201207867 六、發明說明： 【發明所屬之技術領域】 本發明關於一種適合用於形成電極及導體之無錯導 電糊，其係在各種型式之基板（如陶瓷基板與金屬基板） 上及在電子組件等之上以高溫燒製。 【先前技術】 通常導電糊係將作為主成分之包括金屬（如銀、銀- 鈀、銅、鎳等）的導電粉末、及作為無機黏合劑之玻料 均勻地分散於包括樹脂與溶劑之有機媒液中以形成糊而 製is此外’依照需求而添加金屬氧化物（如氣化叙、 氧化銅等）。 將導電糊藉各種方法（如網版印刷、浸潰、別塗等） 塗佈於各種型式之基板及電子組件的端部分上以形成預 疋圖案。然後將導電糊以約7〇〇至95〇它之高溫燒製而 形成導電膜（厚膜導體）。 近來隨環境顧慮增加而愈要求用於導電糊之破料應 無鉛。無鉛玻料為完全不包括鉛或僅包括如無町避免之 雜質的微量鉛（例如5〇ppm以下）之玻璃。;見己建議一 種使用銘硼石夕酸鹽玻璃作為無錯玻料之導電糊（參見日 本公告未審查申請案第Sh〇U50-1 61692號）。 為了將引線$久@并丨_ -各種i式之電子組件附接在導電膜上 以精知接將電子έ且杜vA r 、、且件女裝於印刷電路板等，或者為了將201207867 VI. Description of the Invention: [Technical Field] The present invention relates to an error-free conductive paste suitable for forming electrodes and conductors, which are used on various types of substrates (such as ceramic substrates and metal substrates) and in electronic components. The above is fired at a high temperature. [Prior Art] Generally, a conductive paste is used as a main component, and a conductive powder including a metal (such as silver, silver-palladium, copper, nickel, etc.) and a glass material as an inorganic binder are uniformly dispersed in an organic resin including a solvent and a solvent. In the vehicle liquid, a paste is formed to prepare, and in addition, a metal oxide (such as gasification, copper oxide, etc.) is added according to the demand. The conductive paste is applied to various types of substrates and end portions of the electronic components by various methods (e.g., screen printing, dipping, coating, etc.) to form a pre-twist pattern. Then, the conductive paste is fired at a high temperature of about 7 Torr to 95 Å to form a conductive film (thick film conductor). Recently, as the environmental concerns increase, the more demanding materials for the conductive paste should be lead-free. The lead-free glass material is a glass which does not include lead at all or includes only a trace amount of lead (for example, 5 〇 ppm or less) which is free of impurities which are avoided by the town. It is suggested that a conductive paste using borax silicate glass as the error-free glass material is proposed (see Japanese Unexamined Application No. Sh〇U50-1 61692). In order to attach the lead wire to a long time @丨丨_ - various i-type electronic components are attached to the conductive film to precisely connect the electronic device and the v-r, and the device is printed on a printed circuit board, etc., or
導電膜隔離水分鱼方鹿 *以 J 在導電膜上m ，』照需求在$行電鍍程序後 、7成坏锡層。即焊錫層係將基板浸潰 焊錫浴中，或者在預定伤罢忐必 极，又，貝於熔融 位置處將焊錫糊印刷在導電膜上 ~ 3 ** 201207867 而形成。然後焊锡屉A、# 動。 ^進行實際焊接時因加“重新流 用於形成此厚膜導電電路及電極 導電度、基板黏著強声μβ 糊應滿足如 5至度、焊錫耐瀝濾力（焊接射 等之各種特徵。 冲接耐熱性） 具體而言’近族與咖 放電子領域強烈地要求焊 無鉛，且開始使用各種刑々^ 晋尺焊锡材料亦 使用之鉛-錫焊錫。孭古 上最吊 眾……26。。。高…之錫_:·锡:而 (Sn/3Ag/0.5Cu；)。 ’ 鋼桿錫 然而在使用如μ、+，_ 生以下之靜。S 銅焊錫之高熔點焊錫時發 ^ P因為導電糊習知上係假定使用焊接、、田 度為約230至24(ΓΓ夕奴姐p日，日 用垾接/皿 C之釔-錫烊錫而設計及發展。 使用高熔點焊錫時，3 u此在 屬擴散且溶於炼融烊錫中，及發生所謂之「焊=金 現象的可能性增加。 月之¥錫遞慮」 關於以上之困擾，例如曰本公告未審 06-228572 號建議 _ 種使用 Si〇2_B2〇3_Ai2〇3·⑽ μ =璃粉末，氧化紹粉末改良經燒製導電膜之焊錫耐;歷 ’'而阻止烊錫瀝濾現象的導電糊。 然而在要求甚至更嚴厲條件 錫耐遞渡力應更為改良。 …’導電膜之焊 【發明内容】 之主要目的為提供一種可改良焊錫财遞 導電糊’特別是在用於形成欲焊接之導電膜及電 -4 - 201207867 本發明之第一態樣提供一種導電糊’其係包括（A) 導電4末，（B)包括氧化物當量為總共8 5重量％以上之下 述成分且實際上不包括鉛的玻料，該成分（在玻料中之 比例）為16至47重量％之Si〇2、33至52重量％之Al2〇3、 3至15重量％之MgO、15至45重量％之B2〇3，及（〇有 機媒液。 【實施方式】 本發明之導電糊係包括（A)導電粉末，（B)玻料，及 (C)有機媒液作為重要成分。 以下詳述各（A)導電粉末，（B)玻料，及（c)有機媒液。 (A)導電粉末 在本發明中導電粉末並未特別地限制。然而其可使 用例如貴重今厲去、古^•丄& ζ M h h 屬 免、銘、金等）、驗性金 ^末；如銅、錄、姑、鐵等卜包括以上金屬之合金 ιί,”中將各粒子之表面覆以其他導電性材料的複合 在本發明中，即佶县 末（趨於h .， 使用包括銀作為主成分之粉 :誶錫瀝濾）作為導電粉末 錫耐瀝濾力。且俨而+ β 于仍獲侍優良之焊 ° ’即使是在使用盆中導恭♦、古由 之銀摻合比例為7〇重量％以上的銀；-π 效地抑制銀之煤 導电私末時，仍可有 艮之卜錫/歷濾。同時由於 表面上的塗銀之銅粉末 在於各拉子之 1至30重量严…γ即使疋在銀含量為少量（例如 至二:j 大為改良焊錫耐瀝遽力。 於由包括銀作為主成分 末，關於焊錫耐瀝濾：組成的銀導電粉 導電度及銀移動阻止，除了銀 201207867 以外，其可摻合鈿、 ^ ^ ^ ^ 鉑、金、銅、鎳等作為成Conductive film to isolate the water fish deer * to J on the conductive film m, 』 according to demand after the line plating process, 7 into the bad tin layer. That is, the solder layer is formed by dipping the substrate into the solder bath or by smashing the predetermined damage, and printing the solder paste on the conductive film at the molten position ~ 3 ** 201207867. Then the solder drawers A and # move. ^In the actual welding, due to the addition of "reflow for the formation of this thick film conductive circuit and electrode conductivity, the substrate adhesion strong sound μβ paste should meet various characteristics such as 5 to degree, solder leaching resistance (welding shot, etc.) Heat resistance) In particular, the 'near family and coffee electronics field strongly demanded that lead-free soldering, and began to use a variety of penalties ^ lead-tin solder used in the solder material. The most popular people in the ancient...26. High... Tin _: · Tin: and (Sn/3Ag/0.5Cu;). 'Steel rod tin is used in the static of the following, such as μ, +, _. When S high-melting solder of copper solder is issued ^ P Because the conductive paste is conventionally designed to be welded, and the field is about 230 to 24 (ΓΓ夕奴姐 p日, daily use / / / C C 钇 烊 烊 烊 烊 烊 烊 。 。 。 。 。 。 。 。 。 。 。 。 , 3 u This is diffuse and soluble in smelting bismuth tin, and the so-called "welding = gold phenomenon is likely to increase. The moon's ¥ tin considerations" Regarding the above problems, for example, this announcement has not been reviewed 06- Recommendation No. 228572_ Use Si〇2_B2〇3_Ai2〇3·(10) μ=glass powder, oxidized powder modified burned The conductive film is resistant to solder; it is a conductive paste that prevents the phenomenon of bismuth leaching. However, in demanding even more severe conditions, the tin-resistant transfer force should be improved. ... 