201213269 六、發明說明： 【發明所屬之技術領域】 本發明係關於不含鉛之厚膜導體形成用組成物，尤其 關於用以形成用作為晶片電阻器的上面電極之厚膜導體的 組成物。此外，係關於使用該組成物形成的厚膜導體，以 及至少將該厚膜導體適用在上面電極的晶片電阻器。 【先前技術】 使用厚膜技術來形成厚膜導體時，通常將導電率高的 導電粉末與玻璃粉末等的氧化物粉末一同分散於有機載體 (organic vehicle)中，得到膏狀的厚膜導體形成用組成 物，並使用網板印刷法或其他塗佈手段，於氧化鋁基板等 之陶瓷基板上將該厚膜導體形成用組成物塗佈為既定形 狀，以500°C至900°C進行燒製來。 構成厚膜導體形成用組成物之材料中，導電粉末是由 選自導電率高的Au、Ag、Pd及Pt之至少1種金屬所構成， 並採用平均粒徑10# m以下的金屬粉末。此等金屬中，由 於較便宜，故一般係使用Ag粉末及Pd粉末，但就導電性 更良好之觀點來看，係採用Ag粉末作為導電粉末的主材 料。 另一方面，至目前為止係採用容易控制軟化點且化學 耐久性高之硼矽酸鉛或是鋁硼矽酸鉛系作為玻璃粉末。然 而，就近年來防止環境污染之觀點來看，乃要求不含鉛之 厚膜導體形成用組成物，因而積極探討玻璃粉末的無鉛化。 使用此般之厚膜導體形成用組成物所形成之厚膜導 4 323345 201213269 體，係適合使用作為電子工業中所用之晶片電阻器、電阻 網路、混成ic等之電子零件的電極等。當中的晶片電阻 器，如第1圖所示意顯示，係具備：氧化鋁基板；以厚膜 導體所形成之由上面電極、側面電極與内面電極所構成之 内部電極；由氧化釕系厚膜所構成之電阻；與覆蓋電阻之 絕緣玻璃保護膜，而所暴露出的電極面為了提昇焊接性， 分別係藉由電解覆鍍而進一步形成由Ni鍍層所構成之中 間電極、與由Sn-Pb焊料鍍層或以Sn系合金的無鉛焊料鍍 層取代此者所構成之外部電極。 目前，作為導體粉末所主要採用之Ag，為特別對於硫 化為極脆弱之材料。晶片電阻器係藉由Ni鍍層或焊料鍍層 的塗層（coating)，來謀求對於由Ag系厚膜導體所構成之 電極的保護，在一般的使用中不會產生Ag硫化的問題。然 而，當在施以如熱老化（heat aging)或冷熱循環的嚴苛條 件下使用晶片電阻器時，由於應力而會在由絕緣玻璃所構 成之保護膜與焊料鍍層及Ni鍍層之界面上產生間隙，或是 由於電阻器之製造步驟上的缺失等而發生保護膜的位置偏 移等，導致内部電極暴露出，而因為空氣中的硫性氣體使 Ag硫化，有時會導致電極的短路。尤其在產生火山性氣體 之溫泉地區等之空氣中的硫性氣體濃度高之地區中，容易 因Ag的硫化發生電極短路等問題。 此外，在製造步驟或構裝步驟中，係對晶片電阻器等 之電子零件進行焊接，惟此時當内部電極暴露出，Ag等金 屬材料會在焊料中擴散，使導體部分消失、斷線而導致產 5 323345 201213269 生焊料侵蝕。焊料亦逐漸從63Sn/37Pb等之Sn-Pb系共晶 焊料（eutectic solder)取代為無鉛且組成為％含量高的 烊料，由於該Sn系合金焊料的熔點高，所以焊料溫度亦有 提高之傾向。伴隨著此般焊料組成的改變和焊料溫度的提 高，亦有著變得較以往容易發生焊料侵飯之問題。 對應於此般由Ag系厚膜導體所構成之電極的硫化或 因焊料侵蝕所造成的短路之方法，一般係進行將Pd添加於 作為導體粉末的Ag中之方法。例如，日本特開2004-250308 號公報係揭示一種為了防止Ag因硫性氣體所造成之硫 化’使用耐酸性優異之Bi系玻璃粉末，並一同添加〇. 3至 2重量％的Pd粉末之内容。但是，對於硫化係僅藉由目視 來觀察Ag系電極的變色，尚未對於該效果進行定量性的探 討。 然而’ Pd粉末本身的使用，會有因電極之比電阻值的 上升或電極之膜強度的降低而造成與基板的接觸 低，並且導致成本上升之問題。此外，日本特開平7_33=〇2 號公報中，係使用經Ag被覆的Pd粉末作為電極材料，以 求使燒製後之賴緊密性提升朗硫化。“，此般粉末 的使用更將導致成本上升，於實用方面仍具問題。 亦有探討對晶片電阻器的構造下功夫來防止電極硫1 之作法。例如日本特開2002-64003號公報的技術中， 容易產生間隙之部位的上面電極上，形成Pd含有率 以上的Ag系厚膜導體作為保護層。此外，π # ’ 1日本特開2003 224001號公報的技術中，係形成釕電阻體層作為门樣的十 323345 6 201213269 -護層。但是，追加此等新構造者，會在晶片 化或成本方面產生問題。 的小型 此外’如日本特開2004-221006號公報 2002-324428號公報所揭示，亦考量到設置藉由：：：開 性之碳膏所形成之保護層。然而，碳保護層存在有使， 電性降低等問題，而訴求為可在不設置碳保護芦 =胸硫化。目前仍無法料以碳材料來形成保護層^ 小:石二材料’來有效地達到Ag系厚膜導體的耐硫化。- 言，對於焊料韻之對策’以Ag系電極材料而 本特開__327356號公報等所記載，= 用添加Pd之方法。然而，需添加約 为又疋如 作為焊料侵料策，如上述般 冑里伤的Pd以 升等種種的問題。此外，當此等添H極的比電阻值上201213269 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a composition for forming a thick film conductor containing no lead, and more particularly to a composition for forming a thick film conductor used as an upper electrode of a wafer resistor. Further, it relates to a thick film conductor formed using the composition, and a wafer resistor in which at least the thick film conductor is applied to the upper electrode. [Prior Art] When a thick film conductor is used to form a thick film conductor, a conductive powder having a high conductivity is usually dispersed together with an oxide powder such as a glass powder in an organic vehicle to obtain a thick film conductor formed in a paste form. The composition for forming a thick film conductor is applied to a ceramic substrate such as an alumina substrate by a screen printing method or another coating means in a predetermined shape, and is fired at 500 ° C to 900 ° C. System. In the material constituting the composition for forming a thick film conductor, the conductive powder is composed of at least one metal selected from the group consisting of Au, Ag, Pd, and Pt having high conductivity, and a metal powder having an average particle diameter of 10 # m or less is used. Among these metals, Ag powder and Pd powder are generally used because they are relatively inexpensive, but Ag powder is used as a main material of the conductive powder from the viewpoint of better conductivity. On the other hand, as a glass powder, lead borosilicate or lead borosilicate is used as a glass powder which is easy to control the softening point and has high chemical durability. However, in view of the prevention of environmental pollution in recent years, a composition for forming a thick film conductor containing no lead is required, and therefore, lead-free glass powder is actively discussed. A thick film conductor formed by using such a thick film conductor forming composition is preferably an electrode which is used as an electronic component such as a chip resistor, a resistor network, or a hybrid ic used in the electronics industry. The wafer resistor as shown in Fig. 1 is characterized by: an alumina substrate; an internal electrode composed of a top electrode, a side electrode and an inner electrode formed by a thick film conductor; and a thick film made of yttrium oxide a resistor formed by the insulating glass protective film covering the resistor, and the exposed electrode surface is further formed by an electrolytic plating to form an intermediate electrode composed of a Ni plating layer and a Sn-Pb solder by electrolytic plating. The external electrode composed of this is replaced by a plating layer or a lead-free solder plating layer of a Sn-based alloy. At present, Ag, which is mainly used as a conductor powder, is a material which is extremely weak especially for vulcanization. The wafer resistor is protected by an electrode formed of an Ag-based thick film conductor by coating of a Ni plating layer or a solder plating layer, and does not cause the problem of Ag vulcanization in general use. However, when a wafer resistor is used under severe conditions such as heat aging or cold heat cycle, stress is generated at the interface between the protective film made of insulating glass and the solder plating layer and the Ni plating layer. The gap or the positional deviation of the protective film due to the absence of the manufacturing steps of the resistor or the like causes the internal electrode to be exposed, and the sulfur is vulcanized in the air to cause the short circuit of the electrode. In particular, in a region where the concentration of sulfur gas in the air such as a hot spring region where volcanic gas is generated is high, problems such as short-circuiting of the electrode due to vulcanization of Ag are liable to occur. In addition, in the manufacturing step or the mounting step, the electronic components such as the chip resistors are soldered, but when the internal electrodes are exposed, metal materials such as Ag are diffused in the solder, and the conductor portions are eliminated and disconnected. Lead to the production of 5 323345 201213269 raw solder erosion. The solder is also gradually replaced by a Sn-Pb eutectic solder such as 63Sn/37Pb to a lead-free material having a high content of %. Since the melting temperature of the Sn-based alloy solder is high, the solder temperature is also improved. tendency. Along with the change in the composition of the solder and the increase in the solder temperature, there is also a problem that solder penetration is more likely to occur than in the past. In the method of vulcanization of an electrode composed of an Ag-based thick film conductor or a short circuit caused by solder corrosion, a method of adding Pd to Ag as a conductor powder is generally performed. For example, Japanese Laid-Open Patent Publication No. 2004-250308 discloses a Bi-type glass powder which is excellent in acid resistance