瓷添加材1〇g〜2〇g而得之州糊，乾燥塗膜 之高密度化更為顯著。 【發明之效果】 由前述實施例可知，依本發明之導體形成用粉末及以 該導體形成用粉末材料為主要成分之導體糊，可使用以構. 成陶瓷基材上之乾燥塗膜之導體形成用粉末材料的充填率· 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公爱) (請先閲讀背面之注意事项再填窝本頁)V -22- 594795 A7 ~ --------- B7_ V. Description of the invention (2) Film thickness' to calculate the coating film density. The results are shown in Table 1. [Table 1] A conductor paste Example 1 Comparative example 1 Comparative example 2 Average particle size of Ni powder ___ Diameter (μηι) Addition of barium titanate (g / 100gNi)-Average particle size (um) 0.5 0.5 0.5 10.0 0.1 10.0 0.2 Without adding film feeding density (g / cm3) 5.05 4.65 4.75 As can be seen from Table 1, the dry coating film obtained from the conductor paste of Example 1 ...... .................... (Please read the precautions on the reverse side before filling out this page) The drunk level is significantly higher than that of the dry coating film obtained from each of the conductor pastes of Comparative Example 1 and Comparative Example 2. From this result, by adding and mixing a suitable amount of barium titanate powder having an average particle diameter of less than one-fourth of the powder as a culprit powder of the main metal powder, the powder for forming a conductor for forming a dry coating film can be improved. The filling rate of the material can further densify the structure of the film guide. In contrast, adding and mixing an average particle diameter exceeding one-fourth of the aforementioned Ni powder, that is, a conductive paste obtained by barium titanate powder having a larger particle diameter (Comparative Example), not only cannot increase the filling rate, but also cannot achieve The density of the dry coating film is higher, and the filling rate is reduced more than the case where barium titanate powder (Comparative Example 2) is not added (see Table 1). <Example 2> Example 2 is a Ni paste in which state powders having substantially the same composition are used as supplementary fine powders. In other words, to the state paste (hereinafter referred to as "main Ni powder") with an average particle diameter of about 0 (1), g of Ni paste (hereinafter referred to as "sub-Ni powder") having an average particle size of about 0 is added. ) 94g, and the powder material for conductor formation of this embodiment is prepared by mixing and mixing with a stool. That is, the secondary Ni powder of the powder material for conductor formation in this embodiment. (That is, equivalent to the aforementioned filling and refilling, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public love) -23- 594795 A7 — ____B7_ V. Invention Note (21) The content of the fine powder metal powder) is 8.6% by weight of the entire powder material for conductor formation. Next, using this powder material for conductor formation, the same stirring treatment as in the foregoing embodiment 1 was performed to prepare the Ni paste of this embodiment. <Example 3> Sub-Ni powder 14 "g was added to 100 g of main Ni powder, and the powder material for conductor formation of this example was prepared by stirring and mixing alone. That is, the content rate of the secondary Ni powder of the powder material for forming a V body in this example is 12.9 wt% of the entire powder material for forming a conductor. Next, using this powder material for conductor formation, the same stirring treatment as in the foregoing embodiment 1 was performed to prepare the Ni paste of this embodiment. <Example 4> 100 g of main Ni powder was added with 20.8 g of sub Ni powder, and the powder material for conductor formation of this example was prepared by mixing and mixing. That is, the content rate of the secondary Ni powder of the powder material for conductor formation in this example is 17.2 wt% of the entire powder material for conductor formation. Next, using this powder material for conductor formation, the same stirring treatment as in the foregoing embodiment 1 was performed to prepare the Ni paste of this embodiment. <Comparative Example 3> 100 g of main Ni powder was added to 100 g of sub Ni powder, and the powder material for conductor formation of this comparative example was prepared by mixing and mixing. That is, the content rate of the secondary Ni powder of the powder material for conductor formation in this comparative example is 50% by weight of the entire powder material for conductor formation. Next, the powder material for conductor formation was subjected to the same agitation treatment as in Example 1 above to prepare the Ni paste of this comparative example. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order 丨 -24- 594795 [Table 2] A7 _____B7__ V. Description of the invention (22) <Comparative Example 4> The main Ni powder (different from the user of Comparative Example 2) was used as a powder material for conductor formation without adding a secondary Ni powder, and the same stirring treatment as in Example 1 was performed to prepare this comparison. Examples of Ni paste. <Test Example 2: Evaluation of Coating Film Density (Part 2)> Next, Ni coatings of Examples 2 to 4 and Comparative Examples 3 and 4 were used, and a coating film density evaluation test was performed under the same conditions as in Test Example 1 described above. The results are shown in Table 2. Conductor paste Primary Ni powder average particle size (μπι) Content rate (wt%) Secondary Ni powder average particle size content rate (wt%) Example 2 Example 3 Example 4 Comparative example 3 Comparative example 4 0.5 91.4 0.5 87.1 0.5 82.8 0.5 50.0 0.5 100.0 0.1 8.6 0.1 12.9 0.1 17.2 0.1 50.0 0 Coating film density (g / cm 3) 5.67 5.73 5.69 5.41 5.61 As can be seen from Table 2, the dry coating films obtained from the respective pastes of Examples 2 to 4 Any of the 'densities' exceeded the density of the dry coating film obtained from each of the pastes of Comparative Examples 3 and 4. From this result, by adding and mixing an appropriate amount of the auxiliary Ni powder having an average particle size of less than one-fourth of the powder to the main Ni powder, it is possible to extract 1¾ of a powder material for forming a conductor for forming a dry coating film (ie,% Powder), and can further densify the structure of the film-like Ni conductor. On the other hand, the Ni paste obtained by adding and mixing an excessive amount of sub-Qin powder to the main Ni powder (Comparative 3), not only cannot improve the filling rate, that is, it cannot achieve the same rush rate of the dry coating film, and no auxiliary Ni powder is added. (Comparative example, the filling rate is reduced (refer to Table 2). ^ The paper size applies the Zhongguanjia standard _ A4 size (2iqx297 public love) (Please read the precautions on the back before filling this page). -25- 594795 V. Description of the invention (23) <Experimental Example 3: Evaluation of Coating Film Density (Part 3)> Barium titanate powder (average particle size of about 0.1 μm) was used as a ceramic additive (that is, the filler of the present invention Fine powder) is used to prepare several kinds of Ni pastes with different added amounts, and the relationship between the added amount and the coating film density is checked. That is, for Ni powders with an average particle size of about 0.4 μm. g, adding Og, 7.5g, 10g, 12-5g, 15g, 17.5g, 20g or 30g of the aforementioned barium titanate powder, and by stirring and mixing, to prepare 8 kinds of conductors with different addition amounts of barium titanate powder Powder material. Second, the same stirring place as in the previous embodiment 1. The Ni paste was prepared by using the aforementioned powder material for conductor formation. Next, the coating film density evaluation test of each Ni paste was performed under the same conditions as in Test Example 1. The results are shown in Table 3 and Figure 1. [第Table 3] The amount of ceramic additives (g / 100gNi) 0 7.5 10 12.5 15 17.5. 20 30 Dry coating density (g / cm3) 5.38 5.74 5.76 5.77 5.79 5.8 5.79 5.63 As shown in Table 3 and Figure 1, The dry coating film formed from the Ni paste with the ceramic additive added in this test example has a higher density than the dry coating film formed from the Ni paste without the ceramic additive (barium titanate powder) added at all, especially for NilOOg The state paste obtained by adding ceramic additives 10g to 20g, the density of the dried coating film is more significant. [Effects of the Invention] As can be seen from the foregoing examples, the powder for conductor formation according to the present invention and the powder used for the conductor formation according to the present invention. The powder for conductor formation is used as the main component of the conductor paste. The filling rate of the powder for conductor formation as a dry coating film on a ceramic substrate can be used. The paper size applies to the Chinese National Standard (CNS) A4 (210X297). Public Love) (Please read first Note the back of the nest reloading the page)
V :訂· •26- 594795 A7 _______B7 五、發明説明（24 ) 較習知提高。因此，藉由將本發明之導體糊應用於形成 MLCC #陶瓷電子零件之膜狀導體上，可製造業已形成緻 密構造之薄膜狀導體之陶瓷電子零件，而該緻密構造之薄 膜狀導體係導電性等電特性及黏合強度等機械特性優越 者0 ........................裝----- (請先閲讀背面之注意事项再填窝本頁) .訂| •線· 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） •27-V: Ordered • 26- 594795 A7 _______ B7 V. Description of the invention (24) is better than conventional. Therefore, by applying the conductor paste of the present invention to a film-like conductor forming an MLCC #ceramic electronic part, it is possible to manufacture a ceramic electronic part that has formed a densely-shaped film-like conductor, and the densely-structured film-like conductive system is conductive. Those with excellent mechanical properties, such as isoelectric properties and adhesive strength, etc. 0 .............. install ----- (Please read the precautions on the back first Refill this page). Order | • Thread · This paper size applies to China National Standard (CNS) A4 (210X297 mm) • 27-