'The welding of conductive film 【Abstract】 The main purpose In order to provide a conductive paste for improving soldering, particularly in forming a conductive film to be soldered and electric - 4, 201207867, a conductive paste is provided which includes (A) a conductive electrode (B) A glass material comprising the following components having an oxide equivalent of a total of 85 wt% or more and actually excluding lead, the composition (ratio in the glass frit) being 16 to 47% by weight of Si〇2, 33 To 52% by weight of Al2〇3, 3 to 15% by weight of MgO, 15 to 45% by weight of B2〇3, and (〇 organic vehicle liquid. [Embodiment] The conductive paste of the present invention comprises (A) conductive powder (B) glass material, and (C) organic vehicle liquid as an important component. Each of (A) conductive powder, (B) glass material, and (c) organic vehicle liquid are described in detail below. (A) Conductive powder in the present invention The medium-conducting powder is not particularly limited. However, it can be used, for example, to be expensive, and to be used. ζ M hh is exempt, Ming, Jin, etc.), and the test gold is the end; such as copper, recorded, aunt, iron, etc., including the alloy of the above metal ιί," the surface of each particle is coated with other conductive materials. In the present invention, that is, at the end of the county (towards h., using a powder containing silver as a main component: bismuth leaching) as a conductive powder tin leaching resistance, and 俨 and + β are still excellent in welding. ° 'Even in the use of pots, the silver blending ratio of silver is more than 7〇% by weight; -π effectively inhibits the silver coal conductive private, there may still be 卜Buxi / Calendar filter. At the same time, since the silver-coated copper powder on the surface is 1 to 30 weights of each puller, γ even if the yttrium is in a small amount of silver (for example, to two: j is a modified solder resisting leaching force. At the end of the composition, the solder leaching resistance: the composition of the silver conductive powder conductivity and silver movement prevention, in addition to silver 201207867, it can be blended with 钿, ^ ^ ^ ^ platinum, gold, copper, nickel, etc.
關於導電度及成本，較佳A 曰 —权住馮其他成分之總量為 重量％。具體而言’較佳為摻合鈀作為其他成 其他金屬之混合粉末、合金粉末或複合粉末、 混合粉末均可作為銀導電粉末。在此，在本說 例如0.1「至」30重量％之表示形式係表示 上至30重量。/。或以下的範圍，且在全部說明書 意義適用於類似之表示形式。 至於導電粉末，其可使用平均粒度為〇」. 之粉末。此外，其可混合兩種或以上之平均粒 導電粉末。導電粉末之形狀並未限制，且可適 球形粉末及片型粉末。此外，其可混合兩種或 狀不同的導電粉末。 (B)玻料 本發明之玻料為包括Si02、Al2〇3、Mg() 作為主成分之鋁硼矽酸鹽玻料，且其組成物係 形成稠密之經燒製金屬-玻璃媒結構。具體而士 包括氧化物當量為總共8 5重量％以上之下述 分，且實際上不包括鉛。 16至47重量％之Si〇2、33至52重量〇/〇之 至15重量％之MgO、及15至45重量％之β2〇 在此’各成分「Si〇2、ΑΙ2Ο3、Mg〇、 為在玻料中之比例。 此外，各成分僅需依照氧化物當量之量& 中，且不表示該成分必須為以上氧化物而擦 中。例如其可包括SiO作為Si02。 分。然而 0.1 至 30 分。銀與 或以上之 明書中， 重量％以 中相同之 L 1 0微米 度不同的 當地使用 以上之形 ‘與 B2〇3 經選擇以 ，玻料係 組成的成 A12 Ο 3 ' 3 3 0 」之含量 括於玻料 合在玻料 201207867 至於玻料，較佳為使用平均粒度為1 ·〇 粉末。此外，較佳為相對i00重量份之導 至1 5重^:份之玻料。在玻料少於丨重量份 力及基板黏著性趨於降低。此外，在玻料連 時導電膜之導電度趨於過度降低。更佳之 1 0重量份。 以下係針對各成分說明限制玻料組成Regarding conductivity and cost, it is preferred that A 曰 - the total amount of other components of von von is % by weight. Specifically, it is preferable to blend palladium as a mixed powder of other other metals, an alloy powder or a composite powder, or a mixed powder as a silver conductive powder. Here, in the present description, for example, 0.1 to 30% by weight of the expression is expressed up to 30% by weight. /. Or the scope of the following, and the meaning of the entire specification applies to similar representations. As the conductive powder, a powder having an average particle size of 〇" can be used. Further, it is possible to mix two or more kinds of average particle conductive powders. The shape of the conductive powder is not limited, and a spherical powder and a sheet type powder can be suitably used. Further, it is possible to mix two or different kinds of conductive powders. (B) Glass material The glass material of the present invention is an aluminum boron phthalate glass material including SiO 2 , Al 2 〇 3 , and Mg ( ) as a main component, and the composition thereof forms a dense fired metal-glass dielectric structure. The specific sage includes the following points in which the oxide equivalent is a total of 85 wt% or more, and does not actually include lead. 16 to 47% by weight of Si〇2, 33 to 52% by weight/〇 to 15% by weight of MgO, and 15 to 45% by weight of β2〇. Here, the components “Si〇2, ΑΙ2Ο3, Mg〇, In addition, the components are only required to be in accordance with the amount of oxide equivalent & and do not mean that the component must be the above oxide. For example, it may include SiO as SiO 2 . 30 points. In the silver or above, the weight % is the same as the L 1 0 micron in the local use of the above shape 'B2〇3 is selected, the glass system is composed of A12 Ο 3 ' 3 The content of 3 0 ” is included in the glass material in the glass material 201207867. For the glass material, it is preferred to use an average particle size of 1 · 〇 powder. Further, it is preferably a glass material which is guided to 15 parts by weight relative to i00 parts by weight. The glass strength is less than the weight of the crucible and the adhesion of the substrate tends to decrease. In addition, the conductivity of the conductive film tends to be excessively lowered when the glass is continuous. More preferably 10 parts by weight. The following is a description of the composition of each component to limit the composition of the glass
SiCh之含量係在16至47重量％之範 含罝小於1 6重量。/。時無法形成稠密之經燒 瀝濾力降低。此外，在Si〇2含量為16至 圍外時難以達成玻化，因此該Si02含量不 容易性，進一步較佳為Si〇2含量為2〇至 別是在20至33重量％之範圍内。The content of SiCh is in the range of 16 to 47% by weight, and the content of cerium is less than 16% by weight. /. It is impossible to form a dense burnt leaching force. Further, it is difficult to achieve vitrification when the Si〇2 content is 16 to the outside, so the SiO 2 content is not easy, and it is further preferable that the Si 〇 2 content is 2 〇 to 20 to 33 % by weight.
