200949861 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種導電性糊組成物，特別是關於一種 忐以950至1200 C之高溫燒成的耐熱導電性糊組成物。 【先前技術】 以形成電子電路或積層電子零件中各種基板之導電電 路或電極的方法而δ，一般大多使用導電性糊。 © 導電性糊，一般係由樹脂系黏合劑與溶劑所構成之有 機媒液（vehicle)中分散有作為導電成分之金屬導體粉末的 糊組成物’其於印刷或塗佈於陶瓷基板或陶瓷生胚片等之 後，藉由燒成使該有機媒液蒸發、分解，使剩下之導電成 为成為燒結體以形成電氣之優良導體，藉由該導電成分之 燒結體形成導電電路或電極。實際之使用上，係在將導電 性糊塗布或填充於陶瓷基板或陶瓷生胚片之表面或内部之 孔的狀態下’與該基板或板片一起實施加熱處理以蒸發、 ❹ 分解以除去有機媒液，並將作為導電成分之金屬導體粉末 彼此燒結而形成可通電之導電電路或電極。 導電成分而言’考量到價格、導電性及可在大氣中燒 成等因素，係廣泛使用Ag粉末。然而，在印刷或塗布有 導電性糊之陶瓷基板或陶瓷生胚片以約900°C前後之低溫 燒成時，雖能以Ag粉末來對應，但依用途該陶瓷基板或 陶瓷生胚片有時會以約9501至1200°C之高溫燒成。此時， 若以Ag粉末用作為導體之糊來形成配線或電極時，Ag 5 200949861 會擴散至基板或板片内，而使得有時會產生斷線或偏析等 不良情形。推測其係由於Ag之熔點約為961 9t：與燒成溫 度相較較低。因此，以往係採用下述方法，亦即藉由採用 使熔點較Ag高且即使在大氣中燒成亦不氧化之ρ《ΐ77〇<^ ) 及Pd(熔點為1550。〇等貴金屬與Ag合金化的方法、或將 耐熱金屬層之被膜形成於Ag粉末之表面的方法，以確保 導體之耐熱性。 G 例如，專利文獻1揭示有一種附有耐熱金屬層之銀粉， 其係將鎳、鎳合金、鈷或鈷合金等耐熱金屬層之被膜形成 於銀粉末之表面。 專利文獻1 ·日本特開2003 — 306701號公報 【發明内容】 然而，若為了提升耐熱性而使用屬貴金屬之Pt或Pd 時會有使導電性糊之製造成本上升之缺點。不使用貴金 ❹ 屬而提升導體之耐熱性的方法，如專利文獻1所揭示將耐 熱金屬層之被膜形成於Ag粉末之表面的方法，由於會增 加鍍敷等之被膜形成步驟，因此同樣地製造成本亦會上 升。 本發明係有鑑於習知技術所具有之此種問題點，其目 的在於提供一種電阻值較低之導電性糊組成物，其無須使 用將Ag與Pt或Pd等咼價貴金屬合金化或故意於Ag粉末 表面形成耐熱金屬層等方法，而含有具耐熱性之導體。 本發明人發現，藉由使用一般認為合金化會使軟化點 6 200949861 下降而不賦予耐熱性之Ag與Ni合金之霧化粉末，可獲得 具有耐熱性之導體，本發明之導電性糊組成物，其特徵在 ；係於AgNl合金之霧化粉末添加有含有cu之物質來作 為導電成分者。 亦即，若在大氣環境氣氛將Ag與Ni合金之霧化粉末 加以燒成時，在燒成_合金中之Ni會氧化，而於娜合 金之霧化粉末之表面形成Ni之氧化物。由於以此方式於 ❹ ❿BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste composition, and more particularly to a heat-resistant conductive paste composition which is fired at a high temperature of 950 to 1200 C. [Prior Art] A conductive paste is generally used in a method of forming a conductive circuit or an electrode of various substrates in an electronic circuit or a laminated electronic component. © Conductive paste is generally a paste composition in which a metal conductor powder as a conductive component is dispersed in an organic vehicle composed of a resin-based adhesive and a solvent. It is printed or coated on a ceramic substrate or ceramic. After the green sheet or the like, the organic vehicle liquid is evaporated and decomposed by firing, and the remaining conductive material becomes a sintered body to form an electric excellent conductor, and a conductive circuit or an electrode is formed by the sintered body of the conductive component. In actual use, the conductive paste is coated or filled in a hole on the surface or inside of the ceramic substrate or the ceramic green sheet, and heat treatment is performed together with the substrate or the sheet to evaporate and decompose to remove organic matter. The vehicle liquid and the metal conductor powder as a conductive component are sintered to each other to form a conductive circuit or electrode that can be energized. In terms of conductive components, Ag powder is widely used in consideration of factors such as price, conductivity, and firing in the atmosphere. However, when a ceramic substrate or a ceramic green sheet printed or coated with a conductive paste is fired at a low temperature of about 900 ° C, it can be made of Ag powder, but the ceramic substrate or ceramic green sheet has a use depending on the application. It is fired at a high temperature of about 9501 to 1200 °C. At this time, when a wiring or an electrode is formed using Ag powder as a paste of a conductor, Ag 5 200949861 may diffuse into the substrate or the sheet, which may cause a problem such as disconnection or segregation. It is presumed that the melting point of Ag is about 961 