for preventing vulcanization of Ag due to a sulfur gas, and is added together with 3 to 2% by weight of Pd powder. . However, the discoloration of the Ag-based electrode was observed only by visual observation of the vulcanization system, and this effect has not been quantitatively examined. However, the use of the Pd powder itself causes a problem that the contact with the substrate is low due to an increase in the specific resistance of the electrode or a decrease in the film strength of the electrode, and the cost rises. Further, in Japanese Laid-Open Patent Publication No. Hei 7-33=〇2, an Ag-coated Pd powder is used as an electrode material in order to improve the compactness after firing. "The use of such a powder will lead to an increase in cost, and it is still problematic in practical use. It is also discussed to work on the structure of the chip resistor to prevent the electrode sulfur 1. For example, the technique of Japanese Laid-Open Patent Publication No. 2002-64003 In the upper electrode of the portion where the gap is likely to occur, an Ag-based thick film conductor having a Pd content or higher is formed as a protective layer. Further, in the technique of π # '1, Japanese Laid-Open Patent Publication No. 2003-224001, a tantalum resistor layer is formed. In the case of the above-mentioned new structure, there is a problem in the wafer formation or the cost. The small size is disclosed in Japanese Laid-Open Patent Publication No. 2004-221006, No. 2002-324428. It is also considered to set the protective layer formed by the ::: open carbon paste. However, the carbon protective layer has problems such as lowering the electrical properties, and the claim is that the carbon protection reed = chest vulcanization can be set. At present, it is still impossible to form a protective layer with a carbon material: a small stone material to effectively achieve the sulfurization resistance of the Ag-based thick film conductor. - In other words, the countermeasure against the solder rhyme is based on the Ag-based electrode material. The method of adding Pd is described in the Japanese Patent Publication No. __327356, etc. However, it is necessary to add a problem such as Pd as a solder intrusion, as described above. When the specific resistance of these added H poles is
Pd及、其上，， 材枓較少時，對於An、Pd and, above, when there are fewer materials, for An,
Pt之添加材料，當焊接於 、AU 侵蝕。 予膜導體時仍會產生焊料 作為此般對於焊料侵蝕之 6,3616號公報所記載 ^ ’如曰本特開平 系坡璃粉末、μ2〇·末、Sitt^Pb〇-s仙一⑽~m2〇3 機栽體者作為厚膜導體形成用 與導電粉末分散於有 製時，使稱為！弓長石（an〇rthit ’並於該組成物的燒 晶相析出於厚膜導體的内部之方法_亂⑹之針狀的結 然*，該厚膜導體形成用物 玻璃粉末，並且在約長石的生成^物中，係使用含有Pb之 於無鉛化厚膜導體中之鈣長石 以Pb的存在為必要，對 、生成並無進一步說明。 323345 7 201213269 對此，日本特開平7-97269號公報及日本特開2001_ 114556號公報中’係揭示有藉由將含有Si〇2-B2〇3-Ah〇3-CaO 系玻璃粉末與A12〇3粉末之厚膜導體形成用組成物進行燒 製，使鈣長石析出於厚膜導體之内容。然而，此時為了析 出足夠大的鈣長石，因為該結晶化溫度為高（玻璃的軟化溫 度高），故需為900。(：以上的高溫。當以900°c以上的溫度 燒製厚膜導體形成用組成物時，由於厚膜導體過度燒製， 且Ag的熔點低，故使由Ag系厚膜導體所構成之電極成為 島狀’而有難以形成均質的電極等問題。 本發明者們在日本特開2006-228572號公報中，係揭 示有藉由使用Si〇2-B2〇3-Ah〇3-CaO-Li2〇系玻璃粉末作為玻 璃系粉末，來降低玻璃的軟化溫度，而即使藉由進行未達 900°C的燒製’亦可使鈣長石均一地析出於厚膜内部之内 容。藉由此方法，雖確認到關於耐焊料侵蝕性之顯著提升， 但藉由本發明者們進一步的評估探討，乃發現到當使用以 Ag粉末作為主要導電材料之厚膜導體形成用組成物來形成 晶片電阻器的上面電極，在如上述之硫性氣體濃度高的特 殊環境下使用該晶片電阻器的情形下，被指摘為可能隨著 時間經過而產生上面電極的硫化，而要求進一步的改善其 财硫化性。 [先前技術文獻] ...Pt added material when welded to, AU erosion. In the case of a pre-film conductor, solder is still generated as a result of the soldering of the solder. As described in the Japanese Patent No. 6,3616, it is described as follows: '曰曰本特开平坡璃璃粉,μ2〇·末, Sitt^Pb〇-s仙一(10)~m2〇 3 When the carrier is formed as a thick film conductor and the conductive powder is dispersed, it is called! Bow feldspar (an〇rthit ' and the method of crystallizing the phase of the composition out of the thick film conductor _ _ (6) needle-like sturdy *, the thick film conductor forming glass powder, and in the feldspar In the case of the use of Pb in the lead-free thick film conductor, the presence of Pb is necessary, and the formation and the production are not further described. 323345 7 201213269 Japanese Patent Laid-Open No. Hei 7-97269 Japanese Laid-Open Patent Publication No. 2001-114556 discloses that a composition for forming a thick film conductor containing Si〇2-B2〇3-Ah〇3-CaO-based glass powder and A12〇3 powder is fired. The calcium feldspar is precipitated as a thick film conductor. However, at this time, in order to precipitate a sufficiently large anorthite, since the crystallization temperature is high (the softening temperature of the glass is high), it is required to be 900. (: The above high temperature. When the composition for forming a thick film conductor is fired at a temperature of 900 ° C or higher, since the thick film conductor is excessively fired and the melting point of Ag is low, the electrode made of the Ag thick film conductor is island-shaped. It is difficult to form a problem such as a homogeneous electrode. In Japanese Laid-Open Patent Publication No. 2006-228572, it is disclosed that the glass softening temperature is lowered by using Si〇2-B2〇3-Ah〇3-CaO-Li2 lanthanum glass powder as a glass-based powder. Even if the firing is performed at less than 900 ° C, the anorthite can be uniformly deposited inside the thick film. By this method, a significant improvement in solder corrosion resistance is confirmed, but by the present invention Further evaluation and investigation revealed that the upper electrode of the wafer resistor was formed using a composition for forming a thick film conductor using Ag powder as a main conductive material, and was used in a special environment having a high sulfur gas concentration as described above. In the case of the wafer resistor, it is implied that vulcanization of the upper electrode may occur over time, and further improvement of its vulcanization property is required. [Prior Art Literature] ...
[專利文獻] [專利文獻1]日本特開2004-250308號公報 [專利文獻2]日本特開平7-335402號公報 8 323345 201213269 [專利文獻3]日本特開2〇〇3_224〇〇1號公報 [專利文獻4]日本特開2004-221006號公報 [專利文獻5]日本特開2〇〇2_324428號公報 [專利文獻6]日本特開2〇〇4_327356號公報 [專利文獻7]日本特開平6-223616號公報 [專利文獻8]日本特開平7-97269號公報 [專利文獻9]日本特開200卜114556號公報 [專利文獻ίο]日本特開2〇〇6_22857 【發明内容】 叛 (發明欲解決之課題） 本發明之目的在於以低成本提供 厚膜導體形成用心與， 化物粉末，:導成=導電財、氧 組成物，其射“：至少含有Ag 體形成用 且含有Si〇2-B2〇3、A] ^ p n τ.々末作為則述導電粉末， 為前述氧化物粉末，並:添二粉末作 較佳為相對卜♦刀末作為則述添加物。 為1至10質量份粉末100質量份，前述碳粉末 末為i 勝Ca0_Li2〇系玻璃粉 此外，較佳係前述nA1t CG至„8質量份。 末的組成比’為咖:20至60質.2〇:— a〇-Ll20系破璃粉 Al2〇3 : 2至25質旦。/ Γ Λ 以’祕.2至25質量％， 質里 ％，Ca〇:20 至 5〇 質量 ％，及 Li2〇:〇.5 323345 9 201213269 至6質量％ 〇 本發明中，相對於前述Ag粉末1〇〇質量份，可進一步 添加〇·1至5質量份之選自Au、pdApt的至 導電粉末。 娜马 導電粉末- 、本發明之厚膜導體的特徵為：將上述厚膜導體形成用 ，成物塗佈於陶£基板後，藉由以5GG°C以上且未達議 C之溫度下進行燒製所得，於内 地析出 且前述Li2〇被固定化在約長石。 $長石並 再者’本糾之晶片電阻器，係具備·前述㈣ 二於„亥陶瓷基板上且由上面電極、侧面電極‘ :冓成之内部電極;形成於該陶究基板及該上面= =膜;覆蓋該電阻膜之絕緣破璃 部電極朗所構叙巾㈣極；=則述内 之外部電極之晶片電阻^，I 〔、由^该層所構成 係僅由本發明之厚膜導體所構成。*♦‘、、.至少前述上面電極 (發明之效果） 對材之厚膜導體形成用組成物，係提俾-種僅 對材科下功夫，即可不單防切触 t供種僅 異之無鉛厚膜導體形成用組成物。、’、、化性亦優 件， 的硫化或焊_。此外可 下功夫或使用特殊材料，而具有能夠有效率構造 供如此之硫化或焊料_造叙崎故障少 323345 201213269 之效果。 【實施方式】 本發明之厚膜導體形成用組成物的特徵在於含有 Si〇2-B2〇3-Al2〇3一Ca0_Li2〇系玻璃粉末與Α12〇3粉末，於導電 膏的燒製時，藉由使前述玻璃粉末與Al2〇3粉末反應，可得 到鈣長石均一地析出於厚膜導體内部之厚膜導體。使用該 厚膜導體時’藉由使微量之厚膜導體中的貴金屬熔出於焊 料，鈣長石將以棘狀暴露於厚膜導體的表面。鈣長石為針 狀的結晶，當鈣長石以棘狀暴露於厚臈導體的表面時，焊 料會因表面張力而不會到達貴金屬，所以不會發生焊料侵 名虫。 本發明Τ ..........双喁粉不之外復含 有Ah〇3粉末’是為了實現約長石於厚料體内部的均一析 出之故。