AhO3之含量係在33至52重量％之範 含量小於33重量％時焊錫耐瀝濾力降低。 含量超過52重量％時’由於在製造玻璃時 度熔化原料而造成玻化困難。關於玻化容 較佳為AhO3含量為48重量％以下。此外 量大時如抗化學力之特徵趨於改良。因此 含量為3 5重量％以上。The content of AhO3 is such that the solder leaching resistance is lowered when the content of 33 to 52% by weight is less than 33% by weight. When the content exceeds 52% by weight, it is difficult to vitrify due to the melting of the raw material during the production of the glass. The glass content is preferably 48% by weight or less of the AhO3 content. In addition, the characteristics of chemical resistance tend to improve when the amount is large. Therefore, the content is 35% by weight or more.
MgO有效地擴大玻化範圍，且Mg〇 丄5重量％之範圍内。在MgO含量小於3 | 難。此外，即使是在MgO含量超過15 | 瀝濾力仍降低。具體而言’為了獲得優良 力，較佳為M g 0含量為1 〇重量％以下。 至5 · 0微米之 電粉末摻合1 時焊錫耐瀝濾 登過1 5重量份 玻料量為2至 物之原因。 圍内。在Si02 製膜且焊錫耐 47重量％之範 佳。關於玻化 40重量％，特 圍内。在Al2〇3 此外’在Al2〇3 需要過高之溫 易性，進一步 ，在ai2o3含 特佳為ai2〇3 含量係在3至 [量°/〇時玻化困 r量％時焊錫耐 之焊錫耐瀝濾 201207867 B2〇3在玻料中表現如同 至45重量％之範圍内。 月丨 里係在15 廿仏Λ Β2〇3含量小於15重量％睥， 其作為助熔劑之效果降低。 里里/〇 f 重量％時焊錫耐瀝濾力降 ，在B2。3含量超過45 抗化學力㈣於降低广因：特:外’在Μ3含量增加時 %以下。 U此特佳為仏〇3含量為40重量 此外，在玻料中可佑日g +上 了依照而求而包括Si〇2、Al2〇3、MgO effectively expands the vitrification range and is within the range of 5 wt% of Mg〇. It is difficult to have a MgO content of less than 3 | In addition, even at MgO levels exceeding 15 | leaching power is still reduced. Specifically, in order to obtain an excellent force, the M g 0 content is preferably 1% by weight or less. When the electric powder is blended to 5 · 0 μm, the solder is leached and leached. The reason why 15 parts by weight of the glass material is 2 to the material is obtained. Inside. The film is formed on Si02 and the solder is resistant to 47% by weight. About 40% by weight of vitrification, within the range. In Al2〇3, in addition, 'the temperature is too high in Al2〇3, and further, in ai2o3, the content of ai2〇3 is in the range of 3 to [quantity °/〇 when the glass is trapped in the amount of r Solder leaching resistance 201207867 B2〇3 performs as far as 45% by weight in the glass. In the New Moon, the content of 15 廿仏Λ 〇 2 〇 3 is less than 15% by weight, and its effect as a flux is lowered.里里/〇 f When the weight is %, the solder is resistant to leaching, and the B2. 3 content exceeds 45. The chemical resistance (4) is reduced by the wide factor: special: the outer '% when the Μ3 content increases. U is particularly good for the content of 仏〇3 is 40%. In addition, in the glass material, it is possible to include the 〇3, Al2〇3,
Mg〇、與B2〇3以外之成分。 睛形車交佳為其他成分之總量係在氧化物當量 舌：。至15重量％之範圍内。在其他成分之含量超過15 改：ί時：本發明鋁硼矽酸鹽玻璃之優良焊錫耐瀝濾力 可此降低焊錫耐瀝濾力。 至於其他之成分’其可包括其他之金屬氧化物、齒 m 〃要不損及焊錫耐遞滤力與抗化學力。例如驗全 屬，驗土金屬之氧化物（如Ba〇、Ca〇、Sr〇、Li2〇= 係：^似Mg〇之情形而有交文地擴大玻化範圍且 :度，Ti〇2· Zn〇2改良導電膜之基板黏著性、 烊錫耐瀝濾力。本發明之玻料可進一步包括各種型/、 氧化物作為其他成分，如WO、M〇〇3、 J之 由於卜、+、— 川3等。然而 、述之裱境顧慮，其實際上不包括鉛成分 亦不白缸、 且孕乂佳為 原料混合及熔 而製造。除了 噴灑熱解法、 破料係藉由將組成玻料之各成分的 化’將炫融材料驟冷及將經驟冷原料研磨 此般製法，玻科亦可藉如溶膠-凝膠法、 霧化等之各種方法製造。 201207867 (c)有機媒液 酸酯 _ 方面，至於 、等之有機溶劑、水、 酮、喊 '酯 至於有機媒液，其可使用有機黏合叫 於有機黏合劑，其可使用纖維素、丁醛;：溶劑等。至 樹脂、酚樹脂、醇酸樹脂、松脂醇等。另知、丙烯 溶劑，其可使用醇 或以上之組合溶劑 有機媒液之量並未特別地限制，且可 佈方法而適當地調整成其中可將 =用逆及塗 適量。 規成刀保留於糊中之 此外，為了改良導雷肢夕I k μ μ 凡守电膜之基板黏著性與 :瀝濾力’本發明之導電糊可包括(D)金屬氧化：作為任 忍成分。其可摻合僅一種金屬氧化物，或者可組合掺合 兩種或以上之金屬氧化物。 至於金屬氧化物’其可建議習知上用於導電糊之各 種型式之金屬氧化物，如氧化级、氧化錯、氧化銅、錯 氧化紹I化石夕、氧化鈦、氧化鎂、氧化鑭等。具 體而〇較佳為使用氧化鍅（Zr02)、氧化鈦（Ti〇2、TiO)、 氧化鋅（ZnO)等。至於金屬氧化物較佳為使用平均粒度 為5.0 (故米以下之粉末。此外，其可將金屬氧化物以金 屬氧化物之先質（如有機金屬化合物）摻合。 此外’為了調整印刷特徵等，本發明之導電糊可適 田地包括以上（A)至（D)以外之添加劑，如塑化劑、如高 級月曰肪I與脂肪酸酯之分散劑、及通常添加之表面活性 劑，又可添加固態樹脂，如樹脂粒。 例4本發明之導電糊可如下而製造。 201207867 依照需求將（A)導電粉末、（B)玻料與（D)金屬氧化物 及其他添加劑按合適之比例製備及混合，且將以上混合 物均勻地分散於（C)有機媒液中而處理成糊。 依照需求而摻合之（A)導電粉末、（B)玻料與金屬氧 化物的比例並未特別地限制’且依照目的及用途而將其 適當地調整成正常使用之範圍内。較佳為相對丨〇〇重量 份之（A)導電粉末係摻合約1至1 5重量份之（B)玻料、及 總共約0至約1〇重量份之金屬氧化物。 本發明之導電糊係用於在基板及電子組件上形成導 體及電極。在此係敘述在基板上形成電極之情形作為實 例。 將導電糊藉合適之方法（如網版印刷、浸潰、刷塗 等）塗佈在基板上以形成預定圖案，然後將已塗佈導電 糊之基板以約700至9501之高溫燒製。在燒製程序中， 包括於本發明導電糊中之玻料隨溫度增加而軟化及流 動，且玻料分散於全部膜中而因將導電粉末之表面濕潤 而利於燒結。以此方式形成稠密之經燒製金屬膜結構的 經燒製導電膜。此外，因黏度由於溫度增加而降低，故 至少一部分之玻料移動至基板與導電膜之間的界面，且 將導電臈堅固地黏附於基板。 此外，在燒製程序中，如果在玻料被流體化時有機 材料（如媒液）殘留在膜中且導電粉末開始燒結，則因 由於有機材料在高溫分解所產生之氣體被封包於膜中而 可能造成氣泡（泡沫）。因此不僅破壞外觀，經燒製導 電膜之密度亦降低。本發明之玻料由於玻料在燒製時之 流動性而可有效地抑制氣泡。 -10- 201207867 依照本發明之導電糊，經燒製金屬膜因玻璃殘留在 經燒製金屬粒子之間的界面處而堅固地維持，且形成稠 密之經燒製金屬膜結構。因此幾乎不發生焊錫遞遽且可 獲#具有高黏著強度之導電膜。即使是在經燒製膜之一 部分表面中發生焊錫瀝濾時，瀝濾仍不易進展至較低部 分，因此假定徹底地改良焊錫抗瀝濾力。 在此，在對由本發明導電糊所獲得之導電膜進行 SEM觀察時’其發現一些假定由玻料所形成之細微結晶 以網狀外觀沉積於導電膜中’且形成高稍密膜結構的情 形。在其中沉積此種結晶之導電膜令，其假定導電粉末 係特別堅固地保留’結果淳錫抗瀝渡力徹底地改良。然 而即使是在其中之結晶無法以SEM清楚地觀察的導電膜 之情形’相較於習知導電膜仍獲得非常良好之焊錫抗瀝 夕，在對本發明之糊添加氧化鍅、氧化鋅與氧化 鈦作為金属氧化物(D)時’其可更容易地形成以社 構’及更為強化導電膜 ' 瀝據。 线之&度，且可更確定地防止焊錫 如抗Γ二除：焊錫抗遞遽力’本發明之導電糊係具有 “、黏者強度之良好特徵。