9t: it is lower than the firing temperature. Therefore, in the past, the following methods have been employed, that is, by using a ρ "ΐ77〇<^" and a Pd (melting point of 1550) which is higher in melting point than Ag and which is not oxidized even in the atmosphere. A method of alloying or a method of forming a film of a heat resistant metal layer on the surface of the Ag powder to ensure heat resistance of the conductor. G For example, Patent Document 1 discloses a silver powder with a heat resistant metal layer, which is made of nickel, A film of a heat-resistant metal layer such as a nickel alloy, a cobalt or a cobalt alloy is formed on the surface of the silver powder. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-306701. SUMMARY OF THE INVENTION However, in order to improve heat resistance, Pt or a precious metal is used. Pd has a disadvantage of increasing the manufacturing cost of the conductive paste. A method of improving the heat resistance of the conductor without using a noble metal, as disclosed in Patent Document 1, a method of forming a film of a heat resistant metal layer on the surface of the Ag powder Since the film forming step such as plating is increased, the manufacturing cost is also increased in the same manner. The present invention has such a problem in view of the prior art, and its object is to provide A conductive paste composition having a low electric resistance value, which does not require the use of a method of alloying Ag with a noble metal such as Pt or Pd or deliberately forming a heat resistant metal layer on the surface of the Ag powder, and contains a conductor having heat resistance. It has been found that a conductive paste having a heat resistance can be obtained by using an atomized powder of an Ag and a Ni alloy which is generally considered to be alloyed to lower the softening point 6 200949861 without imparting heat resistance, and the conductive paste composition of the present invention The atomized powder of the AgNl alloy is added with a substance containing cu as a conductive component. That is, if the atomized powder of Ag and Ni alloy is fired in an atmospheric atmosphere, the alloy is fired. Ni is oxidized, and the oxide of Ni is formed on the surface of the atomized powder of Na Na alloy.
AgNl合金之霧化粉末之表面自然形成氧化物之被膜， 因，恰好呈現於Ag粉末表面實施氧化物之塗布的狀態， 而提升耐熱性。又，由於r r a > 由於Cu在100〇°c以下會氧化而成為The surface of the atomized powder of the AgNl alloy naturally forms an oxide film, and the heat resistance is improved by the fact that the surface of the Ag powder is coated with an oxide. Further, since r r a > is oxidized due to oxidation of 100 〇 ° C or less
CuO ’在1000°c以上之 服度會成為Cu2〇(熔點為1230。〇， 因此可進一步提升耐熱性。 物，：發明，可提供一種電阻值較低之導電性糊組成 故音二Γ使用將Ag與Pt或Pd等高價貴金屬合金化或 熱性之導體。 （，，、金屬層專方法，而含有具对 【實施方式】 :二針對用以實施本發明之最佳形態作說明。 ^粉末相同之方法獲二雷之步驟，而能以與製作霧化 性之導電成分。于導電成分，因此可廉價製作具对熱 霧化法（atomizing)係指為了 升耐熱金屬材料之可靠 砠成或組織以提 靠洗，从製得均質且微細之組織所實 7 200949861 施的方法’係將金屬之熔液喷霧並予以急速冷卻加以微細 化的方法。本發明可採用之霧化法係有以下所說明之水霧 化法、氣體霧化法、及真空霧化法等。 (1) 水霧化法係將射出壓力為15MPa左右之高壓水 噴射至熔融金屬之熔流的方法，可製得平均粒徑約為丨 之微粉。所製得之微粉形狀大多不一定◦冷卻速度約為ι〇3 〜10 K/sec。若喷射超過20MPa之高壓喷射水時，即可製 得數μηι左右之粒徑的微粉。 ❹ (2) 氣體霧化法係將&或Ar氣體喷霧以取代水霧化 之高壓水的方法。可製得氧化較少且為球狀之粉末。氣體 噴霧方式有自然落下式與拘束式。 (3) 真空霧化法係於真空中藉由壓差喷出充分吸收有 &之熔融金屬的方法，可製得球狀之粉末。純度係與氣體 噴霧所製造者相同程度。 (4) 其他霧化法亦可採用「藉由相對之輥間之空蝕現 ❹ 象（caviatation)將熔融金屬流予以粉化，在水中驟冷之雙輥 霧化法」、「藉由與旋轉體之碰撞將熔融金屬流粉化，在 水中驟冷之衝擊霧化法」、或「將熔融金屬流注入旋轉之 水中，以製得急速冷卻凝固粉之旋轉水霧化法」等。 由於Ag之合金粉末相較於Ag為1〇〇%之粉末其電阻 會變高，因此為了抑制電阻值之上升，藉由燒成於Ag粉 末之表面所形成之氧化物的被膜厚度係以較薄者為較佳 另一方面，若形成於Ag粉末表面之氧化物的被臈厚度過 薄時，則耐熱性會無法提升。