亦即’當未將㈣3粉末混合於前述玻璃粉末時， 將導致在所得的相導體與喊基板之界_近多量地析 出舞長石’所以無法充分地得到抑制焊料侵狀效果。因 二為張力使焊料不會到達貴金屬，需使駐 石的棘長度需為^以 藉由祕所暴= 度未達l//m之細料蛀日 較佳為3em以上。長 谭料中移動，導致t”9# t ’簡長騎從厚膜導體中往 舞長石，亦可充分地得到抑制焊料侵韻之效果。 璃粉末與-粉⑽-㈣系玻 出足夠大的鈣長石，J 口％析出。但是，此時為了使析 尚為_t以上的高溫。對此，本發 323345 11 201213269 明中’由於破璃粉末中含有LhO ’故即使在更低溫下亦可 使析出約長石。 本發明中’相對於導電粉末1〇〇質量份，前述Ah〇3 粉末為0.1至8質量份’較佳為〇·5至3質量份。當用作 為氧化物粉末之Ah〇3粉末相對於導電粉末之1〇〇質量份係 少於0.1質量伤時’弼長石的析出變少，變得容易發生焊 料侵蝕。鈣長石為Si、A1與Ca的複合氧化物，尤其當未 充分供給A1時’將不會發生鈣長石的析出。此外，飼長石 的析出對於發揮耐硫化性亦為必要。亦即，即使僅將碳粉 末添加於玻璃粉末，亦無法充分發揮耐.硫化性，唯有藉: 碳粉末的添加與約長石的析出之組合，才可充分發揮^ 化性。另-方面，Al2〇3粉末的添加量大於8質量份時，不 僅使接觸電阻增大’與㈣基板之崎強度亦會降低。 用作為氧化物粉末之Ah〇3粉末的平均粒徑，期望為3 _以下’較佳為〇·5至⑹之範祕粉末的平 均粒徑超過^時，不制長石難以均—地析出於厚 體内部’並且厚膜導體的表面變粗，而有和用以測定電子 零件的特性之探針（prQbe)的接觸電阻增大之疑慮。又， 祕粉末的形狀雖無特別限定，惟就與玻璃粉末之均一混 合化、約長石的均一批ψ於夕作 狀者。 析出化之觀點來看，較佳為球狀或粉 •......... 本發明令，用作為氧化物粉末之·—Β2〇3_Αΐ2〇·—[Patent Document 1] JP-A-2004-250308 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 7-335402 No. 8 323345 201213269 [Patent Document 3] JP-A-2002-3_224 [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. 2-324. [Patent Document 8] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Problem to be Solved The object of the present invention is to provide a thick film conductor forming core and a compound powder at a low cost, which is a conductive material and an oxygen composition, and which emits "at least Ag-containing material and contains Si〇2- B2〇3, A] ^ pn τ. As a conductive powder, it is the above-mentioned oxide powder, and it is preferable to add two powders as the additive. 100 parts by mass of the powder, the carbon powder at the end is i wins Ca0_Li2 bismuth glass In addition, the preferred system to nA1t CG "8 parts by mass. The composition ratio of the end is 'coffee': 20 to 60 mass. 2〇: — a〇-Ll20 is a broken glass powder Al2〇3: 2 to 25 quality denier. / Γ Λ to 'secret. 2 to 25 mass%, mass %, Ca 〇: 20 to 5 〇 mass%, and Li2 〇: 〇.5 323345 9 201213269 to 6 mass% 〇 In the present invention, relative to the aforementioned Ag To the powder of 1 part by mass, 1 to 5 parts by mass of the conductive powder selected from the group consisting of Au and pdApt may be further added. Nama Conductive Powder - The thick film conductor of the present invention is characterized in that the thick film conductor is formed, and the product is applied to a ceramic substrate, and is then carried out at a temperature of 5 GG ° C or higher and not at C temperature. The fired product was precipitated in the interior and the Li 2 lanthanum was immobilized on about feldspar. $ feldspar and again 'this correcting chip resistor, is equipped with the above (four) two on the hai ceramic substrate and from the upper electrode, the side electrode ': the internal electrode of the ;; formed on the ceramic substrate and the above = = film; the insulating glass portion of the resistive film is covered by the electrode (four) pole; = the chip resistance of the outer electrode is ^, I [, consists of the layer only by the thick film conductor of the present invention The composition of the above-mentioned upper electrode (the effect of the invention) is a composition for forming a thick film conductor of a material, and it is only for the material of the material, that is, not only the anti-cutting t-species It is only a composition for forming lead-free thick film conductors, ', and is also excellent in vulcanization or soldering. It can be used with special materials, and has an efficient structure for such vulcanization or soldering_ [Embodiment] The composition for forming a thick film conductor of the present invention is characterized by containing Si〇2-B2〇3-Al2〇3-Ca0_Li2 bismuth-based glass powder and Α12〇3 powder. When the conductive paste is fired, by making the aforementioned glass The glass powder reacts with the Al2〇3 powder to obtain a thick film conductor in which the anorthite is uniformly deposited inside the thick film conductor. When the thick film conductor is used, 'by melting a small amount of precious metal in the thick film conductor out of the solder, calcium The feldspar will be exposed to the surface of the thick film conductor in a spinous shape. The anorthite is a needle-like crystal. When the anorthite is exposed to the surface of the thick tantalum conductor in a ratchet shape, the solder will not reach the precious metal due to the surface tension, so it will not The occurrence of solder invading insects. The present invention Τ ..... bismuth powder does not contain Ah 〇 3 powder 'in order to achieve uniform precipitation of feldspar inside the thick material. When the powder of the (4) 3 is not mixed with the glass powder, the dance feldspar is precipitated in the vicinity of the obtained phase conductor and the substrate. Therefore, the effect of suppressing the solder intrusion cannot be sufficiently obtained. If you don't reach the precious metal, you need to make the length of the spine of the stone to be ^ by the secret violence = less than l / / m of fine material, preferably more than 3em. The long tan in the movement, resulting in t"9 # t '简长骑from the thick film conductor to the dancing feldspar, can also The effect of suppressing solder intrusion is sufficiently obtained. The glass powder and the powder (10)-(iv) are made of a large enough anorthite, and the J-portion is precipitated. However, at this time, in order to cause the precipitation to be a high temperature of _t or more. In this regard, the present invention discloses that the feldspar can be precipitated even at a lower temperature because the Lhr is contained in the broken glass powder. In the present invention, the aforementioned Ah 3 powder is 0.1 to 8 parts by mass, preferably 5 to 3 parts by mass, per part by mass of the conductive powder. When the amount of the Ah 〇 3 powder used as the oxide powder is less than 0.1 mass part with respect to 1 part by mass of the conductive powder, precipitation of celsian feldspar becomes small, and solder erosion is likely to occur. The anorthite is a composite oxide of Si, A1 and Ca, and especially when A1 is not sufficiently supplied, precipitation of anorthite will not occur. In addition, precipitation of feldspar is also necessary to exert sulfidation resistance. In other words, even if only the carbon powder is added to the glass powder, the vulcanization resistance cannot be sufficiently exhibited, and only the combination of the addition of the carbon powder and the precipitation of the feldspar can fully exert the chemical properties. On the other hand, when the amount of the Al2〇3 powder added is more than 8 parts by mass, not only the contact resistance is increased, but also the (s) substrate strength is lowered. When the average particle diameter of the Ah 〇 3 powder used as the oxide powder is desirably 3 Å or less, it is preferable that the average particle diameter of the 秘 5 to (6) virgin powder exceeds ^, and it is difficult to uniformly precipitate the feldspar. The inside of the thick body is thicker and the surface of the thick film conductor is thicker, and there is a concern that the contact resistance of the probe (prQbe) for measuring the characteristics of the electronic component is increased. Further, the shape of the secret powder is not particularly limited, but it is uniformly mixed with the glass powder, and a group of feldspars are used in the evening. From the viewpoint of precipitation, it is preferably spherical or powder..... The present invention is used as an oxide powder - Β2〇3_Αΐ2〇·-