例如本發 〜輪何型式之基板，包括絕緣基板(如陶‘電板糊 歹如氧化銘、鈦酸鋇等）、祐链苴4 寺）玻璃基板及玻璃陶瓷基板、 2表面上形成絕緣膜之金屬基板（如不 板 具有高點著強度之優良厚膜導體。 均 -11- 201207867 本發明之導電糊適合用 厚膜導體電路、電極等。具 較佳地用於形成陶瓷片型組 電容與多層片型導體）及其 形成陶瓷多層基板之表面導 明之導電糊燒製所獲得之導 渡力。因此例如本發明之導 焊錫塗覆的電組件之端電極 電極。然而可由本發明獲得 例如可較佳地用於欲整體浸 之不同位置處使電極附接焊 而言，由本發明所獲得之導 主要電極。此外，由本發明 優良之抗酸力，因此可較佳 之電極。 於 在 各 種 型 式 之 基 板 上 形 成 體 而 5 本發 明 之 導 電 糊 可 件 ( 如 片 型 電 阻 多 層 片 型 他 電 子 組 件 之 電 極 ， 及 用 於 電 層 等 0 具 體 而 ί 將 本發 膜 係 具 有 優 良 之 焊 錫 抗 遞 電 糊 適 合 用 於 將 進 行 焊 接 或 > 及 欲 連 接 電 組 件 之 基板 上 之 導 電 膜 未 必 需 要 焊 接 > 且 潰 於 焊 錫 浴 中 以 在 基板 刖 後 錫 之 基板 上 導 電 圖 案 0 具 體 電 膜 較 佳 為 作 為 片 型 電 阻 之 所 獲 得 之 導 電 膜 經 證 實 具 有 地 用 於 例 如 欲 進 行 電 鍍 程 序 〔具體實施例〕 電糊組成物彼此 之性質、特徵等 不同 本發明之具體實施例係製備導 之複數種類的樣品，及評估各樣品 (1)樣品之製備 (1.1)玻料之製備 將玻璃原料混合以具有下示表i 物，且將各混合物以1 600°c之溫度加熱不之玻璃組成 熔化，及使熔融混合物在石墨上H1至丨.5小時而 中而驟冷。將驟冷所獲得之玻狀材料以1入輥式驟冷機 化銘球）研磨48小時，及製借伞仏Ύ 泉磨機（使用氧 入衣備十均粒度Λ 八号約2 · 5微米之 201207867 玻料「A」至「0」。平^ $ 十均粒度為使用雷射繞射粒度分 儀所測量之5 0 %粒度分右 及刀布累積比例值（D50)(按曹詈 計）。在此，玻料「B !之周祖—， 」之原枓在1 6 0 0 C之溫度不熔化， 因此無法製備玻料主+ , 料係附加*而表示。 表1Components other than Mg〇 and B2〇3. The total amount of the other parts of the eye-shaped car is in the oxide equivalent tongue:. Up to 15% by weight. When the content of other ingredients exceeds 15: ί: The excellent solder leaching resistance of the aluminum borosilicate glass of the present invention can reduce the leaching resistance of the solder. As for other ingredients, which may include other metal oxides, the teeth do not damage the solder's resistance to filtration and chemical resistance. For example, the whole genus, the oxide of the soil test (such as Ba〇, Ca〇, Sr〇, Li2〇 = system: ^ like Mg 〇 and there is a text to expand the vitrification range and: degree, Ti 〇 2 · Zn〇2 improves the substrate adhesion of the conductive film and the lining resistance of the tin-tin. The glass material of the present invention may further include various types/oxides as other components, such as WO, M〇〇3, J, and , - Chuan 3, etc. However, the dilemma mentioned, it does not actually include the lead component and the white tank, and the pregnancy is good for the mixing and melting of the raw materials. In addition to the spray pyrolysis method, the broken material system will be composed. The chemical composition of the glass material is used to rapidly cool the material and to grind the quenched material. The glass can also be produced by various methods such as sol-gel method and atomization. 201207867 (c) Organic In the case of the organic solvent, water, ketone, and ketone as the organic vehicle, the organic binder can be used as an organic binder, and cellulose, butyraldehyde, solvent, and the like can be used. To resin, phenol resin, alkyd resin, rosinol, etc. Also known as propylene solvent, which can The amount of the organic solvent of the alcohol or the combination of the above solvents is not particularly limited, and can be appropriately adjusted to be a method in which it can be used in the reverse and the appropriate amount. The gauge knife is retained in the paste, in addition, in order to improve the mine guide Ik μ μ The adhesion of the substrate of the Shouban film: leaching force 'The conductive paste of the present invention may include (D) metal oxidation: as a forbearance component, which may be blended with only one metal oxide, or Combining two or more metal oxides in combination. As for the metal oxides, it is suggested that various types of metal oxides for conductive pastes, such as oxidation grade, oxidation fault, copper oxide, and mis-oxidized I fossils, are suggested. Further, titanium oxide, magnesium oxide, cerium oxide, etc. Specifically, cerium oxide (ZrO 2 ), titanium oxide (Ti 〇 2, TiO), zinc oxide (ZnO), etc. are preferably used. As for the metal oxide, it is preferred to use The average particle size is 5.0 (the powder below the meter. In addition, the metal oxide can be blended with a precursor of a metal oxide (such as an organometallic compound). Further, in order to adjust the printing characteristics and the like, the conductive paste of the present invention can be adapted. The field includes the above Additives other than A) to (D), such as plasticizers, dispersants such as high-grade sulphur I and fatty acid esters, and commonly added surfactants, may also be added with solid resins such as resin granules. The conductive paste of the invention can be produced as follows: 201207867 According to requirements, (A) conductive powder, (B) glass material and (D) metal oxide and other additives are prepared and mixed in an