TW202311447A

TW202311447A - Electrode paste and method of preparing electrode thick film therefrom

Info

Publication number: TW202311447A
Application number: TW110133483A
Authority: TW
Inventors: 江傳宗; 劉賾銘; 李皇諭
Original assignee: 道登電子材料股份有限公司
Priority date: 2021-09-09
Filing date: 2021-09-09
Publication date: 2023-03-16

Abstract

An electrode paste and a method of preparing electrode thick film therefrom are provided. The electrode paste comprises 70~90 wt% of metal powder; 1~8 wt% of glass composition; 5~30 wt% of organic binder; and 2~30 wt% of solvent; wherein the glass composition is Li₂O-ZnO-Al₂O₃-Na₂O-SrO-V₂O₅-B₂O₃-SiO₂. The electrode paste may be sintered in a lower temperature, while the electrode thick film prepared therefrom has excellent electrical performance.

Description

電極膏體及電極厚膜之製備方法Preparation method of electrode paste and electrode thick film

本發明關於一種電極膏體及電極厚膜之製備方法，尤指一種應用於製備厚膜晶片電阻的電極膏體以及使用其之製備電極厚膜的方法。The present invention relates to an electrode paste and a method for preparing an electrode thick film, in particular to an electrode paste used in the preparation of a thick film chip resistor and a method for preparing an electrode thick film using the same.

於現今的電子產品中，電阻是應用最為廣泛的被動元件之一，其應用範圍包含高頻晶片電阻、車載車用電子產品、消費性電子產品、及家電產品等。其中常見的厚膜晶片電阻，採用厚膜工藝印刷而成，這種電阻有多種形狀，主要多應用在功率電阻和精密電阻中。In today's electronic products, resistors are one of the most widely used passive components, and their applications include high-frequency chip resistors, automotive electronics, consumer electronics, and home appliances. Among them, the common thick film chip resistors are printed by thick film process. This kind of resistors have various shapes and are mainly used in power resistors and precision resistors.

在厚膜晶片電阻的導電漿料製作技術中，導電金屬粉大多以金或銀等貴重金屬粉末為主，尤其以銀粉末的應用最廣泛。然其成本較高以外，使用銀金屬作為導電膏的材料並應用於電容器或電阻時，在溼熱條件下銀離子遷移性高，故容易影響元件本身的電性，一般而言添加鈀金屬可抑制此問題，然而，鈀金屬的價格又高於銀金屬，故整體導電漿料不符主流的成本考量。In the conductive paste production technology of thick film chip resistors, the conductive metal powder is mostly precious metal powder such as gold or silver, especially silver powder is the most widely used. However, in addition to its high cost, when silver metal is used as the material of conductive paste and applied to capacitors or resistors, silver ion migration is high under hot and humid conditions, so it is easy to affect the electrical properties of the component itself. Generally speaking, adding palladium metal can inhibit However, the price of palladium metal is higher than that of silver metal, so the overall conductive paste does not meet the mainstream cost considerations.

為了解決上述問題，使用價格相對低廉的卑金屬來取代貴重金屬以做為導電材料的方法日漸成為趨勢，例如使用銅、鎳、或鋁金屬。其中，鋁金屬雖然有較好的化學穩定性，然作為電極時，其與基板間的貼附性與耐硫化的測試結果不如預期。而當使用銅或鎳金屬作為電極時，因穩定性的問題需要在低氧狀態下進行燒結，而目前的解決方案大多是使用包括稀土金屬摻雜的玻璃粉末，其價格昂貴以外，高頻導電的特性不如預期。In order to solve the above problems, it is increasingly becoming a trend to replace noble metals with relatively cheap base metals as conductive materials, such as copper, nickel, or aluminum. Among them, although aluminum metal has good chemical stability, when it is used as an electrode, the test results of its adhesion to the substrate and resistance to sulfuration are not as expected. When copper or nickel metal is used as the electrode, sintering in a low-oxygen state is required due to stability problems. Most of the current solutions use glass powder doped with rare earth metals, which are expensive and high-frequency conductive. properties are not as expected.

因此，目前急需一種新穎的電極膏體，其組成中使用卑金屬取代貴重金屬以大幅降低製備成本以外，其與基板材料之間具有優異的接著力以及低介電損耗特性，且相較於銀電極材料而言，可於相對低溫下進行燒結並達到緻密，尤其應用於晶片電阻的陶瓷基材上可以做一次性共燒，可大幅降低燒結成本以及簡化製備程序。Therefore, there is an urgent need for a novel electrode paste, which uses base metals instead of precious metals to greatly reduce the preparation cost, and has excellent adhesion and low dielectric loss characteristics with the substrate material, and compared with silver As far as electrode materials are concerned, they can be sintered at a relatively low temperature to achieve densification, especially for ceramic substrates used in chip resistors, which can be co-fired at one time, which can greatly reduce the sintering cost and simplify the preparation process.

為達上述目的，本發明提供一種電極膏體，該電極膏體包括：70~90 wt%的金屬粉末；1~8 wt%的玻璃組成物；5~30 wt%的有機黏結劑；以及2~30 wt%的溶劑；其中，該玻璃組成物為Li ₂O-ZnO-Al ₂O ₃-Na ₂O-SrO-V ₂O ₅-B ₂O ₃-SiO ₂，包括0.5~5 wt%的Li ₂O、20~50 wt%的ZnO、1~5 wt%的Al ₂O ₃、1~10 wt%的Na ₂O、0.5~5 wt%的SrO、1~15 wt%的V ₂O ₅、20~50 wt%的B ₂O ₃、以及1~10 wt%的SiO ₂。 In order to achieve the above object, the present invention provides an electrode paste, which comprises: 70-90 wt% metal powder; 1-8 wt% glass composition; 5-30 wt% organic binder; and 2 ~30 wt% solvent; wherein, the glass composition is Li ₂ O-ZnO-Al ₂ O ₃ -Na ₂ O-SrO-V ₂ O ₅ -B ₂ O ₃ -SiO ₂ , including 0.5~5 wt% Li ₂ O, 20~50 wt% ZnO, 1~5 wt% Al ₂ O ₃ , 1~10 wt% Na ₂ O, 0.5~5 wt% SrO, 1~15 wt% V ₂ O ₅ , 20-50 wt% of B ₂ O ₃ , and 1-10 wt% of SiO ₂ .

於一實施態樣中，該電極膏體於一惰性氣體下進行一燒結步驟所製得的一電極厚膜的片電阻小於7 mΩ。In an embodiment, the electrode paste is subjected to a sintering step under an inert gas so that the sheet resistance of an electrode thick film is less than 7 mΩ.

於一實施態樣中，該玻璃組成物的軟化點在400~900 °C。In an embodiment, the glass composition has a softening point of 400-900°C.

於一實施態樣中，該玻璃組成物的平均粒徑為1~10μm。In an embodiment, the average particle size of the glass composition is 1-10 μm.

於一實施態樣中，該金屬粉末為一銅粉、一銀包銅粉、或一BaTiO ₃粉。其中，該銀包銅粉中銀與銅的比例為20：80 wt%。 In an embodiment, the metal powder is a copper powder, a silver-coated copper powder, or a BaTiO ₃ powder. Wherein, the ratio of silver to copper in the silver-coated copper powder is 20:80 wt%.

於一實施態樣中，該金屬粉末的平均粒徑為0.1 ~10μm。In an embodiment, the average particle size of the metal powder is 0.1-10 μm.

於一實施態樣中，該有機黏結劑為一熱硬化性樹脂、一熱塑性樹脂、或其混合物。其中，該熱硬化性樹脂係至少一選自由環氧樹脂、胺酯樹脂、乙烯酯樹脂、矽酮樹脂、酚樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯樹脂、及聚醯亞胺樹脂所組成之群組，該熱塑性樹脂係至少一選自由乙基纖維素、丙烯酸樹脂、醇酸樹脂、飽和聚酯樹脂、丁醛樹脂、聚乙烯醇、及羥丙基纖維所組成之群組。In one embodiment, the organic binder is a thermosetting resin, a thermoplastic resin, or a mixture thereof. Wherein, the thermosetting resin is at least one selected from epoxy resin, urethane resin, vinyl ester resin, silicone resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate The group consisting of ester resin and polyimide resin, the thermoplastic resin is at least one selected from ethyl cellulose, acrylic resin, alkyd resin, saturated polyester resin, butyral resin, polyvinyl alcohol, and hydroxy A group composed of propyl fibers.