因此，必須考量電阻值二耐 200949861 熱性之均衡以選擇較佳之合金組成。亦即，以々為9〇〇 〜99.9重量％且犯為（M〜10.0重量％較佳。若Ni未滿〇1 重綱’則無法獲得與岣為100%之粉末相同程度的耐 熱性。另-方面Ni超過動重量科，則電阻值會 變高而不適合使用作為導電性糊。The CuO's service at 1000 ° C or higher will become Cu 2 〇 (melting point is 1230. 〇, therefore, the heat resistance can be further improved. Object: Invented, a conductive paste having a lower resistance value can be provided. Ag is alloyed with a high-priced noble metal such as Pt or Pd or a thermally conductive conductor. (,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The same method obtains the steps of the second ray, and can produce the atomized conductive component in the conductive component, so that it can be inexpensively manufactured. The atomizing method refers to the reliable formation of the heat-resistant metal material or The tissue is washed and cleaned, and the method of applying the homogeneous and fine structure is the method of spraying the molten metal of the metal and rapidly cooling it to be refined. The atomization method which can be used in the present invention is The water atomization method, the gas atomization method, the vacuum atomization method, etc. described below. (1) The water atomization method is a method of spraying high-pressure water having an injection pressure of about 15 MPa to a molten metal melt stream. Average grain The diameter of the powder is about 丨. The shape of the fine powder is not necessarily the cooling rate of about ι〇3 to 10 K/sec. If the high-pressure spray water of more than 20 MPa is sprayed, the particle size of several μηι can be obtained.微 (2) The gas atomization method is a method of spraying & or Ar gas to replace the water atomized high-pressure water. It can produce a powder which is less oxidized and spherical. The gas spray method naturally falls. (3) Vacuum atomization method is a method in which a molten powder is sufficiently absorbed by a pressure difference in a vacuum to obtain a spherical powder. The purity is the same as that of a gas spray manufacturer. (4) Other atomization methods may also employ a "two-roll atomization method in which a molten metal stream is pulverized by a cavitation between rolls, and a two-roll atomization method is performed in water." An impact atomization method in which a molten metal is pulverized by collision with a rotating body, and is quenched in water, or a "spinning water atomization method in which a molten metal stream is injected into a rotating water to obtain a rapid cooling solidified powder" Since the alloy powder of Ag is 1% by weight of powder compared to Ag Since the resistance becomes high, in order to suppress the increase in the resistance value, the film thickness of the oxide formed by firing on the surface of the Ag powder is preferably thinner, and the oxidation formed on the surface of the Ag powder. When the thickness of the bedding of the object is too thin, the heat resistance may not be improved. Therefore, it is necessary to consider the balance of the resistance value of the second resistance of 200949861 to select a better alloy composition. That is, the enthalpy is 9 〇〇 to 99.9 wt% and is guilty. It is preferably (M to 10.0% by weight. If Ni is less than 〇1, the heat resistance is not obtained as much as 100% of the powder of yttrium. In addition, if Ni exceeds the kinetic weight, the resistance value becomes high. Not suitable for use as a conductive paste.