appropriate ratio, and the above mixture is uniformly dispersed in (C) is treated as a paste in an organic vehicle. The ratio of (A) conductive powder, (B) glass to metal oxide blended as required is not particularly limited' and is appropriate according to purpose and use. Adjusted to the range of normal use. Preferably, the conductive powder of (A) conductive powder is blended with 1 to 15 parts by weight of (B) glass, and a total of about 0 to about 1 part by weight. Metal oxides. The conductive paste of the present invention is used to form a conductor and an electrode on a substrate and an electronic component. Here, a case where an electrode is formed on a substrate will be described as an example. The conductive paste is coated on the substrate by a suitable method (e.g., screen printing, dipping, brushing, etc.) to form a predetermined pattern, and then the substrate to which the conductive paste has been applied is fired at a high temperature of about 700 to 9501. In the firing process, the glass material included in the conductive paste of the present invention softens and flows as the temperature increases, and the glass material is dispersed in the entire film to facilitate sintering by wetting the surface of the conductive powder. In this way, a fired conductive film of a dense fired metal film structure is formed. Further, since the viscosity is lowered due to an increase in temperature, at least a part of the glass material moves to the interface between the substrate and the conductive film, and the conductive crucible is firmly adhered to the substrate. Further, in the firing process, if an organic material (such as a vehicle liquid) remains in the film when the glass material is fluidized and the conductive powder starts to be sintered, the gas generated by the pyrolysis of the organic material is encapsulated in the film. It may cause bubbles (foam). Therefore, not only the appearance but also the density of the fired conductive film is lowered. The glass material of the present invention can effectively suppress air bubbles due to the fluidity of the glass material during firing. -10- 201207867 In accordance with the conductive paste of the present invention, the fired metal film is firmly maintained by the glass remaining at the interface between the fired metal particles, and a dense fired metal film structure is formed. Therefore, soldering hardly occurs and a conductive film having high adhesion strength can be obtained. Even if solder leaching occurs in the surface of a portion of the fired film, leaching does not easily progress to the lower portion, so it is assumed that the solder leaching resistance is thoroughly improved. Here, in the SEM observation of the conductive film obtained from the conductive paste of the present invention, it was found that some of the fine crystals assumed to be deposited by the glass material were deposited in the conductive film in a mesh-like appearance and formed a high-density film structure. . The conductive film in which such a crystal is deposited is assumed to be a particularly strong retention of the conductive powder. As a result, the tin-resistance against leaching is completely improved. However, even in the case where the crystal in which the crystal cannot be clearly observed by the SEM, a very good solder resist is obtained as compared with the conventional electroconductive film, and cerium oxide, zinc oxide and titanium oxide are added to the paste of the present invention. As the metal oxide (D), it can be more easily formed into a "construction" and a more reinforced conductive film. Wire & degree, and more surely prevent solder such as anti-cracking: solder resisting force 'The conductive paste of the present invention has "good characteristics of adhesion strength. For example, the substrate of the present invention Including insulating substrates (such as ceramic 'electric board paste such as oxidation, barium titanate, etc.), glass chain and glass ceramic substrate, 2 metal substrate with insulating film on the surface (if the plate is high) Excellent thick film conductor with strong intensity. -11-11 201207867 The conductive paste of the present invention is suitable for thick film conductor circuits, electrodes, etc. It is preferably used to form ceramic chip group capacitors and multilayer chip conductors and their formation The surface of the ceramic multilayer substrate is characterized by the conductive force obtained by firing the