於一實施態樣中，該溶劑係至少一選自由有機酸類、芳香族烴類、吡咯啶酮類、醯胺類、酮類、及環狀碳酸酯所組成之群組。其中，該有機酸類可例如為二乙二醇***醋酸酯、二乙二醇丁醚醋酸酯、或醋酸乙酯；該芳香族烴類可例如為甲苯、或二甲苯；該吡咯啶酮類可例如為N-甲基-2-吡咯啶酮(NMP)；該醯胺類可例如為N,N-二甲基甲醯胺(DMF)；該酮類可例如為甲基乙基酮(MEK)；該環狀碳酸酯可例如為萜品醇(Terpineol)；或丁基卡必醇(BC)。In one embodiment, the solvent is at least one selected from the group consisting of organic acids, aromatic hydrocarbons, pyrrolidones, amides, ketones, and cyclic carbonates. Wherein, the organic acids can be, for example, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, or ethyl acetate; the aromatic hydrocarbons can be, for example, toluene or xylene; the pyrrolidones can be Such as N-methyl-2-pyrrolidone (NMP); the amides can be, for example, N,N-dimethylformamide (DMF); the ketones can be, for example, methyl ethyl ketone (MEK ); the cyclic carbonate can be, for example, terpineol (Terpineol); or butyl carbitol (BC).

於一實施態樣中，該電極膏體的黏度為20至100 Pa.s。In an embodiment, the electrode paste has a viscosity of 20 to 100 Pa.s.

於一實施態樣中，該電極膏體更包括至少一金屬氧化物，至少一選自由氧化銅、氧化鉍、氧化錳、氧化鈷、氧化鎂、氧化鉭、氧化鈮、及氧化鎢所組成之群組。In one embodiment, the electrode paste further includes at least one metal oxide, at least one selected from copper oxide, bismuth oxide, manganese oxide, cobalt oxide, magnesium oxide, tantalum oxide, niobium oxide, and tungsten oxide group.

此外，於其他實施態樣中，該電極膏體可更包括至少一添加劑，選自由分散劑、流變改質劑、顏料、無機充填劑、耦合劑、矽烷單體、及消泡劑所組成的群組，對於本領域的技術人員而言，可視需求而添加上述至少一添加劑。In addition, in other implementations, the electrode paste may further include at least one additive selected from dispersants, rheology modifiers, pigments, inorganic fillers, coupling agents, silane monomers, and defoamers For those skilled in the art, at least one of the above additives may be added as required.

一種電極厚膜的製備方法，包括以下步驟：(A) 提供如上文所述的該電極膏體；(B) 將該電極膏體塗佈於一基材上，於一惰性氣體下進行一燒結步驟，使得該電極膏體經燒結而獲得該電極厚膜。A method for preparing an electrode thick film, comprising the following steps: (A) providing the electrode paste as described above; (B) coating the electrode paste on a substrate, and performing a sintering under an inert gas step, so that the electrode paste is sintered to obtain the electrode thick film.

於一實施態樣中，於步驟(B)中，該基材為一陶瓷基板。In an embodiment, in the step (B), the substrate is a ceramic substrate.

於一實施態樣中，於步驟(B)中，該燒結步驟的燒結溫度為900C以下。In an embodiment, in the step (B), the sintering temperature of the sintering step is below 900°C.

於一實施態樣中，於步驟(B)中，該電極厚膜的片電阻率小於7 mΩ。In an embodiment, in step (B), the sheet resistivity of the electrode thick film is less than 7 mΩ.

於一實施態樣中，於步驟(B)中，該電極厚膜與該陶瓷基板之間的附著拉力為2~3 kg。In one embodiment, in step (B), the adhesion tension between the electrode thick film and the ceramic substrate is 2-3 kg.

本發明中，該電極膏體中的該玻璃組成物為Li ₂O-ZnO-Al ₂O ₃-Na ₂O-SrO-V ₂O ₅-B ₂O ₃-SiO ₂，該玻璃組成物有較低的玻璃軟化點，為400~900°C，使得本電極膏體於450~850°C的低溫下具有較優異的燒結附著性。 In the present invention, the glass composition in the electrode paste is Li ₂ O-ZnO-Al ₂ O ₃ -Na ₂ O-SrO-V ₂ O ₅ -B ₂ O ₃ -SiO ₂ , and the glass composition has The lower glass softening point is 400~900°C, which makes the electrode paste have excellent sintering adhesion at a low temperature of 450~850°C.

以下將透過具體實施例說明本發明的電極膏體及包含其之電極厚膜之製備方法。The preparation method of the electrode paste of the present invention and the electrode thick film comprising it will be described below through specific examples.

電極膏體之製備Preparation of Electrode Paste

首先，取Li ₂O、ZnO、Al ₂O ₃、Na ₂O、SrO、V ₂O ₅、 B ₂O ₃、SiO ₂粉末，以總重量為基準，依據以下比例攪拌混合：0.5~5 wt%的Li ₂O、20~50 wt%的ZnO、1~5 wt%的Al ₂O ₃、1~10 wt%的Na ₂O、0.5~5 wt%的SrO、1~15 wt%的V ₂O ₅、20~50 wt%的B ₂O ₃、以及1~10 wt%的SiO ₂。 First, take Li ₂ O, ZnO, Al ₂ O ₃ , Na ₂ O, SrO, V ₂ O ₅ , B ₂ O ₃ , SiO ₂ powders, based on the total weight, stir and mix according to the following ratio: 0.5~5 wt % Li ₂ O, 20~50 wt% ZnO, 1~5 wt% Al ₂ O ₃ , 1~10 wt% Na ₂ O, 0.5~5 wt% SrO, 1~15 wt% V ₂ O ₅ , 20~50 wt% of B ₂ O ₃ , and 1~10 wt% of SiO ₂ .

上述粉末經攪拌混合後放入坩鍋載具中，將粉末連同坩鍋載具一起以電阻爐升溫到1000至1500度之溫度進行熔融步驟2至4小時後，快速倒入去離子水中水萃獲得塊狀之融熔玻璃塊。接著，將熔融玻璃塊利用粗磨機、細磨機及珠磨機等進行研磨約24小時後，形成平均粒徑為1~5 μm的粉末狀玻璃組成物，並具有400~900°C的玻璃軟化點。在此所謂的平均粒徑，係指藉由雷射繞射散射式粒度分佈測定法而得到的體積基準平均粒徑(d50)之意，而玻璃粉料的軟化點，係可使用熱重量測定裝置(TG-DTA 儀器)測定。The above powder is mixed and put into the crucible carrier, and the powder together with the crucible carrier is heated to a temperature of 1000 to 1500 degrees in a resistance furnace for the melting step for 2 to 4 hours, and then quickly poured into deionized water for water extraction Obtain a block of molten glass. Next, the molten glass block is ground for about 24 hours with a coarse grinder, a fine grinder, a bead mill, etc., to form a powdered glass composition with an average particle size of 1-5 μm, and has a temperature of 400-900°C. Glass softening point. The so-called average particle size here refers to the volume-based average particle size (d50) obtained by the laser diffraction scattering particle size distribution measurement method, and the softening point of the glass frit can be measured by thermogravimetry Device (TG-DTA instrument) measurement.

關於金屬粉末，在本實施例中，其粒徑為0.1~10 μm，為了呈現電極膏體的導電性，以增加電極膏體中的金屬粉粒徑者為佳。然而，金屬粉末粒徑過大時，會影響對基板之塗佈性或作業性的情形。或在使用電極膏體形成積層陶瓷電子零件之外部電極時，會有損及電極膏體對陶瓷體之附著能力。因此，只要電極膏體無損及對基板或對陶瓷體的塗佈性或附著性，以使用粒徑較大的金屬粉末為佳。斟酌此等時，本發明中使用的金屬粉末的平均粒徑以0.1~10 μm的範圍內為佳。此外，金屬粉末的製造方法並無特別限定，例如，可藉由還原法、粉碎法、電解法、霧化法、熱處理法或該等之組合而製造。片狀的金屬粉末例如可藉由將球狀或粒狀的金屬粒子通過球磨機等磨碎而製造。Regarding the metal powder, in this embodiment, its particle size is 0.1-10 μm. In order to show the conductivity of the electrode paste, it is better to increase the particle size of the metal powder in the electrode paste. However, when the particle size of the metal powder is too large, the coatability or workability on the substrate may be affected. Or when the electrode paste is used to form the external electrodes of the laminated ceramic electronic parts, it will damage the adhesion ability of the electrode paste to the ceramic body. Therefore, as long as the electrode paste does not damage the coating or adhesion to the substrate or the ceramic body, it is better to use a metal powder with a larger particle size. Taking these into consideration, the average particle diameter of the metal powder used in the present invention is preferably in the range of 0.1 to 10 μm. In addition, the method of producing the metal powder is not particularly limited, and can be produced, for example, by a reduction method, a pulverization method, an electrolysis method, an atomization method, a heat treatment method, or a combination thereof. The flaky metal powder can be produced, for example, by grinding spherical or granular metal particles with a ball mill or the like.