AgNi合金之霧化粉末的平均粒徑，係以丨〇〜1〇, 較佳。未滿Ι.Ομιη之粉末係難以製造。另一方面，若超過 ΙΟ.Ομηι時，則在糊化時容易產生箱而難以製得本發明之目 的之糊。 此外，進行Ag系之導體與低溫燒成陶瓷基板的同時 燒成時’會有兩者之收縮行為大幅不同的缺點。於燒成開 始後，在300〜40(TC下有機物（黏合劑樹脂等）會熱分解， Ag系之導電性糊會因Ag燒結而開始收縮’但由於低溫燒 成陶竟生胚片係以玻璃為主成分，因此一般係在該玻璃成 分開始熔解之650°C附近才開始收縮。 因此，在約400。(：至650。(：附近之溫度區域，Ag系之 導體與低溫燒成陶瓷基板之收縮率的差會隨著溫度上升而 擴大。當兩者之收縮率的差變大時，在兩者之接合部會產 生較大熱應力，有時會造成燒成基板翹曲、或接合部之接 合強度降低而導致接合部剝離。再者，近年來伴隨著電子 零件之無鉛化，陶瓷材料亦逐漸以無鉛之材料為主流。因 此，由於陶瓷之收縮開始溫度係往高溫側移動且陶瓷本身 會結晶化’因此熱收縮之速度亦變得相當快。因此，Ag系 導體之收縮率與低溫燒成陶瓷基板之收縮率的差係更為擴 9 200949861 大’於燒成後之基板產生龜裂或翹曲之情形已變得更為顯 • 著0 因此’若使用本發明之霧化粉末’由於Ni氧化物之被 膜係自然形成於Ag粉末之表面，因此可期待具有提高導The average particle diameter of the atomized powder of the AgNi alloy is preferably 丨〇1 to 1 Torr. Powders that are not full. Ομιη are difficult to manufacture. On the other hand, when it exceeds ΙΟ.Ομηι, it is easy to produce a box at the time of gelatinization, and it is difficult to obtain the paste of the present invention. Further, when the Ag-based conductor and the low-temperature fired ceramic substrate are simultaneously fired, there is a disadvantage that the shrinkage behavior of the two is greatly different. After the start of firing, at 300 to 40 (the organic matter (adhesive resin, etc.) is thermally decomposed under TC, the Ag-based conductive paste starts to shrink due to Ag sintering, but the low-temperature firing of the ceramics is based on glass. The main component is generally contracted at about 650 ° C where the glass component begins to melt. Therefore, at about 400 (: to 650 ° (in the vicinity of the temperature region, the Ag-based conductor and the low-temperature fired ceramic substrate) The difference in shrinkage rate increases as the temperature rises. When the difference between the shrinkage ratios of the two increases, a large thermal stress occurs at the joint between the two, which may cause warpage of the fired substrate or joints. In addition, in recent years, with the lead-free electronic components, ceramic materials have gradually become lead-free materials. Therefore, since the shrinkage start temperature of the ceramics moves toward the high temperature side and the ceramic itself, the bonding strength is lowered. It will crystallize', so the speed of heat shrinkage is also quite fast. Therefore, the difference between the shrinkage ratio of the Ag-based conductor and the shrinkage ratio of the low-temperature fired ceramic substrate is further expanded. 9 200949861 Large's base after firing Cracks or warping of the case has become significantly more pronounced • 0 Thus 'The use of atomized powder of the present invention' Ni-based film due to the natural oxide formed on the surface of the Ag powder, having improved conductivity can be expected