Ll2〇.«^^tb,^i4si〇 ，㈣質《偷2至25質量%翁= 323345 12 201213269 質量％，及Li2〇 : ο. 5至6質量％。 玻璃粉末的組成中，當SiCb少於2〇質量％時，無法充 分供給Si，會難以析出鈣長石而有無法防止焊料侵蝕及硫 化之疑慮。此外，厚膜導體中之玻璃的耐候性、耐水性及 耐酸性有降低之疑慮。另一方面，當81〇2較6〇質量％多時， 玻璃的軟化溫度變得過高，而有鈣長石的析出溫度增高之 傾向。 當B2〇3少於2質量％時，玻璃的軟化溫度有變得過高之 傾向。此外’厚膜導體的玻璃將容易變脆。另一方面，當 B2〇3較25質量％多時’玻璃容易進行分相，厚膜導體中之玻 璃的耐候性、耐水性及耐酸性亦有降低之疑慮。 玻璃粉末的組成中，當Al2〇3少於2質量％時，同樣變 得難以析出鈣長石，此外，厚膜導體中的玻璃容易進行分 相。另一方面，當Al2〇3較25質量％多時，玻璃的軟化溫度 變付過向’而有弼長石的析出溫度變得過高之疑慮。 當CaO少於20質量％時，Ca的供给不充分，將難以析 出妈長石。另一方面’當CaO較50質量％多時，將不易玻 璃化。 L i 2〇具有降低玻璃的軟化溫度之作用，若增加破璃的 軟化溫度的含量，可對應增加的含量而使鈣長石的結晶大 幅成長。因此，玻璃粉末的組成中，當LiA少於〇. i質量 %時，不易以較低溫度使鈣長石析出，此外，所析出之鈣長 石的大小亦容易變小。另一方面，當Li2〇較10質量％多時， 玻璃的耐候性、时水性及对酸性有降低之疑慮。又，當U2〇 323345 13 201213269 於4至6質量％的範圍内時，即使厚膜導體形成用組成物中 所含有之玻璃粉末的含量為少，亦不會損及所得之厚膜導 體的焊料侵餘性’可提升該黏著強度。 本發明之Si〇2-B2〇3-Al2〇3-CaO-Li2〇系玻璃粉末的組成 比中，LhO幾乎完全被納入於膏體燒製中所析出之鈣長石 中而被固定化。因此，即使所形成之電極間具有電位差， U離子亦不會產生遷移。 本發明中所使用之玻璃粉末為Si〇2_B2〇3_Ah〇3_Ca〇_U2() 系，但該組成中亦可含有其他成分，可因應軟化點、耐酸 性等’適當地選擇並含有ZnO、BaO、Ti〇2、Zr〇2、Bi2〇3、 CuO、Mn〇2等成分。 本發明中’Si〇2-B2〇3-Al2〇3-CaO-Li2〇系玻璃粉末的平 均粒從，期望為1 〇 # m以下，較佳為3至之範圍内。 平均粒徑為l〇/zm以上時，玻璃粉末的軟化變慢，而有電 極膜與基板之黏著強度降低之傾向，故不佳。 本發明中’Si〇2-B2〇3-Al2〇3-CaO-Li2〇系玻璃粉末的添 加量’相對於導電粉末1〇〇質量份為〇. 1至15質量份，較 佳為3至8質篁份。當Si〇2-B2〇3_Al2〇3-CaO-Li2〇系玻璃粉 末相對於導電粉末100質量份少於0. 1質量份時，與陶究 基板之黏著強度會降低。此外，變得無法充分地供給用於 辑長石析出之材料。另一方面’當較15質量份多時，不僅 厚膜導體的電阻值會增高，且會有玻璃浮於厚膜導體的表 面、覆鍍性、焊料潤濕性、以及和用以進行特性評估之探 針的接觸電阻劣化之疑慮。 14 323345 201213269 可使用選自Au、Ag、Pd及p 作為導電粉末。由於本發明為七的至夕1種責金屬粉末 發明的對象為至少含有Ag之導人^止Ag的硫化者，所以本 復包含選“u，及Pt的至導I電粉末。但是’可於^中 金屬的添加，作為導電材料乃二種貴金屬粉末。此等貴 及耐硫化性之作用。但是，此、提升Ag的耐焊料侵錄 但為昂貴的貴金屬，所以本發責金屬的财硫化性雖強’ 低此般昂貴金屬的含有率，而^目的在於供給一種可降 臈導體形成用組成物。因此，^勺以低成本進行提供之厚 的Ag作為導電粉末，當需進發明中’可僅使用低成本 加此等貴金屬，較佳為Pd或~^提高财硫化性時，可再添 為相對於Ag的1〇〇 f量份為’尤其就玲成本方面來看， 又，藉由Pd等的添加來抑η量:的Pd。 •量如下：Ag的硫化是由於來自g、爪之理由，可考 當將Ag與Pd等進行合金化時：卜：的s之擴散所引起’ 散至硫化表面，使魏物正從合金表面逐漸擴 富含貴金屬相（N〇ble metal^ 5金科變化為Pd等之 進行，其硫化速度減緩。⑽咖），故隨著硫化的 體中然與玻璃成分的混合體之厚膜導 Γ且添加量所影響，故如周知，正不斷朝藉由 =成物的探討來實現低成本及低Pd化㈣方向進行研 Z亦即’本發_未添加Pd而僅以Ag的組成來作為導 1末時’即可提供㈣發料硫錄之導體形成用 323345 15 201213269 組成物的觀點來看，乃具有顯著效果者。 導電粉末的平均粒徑，就繞製性之觀點來看，較佳為 - 10ym以下。導電粉末的形狀可採用粒狀、片狀等任意形 -狀，並可混合使用。當中，粉狀導電粉末的平均粒徑，就 燒製性之觀點來看，期望較佳為〇. 1至2//m。 本發明中，特徵在於相對於導電粉末1〇〇質量份復添 加碳粉末1至10質量份，較佳為僅添加3至7質量份之點^ 由於碳粉末具有導電性，所以就廣義之導電膏領域中，係 用作為導電粉末之材料。但是，因為在使用 : 厚膜導體形成用組成物中，僅用作為導電材料之^獨添 加，係會使所狀賴導_柄導舰Μ至包含黏^ 強度之電極性能降低者’故通常並不添加。此外，春單 碳粉末作為以Ag作為㈣粉末的讀料但未形成二長石 之厚膜導體形成用組成物的材料而進行添加 當地防止Ag的硫化。 ‘，套適 經由本發明者的反覆摸索及試驗，可確認到： ，末、氧化物粉末、及有機载體所構成之厚 且成二，係至少含有Ag粉末作為前迷導電粉末;;^ s.祕-祕餐Li2G系麵粉末與Αι⑽末 氧化物粉末之厚膜導體形成用組成物中，藉由進—步2 碳粉末作驗加物，可提相得之厚膜導體的耐硫化性。 在確認該效果後，對添加#碳粉末之相導體形成用植成 物於燒製後之電極臈的剖面構造進行觀察後，；^ 發現。 h ^ 323345 16 201213269 - 亦即，所添加之碳粉末係因該作用而對組成物中之 . 璃粉末的熔融動作造成影響’藉由玻璃熔融而黏性降低， 抑制該玻璃移動至與陶竟基板之界面上。藉此，在择心 之電極膜的剖面觀察中，於作為導體之^祕質中，後 的鈣長石結晶與非晶質的玻璃成分係均一地析出為網狀 狀，成為Ag與玻璃氧化物複合化之特殊的骐構造。_目 般構造之理由雖尚未明瞭，但可考量為：該膜構在= 有Ag之電極縣露在硫化環境時，於藉由硫的擴散從3 表面所進行之硫化銀的生成過程中，可抑制硫的擴δ 者。又’由於碳在燒製途中與氧結合成為CG而分解，所= 在燒製後的膜構造中，可考量其絕大部分會消失。 本毛明中所使用之碳粉末的種類、形狀及大小並 別限定’可使用市售作為碳印墨（earbQn地）用途之一般 製品。此般製品中之碳粉末的平均粒徑，以位於㈣ 0·5ρ之範_者為多。由於需均一地分散於膏體中，故 較佳為使用0. 1 左右的粉末。 此外，關於石反粉末的添加量，相對於導電粉末⑽質 量份為1至1G質量份，較佳為3至7質量份。少於！質量 份時’無法充分提升所得之厚料體的耐硫化性。添加 質量Μ上時’燒製_緊密性降低，與喊基板之黏著 強度降低，故不佳。 其他作為厚膜導體形成用組成物的材料之有機載體， 與以往相同，可使用將乙基纖維素' 曱基丙稀酸醋等溶解 於松油醇（Τ6ΓΡίηΘ〇1)、丁基卡必醇（Butyl carbitoi)等之 323345 17 201213269 溶劑而成者ο 道础又ί發明中，除了上述材料粉末之外’以提升厚膜 導體的黏著強度或谭料潤满 、 用之夂絲W職㈣目的，可添加以往所使 用末，例如 Bi203、Si02、Cu0、Zr0 化物粉末。 γ〜礼 W本么月之厚膜導體的特徵，在於將上述本發明之厚膜 導體形成驗成物塗佈於 Η之厚膜 9〇om * 域’以5(Hrc以上未達 =?為以8机至87〇°e之溫度 :;長石 出輪’且前述Li2〇為被固定化在 適用厚膜導體’除了晶片電阻器之外，可適當地 適用在電阻網路、混成IC等之電子零件的電極。尤其 明可=當地適用在晶片電阻器’其係具備：陶瓷基板；形 ^以陶^基板上且由上面電極、侧面電極與内面電極所 4之内j電極；形成於該陶竞基板及該上面電極上之電 阻膜；覆蓋該電阻膜之絕緣玻璃保護膜；由覆蓋前述内部 電極之以錢層所構成之中間電極；與由焊料鍍層所構叙 外部電極之晶片電阻器。亦即，此般晶片電阻器有時會使 用在，性環境等之韻度高的特殊環境卜本發明之：片 電阻益中，至少内部電極中的上面電極僅 ..導體所構成，不雲淼田甘从田, 门〈厚膜 蚀用特心道 其 硫化之構造’亦不需 ^㈣粉末㈣’ β卩使在特殊如韻境下亦可有 效地防止電極的硫化。 了有 又以曰曰片電阻器等之電子零件中形成有厚膜導體之 323345 18 201213269 陶究基板而言，可使用氧化紹基板，尤其為高純度的氧化 銘基板，惟除此之外，亦可適合使用氧化錯基板等。關於 其他構成要素’可使用以往所知之材料來製作，故在 略詳細說明。 (實施例） (玻璃粉末之組成） 表1係顯示6種類之玻璃粉末的組成比（質量…此 當中’玻璃粉末A、B、C、F囊括於本發明之組成範圍。 一方面’玻璃粉末D不含LhO，破璃粉末E不含Ca〇，八 別為本發明之組成範圍外。 刀 (厚膜導體形成用組成物之製作） 相對於由平均粒徑L 5//m的粒狀Ag粉末、 徑〇.1_的粒狀Pd粉末所構成之導電粉末，^立 之組成，將平均粒徑3㈣的玻璃粉末斤示 的則3粉末、平均粒徑0.W炭粉末、與使乙義5输: 素树脂溶解於松油醇溶液所得之有機載體進行混人^維 3報磨機進行揉和，藉此製作出膏狀之厚膜導體 == 粉末與Μ粉末的合計所構成之導電粉末： “十直作為_質量份，將有機載體 =的 雷於太咖所田、 材科’係設為相對於邋 電如末刚貝1份為表2所記載之質量份。 、導 將所製作之厚膜導體形成用組成 銘基板上進行網版印刷，並以15代=質=的氣化 中將乾燥的基板於峰值溫度 850 C進行:分二，绅、’、、爐· 323345 19 201213269 30:¾½境製，形成既定圖案的厚膜導體膜。 所得之厚膜導體的膜厚評估，係藉由使用觸針型的膜 厚計對2. 0ramx2. Omm的電極墊（pad)進行測定。 面積電阻值的評估，係藉由數位萬用電表來測定寬度 ^5ηιιη、長度50_之導體圖案的電阻值，並將所得之值換 鼻為面積電阻值來進行。 耐焊料侵蝕性的評估係以下列方式進行。首先，使用 燒製為寬度0. 5咖、長度50mm之厚膜導體，於保持在27〇 。〇之96.5質量％ Sn-3質量％ Ag_〇 5 f量％ &組成之絲 焊料浴中浸潰10秒後，測定電阻值，以此操作為i次，並 重複進行該操作。當卿彳得的電阻值成為，便 確認焊料侵㈣發生，計算至焊料舰發生為止之次數， 亦即至所測得的電阻值成為㈣以上為止之重複次數，以 此作為耐焊料侵純_估。以重複次數超 好（〇），12次以下者為不良（小 —者為良 此外，耐硫化性的評估係以下列方式進行。為了得到 硫性環境’係採用將市售的機械切肖彳·（含有硫 8〇°C ’將所燒製的電極基板浸潰歸置於糾巾，以促進 評估所使用之機械切削用油的硫份與氣份之 二二量_’全部氯份為23.2㈣ ^爾侵錄的評估，制同樣燒製為寬度q· 5賴、 械厚膜導體，首先測定起始的面積電阻值。將前 述機械切削Μ歸在齡，並將前述相導體燒製基板 323345 20 201213269 以暴露出電極之狀態浸潰於該油中，每隔30分鐘取出基板 並測定面積電阻值。由於切削油中的硫會使電極硫化而從 銀色轉黑’故亦可以目視來確認硫化的狀態。耐硫化性的 判定方法，係確認浸潰油之後至面積電阻值成為1Ω/□以Ll2〇.«^^tb,^i4si〇, (four) quality "steal 2 to 25 mass% Weng = 323345 12 201213269 mass%, and Li2〇: ο. 5 to 6 mass%. In the composition of the glass powder, when the amount of SiCb is less than 2% by mass, Si cannot be sufficiently supplied, and it is difficult to precipitate anorthite, and there is a fear that solder corrosion and sulfurization cannot be prevented. In addition, the weather resistance, water resistance and acid resistance of the glass in the thick film conductor are lowered. On the other hand, when 81〇2 is more than 6% by mass, the softening temperature of the glass becomes too high, and the precipitation temperature of the anorthite tends to increase. When B2〇3 is less than 2% by mass, the softening temperature of the glass tends to become too high. In addition, the glass of the thick film conductor will easily become brittle. On the other hand, when B2〇3 is more than 25% by mass, the glass is easily phase-separated, and the weather resistance, water resistance and acid resistance of the glass in the thick film conductor are also lowered. In the composition of the glass powder, when Al2?3 is less than 2% by mass, it is also difficult to precipitate anorthite, and the glass in the thick film conductor is easily separated. On the other hand, when the amount of Al2〇3 is more than 25% by mass, the softening temperature of the glass becomes excessively large, and the precipitation temperature of the celsian feldspar becomes excessively high. When the CaO is less than 20% by mass, the supply of Ca is insufficient, and it is difficult to precipitate the feldspar. On the other hand, when CaO is more than 50% by mass, it is difficult to be vitrified. L i 2〇 has an effect of lowering the softening temperature of the glass. When the content of the softening temperature of the glass is increased, the crystal of the anorthite can be greatly increased in accordance with the increased content. Therefore, in the composition of the glass powder, when