關於有機黏結劑，於本實施例中，可為熱硬化性樹脂、熱塑性樹脂、或其混合物，其中，熱硬化性樹脂可例如為環氧樹脂、胺酯樹脂、乙烯酯樹脂、矽酮樹脂、酚樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯樹脂、或聚醯亞胺樹脂；熱塑性樹脂可例如為乙基纖維素、丙烯酸樹脂、醇酸樹脂、飽和聚酯樹脂、丁醛樹脂、聚乙烯醇、或羥丙基纖維素。有機黏結劑的使用主要使得電極膏體中之金屬粉末相互連接，並於電極膏體燒結時因燃燒而被移除。Regarding the organic binder, in this embodiment, it can be a thermosetting resin, a thermoplastic resin, or a mixture thereof, wherein the thermosetting resin can be, for example, epoxy resin, urethane resin, vinyl ester resin, silicone resin, Phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, or polyimide resins; thermoplastic resins may be, for example, ethyl cellulose, acrylic resins, alkyd resins, saturated Polyester resin, butyral resin, polyvinyl alcohol, or hydroxypropyl cellulose. The use of the organic binder mainly makes the metal powder in the electrode paste interconnected, and is removed by burning when the electrode paste is sintered.

而溶劑可為至少一選自由有機酸類、芳香族烴類、吡咯啶酮類、醯胺類、酮類、及環狀碳酸酯所組成之群組，其中，有機酸類可例如為二乙二醇***醋酸酯、二乙二醇丁醚醋酸酯、醋酸乙酯等；芳香族烴類可例如為甲苯、或二甲苯等；吡咯啶酮類可例如為N-甲基-2-吡咯啶酮(NMP)等；醯胺類可例如N,N-二甲基甲醯胺(DMF)等；酮類可例如為甲基乙基酮(MEK)等；環狀碳酸酯類可例如為萜品醇(Terpineol)、或丁基卡必醇(BC)等。本領域人士可依據實際需求選擇有機黏結劑及溶劑的組成成分，此屬於本領域習知範疇，在此不進一步討論。The solvent can be at least one selected from the group consisting of organic acids, aromatic hydrocarbons, pyrrolidones, amides, ketones, and cyclic carbonates, wherein the organic acids can be, for example, diethylene glycol Diethyl ether acetate, diethylene glycol butyl ether acetate, ethyl acetate, etc.; aromatic hydrocarbons can be, for example, toluene, or xylene, etc.; pyrrolidones can, for example, be N-methyl-2-pyrrolidone ( NMP) etc.; amides can be N,N-dimethylformamide (DMF) etc.; ketones can be methyl ethyl ketone (MEK) etc.; cyclic carbonates can be terpineol (Terpineol), or butyl carbitol (BC), etc. Those skilled in the art can select the components of the organic binder and the solvent according to the actual needs, which belong to the common knowledge in the art and will not be further discussed here.

接下來，取70~90wt%的金屬粉末(銅粉、銀包銅粉(Ag/Cu: 20/80wt%)、或BaTiO ₃粉末)、1~8 wt%的上述粉末狀玻璃組成物、5~30 wt%的有機黏結劑、以及2~30 wt%的溶劑。經充分混合並以三輥軋機(three roll mills)研磨分散後，再經過過濾及脫泡作業，即獲得本發明之電極膏體。於其他實施態樣中，可使用珠磨機、球磨機、旋轉式混合機或雙軸混合機等進行上述材料的研磨及分散的程序。 Next, take 70~90wt% of metal powder (copper powder, silver-coated copper powder (Ag/Cu: 20/80wt%), or BaTiO ₃ powder), 1~8 wt% of the above powdered glass composition, 5 ~30 wt% organic binder, and 2~30 wt% solvent. The electrode paste of the present invention is obtained after thorough mixing, grinding and dispersion with three roll mills, and then filtering and defoaming. In other implementations, bead mills, ball mills, rotary mixers or twin-shaft mixers can be used to grind and disperse the above materials.

於其他實施態樣中，該電極膏體可更包含添加劑，例如可包含分散劑、流變改質劑、顏料、無機充填劑(例如，氧化鋅、碳酸鋇粉等)、耦合劑(例如，γ-環氧丙氧基丙基三甲氧基矽烷等的矽烷偶合劑、四辛基雙(二-十三烷基亞磷酸)鈦酸酯等的鈦酸酯偶合劑等)、矽烷單體(例如，參(3-(三甲氧基矽基)丙基)三聚異氰酸酯)、或消泡劑，以進一步改變該電極膏體的特性，增加其塗佈性、穩定性等。In other embodiments, the electrode paste may further include additives, such as dispersants, rheology modifiers, pigments, inorganic fillers (for example, zinc oxide, barium carbonate powder, etc.), coupling agents (for example, Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, titanate coupling agents such as tetraoctylbis(di-tridecylphosphite) titanate, etc.), silane monomers ( For example, ginseng (3-(trimethoxysilyl)propyl) tripolyisocyanate), or defoamer, to further change the characteristics of the electrode paste, increase its coating, stability and so on.

於其他實施態樣中，可視需求於該電極膏體中添加金屬氧化物，例如可添加氧化銅、氧化鉍、氧化錳、氧化鈷、氧化鎂、氧化鉭、氧化鈮、或氧化鎢。當電極膏體含有金屬氧化物時，電極膏體的焊料耐熱性會提高。尤其，當添加氧化鉍時，可促進金屬粉燒結的同時，提高導電性膠的焊料濕潤性。In other embodiments, metal oxides, such as copper oxide, bismuth oxide, manganese oxide, cobalt oxide, magnesium oxide, tantalum oxide, niobium oxide, or tungsten oxide, may be added to the electrode paste as required. When the electrode paste contains a metal oxide, the solder heat resistance of the electrode paste improves. In particular, when bismuth oxide is added, the sintering of the metal powder can be promoted, and the solder wettability of the conductive paste can be improved.

本實施例中所製備的電極膏體的黏度在於20~100 Pa∙s，在此範圍內，電極膏體的塗佈性或處理性會變得良好，可均勻地將電極膏體塗佈至基板上。The electrode paste prepared in this example has a viscosity of 20 to 100 Pa∙s. Within this range, the applicability or handleability of the electrode paste will become better, and the electrode paste can be evenly applied to on the substrate.

電極厚膜的製備Preparation of electrode thick film

首先，提供一陶瓷基板，該陶瓷基板係將積層的介電薄片加壓後，將該介電薄片燒結而得。Firstly, a ceramic substrate is provided, and the ceramic substrate is obtained by pressing the stacked dielectric sheets and then sintering the dielectric sheets.

將上述的電極膏體塗佈於該陶瓷基板的端面上，接著，將塗佈有電極膏體的陶瓷基板放入電爐內，並於惰性氣體的環境下以850~900°C的溫度進行燒結程序，藉由燒結程序，該電極膏體中的金屬粉末會互相燒結，同時電極膏體中的有機黏結劑、溶劑等成分會被燒除，進而得到具導電圖案的電極厚膜，所形成的電極厚膜的導電性極高，且電遷移耐性、焊料耐熱性及對陶瓷基板的附著性優異。Apply the above-mentioned electrode paste on the end surface of the ceramic substrate, then put the ceramic substrate coated with the electrode paste into an electric furnace, and sinter at a temperature of 850~900°C in an inert gas environment Through the sintering process, the metal powders in the electrode paste will be sintered with each other, and at the same time, the organic binder, solvent and other components in the electrode paste will be burned off, and then a thick electrode film with a conductive pattern will be obtained. Electrode thick film has extremely high conductivity, and is excellent in electromigration resistance, solder heat resistance, and adhesion to ceramic substrates.