體之熱收縮開始溫度的作用。因此，可抑制基板之龜裂 翹曲的產生。 S 較佳為將含有Cu之物質以Cu換算為〇」至15 〇重量 %添加於導電性糊中。若以Cu換算未滿〇ι重量％ 盔 法提升耐熱性，若以^換算超過15 〇重量時，則電阻: 會變高。含有Cu之物質而言，可選自Cu、Cu〇 Cu2〇、The heat shrinkage of the body begins to function as a temperature. Therefore, the occurrence of crack warpage of the substrate can be suppressed. S is preferably added to the conductive paste in a mass ratio of Cu to 5% by weight in terms of Cu. If the heat resistance is increased by the helmet method in the range of less than 5% by weight in terms of Cu, if the weight is more than 15 换算, the resistance will increase. The substance containing Cu may be selected from Cu, Cu〇 Cu2〇,
Cu之無機鹽或Cu之有機酸鹽中之i種以上之物質。α之 無機鹽而言，可列舉例如氯化銅或石肖酸銅等。Cu之有機酸 鹽而言，可列舉例如油酸鋼、檸檬酸銅、葡萄糖酸銅、及 苯二甲酸銅等。 導電性糊中導體粉末與有機媒液之比例，可採用一般 ©之換合比例。例如，導體粉末重量份對有機媒液重量份係 以8〇對2〇至9〇對1〇較佳。若導體粉末未滿80重量份（有 機媒液超過20重量份）時， 貝J由於導體之電阻值會變高而 降低電氣特性因此不佳。甚道秘 右导體粉末超過90重量份（有機 媒液未滿10重量份）時，則 么交必丄 則由於無法獲得適切之糊黏度而 杜 配線圖案形成之作業效率因此不 佳。 有機媒液係包含黏合劍樹脂（ 脂、及丙烯酸系樹脂等）、與 办 r ' 、有機4劑（例如，松香醇、及 10 200949861 * 乙酸丁卡必醇酯等），視須要亦可添加可塑劑、分散劑、或 玻璃料（glass frit)等。 [實施例] 以下’雖說明本發明之實施例，但本發明並不限於下 述實施例，在不逸脫本發明之技術範圍内可作適當變更與 修正。 如以下表1所示’將平均粒徑為5 μιη之Ag與Ni之 合金（Ag為97重量％，Ni為3重量％)的霧化粉末（以N2 赁霧所製成者）75至80重量％、以Cu換算含有Cu之物質 為0.1至15.0重量％、及以松香醇溶解乙基纖維素樹脂之 有機媒液1 0.0至1 9.9重量％使用三輥磨機加以混合，以 製得導電性糊。 又’為了供比較，如以下表2所示，將同上之Ag與 Ni之合金的霧化粉末8〇重量％、及同上之有機媒液2〇重 量％使用二輥磨機加以混合，或將同上之Ag與Ni之合金 Q 的霧化粉末80重量％、不含CU之無機物5.0重量％、及 同上之有機媒液15.0重量％使用三輥磨機加以混合藉此 製得比較例之導電性糊。 接著，使用此等導電性糊，藉由網版印刷於氧化鋁基 板（未圖不）上形成如圖i所示之配線圖案丄，以12〇力進行 10 77鐘之乾燥後，以大氣環境氣氛下之批式燒成爐 type kiln) ’針對實施例6係在以12〇〇它保持分鐘之條 件下燒成針對其他所有實施例及比較例則在以！ i 5〇。〔保 持20分鐘之條件下燒成。 11 200949861 接著，以目視確認燒成後之基板表面有無斷線。又， 在圖1所示之配線圖案1中，針對圖2所示之配線圖案2(線 寬w=10(^m)，測量將電阻換算成每單位面積之數值的薄 片電阻值ΟπΩ/ππηνίΟμπι)。將該有無斷線及薄片電阻值表 示於表1及表2。 [表1] ❹Any one or more of the inorganic salt of Cu or the organic acid salt of Cu. Examples of the inorganic salt of α include copper chloride or copper lithosperate. Examples of the organic acid salt of Cu include oleic acid steel, copper citrate, copper gluconate, and copper phthalate. The ratio of the conductor powder to the organic vehicle in the conductive paste can be adjusted in the usual ratio of ©. For example, the weight fraction of the conductor powder is preferably 8 Å to 2 Torr to 9 Torr to 1 Å by weight based on the weight of the organic vehicle. When the conductor powder is less than 80 parts by weight (more than 20 parts by weight of the organic solvent), the shell J is deteriorated because the resistance value of the conductor becomes high and the electrical characteristics are lowered. When the right conductor powder exceeds 90 parts by weight (the organic medium is less than 10 parts by weight), the work efficiency of the formation of the wiring pattern is not good because the appropriate paste viscosity cannot be obtained. The organic medium contains adhesive resin (fat, acrylic resin, etc.), and R', organic 4 (for example, rosin alcohol, and 10 200949861 * butyl carbitol acetate, etc.), if necessary, can also be added A plasticizer, a dispersant, or a glass frit. [Embodiment] The following is a description of the