LiA is less than 0.1% by mass, it is difficult to precipitate the anorthite at a relatively low temperature, and the size of the precipitated anorthite is also likely to be small. On the other hand, when Li2 is more than 10% by mass, the weather resistance, water repellency, and acidity of the glass are lowered. Further, when U2〇323345 13 201213269 is in the range of 4 to 6 mass%, even if the content of the glass powder contained in the thick film conductor forming composition is small, the solder of the obtained thick film conductor is not damaged. Invasiveness can increase the adhesion strength. In the composition ratio of the Si〇2-B2〇3-Al2〇3-CaO-Li2 lanthanide-based glass powder of the present invention, LhO is almost completely incorporated into the anorthite precipitated in the paste firing and fixed. Therefore, even if there is a potential difference between the electrodes formed, U ions do not migrate. The glass powder used in the present invention is Si〇2_B2〇3_Ah〇3_Ca〇_U2(), but the composition may contain other components, and may appropriately select and contain ZnO, BaO in view of softening point, acid resistance, and the like. , Ti〇2, Zr〇2, Bi2〇3, CuO, Mn〇2 and other components. In the present invention, the average particle size of the 'Si〇2-B2〇3-Al2〇3-CaO-Li2 lanthanide-based glass powder is desirably 1 〇 # m or less, preferably 3 to 10,000. When the average particle diameter is l〇/zm or more, the softening of the glass powder is slow, and the adhesion strength between the electrode film and the substrate tends to be lowered, which is not preferable. In the present invention, the amount of 'Si〇2-B2〇3-Al2〇3-CaO-Li2 lanthanide-based glass powder is '1 to 15 parts by mass, preferably 3 to 1 part by mass relative to the conductive powder. 8 quality 篁. When the Si〇2-B2〇3_Al2〇3-CaO-Li2 lanthanide glass powder is less than 0.1 part by mass relative to 100 parts by mass of the conductive powder, the adhesion strength to the ceramic substrate is lowered. Further, it becomes impossible to sufficiently supply the material for the precipitation of the feldspar. On the other hand, when the amount is more than 15 parts by mass, not only the resistance value of the thick film conductor will increase, but also the surface of the glass floating on the thick film conductor, the plating property, the solder wettability, and the evaluation of the characteristics. The contact resistance of the probe is degraded. 14 323345 201213269 A conductive powder selected from the group consisting of Au, Ag, Pd and p can be used. Since the present invention is a material of the seventh invention, the object of the invention is a vulcanization agent containing at least Ag, and therefore, the inclusion of "u, and Pt to the electro-powder." The addition of metal in the middle of the metal, as a conductive material is two kinds of precious metal powder. These are expensive and resistant to sulfidation. However, this improves the solder resistance of Ag but is expensive precious metal, so this is responsible for the metal Although the vulcanization is strong, the content of the expensive metal is low, and the purpose is to supply a composition for forming a reduced antimony conductor. Therefore, the thick Ag is supplied as a conductive powder at a low cost, and it is necessary to enter the invention. In the middle of 'only low-cost addition of such precious metals, preferably Pd or ~ ^ to improve the vulcanization, can be added to the amount of 1〇〇f relative to Ag is 'in particular, in terms of cost, The Pd is suppressed by the addition of Pd, etc. • The amount is as follows: The vulcanization of Ag is due to the reason of g and claws, and it is possible to alloy Ag and Pd, etc.: Caused by the scattering to the vulcanized surface, so that the Wei material is gradually expanding from the surface of the alloy It is rich in precious metal phase (N〇ble metal^ 5 is changed to Pd, etc., and its vulcanization rate is slowed down. (10) Coffee), so thick film is introduced and added with the mixture of vulcanized body and glass component. The amount is affected, so as is well known, the low-cost and low-Pd (four) direction is being studied by the discussion of the object, that is, the 'this hair _ is not added Pd but only the composition of Ag is used as the guide 1 At the end of time, it is possible to provide (4) conductor formation for the emission of sulfur. 323345 15 201213269 The composition has a significant effect. The average particle diameter of the conductive powder is preferably from the viewpoint of the winding property. The shape of the conductive powder may be any shape of a granular shape, a sheet shape, or the like, and may be used in combination. Among them, the average particle diameter of the powdery conductive powder is preferably from the viewpoint of fireability. In the present invention, it is characterized in that 1 to 10 parts by mass, more preferably only 3 to 7 parts by mass, of the carbon powder is added to 1 part by mass of the conductive powder. The powder is electrically conductive, so it is used as a guide in the field of conductive pastes in a broad sense. The material of the powder. However, because it is used in the composition for forming thick film conductors, it is only used as a conductive material, which will reduce the performance of the electrode to the electrode containing the adhesive strength. In addition, the spring single carbon powder is added as a material for forming a composition for forming a thick film conductor which does not form a feldspar with Ag as a material for reading the powder of (4) powder, and is locally added to prevent the vulcanization of Ag. According to the inventors of the present invention, it can be confirmed that: the end, the oxide powder, and the organic carrier are thick and formed, and at least contain Ag powder as the conductive powder; s. The thick-film conductor forming composition of the secret-secret Li2G base powder and the Αι(10) terminal oxide powder can be obtained by the step 2 carbon powder as an additive, and the sulfidation resistance of the thick film conductor can be obtained. . After confirming the effect, the cross-sectional structure of the electrode crucible after the formation of the phase-forming conductor of the carbon powder was observed, and then found. h ^ 323345 16 201213269 - that is, the added carbon powder has an effect on the melting action of the glass powder in the composition by the action 'the viscosity is lowered by the melting of the glass, and the glass is prevented from moving to the ceramic On the interface of the substrate. Therefore, in the cross-sectional observation of the electrode film of the selected one, in the secret of the conductor, the later anorthite crystal and the amorphous glass component are uniformly precipitated into a network shape, and become Ag and glass oxide. A special 骐 structure that is compounded. Although the reason for the _ mesh structure is not clear, it can be considered as follows: when the film is in the vulcanized environment, the electrode is formed in the formation of silver sulfide from the surface