為了更清楚展示本發明中使用特定玻璃組成物以及使用卑金屬銅或銀包銅粉(Ag/Cu: 20/80 wt%)作為金屬粉末，對於電極膏體及其所製備的電極厚膜的優異電性以及與陶瓷基板之間有優異附著性的確有其貢獻，以下測試例將針對使用市售的銀電極膏體與本發明所提供的電極膏體，於陶瓷基板上製備成電極厚膜，並對其做耐硫化測試及電極附著拉力測試，硫化測試係使用型號為ASTMB809-95硫化測試機進行，其中，以水、硝酸鉀、及硫化粉末作為介質，將厚膜晶片樣本置於其中，並升溫至60-90°C間做800-1000小時的壽命測試；電極附著拉力測試係使用材料試驗機(型號AMETEK-LS1)，以鍍錫銅線(線徑3.5mm，線長15mm)焊接試片兩端，再以Speed:30mm/min做拉力測試。In order to show more clearly the use of specific glass composition and the use of base metal copper or silver-coated copper powder (Ag/Cu: 20/80 wt%) as metal powder in the present invention, for the electrode paste and the prepared electrode thick film Excellent electrical properties and excellent adhesion to ceramic substrates do contribute. The following test examples will use commercially available silver electrode paste and the electrode paste provided by the present invention to prepare electrode thick films on ceramic substrates. , and perform sulfuration resistance test and electrode adhesion tensile test on it. The sulfuration test is carried out using a model ASTMB809-95 vulcanization tester, in which water, potassium nitrate, and vulcanization powder are used as the medium, and the thick film wafer sample is placed in it. , and heat up to 60-90°C to do a life test of 800-1000 hours; the electrode adhesion tensile test system uses a material testing machine (model AMETEK-LS1), with tinned copper wire (wire diameter 3.5mm, wire length 15mm) Weld both ends of the test piece, and then do a tensile test at Speed: 30mm/min.

其中，比較例1係使用市售的銀-鈀電極膏體(PP-8020)、比較例2係使用市售的銀電極膏體(PE-7015)、實施例1至實施例5-9係使用本發明所提供的電極膏體，其中金屬粉末為銅粉末，測試結果如下表1；另外，實施例6至實施例10-9係使用本發明所提供的電極膏體，其中金屬粉末為銀包銅(Ag/Cu: 20/80 wt%)粉末，測試結果如下表2。Wherein, comparative example 1 uses commercially available silver-palladium electrode paste (PP-8020), comparative example 2 uses commercially available silver electrode paste (PE-7015), embodiment 1 to embodiment 5-9 are Using the electrode paste provided by the present invention, wherein the metal powder is copper powder, the test results are shown in Table 1; in addition, Example 6 to Example 10-9 are using the electrode paste provided by the present invention, wherein the metal powder is silver Copper-clad (Ag/Cu: 20/80 wt%) powder, the test results are shown in Table 2 below.