conductive paste. Thus, for example, the terminal electrode of the solder-coated electrical component of the present invention can be obtained by the present invention, for example, preferably for use in overall immersion. The main electrode obtained by the present invention in the case of electrode attachment welding at different positions. Further, the electrode of the present invention is excellent in acid resistance, so that the electrode can be preferably used in various types of substrates. Forming the upper body and 5 the conductive paste of the present invention (such as the electrode of the chip type resistive multilayer sheet type electronic component, and for the electric layer, etc., specifically, the film has an excellent solder anti-electric paste suitable for The conductive film on the substrate to be soldered or <and the substrate to be connected to the electrical component does not necessarily need to be soldered> and is broken in the solder bath to electrically conductive the pattern on the substrate of the substrate after the tin. The specific film is preferably used as a sheet. The conductive film obtained by the type resistor is confirmed to have, for example, a plating process to be performed. [Specific embodiment] The specific embodiment of the present invention differs from the nature, characteristics, and the like of the present invention. And evaluation of each sample (1) Preparation of the sample (1.1) Preparation of the glass material The glass raw materials were mixed to have the following materials, and each mixture was heated at a temperature of 1 600 ° C to melt the glass composition and melted. The mixture is on the graphite for H1 to 丨.5 hours. And quenching. The glass material obtained by quenching is ground by a 1 minute roll quenching machine for 48 hours, and the umbrella is used for the spring mill (using oxygen to prepare the cloth for the average particle size Λ 8 2 · 5 micron 201207867 Glass "A" to "0". Flat ^ $ Ten-grain size is the 50% particle size distribution and the cumulative value of the knife (D50) measured by the laser diffraction particle size analyzer ( According to Cao Yu), here, the original material of the glass material "Zhou Zhouzu," is not melted at a temperature of 1 600 ° C, so it is impossible to prepare the main material of the glass material, and the material system is attached with *. Table 1
(1.2)樣品1之製備 在下表中，本發明範圍以外之玻 使用三親磨機，將100重量份之平均粒度為〇 4微 未之球形銀粉與平均粒度為25微米之球形銀粉的銀粉 品口物（1 · 1重罝比）、4重量份之玻料F、及3 5重量份 之”重量％之乙基纖維素、4重量％之環氧樹脂與9〇 重量％之丁基卡必醇所形成的有機媒液混合及捏合。進 一步添加丁基卡必醇作為稀釋劑，且將黏度調整成在ι〇 rpm為300至600 Pa.s而製造導電糊。 然後使用250篩目之網板，將以上之導電糊網版印 刷在氧化鋁基板上，及將氧化鋁基板在85〇它之最高溫 度維持10分鐘而燒製以獲得測試片（其上形成預定圖= 之導電膜的氧化鋁基板）。將該測試片示為「樣品丨」。 -13- 201207867 (1 ·3)樣品2至1 5及比較樣品1至6之製備 將金屬粉末 '玻料Α及C至0、及各種金屬氧化物 以表2及3所示之比例混合，且如（1.2)所述而類似地製 造導電糊。然而樣品5及1 2係各以表中所示比例使用銀 粉與鎳粉之混合物或銀粉與鈀粉之混合物代替銀粉。其 使用與樣品1相同之媒液及稀釋劑，且將黏度調整成在 10 rpm 為 300 至 600 Pa.s。 201207867 <N< |樣品5 I 99.0 1 P 〇 〇 rn 1 1 1 ! 4.29 〇 〇 |樣品4 I 100.0 1 1 〇 ο rn 1 1 1 5.60 〇 〇 |樣品3 I 100.0 1 1 HH ο 寸 1 1 1 | 5.22 I 〇 〇 樣品2 100.0 1 1 ϋ ο 寸 1 » 1 ；5.31 〇 〇 |樣品1 | 100,0 | 1 1 ο 1 1 t 4.75 〇 〇 比較樣品6 100.0 1 « * ρ — I 1 1 1 2.85 〇 X 比較樣品5 100.0 1 1 ί·» q 1 1 t 2.85 〇 X 比較樣品4 100.0 1 1 * ω o 1 1 t 1 4.07 〇 X 比較樣品3 | 100.0 1 1 # Ρ p — 1 1 1 3.23 X X 比較樣品2 100.0 1 1 * υ p 寸’ 1 1 1 2.50 X X 比較樣品1 100.0 1 1 * < p 4 1 1 1 2.88 X X Ag粉 | Pd粉 Ni粉 1種類1 1 Ti〇2 | 1 ΖηΟ 1 ZrO, | 片電阻值[ηιΩ/匚]] 焊錫抗瀝濾力 氣泡 導電粉末 (重量份） 玻料 (重量份） 金屬氧化物 (重量份） e^ 樣品15 100.0 1 1 〇 〇 ο 〇 6.04 〇 〇 樣品14 100.0 1 1 Ο 〇 I m ο 1 5.00 〇 〇 樣品13 100.0 1 1 Ο ο ΓΊ ιη Ο 1 1 1 5.94 〇 〇 樣品12 95.0 〇 1 〇 Ο ^Τ) ο Ο ο 23.07 〇 〇 樣品11 100.0 1 1 〇 ο Ο 1 1 2.84 〇 〇 樣品10 100.0 1 1 Ο cn in ο 1 1 2.77 〇 〇 樣品9 o' 1 1 2 ο rn ο 1 1 3.10 〇 〇 樣品8 100.0 1 1 Ο ΓΛ Ο 1 1 2.99 〇 〇 樣品7 100.0 1 1 K Ο — ο ο »〇 ο 6.22 〇 〇 樣品6 | 100.0 1 1 α ρ — Ο Ο w-> tr> Ο 1_531 1 〇 〇 Ag粉 Pd粉1 Ni粉 種類 I Ti〇2 1 [ΖηΟ 1 1 Zr02 1 片電阻值[γπΩ/ΙΖΙ] 焊錫抗瀝濾力 氣泡 導電粉末 (重量份） 玻料 (重量份） 金屬氧化物 (重量份） s τ 201207867 皮對所獲得之導電糊進行類似前節(1 · 2)所述程序之裎 序以製備複數個測試片。將該測試片各示為「樣品2至 15」及「比較樣品1至6」。 (2)各樣品之性質、特徵等之評估 對各樣品U 15及比較樣品& 6測 抗…。各測量及評估項目之細節： = 至15及比較樣品…之測量及評估 、，°禾不於以上之表2及3。 (2.1) 氣泡之評估 目視地觀察各樣品。在未發現氣泡時將 〇」，及在發現氣泡時將樣品評估為「X」。 (2.2) 測量片電阻值（導電度之評估） 在各樣品中，藉數付&田+ μ , H，2002 型，測量 r 圍 η (如叫 InStrUments 毫米之0幸1 至2〇Ω)測量Ο.6毫米X62.5 間的電阻值。將所獲得之電阻值轉換 成膜厚為10微米之片電阻值。 “且值轉換 (2.3) 焊錫抗瀝濾力之評估 將各樣品^^清於^日士 Ρ日 。。之Sn/3Ag/〇.5Cu焊锡::中？後浸潰於溫度為26。 潰於焊錫浴中重複納共3 /日可1〇秒及取出。將此浸 後測量各樣品之導二:欠。在將樣品從焊錫浴取出之 估各樣品之桿锡抗渥濾力電阻值，且由所測量之結果評 量時，將樣品評估為「具體而言，在電阻值為可測 之上限時，將樣品評估為」「’及在電阻值超過測量範圍 句 X | ο '16- 201207867 使用本發明範圍内之破料？