embodiments of the present invention, but the present invention is not limited to the embodiments described below, and may be appropriately modified and modified without departing from the technical scope of the present invention. As shown in Table 1 below, an atomized powder of an alloy of Ag and Ni (Ag of 97% by weight and Ni of 3% by weight) having an average particle diameter of 5 μm (manufactured by N2 mist) 75 to 80 % by weight, 0.1 to 15.0% by weight of a substance containing Cu in terms of Cu, and 0.0 to 19.9% by weight of an organic vehicle solution in which an ethyl cellulose resin is dissolved in rosin alcohol, and are mixed using a three-roll mill to obtain a conductive material. Sex paste. 'For comparison, as shown in the following Table 2, the atomized powder of the alloy of Ag and Ni is 〇8 wt%, and the same organic solvent 2 wt% is mixed using a two-roll mill, or 80% by weight of the atomized powder of the alloy Q of Ag and Ni, 5.0% by weight of the inorganic substance not containing CU, and 15.0% by weight of the organic vehicle liquid as above, which were mixed using a three-roll mill to obtain the conductivity of the comparative example. paste. Next, using these conductive pastes, a wiring pattern 如图 as shown in FIG. 1 is formed on the alumina substrate (not shown) by screen printing, and dried for 10 77 hours at 12 〇, and then atmospheric atmosphere. The batch type firing furnace type kiln) in the atmosphere is fired under the conditions of 12 〇〇 for 2 minutes for all other examples and comparative examples. i 5〇. [Breaze in the condition of 20 minutes. 11 200949861 Next, it was visually confirmed whether or not the surface of the substrate after firing was broken. Moreover, in the wiring pattern 1 shown in FIG. 1, with respect to the wiring pattern 2 shown in FIG. 2 (line width w=10 (^m), the sheet resistance value ΟπΩ/ππηνίΟμπι which converts the electric resistance into the value per unit area is measured. ). The presence or absence of the disconnection and sheet resistance values are shown in Tables 1 and 2. [Table 1] ❹
G Ϊ 姐成(重 Έ%Γ^—- 牯性 Ag/Ni 合金霧 化粉 Cu CuO Cu20 油酸鋼 CuCl2 有機 媒液 導體薄片電 阻(ιηΩ/〇 /ΙΟμιη) 導體 斷線 實施例1 80.0 0.1 0 0 0 〇 IQ Q < 實施例2 80.0 0.5 0 0 0 ~~ **~ 0 19.5 3 無 實施例_3 80.0 1.0 0 0 0 0 1Q 0 3 無 實施例4 80.0 3.0 0 0 0〜 0 17.0 4 無 實施例5 80.0 5.0 0 0 0 0 15.0 5 無 實施例6 80.0 5.0 0 0 0 0 15.0 5 無 實施例7 75.0 15.0 0 0 0 0 10.0 30 無 實施例8 80.0 0 0.2 0 0 0 19.8 5 無 實施例9 80.0 0 1.5 0 0 0 ， 18.5 3 無 實施例10 80.0 0 2.5 0 0 0 17.5 3 無 實施例11 80.0 0 3.5 0 0 0 16.5 4 無 實施例12 80.0 0 6.0 0 0 0 14.0 6 無 實施例13 80.0 0 0 2.0 0 0 18.0 4 無 實施例14 80.0 0 0 0 4.0 0 16.0 4 無 實施例15 80.0 0 0 0 0 19.0 3 無 [表2 且成(重 ί%) -- 特性 Ag/Ni 合金喷 霧粉 ZnO MgO Zr〇2 Pd Μη02 有機 媒液 導體薄片電 阻(ιηΩ/口 /ΙΟμιη) 導體 斷線 比較例1 80.0 0 0 0 0 0 20.0 無法測量 有 比較例2 80.0 5.0 0 0 0 0 15.0 無法測量 有 比較例3 80.0 0 5.0 0 0 0 15.0 無法測量 有 比較例4 80.0 0 0 5.0叫 0 I 0 15.0 無法測量 有 比較例5 80.0 0 0 0 5.0 0 15.0 無法測量"Ί 有 比較例6 80.0 0 0 0 0 5.0 15.0 無法測量 有 12 200949861 • 如表1所示，本發明之實施例1至15相關者皆無法在 配線圖案觀察到斷線，可知本發明之導電性糊組成物係具 有至1200°C之耐熱性且為電阻值較低之導電物質。 