表1 金屬粉末(wt%) 鈦酸鋇BaTiO ₃(wt%) 玻璃成份中ZnO/B ₂O ₃比值玻璃組成物(wt%) 高分子樹脂(wt%) 有機溶劑(wt%) 燒結溫度(C) 片電阻(mΩ) 300次迴圈耐硫化接著力(Kg) 300次迴圈耐硫化電阻變化率ΔR (mΩ) 比較例1 Ag-Pd=80 2% - 0 5 15 850~900 55 ＞1kg ＞1% 比較例1-1 Ag-Pd=80 2% 49/22.40 0.5 5 15 850~900 48 ＞1kg ＞1% 比較例1-2 Ag-Pd=75 2% 26.65/49.08 1 5 15 850~900 45 ＞1kg ＞1% 比較例1-3 Ag-Pd=70 2% 40.68/34.51 3 5 15 850~900 36 ＞1kg ＞1% 比較例1-4 Ag-Pd=65 2% 36.39/41.40 5 5 15 850~900 38 ＞1kg ＞1% 比較例1-5 Ag-Pd=60 2% 43.82/30.06 8 5 15 850~900 40 ＞1kg ＞1% 比較例1-6 Ag-Pd=80 2% 28.49/35.57 0.5 5 15 850~900 60 ＞1kg ＞1% 比較例1-7 Ag-Pd=75 2% 18.47/48.15 1 5 15 850~900 56 ＞1kg ＞1% 比較例1-8 Ag-Pd=70 2% 32.11/48.30 3 5 15 850~900 45 ＞1kg ＞1% 比較例1-9 Ag-Pd=65 2% 27.83/50.19 5 5 15 850~900 48 ＞1kg ＞1% 比較例1-10 Ag-Pd=60 2% 27.37/38.15 8 5 15 850~900 50 ＞1kg ＞1% 比較例2 Ag=80 2% - 0 5 15 850~900 12 ＞1kg ＞1% 比較例2-1 Ag=80 2% 49/22.40 0.5 5 15 850~900 10 ＞1kg ＞1% 比較例2-2 Ag=75 2% 26.65/49.08 1 5 15 850~900 11 ＞1kg ＞1% 比較例2-3 Ag=70 2% 40.68/34.51 3 5 15 850~900 13 ＞1kg ＞1% 比較例2-4 Ag=65 2% 36.39/41.40 5 5 15 850~900 10 ＞1kg ＞1% 比較例2-5 Ag=60 2% 43.82/30.06 8 5 15 850~900 8 ＞1kg ＞1% 比較例2-6 Ag=80 2% 28.49/35.57 0.5 5 15 850~900 12.6 ＞1kg ＞1% 比較例2-7 Ag=75 2% 18.47/48.15 1 5 15 850~900 13.9 ＞1kg ＞1% 比較例2-8 Ag=70 2% 32.11/48.30 3 5 15 850~900 16.4 ＞1kg ＞1% 比較例2-9 Ag=65 2% 27.83/50.19 5 5 15 850~900 12.9 ＞1kg ＞1% 比較例2-10 Ag=60 2% 27.37/38.15 8 5 15 850~900 10.1 ＞1kg ＞1% 實施例1 Cu=80 2% 49/22.40 0.5 5 15 850-900 7 ＞2kg ＜1% 實施例1-1 Cu=80 2% 26.65/49.08 1 5 15 850-900 6.5 ＞2kg ＜1% 實施例1-2 Cu=80 2% 40.68/34.51 3 5 15 850-900 5.5 ＞2kg ＜1% 實施例1-3 Cu=80 2% 36.39/41.40 5 5 15 850-900 4.3 ＞2kg ＜1% 實施例1-4 Cu=80 2% 43.82/30.06 8 5 15 850-900 3.8 ＞2kg ＜1% 實施例1-5 Cu=80 2% 28.49/35.57 0.5 5 15 850-900 6.5 ＞2kg ＜1% 實施例1-6 Cu=80 2% 18.47/48.15 1 5 15 850-900 6.0 ＞2kg ＜1% 實施例1-7 Cu=80 2% 32.11/48.30 3 5 15 850-900 5.1 ＞2kg ＜1% 實施例1-8 Cu=80 2% 27.83/50.19 5 5 15 850-900 4.0 ＞2kg ＜1% 實施例1-9 Cu=80 2% 27.37/38.15 8 5 15 850-900 3.5 ＞2kg ＜1% 實施例2 Cu=75 2% 49/22.40 0 5 15 850-900 6.8 ＞2kg ＜1% 實施例2-1 Cu=75 2% 26.65/49.08 1 5 15 850-900 6.4 ＞2kg ＜1% 實施例2-2 Cu=75 2% 40.68/34.51 3 5 15 850-900 5.8 ＞2kg ＜1% 實施例2-3 Cu=75 2% 36.39/41.40 5 5 15 850-900 4.7 ＞2kg ＜1% 實施例2-4 Cu=75 2% 43.82/30.06 8 5 15 850-900 3.6 ＞2kg ＜1% 實施例2-5 Cu=75 2% 28.49/35.57 0 5 15 850-900 6.0 ＞2kg ＜1% 實施例2-6 Cu=75 2% 18.47/48.15 1 5 15 850-900 5.6 ＞2kg ＜1% 實施例2-7 Cu=75 2% 32.11/48.30 3 5 15 850-900 5.1 ＞2kg ＜1% 實施例2-8 Cu=75 2% 27.83/50.19 5 5 15 850-900 4.1 ＞2kg ＜1% 實施例2-9 Cu=75 2% 27.37/38.15 8 5 15 850-900 3.2 ＞2kg ＜1% 實施例3 Cu=70 2% 49/22.40 0.5 5 15 850-900 6.2 ＞2kg ＜1% 實施例3-1 Cu=70 2% 26.65/49.08 1 5 15 850-900 6 ＞2kg ＜1% 實施例3-2 Cu=70 2% 40.68/34.51 3 5 15 850-900 5.3 ＞2kg ＜1% 實施例3-3 Cu=70 2% 36.39/41.40 5 5 15 850-900 4.2 ＞2kg ＜1% 實施例3-4 Cu=70 2% 43.82/30.06 8 5 15 850-900 3.9 ＞2kg ＜1% 實施例3-5 Cu=70 2% 28.49/35.57 0 5 15 850-900 5.58 ＞2kg ＜1% 實施例3-6 Cu=70 2% 18.47/48.15 1 5 15 850-900 5.4 ＞2kg ＜1% 實施例3-7 Cu=70 2% 32.11/48.30 3 5 15 850-900 4.77 ＞2kg ＜1% 實施例3-8 Cu=70 2% 27.83/50.19 5 5 15 850-900 3.78 ＞2kg ＜1% 實施例3-9 Cu=70 2% 27.37/38.15 8 5 15 850-900 3.51 ＞2kg ＜1% 實施例4 Cu=65 2% 49/22.40 0.5 5 15 850-900 6.9 ＞2kg ＜1% 實施例4-1 Cu=65 2% 26.65/49.08 1 5 15 850-900 6 ＞2kg ＜1% 實施例4-2 Cu=65 2% 40.68/34.51 3 5 15 850-900 5.4 ＞2kg ＜1% 實施例4-3 Cu=65 2% 36.39/41.40 5 5 15 850-900 4.9 ＞2kg ＜1% 實施例4-4 Cu=65 2% 43.82/30.06 8 5 15 850-900 3.8 ＞2kg ＜1% 實施例4-5 Cu=65 2% 28.49/35.57 0 5 15 850-900 6.6 ＞2kg ＜1% 實施例4-6 Cu=65 2% 18.47/48.15 1 5 15 850-900 5.7 ＞2kg ＜1% 實施例4-7 Cu=65 2% 32.11/48.30 3 5 15 850-900 5.1 ＞2kg ＜1% 實施例4-8 Cu=65 2% 27.83/50.19 5 5 15 850-900 4.7 ＞2kg ＜1% 實施例4-9 Cu=65 2% 27.37/38.15 8 5 15 850-900 3.6 ＞2kg ＜1% 實施例5 Cu=60 2% 49/22.40 0.5 5 15 850-900 6.7 ＞2kg ＜1% 實施例5-1 Cu=60 2% 26.65/49.08 1 5 15 850-900 5.8 ＞2kg ＜1% 實施例5-2 Cu=60 2% 40.68/34.51 3 5 15 850-900 5.2 ＞2kg ＜1% 實施例5-3 Cu=60 2% 36.39/41.40 5 5 15 850-900 4.8 ＞2kg ＜1% 實施例5-4 Cu=60 2% 43.82/30.06 8 5 15 850-900 3.7 ＞2kg ＜1% 實施例5-5 Cu=60 2% 28.49/35.57 0 5 15 850-900 5.6 ＞2kg ＜1% 實施例5-6 Cu=60 2% 18.47/48.15 1 5 15 850-900 4.8 ＞2kg ＜1% 實施例5-7 Cu=60 2% 32.11/48.30 3 5 15 850-900 4.3 ＞2kg ＜1% 實施例5-8 Cu=60 2% 27.83/50.19 5 5 15 850-900 3.9 ＞2kg ＜1% 實施例5-9 Cu=60 2% 27.37/38.15 8 5 15 850-900 3.1 ＞2kg ＜1% Table 1 Metal powder (wt%) Barium titanate BaTiO ₃ (wt%) ZnO/B ₂ O ₃ ratio in glass composition Glass composition (wt%) Polymer resin (wt%) Organic solvent(wt%) Sintering temperature (C) Sheet resistance (mΩ) 300 cycles resistance to vulcanization Adhesion (Kg) 300 cycles of anti-sulfurization resistance change rate ΔR (mΩ) Comparative example 1 Ag-Pd=80 2% - 0 5 15 850~900 55 ＞1kg ＞1% Comparative example 1-1 