of the 3 by the diffusion of sulfur. It can inhibit the expansion of sulfur. Further, since carbon is decomposed by the combination of oxygen and CG in the middle of firing, it is considered that most of the film structure after firing is lost. The type, shape and size of the carbon powder used in the present invention are not limited to 'a general product which is commercially available as a carbon ink (earbQn). The average particle size of the carbon powder in such a product is more than the range of (4) 0·5ρ. The powder of about 0.1 is preferably used because it needs to be uniformly dispersed in the paste. Further, the amount of the stone inverse powder to be added is 1 to 1 G by mass, preferably 3 to 7 parts by mass, based on the mass of the conductive powder (10). less than! When the mass is used, the sulfidation resistance of the obtained thick material cannot be sufficiently improved. When the mass is added, the firing degree is lowered, and the adhesion strength to the substrate is lowered, which is not preferable. Other organic materials which are materials for forming a thick film conductor can be used in the same manner as in the related art, and ethyl cellulose 'mercapto acryl vinegar or the like can be dissolved in terpineol (Τ6ΓΡίηΘ〇1), butyl carbitol. (Butyl carbitoi), etc. 323345 17 201213269 Solvent-derived ο Dao and 发明Invention, in addition to the above-mentioned material powder, 'to enhance the adhesion strength of thick-film conductors or to fill up the tan, use the silk W (4) purpose It is possible to add a conventionally used terminal such as Bi203, SiO 2 , Cu 0 or Zr0 compound powder. The characteristic of the thick film conductor of γ 礼 本 本 在于 在于 在于 在于 在于 本 本 本 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚 厚The temperature is from 8 to 87 〇 °: feldspar exit wheel 'and the above Li2 〇 is fixed to the thick film conductor'. In addition to the chip resistor, it can be suitably applied to a resistor network, a hybrid IC, or the like. The electrode of the electronic component, in particular, is applicable locally to the wafer resistor 'which has a ceramic substrate; the shape is on the ceramic substrate and is composed of the upper electrode, the side electrode and the inner electrode 4; a ceramic substrate and a resistive film on the upper electrode; an insulating glass protective film covering the resistive film; an intermediate electrode formed by a layer of money covering the internal electrode; and a chip resistor constituting an external electrode by a solder plating layer That is to say, such a chip resistor is sometimes used in a special environment with a high degree of rhyme, such as a sexual environment. In the sheet resistance benefit, at least the upper electrode in the internal electrode is composed only of a conductor, not Yuntian Tian Gan from the field, the door < thick eclipse The structure of the vulcanization of the special heart does not need to be (4) powder (4) 'β卩 makes it possible to effectively prevent the vulcanization of the electrode in special circumstances such as the rhyme. Thick film conductor 323345 18 201213269 For the ceramic substrate, it is possible to use a oxidized substrate, especially a high-purity oxidized substrate, but it is also suitable for use with an oxidized substrate or the like. (Prepare) (Composition) (Composition of glass powder) Table 1 shows the composition ratio of six types of glass powders (mass... among them, 'glass powders A, B, C, F is included in the composition range of the present invention. On the one hand, 'glass powder D does not contain LhO, and glass powder E does not contain Ca 〇, and eight is outside the composition range of the invention. Knife (manufacture of a composition for forming a thick film conductor) The conductive powder composed of the granular Ag powder having an average particle diameter L 5//m and the granular Pd powder having a diameter of 11_, and the composition of the glass powder having an average particle diameter of 3 (four) 3 powder, average particle size 0. W carbon powder, The organic carrier obtained by dissolving the cytosolic resin in the terpineol solution is mixed with a micro-reporter to prepare a thick film conductor of the cream == the total of the powder and the bismuth powder Conductive powder consisting of: "Ten straight as _ mass parts, the organic carrier = Lei Yutai, Tianke, and the family" are set to the mass parts as shown in Table 2 with respect to 1 part of the sputum. Screen printing on the substrate of the thick film conductor formed by the guide, and drying the substrate at a peak temperature of 850 C in 15 gasification = mass = 2, 绅, ', , furnace · 323345 19 201213269 30: 3⁄41⁄2 environment, forming a thick film conductor film of a predetermined pattern. The measurement of the film thickness of the obtained thick film conductor was carried out by using a stylus type film thickness meter to measure an electrode pad of 2.0 mmx2. The area resistance value is evaluated by measuring the resistance value of the conductor pattern of the width ^5 η ιη, length 50 _ by a digital multimeter, and changing the value to the area resistance value. The evaluation of solder erosion resistance was carried out in the following manner. First, a thick film conductor fired to a width of 0.5 coffee and a length of 50 mm was used, and was kept at 27 。. 96.5 mass% Sn-3 mass% Ag_〇 5 f quantity % & composition of the wire After immersing in the solder bath for 10 seconds, the resistance value was measured, and this operation was performed i times, and this operation was repeated. When the resistance value of the 彳 彳 is confirmed, it is confirmed that the solder intrusion (4) occurs, and the number of times until the occurrence of the solder ship is calculated, that is, the number of repetitions until the measured resistance value becomes (4) or more, as the solder penetration intensive estimate. The number of repetitions is super good (〇), and those of 12 or less are bad (small---------------------------------------------------------------------------------------------------------------------------------------------------------------------- · (containing sulfur 8 〇 ° ° ° ° The electrode substrate is immersed in the correction towel to promote the evaluation of the amount of sulfur and gas used in the mechanical cutting oil used _ 'all chlorine 23.2 (4) The evaluation of the intrusion, the system is also fired into a width q·5 Lai, mechanical thick film conductor, first measure the initial area resistance value. The above mechanical cutting is attributed to the age, and the phase conductor is fired. Substrate 323345 20 201213269 The substrate is immersed in the oil in the state where the electrode is exposed, and the substrate is taken out every 30 minutes to measure the area resistance value. Since the sulfur in the cutting oil vulcanizes the electrode and turns from silver to black, it can also be visually observed. The state of vulcanization was confirmed. The method for determining the sulphur resistance was confirmed to be 1 Ω/□ after the oil was immersed until the area resistance value was 1 Ω/□.