然而，由於比較例1未添加任何AgNi合金之霧化粉 末’比較例2至6則於AgNi合金之霧化粉末添加不含Cu 之無機物’因此可在圖1所示之圖案1的某些部位確認到 $ 斷線，而無法測量薄片電阻。 產業上之可利用性 本發明之導電性糊組成物由於耐熱性優異，因此可在 暴露於高溫使用環境下之電子零件相關產業廣泛使用。 【圖式簡單說明】 圖1係表示配線圖案之一例的俯視圖。 圖2係表示圖1之配線圖案的一部分的圖。 ❹ 【主要元件符號說明】 1 配線圖案 2 配線圖案 13G Ϊ 姐成(重Έ%Γ^—- Ag Ag/Ni alloy atomized powder Cu CuO Cu20 oleic acid steel CuCl2 organic medium liquid conductor sheet resistance (ιηΩ/〇/ΙΟμιη) conductor disconnection example 1 80.0 0.1 0 0 0 〇IQ Q < Example 2 80.0 0.5 0 0 0 ~~ **~ 0 19.5 3 None Example _3 80.0 1.0 0 0 0 0 1Q 0 3 No Example 4 80.0 3.0 0 0 0~ 0 17.0 4 None Example 5 80.0 5.0 0 0 0 0 15.0 5 No Example 6 80.0 5.0 0 0 0 0 15.0 5 No Example 7 75.0 15.0 0 0 0 0 10.0 30 No Example 8 80.0 0 0.2 0 0 0 19.8 5 No implementation Example 9 80.0 0 1.5 0 0 0 , 18.5 3 No Example 10 80.0 0 2.5 0 0 0 17.5 3 None Example 11 80.0 0 3.5 0 0 0 16.5 4 No Example 12 80.0 0 6.0 0 0 0 14.0 6 No Example 13 80.0 0 0 2.0 0 0 18.0 4 None Example 14 80.0 0 0 0 4.0 0 16.0 4 None Example 15 80.0 0 0 0 0 19.0 3 None [Table 2 and into (weight %) -- Characteristic Ag/Ni alloy Spray powder ZnO MgO Zr〇2 Pd Μη02 Organic medium liquid conductor sheet resistance (ιηΩ/口/ΙΟμιη) Conductor disconnection comparison example 1 80.0 0 0 0 0 0 20.0 Unable to measure with comparison example 2 80 .0 5.0 0 0 0 0 15.0 Unable to measure with comparison example 8 80.0 0 5.0 0 0 0 15.0 Unable to measure with comparison example 4 80.0 0 0 5.0 is called 0 I 0 15.0 Unable to measure with comparison example 8 8 0 0 0 0 5.0 0 15.0 Measurement "ΊComparative Example 6 80.0 0 0 0 0 5.0 15.0 Unmeasured with 12 200949861 • As shown in Table 1, none of the embodiments 1 to 15 of the present invention can observe the disconnection in the wiring pattern, and the present invention is known. The conductive paste composition has a heat resistance to 1200 ° C and is a conductive material having a low electric resistance value. However, since Comparative Example 1 does not add any atomized powder of an AgNi alloy, 'Comparative Examples 2 to 6 are in the AgNi alloy. The atomized powder was added with an inorganic substance containing no Cu. Therefore, it was confirmed that the wire was broken at some portions of the pattern 1 shown in Fig. 1, and the sheet resistance could not be measured. Industrial Applicability The conductive paste composition of the present invention is excellent in heat resistance, and therefore can be widely used in an electronic component related industry exposed to a high-temperature use environment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing an example of a wiring pattern. Fig. 2 is a view showing a part of the wiring pattern of Fig. 1. ❹ [Main component symbol description] 1 Wiring pattern 2 Wiring pattern 13