Ag-Pd=80 2% 49/22.40 0.5 5 15 850~900 48 ＞1kg ＞1% Comparative example 1-2 Ag-Pd=75 2% 26.65/49.08 1 5 15 850~900 45 ＞1kg ＞1% Comparative example 1-3 Ag-Pd=70 2% 40.68/34.51 3 5 15 850~900 36 ＞1kg ＞1% Comparative example 1-4 Ag-Pd=65 2% 36.39/41.40 5 5 15 850~900 38 ＞1kg ＞1% Comparative example 1-5 Ag-Pd=60 2% 43.82/30.06 8 5 15 850~900 40 ＞1kg ＞1% Comparative Examples 1-6 Ag-Pd=80 2% 28.49/35.57 0.5 5 15 850~900 60 ＞1kg ＞1% Comparative Examples 1-7 Ag-Pd=75 2% 18.47/48.15 1 5 15 850~900 56 ＞1kg ＞1% Comparative Examples 1-8 Ag-Pd=70 2% 32.11/48.30 3 5 15 850~900 45 ＞1kg ＞1% Comparative Examples 1-9 Ag-Pd=65 2% 27.83/50.19 5 5 15 850~900 48 ＞1kg ＞1% Comparative Examples 1-10 Ag-Pd=60 2% 27.37/38.15 8 5 15 850~900 50 ＞1kg ＞1% Comparative example 2 Ag=80 2% - 0 5 15 850~900 12 ＞1kg ＞1% Comparative example 2-1 Ag=80 2% 49/22.40 0.5 5 15 850~900 10 ＞1kg ＞1% Comparative example 2-2 Ag=75 2% 26.65/49.08 1 5 15 850~900 11 ＞1kg ＞1% Comparative example 2-3 Ag=70 2% 40.68/34.51 3 5 15 850~900 13 ＞1kg ＞1% Comparative example 2-4 Ag=65 2% 36.39/41.40 5 5 15 850~900 10 ＞1kg ＞1% Comparative example 2-5 Ag=60 2% 43.82/30.06 8 5 15 850~900 8 ＞1kg ＞1% Comparative example 2-6 Ag=80 2% 28.49/35.57 0.5 5 15 850~900 12.6 ＞1kg ＞1% Comparative example 2-7 Ag=75 2% 18.47/48.15 1 5 15 850~900 13.9 ＞1kg ＞1% Comparative example 2-8 Ag=70 2% 32.11/48.30 3 5 15 850~900 16.4 ＞1kg ＞1% Comparative example 2-9 Ag=65 2% 27.83/50.19 5 5 15 850~900 12.9 ＞1kg ＞1% Comparative example 2-10 Ag=60 2% 27.37/38.15 8 5 15 850~900 10.1 ＞1kg ＞1% Example 1 Cu=80 2% 49/22.40 0.5 5 15 850-900 7 >2kg <1% Example 1-1 Cu=80 2% 26.65/49.08 1 5 15 850-900 6.5 >2kg <1% Example 1-2 Cu=80 2% 40.68/34.51 3 5 15 850-900 5.5 >2kg <1% Example 1-3 Cu=80 2% 36.39/41.40 5 5 15 850-900 4.3 >2kg <1% Example 1-4 Cu=80 2% 43.82/30.06 8 5 15 850-900 3.8 >2kg <1% Example 1-5 Cu=80 2% 28.49/35.57 0.5 5 15 850-900 6.5 >2kg <1% Examples 1-6 Cu=80 2% 18.47/48.15 1 5 15 850-900 6.0 >2kg <1% Example 1-7 Cu=80 2% 32.11/48.30 3 5 15 850-900 5.1 >2kg <1% Examples 1-8 Cu=80 2% 27.83/50.19 5 5 15 850-900 4.0 >2kg <1% Examples 1-9 Cu=80 2% 27.37/38.15 8 5 15 850-900 3.5 >2kg <1% Example 2 Cu=75 2% 49/22.40 0 5 15 850-900 6.8 >2kg <1% Example 2-1 Cu=75 2% 26.65/49.08 1 5 15 850-900 6.4 >2kg <1% Example 2-2 Cu=75 2% 40.68/34.51 3 5 15 850-900 5.8 >2kg <1% Example 2-3 Cu=75 2% 36.39/41.40 5 5 15 850-900 4.7 >2kg <1% Example 2-4 Cu=75 2% 43.82/30.06 8 5 15 850-900 3.6 >2kg <1% Example 2-5 Cu=75 2% 28.49/35.57 0 5 15 850-900 6.0 >2kg <1% Example 2-6 Cu=75 2% 18.47/48.15 1 5 15 850-900 5.6 >2kg <1% Example 2-7 Cu=75 2% 32.11/48.30 3 5 15 850-900 5.1 >2kg <1% Example 2-8 Cu=75 2% 27.83/50.19 5 5 15 850-900 4.1 >2kg <1% Example 2-9 Cu=75 2% 27.37/38.15 8 5 15 850-900 3.2 >2kg <1% Example 3 Cu=70 2% 49/22.40 0.5 5 15 850-900 6.2 >2kg <1% Example 3-1 Cu=70 2% 26.65/49.08 1 5 15 850-900 6 >2kg <1% Example 3-2 Cu=70 2% 40.68/34.51 3 5 15 850-900 5.3 >2kg <1% Example 3-3 Cu=70 2% 36.39/41.40 5 5 15 850-900 4.2 >2kg <1% Example 3-4 Cu=70 2% 43.82/30.06 8 5 15 850-900 3.9 >2kg <1% Example 3-5 Cu=70 2% 28.49/35.57 0 5 15 850-900 5.58 >2kg <1% Example 3-6 Cu=70 2% 18.47/48.15 1 5 15 850-900 5.4 >2kg <1% Example 3-7 Cu=70 2% 32.11/48.30 3 5 15 850-900 4.77 >2kg <1% Example 3-8 Cu=70 2% 27.83/50.19 5 5 15 850-900 3.78 >2kg <1% Example 3-9 Cu=70 2% 27.37/38.15 8 5 15 850-900 3.51 >2kg <1% Example 4 Cu=65 2% 49/22.40 0.5 5 15 850-900 6.9 >2kg <1% Example 4-1 Cu=65 2% 26.65/49.08 1 5 15 850-900 6 >2kg <1% Example 4-2 Cu=65 2% 40.68/34.51 3 5 15 850-900 5.4 >2kg <1% Example 4-3 Cu=65 2% 36.39/41.40 5 5 15 850-900 4.9 >2kg <1% Example 4-4 Cu=65 2% 43.82/30.06 8 5 15 850-900 3.8 >2kg <1% Example 4-5 Cu=65 2% 28.49/35.57 0 5 15 850-900 6.6 >2kg <1% Example 4-6 Cu=65 2% 18.47/48.15 1 5 15 850-900 5.7 >2kg <1% Example 4-7 Cu=65 2% 32.11/48.30 3 5 15 850-900 5.1 >2kg <1% Example 4-8 Cu=65 2% 27.83/50.19 5 5 15 850-900 4.7 >2kg <1% Example 4-9 Cu=65 2% 27.37/38.15 8 5 15 850-900 3.6 >2kg <1% Example 5 Cu=60 2% 49/22.40 0.5 5 15 850-900 6.7 >2kg <1% Example 5-1 Cu=60 2% 26.65/49.08 1 5 15 850-900 5.8 >2kg <1% Example 5-2 Cu=60 2% 40.68/34.51 3 5 15 850-900 5.2 >2kg <1% Example 5-3 Cu=60 2% 36.39/41.40 5 5 15 850-900 4.8 >2kg <1% Example 5-4 Cu=60 2% 43.82/30.06 8 5 15 850-900 3.7 >2kg <1% Example 5-5 Cu=60 2% 28.49/35.57 0 5 15 850-900 5.6 >2kg <1% Example 5-6 Cu=60 2% 18.47/48.15 1 5 15 850-900 4.8 >2kg <1% Example 5-7 Cu=60 2% 32.11/48.30 3 5 15 850-900 4.3 >2kg <1% Example 5-8 Cu=60 2% 27.83/50.19 5 5 15 850-900 3.9 >2kg <1% Example 5-9 Cu=60 2% 27.37/38.15 8 5 15 850-900 3.1 >2kg <1%