至 至15獲得良好之焊錫 L至〇的樣品】 两抗，歷濾力。然而在各估用太基 _ 圍外之玻料A、C及d认l 本發月乾 的比較樣品1至3中，盆焊姐 瀝濾力係評估為「χ」。 /、知錫抗 各使用玻料E、J及κ夕^ “。 久Κ之比較樣品4至6獲得 焊錫抗瀝濾力。然而在導 電膜之表面處觀察到氣泡。 此外在樣。σ 6至1 5中，即使是在將金 :於導電糊時仍獲得良好之焊錫抗遞遽力。此外，：： 口口 5至12之結果發現可充分地獲得本發明之優點，即使 是在摻合Ag以外之金屬粉末作為導電粉末時。 在樣品4、5、8至u、及13至15中，即使是在將 其$成分（Ba0、uw、Ti〇2、Zr〇2)包括於玻料中時仍 獲得良好之焊錫抗瀝濾力。 此外’對於使用玻料Ο之樣品4及13至15，以類 似（2.3)節之說明的方式重複地將各樣品浸潰於焊錫浴中 及測量電阻值，直到電阻值超過測量範圍，及將結果係 評估為「〇」之浸潰總次數示於表4作為焊錫抗瀝遽力 之指標。 “ 表4 樣品4 樣品13 樣品14 樣品15 金屬氧化物 (重量份） Ti02 - 0.5 - 0.5 ZnO - - 0.5 5 0 Zr02 - - 0.5 ~~~ 5 次渭緦次數 --- 3 4 本發明較佳具體實施例之第一態樣提供一種導電 糊’係包括（A)導電粉末’（B)包括氧化物當量為總共85 -17- 201207867 重里％以上之下述成分且實際上不包括鉛的玻料，該成 分f玻料中之比例為16至47重量％之Si〇2、33至52 重I %之Al2〇3、3至15重量％之Mg〇、15至45重量0/〇 之ΙΟ3，及（C)有機媒液。 依照本發明可獲得焊锡抗瀝滤力I良之導電膜及電 極 末 較佳為（A)導電粉末為其中銀為主成分之銀金屬粉 、本發明係使用趨於焊錫瀝濾之銀作為主成分之導電 成刀因此本發明具有焊錫抗瀝濾力之優點可由其獲益 更多。 車乂佳為導電糊進-步包含至少一種選自由氧化锆、 氧化欽與氧化鋅所組成的群組之金屬氧化物。 本發明因使用至少-種選自氧化結、氧化鈦與氧化 鋅之群組而可更為改良導電膜之焊錫抗瀝濾力。 在2010年7月13曰提出之曰 2〇1〇-158793號的全部揭示，包 二申凊案第 圖式、及摘要，在此全部併入作為參考，專利範圍、 雖然已顯不及敘述各種例示具體實施 明不限於所示之具體實施 仁疋本發 口此本發明夕$ 受以下申請專利範圍之範圍限制。 &圍思圖僅 【圖式簡單說明】 益 〇 【主要元件符號說明】 益 0 -18-(1.2) Preparation of Sample 1 In the following table, a glass outside the scope of the present invention was used, using a three-parent mill, 100 parts by weight of a silver powder having an average particle size of 4 micron spherical silver powder and spherical silver powder having an average particle size of 25 micrometers. Oral material (1 · 1 weight ratio), 4 parts by weight of glass F, and 35 parts by weight of "% by weight of ethyl cellulose, 4% by weight of epoxy resin and 9% by weight of butyl card The organic vehicle formed by the alcohol is mixed and kneaded. Further, butyl carbitol is added as a diluent, and the viscosity is adjusted to produce a conductive paste at ι rpm of 300 to 600 Pa.s, and then 250 mesh is used. The stencil, the above conductive paste screen is printed on the alumina substrate, and the alumina substrate is fired at a maximum temperature of 85 维持 for 10 minutes to obtain a test piece (on which a predetermined pattern = conductive film is formed) Alumina substrate). The test piece is shown as "sample 丨". -13- 201207867 (1 ·3) Preparation of Samples 2 to 15 and Comparative Samples 1 to 6 The metal powders 'glass frit and C to 0, and various metal oxides were mixed in the ratios shown in Tables 2 and 3, And a conductive paste was similarly produced as described in (1.2). However, Samples 5 and 12 each used a mixture of silver powder and nickel powder or a mixture of silver powder and palladium powder in the proportions indicated in the table instead of silver powder. It used the same vehicle and diluent as Sample 1, and adjusted the viscosity to 300 to 600 Pa.s at 10 rpm. 201207867 <N< |Sample 5 I 99.0 1 P 〇〇rn 1 1 1 ! 4.29 〇〇|Sample 4 I 100.0 1 1 〇ο rn 1 1 1 5.60 〇〇|Sample 3 I 100.0 1 1 HH ο 1 1 1 | 5.22 I 〇〇 sample 2 100.0 1 1 ϋ ο inch 1 » 1 ; 5.31 〇〇|sample 1 | 100,0 | 1 1 ο 1 1 t 4.75 〇〇Comparative sample 6 100.0 1 « * ρ — I 1 1 1 2.85 〇X Compare sample 5 100.0 1 1 ί·» q 1 1 t 2.85 〇X Compare sample 4 100.0 1 1 * ω o 1 1 t 1 4.07 〇X Compare sample 3 | 100.0 1 1 # Ρ p — 1 1 1 3.23 XX Comparative sample 2 100.0 1 1 * υ p inch ' 1 1 1 2.50 XX Comparative sample 1 100.0 1 1 * < p 4 1 1 1 2.88 XX Ag powder | Pd powder Ni powder 1 type 1 1 Ti〇2 | 1 ΖηΟ 1 ZrO, | Sheet resistance [ηιΩ/匚]] Solder anti-leaching bubble conductive powder (parts by weight) Glass (parts by weight) Metal oxide (parts by weight) e^ Sample 15 100.0 1 1 〇〇ο 〇 6.04 〇〇 sample 14 100.0 1 1 Ο 〇I m ο 1 5.00 〇〇 sample 13 100.0 1 1 Ο ο ΓΊ ιη Ο 1 1 1 5.94 〇〇 sample 12 95.0 〇1 〇Ο ^Τ) ο Ο ο 23.07 〇〇 Item 11 100.0 1 1 〇ο Ο 1 1 2.84 〇〇 sample 10 100.0 1 1 Ο cn in ο 1 1 2.77 〇〇 sample 9 o' 1 1 2 ο rn ο 1 1 3.10 〇〇 sample 8 100.0 1 1 Ο ΓΛ Ο 1 1 2.99 〇〇 sample 7 100.0 1 1 K Ο — ο ο »〇ο 6.22 〇〇 sample 6 | 100.0 1 1 α ρ — Ο Ο w->tr> Ο 1_531 1 〇〇Ag powder Pd powder 1 Ni powder Type I Ti〇2 1 [ΖηΟ 1 1 Zr02 1 sheet resistance [γπΩ/ΙΖΙ] Solder anti-leaching bubble conductive powder (parts by weight) Glass (parts by weight) Metal oxide (parts by weight) s τ 201207867 Pair The obtained conductive paste was subjected to a procedure similar to that described in the previous section (1.2) to prepare a plurality of test pieces. The test pieces were each shown as "samples 2 to 15" and "comparative samples 1 to 6". (2) Evaluation of properties, characteristics, and the like of each sample For each sample U 15 and comparative sample &6; Details of each measurement and evaluation project: = to 15 and comparative sample... measurement and