上為止所耗的時間，以浸潰12小時後面積電阻值未達1Q /□者為良好（〇），1Ω/□以上者為不良（χ)。 黏著強度的評估，係藉由使用96. 5質量％ Sn-3質量％The time taken up until the time when the area resistance value is less than 1Q /□ after 12 hours of immersion is good (〇), and 1 Ω/□ or more is bad (χ). 5质量质量的质量-3质量% By the use of 96.5 mass% Sn-3 mass%
Ag-0.5質量％Cu組成之無鉛焊料，將直徑〇 65mm的％鍍 層銅線焊接於2. 〇mmx2. 〇mm之圖案的厚膜導體上後，往垂 直方向拉伸以使剝離，並測定出剝離時的拉伸力來進行。 [表1] 組成比（質量》) Si〇2 B2〇3 AlzOa CaO Ll2〇3 BaO Zr〇j 5i：〇3 CuO ΜηΓΚ 玻璃粉末A 38. 0 8. 0 15.0 38. 0 1. 0 - 一 一 本發明 玻璃粉束B 38. 0 8. 0 15.0 37. 0 2. 0 — - 一 一 K. iS Pi 本發明 範圍内 玻璃粉末C 40. 〇 5.0 16.0 33. 0 6.0 - - - 一 本發明 範面内 玻璃粉末D 一40. 0 12. 0 13. 0 33. 0 — — 2. 0 —-- 破項粉未t —---- 玻璃粉末P 一45· 0 13.0 5.0 — 2. 0 35. 0 - 一 範圍外 29. 2 4. 7 14.6 23. 3 1.4 — 18. 〇 *—---- 7.0 1.8 耗SJ外 本發明 範面内 ----J, (實施例1至3、比較例1至3) 如表2所示，將Ag粉末與Pd粉末的比率 =3广，將碳粉末的添加量設為相對於導電粉末二 ^為4. Of量份，將齡粉末的添加量係使用玻璃粉 末、b、c、d、e，將該添加量設為3 〇至5 〇質量份之 323345 21 201213269 =:改1各材料的組合及該添加量，製作出膏狀厚膜導 體^成用組成物。所測得之厚膜導體的膜厚、面積電阻值、 黏者強度、郎料侵祕及耐魏性的結果及該評估，分 別如表2所示。 番於2實施例1的玻璃粉末A，將該添加量設為5·〇質 =戶:寻之厚膜導體即使浸潰於焊料12次，該面積電阻值 r:/口以下’未產生斷線，耐焊料侵刪異。此 == 化性，浸潰於含硫的油中12小時後之面積電 :二，耐硫化性亦優異。此外，黏著強度為 ’:可^到作為晶片電阻器的電極用途之充分的強度。 =實施例2的玻璃粉末Β，並將該添加量設為4 〇 厚膜導體;以及使用實施例3的玻璃粉末C 樣::: =為3.”量份所得之厚膜導體，皆得到同 璃/in例1之本發明的組成範圍外且不含u2〇之玻 私末卜㈣添加量設為5Q f量份所得之厚膜 進行第4次的焊料槽浸㈣，面積電阻值成為㈣ 上，耐焊料侵蝕性為差。此 = 以 中2小時後之_阻值為二::硫：：油 採用如比較例1之使用不含以⑷之玻璃粉 。 面得之厚膜導體中，因為在未達9Q『c的燒=溫^成物 長石無法於厚膜導體中充分地析出及成長〜約 導體叫連Pd亦完全被焊輸。從該4=膜 可促進—及成長。此外亦可理解::::= 323345 22 201213269 性的顯現亦需鈣長石的析出。 同樣的，採用比較例2之本發明的組成範圍外之玻璃 ^末E ’將該添加量設為5. G質量份所得之厚膜導體在進 行第2 -人的焊料槽浸潰後，面積電阻值成為 lkQ/[2 以上， 心貝於油中1.5小時後之面積電阻值為1Ω/[=]以上，财煤 料侵蝕性、耐硫化性均差。 即使係採用如比較例2之使用不含CaO之玻續粉末的 組成物而得之厚膜導體，未供給Ca，於厚膜導體中未析出 、弓長石了理解為耐焊料侵钮性及财硫化性之效果均未發 揮。 採用比較例3之位於本發明的組成範圍之破鴇粉末 A ’將該添加量設為5. 〇 f量份即使未添加A·粉末所得 之厚膜導H，在第2 :欠的焊觸浸潰後，面積電阻值成為 = Ω/〇以上，浸潰於油中8小時後之面積電阻值為1Ω/ 以上，耐焊料侵餃性、耐硫化性均差。 如比較例3所示，採用不含Ah〇3粉末，僅由玻璃粉末 構成之組成物作為氧化物粉末材料而得之厚膜導體中， ^厚膜導體巾未均—地析出㉙長石，*集巾地析出於厚膜 體與氧化基板之界面部’可理解㈣焊料侵純及耐 硫化性之效果均未發揮。 323345 23 201213269 [表2]A lead-free solder composed of Ag-0.5 mass% Cu, a %-coated copper wire having a diameter of 〇65 mm is welded to a thick film conductor of a pattern of 〇mmx2. 〇mm, and then stretched in the vertical direction to be peeled off, and measured. The tensile force at the time of peeling is performed. [Table 1] Composition ratio (mass) Si〇2 B2〇3 AlzOa CaO Ll2〇3 BaO Zr〇j 5i: 〇3 CuO ΜηΓΚ Glass powder A 38. 0 8. 0 15.0 38. 0 1. 0 - one by one The glass powder bundle B 38. 0 8. 0 15.0 37. 0 2. 0 — - one K. iS Pi The glass powder C 40 within the scope of the invention 〇 5.0 16.0 33. 0 6.0 - - - A van of the invention In-plane glass powder D - 40. 0 12. 0 13. 0 33. 0 — — 2. 0 —-- Breaking powder is not t —---- Glass powder P -45· 0 13.0 5.0 — 2. 0 35 0 - an out-of-range 29. 2 4. 7 14.6 23. 3 1.4 — 18. 〇*—---- 7.0 1.8 consuming SJ outside the scope of the invention----J, (Examples 1 to 3, Comparative Examples 1 to 3) As shown in Table 2, the ratio of the Ag powder to the Pd powder was 3, and the amount of the carbon powder added was set to 4. The amount of the powder relative to the conductive powder. The addition amount is a glass powder, b, c, d, and e, and the addition amount is 323 345 of the mass of 3 〇 to 5 21. 21 201213269 =: Change the combination of each material and the amount of the addition to make a thick paste. The film conductor is used as a composition. The results of the measured film thickness, area resistance value, adhesive strength, invasiveness and resistance to Wei of the thick film conductor and the evaluation are shown in Table 2. In the glass powder A of the first embodiment, the amount of addition is set to 5. 〇 = = =: If the thick film conductor is immersed in the solder 12 times, the area resistance value r: / or less is not broken. Wire, resistant to soldering. This == chemical, the area of electricity after 12 hours of immersion in sulfur-containing oil: Second, excellent resistance to sulfidation. Further, the adhesive strength is ': sufficient strength to be used as an electrode of the wafer resistor. = glass powder crucible of Example 2, and the addition amount is set to 4 〇 thick film conductor; and the thick film conductor obtained by using the glass powder C sample of Example 3::: = 3." With the glass/in Example 1 of the composition range of the present invention and without the u2〇, the thick film obtained by adding the amount of 5Q f is subjected to the fourth solder bath dipping (four), and the area resistance value becomes (4) The resistance to solder corrosion is poor. This = the resistance value after 2 hours is: 2. Sulfur:: The oil is used as the glass powder of (4) as used in Comparative Example 1. The thick film conductor is obtained. Because, in the less than 9Q "c burning = temperature, the feldspar can not be fully precipitated and grown in the thick film conductor ~ about the conductor called Pd is also completely welded. From the 4 = film can promote - and grow In addition, it is also understood that::::= 323345 22 201213269 The appearance of the alkaloid also requires the precipitation of anorthite. Similarly, the glass of the composition of Comparative Example 2 is used, and the addition amount is set to 5 The thickness of the thick film conductor obtained by G mass part is lkQ/[2 or more after the second-person solder bath is impregnated, and the heart is in the oil. The area resistance value after 1.5 hours is 1 Ω/[=] or more, and the coal erosive property and the sulfidation resistance are both poor. Even if the composition of Comparative Example 2 is used, the composition of the continuation powder containing CaO is used. The film conductor was not supplied with Ca, and it was not precipitated in the thick film conductor, and the effect of the bowstone was understood to be that the solder resisting property and the vulcanization property were not exhibited. The broken powder of Comparative Example 3 which is within the composition range of the present invention was used. A 'the amount of addition is set to 5. 〇f parts of the thick film guide H obtained without adding A· powder, after the second: under-welded contact impregnation, the area resistance value becomes = Ω / 〇 or more, dip After 8 hours of oil collapse, the area resistance value was 1 Ω/above, and the resistance to soldering and dumping resistance was poor. As shown in Comparative Example 3, the composition containing only Ah 〇 3 powder and only glass powder was used. In the thick film conductor obtained as the oxide powder material, the thick film conductor towel does not uniformly precipitate the 29 feldspar, and the * the towel is deposited at the interface portion between the thick film body and the oxidized substrate. (4) Solder infiltration and The effect of sulfidation resistance was not exerted. 323345 23 201213269 [Table 2]