表2 金屬粉末(wt%) 鈦酸鋇BaTiO ₃ (wt%) 玻璃成份中ZnO/B ₂O ₃比值玻璃組成物(wt%) 高分子樹脂(wt%) 有機溶劑(wt%) 燒結溫度 (C) 片電阻(mΩ) 300次迴圈耐硫化接著力(Kg) 300次迴圈耐硫化電阻變化率ΔR (mΩ) 實施例6 銀包銅(80:20)=80 2% 49/22.40 0.5 5 15 850-900 6.8 ＞2kg ＜1% 實施例6-1 銀包銅(80:20)=80 2% 26.65/49.08 1 5 15 850-900 6.3 ＞2kg ＜1% 實施例6-2 銀包銅(80:20)=80 2% 40.68/34.51 3 5 15 850-900 5.3 ＞2kg ＜1% 實施例6-3 銀包銅(80:20)=80 2% 36.39/41.40 5 5 15 850-900 4.2 ＞2kg ＜1% 實施例6-4 銀包銅(80:20)=80 2% 43.82/30.06 8 5 15 850-900 3.7 ＞2kg ＜1% 實施例6-5 銀包銅(80:20)=80 2% 28.49/35.57 0.5 5 15 850-900 6.3 ＞2kg ＜1% 實施例6-6 銀包銅(80:20)=80 2% 18.47/48.15 1 5 15 850-900 5.9 ＞2kg ＜1% 實施例6-7 銀包銅(80:20)=80 2% 32.11/48.30 3 5 15 850-900 5.0 ＞2kg ＜1% 實施例6-8 銀包銅(80:20)=80 2% 27.83/50.19 5 5 15 850-900 3.9 ＞2kg ＜1% 實施例6-9 銀包銅(80:20)=80 2% 27.37/38.15 8 5 15 850-900 3.4 ＞2kg ＜1% 實施例7 銀包銅(80:20)=75 2% 49/22.40 0.5 5 15 850-900 6.6 ＞2kg ＜1% 實施例7-1 銀包銅(80:20)=75 2% 26.65/49.08 1 5 15 850-900 6.2 ＞2kg ＜1% 實施例7-2 銀包銅(80:20)=75 2% 40.68/34.51 3 5 15 850-900 5.6 ＞2kg ＜1% 實施例7-3 銀包銅(80:20)=75 2% 36.39/41.40 5 5 15 850-900 4.6 ＞2kg ＜1% 實施例7-4 銀包銅(80:20)=75 2% 43.82/30.06 8 5 15 850-900 3.5 ＞2kg ＜1% 實施例7-5 銀包銅(80:20)=75 2% 28.49/35.57 0.5 5 15 850-900 5.8 ＞2kg ＜1% 實施例7-6 銀包銅(80:20)=75 2% 18.47/48.15 1 5 15 850-900 5.5 ＞2kg ＜1% 實施例7-7 銀包銅(80:20)=75 2% 32.11/48.30 3 5 15 850-900 5.0 ＞2kg ＜1% 實施例7-8 銀包銅(80:20)=75 2% 27.83/50.19 5 5 15 850-900 4.0 ＞2kg ＜1% 實施例7-9 銀包銅(80:20)=75 2% 27.37/38.15 8 5 15 850-900 3.1 ＞2kg ＜1% 實施例8 銀包銅(80:20)=70 2% 49/22.40 0.5 5 15 850-900 6.0 ＞2kg ＜1% 實施例8-1 銀包銅(80:20)=70 2% 26.65/49.08 1 5 15 850-900 5.8 ＞2kg ＜1% 實施例8-2 銀包銅(80:20)=70 2% 40.68/34.51 3 5 15 850-900 5.1 ＞2kg ＜1% 實施例8-3 銀包銅(80:20)=70 2% 36.39/41.40 5 5 15 850-900 4.1 ＞2kg ＜1% 實施例8-4 銀包銅(80:20)=70 2% 43.82/30.06 8 5 15 850-900 3.8 ＞2kg ＜1% 實施例8-5 銀包銅(80:20)=70 2% 28.49/35.57 0.5 5 15 850-900 5.4 ＞2kg ＜1% 實施例8-6 銀包銅(80:20)=70 2% 18.47/48.15 1 5 15 850-900 5.2 ＞2kg ＜1% 實施例8-7 銀包銅(80:20)=70 2% 32.11/48.30 3 5 15 850-900 4.6 ＞2kg ＜1% 實施例8-8 銀包銅(80:20)=70 2% 27.83/50.19 5 5 15 850-900 3.7 ＞2kg ＜1% 實施例8-9 銀包銅(80:20)=70 2% 27.37/38.15 8 5 15 850-900 3.4 ＞2kg ＜1% 實施例9 銀包銅(80:20)=65 2% 49/22.40 0.5 5 15 850-900 6.7 ＞2kg ＜1% 實施例9-1 銀包銅(80:20)=65 2% 26.65/49.08 1 5 15 850-900 5.8 ＞2kg ＜1% 實施例9-2 銀包銅(80:20)=65 2% 40.68/34.51 3 5 15 850-900 5.2 ＞2kg ＜1% 實施例9-3 銀包銅(80:20)=65 2% 36.39/41.40 5 5 15 850-900 4.8 ＞2kg ＜1% 實施例9-4 銀包銅(80:20)=65 2% 43.82/30.06 8 5 15 850-900 3.7 ＞2kg ＜1% 實施例9-5 銀包銅(80:20)=65 2% 28.49/35.57 0.5 5 15 850-900 6.4 ＞2kg ＜1% 實施例9-6 銀包銅(80:20)=65 2% 18.47/48.15 1 5 15 850-900 5.5 ＞2kg ＜1% 實施例9-7 銀包銅(80:20)=65 2% 32.11/48.30 3 5 15 850-900 5.0 ＞2kg ＜1% 實施例9-8 銀包銅(80:20)=65 2% 27.83/50.19 5 5 15 850-900 4.5 ＞2kg ＜1% 實施例9-9 銀包銅(80:20)=65 2% 27.37/38.15 8 5 15 850-900 3.5 ＞2kg ＜1% 實施例10 銀包銅(80:20)=60 2% 49/22.40 0.5 5 15 850-900 6.5 ＞2kg ＜1% 實施例10-1 銀包銅(80:20)=60 2% 26.65/49.08 1 5 15 850-900 5.6 ＞2kg ＜1% 實施例10-2 銀包銅(80:20)=60 2% 40.68/34.51 3 5 15 850-900 5.1 ＞2kg ＜1% 實施例10-3 銀包銅(80:20)=60 2% 36.39/41.40 5 5 15 850-900 4.6 ＞2kg ＜1% 實施例10-4 銀包銅(80:20)=60 2% 43.82/30.06 8 5 15 850-900 3.6 ＞2kg ＜1% 實施例10-5 銀包銅(80:20)=60 2% 28.49/35.57 0.5 5 15 850-900 5.4 ＞2kg ＜1% 實施例10-6 銀包銅(80:20)=60 2% 18.47/48.15 1 5 15 850-900 4.7 ＞2kg ＜1% 實施例10-7 銀包銅(80:20)=60 2% 32.11/48.30 3 5 15 850-900 4.2 ＞2kg ＜1% 實施例10-8 銀包銅(80:20)=60 2% 27.83/50.19 5 5 15 850-900 3.8 ＞2kg ＜1% 實施例10-9 銀包銅(80:20)=60 2% 27.37/38.15 8 5 15 850-900 3.0 ＞2kg ＜1% Table 2 Metal powder (wt%) Barium titanate BaTiO ₃ (wt%) ZnO/B ₂ O ₃ ratio in glass composition Glass composition (wt%) Polymer resin (wt%) Organic solvent(wt%) Sintering temperature (C) Sheet resistance (mΩ) 300 cycles resistance to vulcanization Adhesion (Kg) 300 cycles of anti-sulfurization resistance change rate ΔR (mΩ) Example 6 Silver clad copper (80:20)=80 2% 49/22.40 0.5 5 15 850-900 6.8 >2kg <1% Example 6-1 Silver clad copper (80:20)=80 2% 26.65/49.08 1 5 15 850-900 6.3 >2kg <1% Example 6-2 Silver clad copper (80:20)=80 2% 40.68/34.51 3 5 15 850-900 5.3 >2kg <1% Example 6-3 Silver clad copper (80:20)=80 2% 36.39/41.40 5 5 15 850-900 4.2 >2kg <1% Example 6-4 Silver clad copper (80:20)=80 2% 43.82/30.06 8 5 15 850-900 3.7 >2kg <1% Example 6-5 Silver clad copper (80:20)=80 2% 28.49/35.57 0.5 5 15 850-900 6.3 >2kg <1% Example 6-6 Silver clad copper (80:20)=80 2% 18.47/48.15 1 5 15 850-900 5.9 >2kg <1% Example 6-7 Silver clad copper (80:20)=80 2% 32.11/48.30 3 5 15 850-900 5.0 >2kg <1% Example 6-8 Silver clad copper (80:20)=80 2% 27.83/50.19 5 5 15 850-900 3.9 >2kg <1% Example 6-9 Silver clad copper (80:20)=80 2% 27.37/38.15 8 5 15 850-900 3.4 >2kg <1% Example 7 Silver clad copper (80:20)=75 2% 49/22.40 0.5 5 15 850-900 6.6 >2kg <1% Example 7-1 Silver clad copper (80:20)=75 2% 26.65/49.08 1 5 15 850-900 6.2 >2kg <1% Example 7-2 Silver clad copper (80:20)=75 2% 40.68/34.51 3 5 15 850-900 5.6 >2kg <1% Example 7-3 Silver clad copper (80:20)=75 2% 36.39/41.40 5 5 15 850-900 4.6 >2kg <1% Example 7-4 Silver clad copper (80:20)=75 2% 43.82/30.06 8 5 15 850-900 3.5 >2kg <1% Example 7-5 Silver clad copper (80:20)=75 2% 28.49/35.57 0.5 5 15 850-900 5.8 >2kg <1% Example 7-6 Silver clad copper (80:20)=75 2% 18.47/48.15 1 5 15 850-900 5.5 >2kg <1% Example 7-7 Silver clad copper (80:20)=75 2% 32.11/48.30 3 5 15 850-900 5.0 >2kg <1% Example 7-8 Silver clad copper (80:20)=75 2% 27.83/50.19 5 5 15 850-900 4.0 >2kg <1% Example 7-9 Silver clad copper (80:20)=75 2% 27.37/38.15 8 5 15 850-900 3.1 >2kg <1% Example 8 Silver clad copper (80:20)=70 2% 49/22.40 0.5 5 15 850-900 6.0 >2kg <1% Example 8-1 Silver clad copper (80:20)=70 2% 26.65/49.08 1 5 15 850-900 5.8 >2kg <1% Example 8-2 Silver clad copper (80:20)=70 2% 40.68/34.51 3 5 15 850-900 5.1 >2kg <1% Example 8-3 Silver clad copper (80:20)=70 2% 36.39/41.40 5 5 15 850-900 4.1 >2kg <1% Example 8-4 Silver clad copper (80:20)=70 2% 43.82/30.06 8 5 15 850-900 3.8 >2kg <1% Example 8-5 Silver clad copper (80:20)=70 2% 28.49/35.57 0.5 5 15 850-900 5.4 >2kg <1% Example 8-6 Silver clad copper (80:20)=70 2% 18.47/48.15 1 5 15 850-900 5.2 >2kg <1% Example 8-7 Silver clad copper (80:20)=70 2% 32.11/48.30 3 5 15 850-900 4.6 >2kg <1% Example 8-8 Silver clad copper (80:20)=70 2% 27.83/50.19 5 5 15 850-900 3.7 >2kg <1% Example 8-9 Silver clad copper (80:20)=70 2% 27.37/38.15 8 5 15 850-900 3.4 >2kg <1% Example 9 Silver clad copper (80:20)=65 2% 49/22.40 0.5 5 15 850-900 6.7 >2kg <1% Example 9-1 Silver clad copper (80:20)=65 2% 26.65/49.08 1 5 15 850-900 5.8 >2kg <1% Example 9-2 Silver clad copper (80:20)=65 2% 40.68/34.51 3 5 15 850-900 5.2 >2kg <1% Example 9-3 Silver clad copper (80:20)=65 2% 36.39/41.40 5 5 15 850-900 4.8 >2kg <1% Example 9-4 Silver clad copper (80:20)=65 2% 43.82/30.06 8 5 15 850-900 3.7 >2kg <1% Example 9-5 Silver clad copper (80:20)=65 2% 28.49/35.57 0.5 5 15 850-900 6.4 >2kg <1% Example 9-6 Silver clad copper (80:20)=65 2% 18.47/48.15 1 5 15 850-900 5.5 >2kg <1% Example 9-7 Silver clad copper (80:20)=65 2% 32.11/48.30 3 5 15 850-900 5.0 >2kg <1% Example 9-8 Silver clad copper (80:20)=65 2% 27.83/50.19 5 5 15 850-900 4.5 >2kg <1% Example 9-9 Silver clad copper (80:20)=65 2% 27.37/38.15 8 5 15 850-900 3.5 >2kg <1% Example 10 Silver clad copper (80:20)=60 2% 49/22.40 0.5 5 15 850-900 6.5 >2kg <1% Example 10-1 Silver clad copper (80:20)=60 2% 26.65/49.08 1 5 15 850-900 5.6 >2kg <1% Example 10-2 Silver clad copper (80:20)=60 2% 40.68/34.51 3 5 15 850-900 5.1 >2kg <1% Example 10-3 Silver clad copper (80:20)=60 2% 36.39/41.40 5 5 15 850-900 4.6 >2kg <1% Example 10-4 Silver clad copper (80:20)=60 2% 43.82/30.06 8 5 15 850-900 3.6 >2kg <1% Example 10-5 Silver clad copper (80:20)=60 2% 28.49/35.57 0.5 5 15 850-900 5.4 >2kg <1% Example 10-6 Silver clad copper (80:20)=60 2% 18.47/48.15 1 5 15 850-900 4.7 >2kg <1% Example 10-7 Silver clad copper (80:20)=60 2% 32.11/48.30 3 5 15 850-900 4.2 >2kg <1% Example 10-8 Silver clad copper (80:20)=60 2% 27.83/50.19 5 5 15 850-900 3.8 >2kg <1% Example 10-9 Silver clad copper (80:20)=60 2% 27.37/38.15 8 5 15 850-900 3.0 >2kg <1%