evaluation, ° ° and not in Tables 2 and 3 above. (2.1) Evaluation of bubbles Each sample was visually observed. When no bubbles are found, 〇", and when the bubbles are found, the sample is evaluated as "X". (2.2) Measuring sheet resistance value (evaluation of conductivity) In each sample, borrowing & field + μ, H, 2002 type, measuring r η (for example, 0 for InStrUments mm 1 to 2 〇 Ω) Measure the resistance between Ο6 mm X62.5. The obtained resistance value was converted into a sheet resistance of a film thickness of 10 μm. “And value conversion (2.3) Evaluation of solder anti-leaching force Each sample was cleaned up on the day of the day. The Sn/3Ag/〇.5Cu solder:: medium and then immersed at a temperature of 26. Repeat for a total of 3 / day in the solder bath for 1 〇 second and take out. After immersing, measure the lead of each sample: owe. Take the sample from the solder bath and estimate the rod tin anti-cracking resistance value of each sample. When the measured result is evaluated, the sample is evaluated as "specifically, when the resistance value is the upper limit of the measurable value, the sample is evaluated as "" and the resistance value exceeds the measurement range sentence X | ο '16 - 201207867 Use of the material within the scope of the invention? Up to 15 samples of good solder L to bismuth] Two-resistance, diafiltering force. However, in each of the estimated BASE _ outside the glass A, C and d l In the comparative samples 1 to 3 of this month's dry, the leaching force of the basin welder was evaluated as “χ”. /, Zhixi anti-glass materials E, J and κ 夕 ^ ". Long-term comparison samples 4 to 6 to obtain solder anti-leaching force. However, bubbles were observed at the surface of the conductive film. Also in the sample. σ 6 In the case of 15, even when gold is used in the conductive paste, a good solder anti-repellency is obtained. In addition, the results of the mouths 5 to 12 are found to be sufficient to obtain the advantages of the present invention, even in the case of blending. When a metal powder other than Ag is used as the conductive powder, in the samples 4, 5, 8 to u, and 13 to 15, even if the component (Ba0, uw, Ti〇2, Zr〇2) is included in the glass Good solder leaching resistance is still obtained during the process. In addition, for samples 4 and 13 to 15 using glass crucibles, each sample was repeatedly immersed in a solder bath in a manner similar to that described in section (2.3). The resistance value is measured until the resistance value exceeds the measurement range, and the total number of times the result is evaluated as "〇" is shown in Table 4 as an indicator of the solder resisting resistance. "Table 4 Sample 4 Sample 13 Sample 14 Sample 15 Metal oxide (parts by weight) Ti02 - 0.5 - 0.5 ZnO - - 0.5 5 0 Zr02 - - 0.5 ~~~ 5 times of times - 3 4 A first aspect of the specific embodiment provides a conductive paste' comprising (A) a conductive powder '(B) comprising the following components having an oxide equivalent of a total of 85 -17 to 201207867 weight percent or more and substantially not including lead The ratio of the component f glass is 16 to 47% by weight of Si〇2, 33 to 52% by weight of Al2〇3, 3 to 15% by weight of Mg〇, and 15 to 45 weights of 0/〇3 And (C) an organic vehicle liquid. According to the present invention, it is preferable that the conductive film and the electrode of the solder resisting leaching force are (A) the conductive powder is a silver metal powder containing silver as a main component, and the present invention is used. The conductive slag which is used as the main component of the leaching of silver by soldering can therefore benefit from the advantages of the solder leaching resistance of the present invention. The ruthenium is preferably a conductive paste-step comprising at least one selected from the group consisting of zirconia and oxidized zirconia. a metal oxide of the group consisting of zinc oxide. The present invention is selected from at least one selected from oxidation The combination of titanium oxide and zinc oxide can improve the solder resisting leaching force of the conductive film. In July 13, 2010, the full disclosure of 〇2〇1〇-158793, the second application The drawings and the abstract are hereby incorporated by reference in their entirety herein in their entirety herein in its entirety herein in its entirety Range Limitation &Weith Map Only [Simplified Schematic Description] Yi Yi [Main Component Symbol Description] Benefit 0 -18-