導電粉末（質董价） 氧化物粉末 添加物 (貧量份） (質量份） 評铦结果 耐焊料侵 Ag粉末 Pd粉末 破碘粉末 AltO>粉末 瓖粉末 祺厚 面積 電阻值 黏著钱度 蝕性成為 21ΙτΩ 為 封硫化性成 為这1Ω為止 耐嬅料 侵杜性 耐碇化性 炼合判定 ("D) ΟηΩ) (Ν) 止之次數 之時問 判定 列定 (次） (hr) f施例1 99.3 0.7 A 5.0 1.0 4.0 8.0 4.4 58 >12 >12 〇 〇 〇 實施例2 99.3 0.7 B 4.0 1.0 4.0 8.2 4.3 54 >12 >12 〇 〇 〇 實施例3 99.3 0.7 C 3.0 1.0 4.0 8.2 4.1 60 >12 >12 〇 〇 〇 比tt例1 99.3 0.7 D 5.0 1.0 4.0 8.0 4.8 27 4 2 X X X 比較例2 ΘΘ. 3 0,7 E 5.0 1.0 4.0 8.3 5.0 51 2 1.5 比較例3 ΘΘ.3 0.7 A 5.0 - 4.0 8.1 4.5 61 2 8 比較侧4 9Θ.3 0.7 F 6.3 1.0 — 8.0 4.7 65 >12 3.5 〇 實施例4 ΘΘ.3 0.7 F 6.3 1.0 1.0 8.2 4.5 67 >12 >12 〇 〇 〇 寊施例5 99.3 0.7 F 6.3 1.0 4.0 8.1 4.6 63 >12 >12 〇 〇 〇 實铯例6 99.3 0.7 F 6.3 1.0 6.0 8.2 4.8 59 >12 >12 〇 〇 〇 賞掩例7 99.3 0.7 F 6.3 0.5 4.0 8.1 4.5 66 >12 >12 〇 〇 〇 霣施例8 99.3 0.7 F 6.3 3.0 4.0 8.2 5.0 59 >12 >12 〇 〇 〇 實《·例9 100.0 0.0 F 6.3 1.0 4.0 8,0 4.5 62 >12 >12 〇 0 〇 比較例5 100.0 0.0 E 5.0 1.0 - 8.3 4.6 52 I 1.5 X 比較例6 98.5 1.5 E 5.0 1.0 8.3 6.5 50 3 4 比枚例7 93.0 7.0 E 5.0 1.0 8.1 13.1 — 47 — 5 -：_ >12 X 〇 X (實施例4至6、比較例4) 實鈿例4、實施例5、實施例6及比較例4，係使用於 本發明的組成範圍之玻璃粉末F。玻璃粉末F係除了本發 月範圍内的玻璃組成之外，為求進一步提升導體特性，僅 添加表2所示之份量的BhO” CuO、Mn〇2者。分別將玻璃F 的添加量设為6· 3質量份，將Ag與Pd的比率（質量比）設 為99. 3: 0.7’並從〇至6 〇質量份改變碳粉末的添加量。 該結果為，使用此等玻璃材料所製作之厚膜導體中， 關於耐谭料侵純’即使浸潰於焊料槽12次，電阻值均未 上升，可得到良好結果。此外，關於黏著強度，亦均超過 6〇N，可視為顯現出上述添加材料之添加效果者。 323345 24 201213269 然而，關於耐硫化性，實施例4至6中，浸潰於油中 12小時後之面積電阻值均未達1 Ω /□，雖可抑制面積電阻 值的上升，但在未添加碳粉末之比較例4中，面積電阻值 在浸潰於油中3.5小時成為1Ω/□以上，财硫化性差。 (實施例7、8) 實施例7、實施例8為實施例5的系列，係分別將Al2〇3 粉末的添加量設為0.5質量份、3.0質量份者。 該結果為，關於耐焊料侵蝕性，即使浸潰於焊料槽12 次，均未觀察到面積電阻值的上升，可得到良好結果，並 且關於耐硫化性，係浸潰於含硫的油中12小時後面積電阻 值未達1Ω/□，可得到良好結果。再者，亦可得到黏著強 度rfj之結果。 (實施例9) 實施例9亦為實施例5的系列，係未添加Pd粉末而僅 由Ag粉末來構成導電粉末者。 該結果為，關於耐焊料侵蝕性，即使浸潰於焊料槽12 次，均未觀察到面積電阻值的上升，可得到良好結果，並 且關於耐硫化性，浸潰於含硫的油中12小時後，面積電阻 值未達1Ω/□，可得到良好結果。再者，亦可得到黏著強 度南之結果。 (比較例5至7) 比較例5、比較例6、比較例7，為分別採用不含CaO 之本發明的組成範圍外之玻璃粉末E，並使用添加Al2〇3粉 末1.0質量份且不添加碳粉末之組成物所得之厚膜導體， 25 323345 201213269 且改變乡且^§ 成中之Pa的中^之Ag粉末與Pd粉末的比率來確認該組 和财硫彳匕彳支之^ , ° ^均Μ有提升耐焊料侵银性 長石與•泰二末二 析出且不具有因轉 的厚膜導體中，耐焊料紐_差、、〜構造之此等比較例 份之=7:，粉末相對於…❶。質量 時後，可抑制面份的比較例7’雖浸潰於油中12小 力心該=:電阻值的上升’發揮耐硫化性，但㈣ 乂下者，耐硫化性亦差。 添加明範圍的實施例9中，即使僅為Ag的組成而未 添加Pd粉末，亦可得到耐 成而未 此外，藉==:: 可理解到本發明中即使將pd 性。 _ 1/10以下，亦可得到同等的耐硫化 (產業上之可利用性） 物，’11由使用本發明之厚膜導體形成用組成 性，並可同能夠以低成本實現财硫化性、耐焊料侵蝕 及抑_2_卩制因Ag的硫化所造成之電極的短路以 之電極的短二=广之貴金屬材料的焊料侵银所造成 ^ 路兩者之厚膜導體形成用組成物。因此，藉由 採肖I發明之厚臈導體升多成用組成物形成的厚膜暮 體=如低成本提供—種即使放置在硫環境氣體 殊％兄下’亦可穩定發揮性能之W電阻n等電子零件， 323345 26 201213269 - 故本發明係於包含晶片零件製造商之電子零件領域可提供 極大貢獻者。 【圖式簡單說明】 第1圖為本發明所適用之晶片電阻器的示意圖。 【主要元件符號說明】 無。 27 323345Conductive powder (quality Dong price) Oxide powder additive (poor portion) (mass parts) Evaluation results Resistance to solder intrusion Ag powder Pd powder iodine powder AltO> Powder 瓖 powder 祺 thick area resistance value adhesion eclipse 21ΙτΩ is the judgment of the resistance to turbidity and the resistance to turbidity. ("D) ΟηΩ) (Ν) The number of times the number of times is determined (times) (hr) f Example 1 99.3 0.7 A 5.0 1.0 4.0 8.0 4.4 58 > 12 > 12 〇〇〇 Example 2 99.3 0.7 B 4.0 1.0 4.0 8.2 4.3 54 > 12 > 12 〇〇〇 Example 3 99.3 0.7 C 3.0 1.0 4.0 8.2 4.1 60 >12 >12 〇〇〇 tt example 1 99.3 0.7 D 5.0 1.0 4.0 8.0 4.8 27 4 2 XXX Comparative Example 2 ΘΘ. 3 0,7 E 5.0 1.0 4.0 8.3 5.0 51 2 1.5 Comparative Example 3 ΘΘ.3 0.7 A 5.0 - 4.0 8.1 4.5 61 2 8 Comparison side 4 9Θ.3 0.7 F 6.3 1.0 — 8.0 4.7 65 > 12 3.5 〇 Example 4 ΘΘ.3 0.7 F 6.3 1.0 1.0 8.2 4.5 67 >12 >12 〇〇 Example 5 99.3 0.7 F 6.3 1 .0 4.0 8.1 4.6 63 >12 >12 〇〇〇Example 6 99.3 0.7 F 6.3 1.0 6.0 8.2 4.8 59 >12 >12 Appreciation of the cover 7 99.3 0.7 F 6.3 0.5 4.0 8.1 4.5 66 >12 >12 Example 8 99.3 0.7 F 6.3 3.0 4.0 8.2 5.0 59 >12 >12 〇〇〇实··Example 9 100.0 0.0 F 6.3 1.0 4.0 8,0 4.5 62 >12 >12 〇0 〇Comparative Example 5 100.0 0.0 E 5.0 1.0 - 8.3 4.6 52 I 1.5 X Comparative Example 6 98.5 1.5 E 5.0 1.0 8.3 6.5 50 3 4 Specific example 7 93.0 7.0 E 5.0 1.0 8.1 13.1 — 47 — 5 - : _ > 12 X 〇 X (Examples 4 to 6 and Comparative Example 4) Example 4, Example 5, Example 6 and Comparative Example 4 are glass powders F used in the composition range of the present invention. In addition to the glass composition in the range of the present month, in order to further improve the conductor characteristics, only the amount of BhO"CuO, Mn〇2 shown in Table 2 is added. The addition amount of the glass F is set to 6.3 parts by mass, the ratio (mass ratio) of Ag to Pd is set to 99. 3: 0.7' and the amount of carbon powder added is changed from 〇 to 6 〇 parts by mass. The result is that using these glass materials In the thick film conductor produced, the resistance of the tantalum material was not increased even if it was immersed in the solder bath 12 times, and good results were obtained. Moreover, the adhesion strength was also more than 6 〇N, which can be regarded as a manifestation. 323345 24 201213269 However, regarding the sulfidation resistance, in the examples 4 to 6, the area resistance values after immersion in the oil for 12 hours were less than 1 Ω / □, although the area was suppressed. In the comparative example 4 in which the carbon powder was not added, the area resistance value was 1 Ω/□ or more after being immersed in the oil for 3.5 hours, and the vulcanization property was inferior. (Examples 7 and 8) Example 7 Example 8 is the series of Example 5, which is a powder of Al2〇3, respectively. The amount of addition is 0.5 parts by mass and 3.0 parts by mass. As a result, even if the solder resisting property is impregnated into the solder bath 12 times, no increase in the area resistance value is observed, and good results can be obtained, and The vulcanization property was obtained by immersing in the sulfur-containing oil for 12 hours, and the area resistance value was less than 1 Ω/□, and good results were obtained. Further, the result of the adhesion strength rfj was obtained. (Example 9) Example 9 In the series of Example 5, the conductive powder was formed only from the Ag powder without adding the Pd powder. As a result, regarding the solder corrosion resistance, no area resistance value was observed even when the solder bath was immersed 12 times. As a result of the rise, good results can be obtained, and with respect to the sulfidation resistance, after 12 hours of immersion in the sulfur-containing oil, the area resistance value is less than 1 Ω/□, and good results can be obtained. Further, the adhesion strength can be obtained as a result. (Comparative Examples 5 to 7) In Comparative Example 5, Comparative Example 6, and Comparative Example 7, glass powder E outside the composition range of the present invention containing no CaO was used, and 1.0 part by mass of Al 2 〇 3 powder was added and not used. Adding carbon powder composition Obtained the thick film conductor, 25 323345 201213269 and changed the ratio of Ag powder and Pd powder in the middle of the town and the middle of the Pa to confirm that the group and the sulphur sulphate ^, ° ^ have improved In the thick-film conductors which are resistant to solder intrusion and feldspar and which do not have a transition, the solder resists are inferior, and the comparative examples of the structure are =7: the powder is relative to ❶. After the mass is satisfied, the comparative example 7' which is capable of suppressing the surface portion is immersed in the oil at 12 small cores. =: the increase in the resistance value is 'resistant to sulfidation resistance, but (4) the underarm is poor in sulfidation resistance. In the ninth embodiment, even if only the composition of Ag is added and Pd powder is not added, resistance can be obtained without further addition. By ==:: It is understood that pd is preferable in the present invention. _ 1/10 or less, the same resistance to vulcanization (industrial availability) can be obtained, and '11 is formed by using the thick film conductor of the present invention to form a constitutive property, and the vulcanization property can be achieved at a low cost. Resistance to solder erosion and suppression of the short circuit of the electrode caused by the vulcanization of Ag, the short film of the electrode = the solder intrusion of the noble metal material caused by the thick metal film conductor composition. Therefore, the thick-film 形成 body formed by the composition of the thick 臈 conductor invented by Xi Xiao I is provided at a low cost, and can be stably exhibited even if it is placed under the sulfur atmosphere. n-Electronic Parts, 323345 26 201213269 - The present invention is therefore a significant contributor to the field of electronic components including wafer component manufacturers. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a wafer resistor to which the present invention is applied. [Main component symbol description] None. 27 323345