由表1及表2所示的測試結果可得知，本發明所提供的電極膏體所製備的電極厚膜在高溫300次循環(相當於2年)耐硫化測試條件下，其對於陶瓷基板的附著力依舊相當高，具有優越的附著接著性能，且電阻在耐硫化測試後，其變化率皆小於1%，顯示可長時間保持優異的電氣特性。From the test results shown in Table 1 and Table 2, it can be known that the electrode thick film prepared by the electrode paste provided by the present invention is under the high-temperature 300 cycles (equivalent to 2 years) sulfuration resistance test conditions, which is relatively good for ceramic substrates. The adhesion is still quite high, with excellent adhesion and adhesion performance, and the change rate of the resistance after the sulfuration resistance test is less than 1%, showing that it can maintain excellent electrical characteristics for a long time.

綜上，本發明所提供的電極膏體可用於製備電氣特性優異的電子元件，尤其特別適合與陶瓷基板進行共燒，於陶瓷基板的端面形成外部電極以製備積層陶瓷電子零件。In summary, the electrode paste provided by the present invention can be used to prepare electronic components with excellent electrical properties, and is especially suitable for co-firing with ceramic substrates to form external electrodes on the end faces of ceramic substrates to prepare laminated ceramic electronic components.

無。none.

無。none.

Claims

一種電極膏體，包括： 70~90 wt%的金屬粉末； 1~8 wt%的玻璃組成物； 5~30 wt%的有機黏結劑；以及 2~30 wt%的溶劑；其中，該玻璃組成物為Li ₂O-ZnO-Al ₂O ₃-Na ₂O-SrO-V ₂O ₅-B ₂O ₃-SiO ₂，包括0.5~5 wt%的Li ₂O、20~50 wt%的ZnO、1~5 wt%的Al ₂O ₃、1~10 wt%的Na ₂O、0.5~5 wt%的SrO、1~15 wt%的V ₂O ₅、20~50 wt%的B ₂O ₃、以及1~10 wt%的SiO ₂。 An electrode paste, comprising: 70-90 wt% metal powder; 1-8 wt% glass composition; 5-30 wt% organic binder; and 2-30 wt% solvent; wherein, the glass composition The compound is Li ₂ O-ZnO-Al ₂ O ₃ -Na ₂ O-SrO-V ₂ O ₅ -B ₂ O ₃ -SiO ₂ , including 0.5~5 wt% Li ₂ O, 20~50 wt% ZnO , 1~5 wt% Al ₂ O ₃ , 1~10 wt% Na ₂ O, 0.5~5 wt% SrO, 1~15 wt% V ₂ O ₅ , 20~50 wt% B ₂ O ₃ , and 1~10 wt% of SiO ₂ .

如請求項1所述的電極膏體，其中，該電極膏體於一惰性氣體下進行一燒結步驟所製得的一電極厚膜的片電阻小於7 mΩ。The electrode paste according to claim 1, wherein the electrode paste is subjected to a sintering step under an inert gas, and the sheet resistance of an electrode thick film is less than 7 mΩ.

如請求項1所述的電極膏體，其中，該玻璃組成物的軟化點在400~900°C。The electrode paste according to claim 1, wherein the glass composition has a softening point of 400-900°C.

如請求項1所述的電極膏體，其中，該玻璃組成物的平均粒徑為1~10μm。The electrode paste according to claim 1, wherein the average particle diameter of the glass composition is 1-10 μm.

如請求項1所述的電極膏體，其中，該金屬粉末為一銅粉、一銀包銅粉、或一BaTiO ₃粉。 The electrode paste as claimed in item 1, wherein the metal powder is a copper powder, a silver-coated copper powder, or a BaTiO ₃ powder.

如請求項1所述的電極膏體，其中，該金屬粉末的平均粒徑為0.1 ~10μm。The electrode paste according to claim 1, wherein the average particle size of the metal powder is 0.1-10 μm.

如請求項1所述的電極膏體，其中，該有機黏結劑為一熱硬化性樹脂、一熱塑性樹脂、或其混合物。The electrode paste according to claim 1, wherein the organic binder is a thermosetting resin, a thermoplastic resin, or a mixture thereof.

如請求項1所述的電極膏體，其中，該溶劑係至少一選自由有機酸類、芳香族烴類、吡咯啶酮類、醯胺類、酮類、及環狀碳酸酯所組成之群組。The electrode paste according to claim 1, wherein the solvent is at least one selected from the group consisting of organic acids, aromatic hydrocarbons, pyrrolidones, amides, ketones, and cyclic carbonates .

如請求項1所述的電極膏體，其中，該電極膏體的黏度為20至100 Pa.s。The electrode paste according to claim 1, wherein the electrode paste has a viscosity of 20 to 100 Pa.s.

如請求項1所述的電極膏體，更包括至少一金屬氧化物，至少一選自由氧化銅、氧化鉍、氧化錳、氧化鈷、氧化鎂、氧化鉭、氧化鈮、及氧化鎢所組成之群組。The electrode paste as described in Claim 1, further comprising at least one metal oxide, at least one selected from copper oxide, bismuth oxide, manganese oxide, cobalt oxide, magnesium oxide, tantalum oxide, niobium oxide, and tungsten oxide group.

一種電極厚膜的製備方法，包括以下步驟： (A) 提供請求項1至請求項10中任一項所述的該電極膏體；以及 (B) 將該電極膏體塗佈於一基材上，於一惰性氣體下進行一燒結步驟，使得該電極膏體經燒結而獲得該電極厚膜。 A method for preparing an electrode thick film, comprising the following steps: (A) providing the electrode paste described in any one of claim 1 to claim 10; and (B) Coating the electrode paste on a substrate, and performing a sintering step under an inert gas, so that the electrode paste is sintered to obtain the electrode thick film.

如請求項11所述的製備方法，於步驟(B)中，該基材為一陶瓷基板。According to the preparation method described in claim 11, in step (B), the substrate is a ceramic substrate.

如請求項11所述的製備方法，於步驟(B)中，該燒結步驟的燒結溫度為900C以下。According to the preparation method described in Claim 11, in step (B), the sintering temperature of the sintering step is below 900C.

如請求項11所述的製備方法，於步驟(B)中，該電極厚膜的片電阻率小於7 mΩ。According to the preparation method described in Claim 11, in step (B), the sheet resistivity of the electrode thick film is less than 7 mΩ.

如請求項11所述的製備方法，於步驟(B)中，該電極厚膜與該陶瓷基板之間的附著拉力為2~3 kg。According to the preparation method described in claim 11, in step (B), the adhesion tension between the electrode thick film and the ceramic substrate is 2-3 kg.