1379315 修正日期101年8月28日 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種電極用組合物和用此組合物製備的 電極。 【先前技術】 對於諸如電阻器、陶兗電容器、熱敏電阻器 (thermistor)、變阻器（varistor)、電漿顯示面板等元件，電 極通常用包含銀粉作為導電填料的組合物並在以網版印刷 法(screen printing)、膠版印刷法(off-set printing)、微影法 (photolithography)等形成圖案之後用焙燒(firing)方法來形 成。 然而，在電極用組合物的形成中使用銀粉作為導電填 料會增加生產成本。使用銀作為導電填料也會由於電子運 動引起的銀組分的遷移而引起用銀粉形成的電極圖案中相 鄰的電極間的電短路。隨後會破壞電極的可靠性。 為了解決這些問題，人們已經致力於開發更加便宜的 導電填料材料來取代銀粉。 # -種導f填料㈣使用！g作為導電填料。但是铭在空 2的:^燒触中會被氧化，造成用含有銘填料的組合物 製成的電極的電導性快速下降。 舍番因為在用上述組合物形成電極時通常培燒過程 過程二：Ϊ2為2填料時，由於隨著每次培燒 度增加，會導致電導性快速下降。 人們已經 為了解決有關使用結作為導電填料的問題， 4 修正曰期101年8月28日 銘或18合金的球形粉末。然而，使用球形粉 末使付，極的阻抗高咖銀粉製備的電極阻抗的幾千倍， 並且在每次焙燒過程中電極阻抗會增加1〇〇/0或更多Γ因 此’包含IS或Is合金㈣形粉末還沒有實際驗生產。 【發明内容】 本發明提供一種電極用組合物，此組合物可以在空氣 中約600 C或更低的溫度進行培燒過程，即使對此組合物 重複進行上述焙燒過程也不會引起絕對阻抗的增加和阻抗 的實質性變化。 根據本發明的一方面，提供一種電極用組合物，包括： 約5〜約95 wt%的鋁粉，此鋁粉具有2.〇或更低的如下列 公式⑴所表示的粒度分佈(particle size distribution)，並且 具有約0.1 μιη彡D5(K約20 μιη範圍内的D50 ;約3〜約 6〇 wt%的有機黏合劑(organic binder);餘量的溶劑： 粒度分佈=(D90-D10)/D50 ------(1) 其中D10、D50和D90表示當總重量為100%時粒度 分佈的累積曲線上在10%、50%和90%的點處的粒徑。 D90-D10 介於 3.58 μιη 至 10.42 μπι。 根據本發明的另一方面，提供了用上述組合物製備的 電極和電衆顯示面板（plasma display panel，PDP)。 為讓本發明之上述特徵和優點能更明顯易懂，下文特 舉實施例，並配合所附圖式作詳細說明如下。 【實施方式】 現在通過下面的詳細描述來更加充分地說明本發 修正日期101年8月28曰 明，其中說明了本發明的部分而不是全部實施方式。實際 上’本發明可以許多不同的形式來實現，不應解釋為限制 成此處所列出的實施方式；更確切地，提供這些實施方式 使得本發明的公開滿足申請的法定要求。 根據本發明的一個實施方式’電極用組合物包括導電 填料、玻璃膠(glass frit)、有機黏合劑和溶劑。 導電填料包括鋁作為主要成分，並且呈粉末形式，尤 其是具有2.0或更低的如下列公式（1)所表示的粒度分佈的 球形粉末形式’並且具有約0.1 μηι彡D50彡約20 μηι範圍 内的D50。 粒度分佈=(D90-D10)/D50 ______(1) 其中D10、D50和D90代表當總重量為100〇/〇時粒度 分佈的累積曲線上在10%、50%和90%的點處的粒徑。 通常’雖然D10、D50和D90可以限定為恒定的值， 但是在這個實施方式中，D10、D5〇和D9〇均被設定為在 如上所述的預定的範圍内，以從粉末狀樣品的顆粒大小方 面表示本發明的範圍。所以，用作導電填料的具有落在這 些範圍内的顆粒大小的鋁粉落在本發明的範圍内。 备用具有如上所述的粒度分佈和顆粒大小的導電填料 製，的組合物彻來形成電極時，得到的電極即使是在約 6〇〇 C或更低的溫度下⑫燒後進行再姐燒棘，其阻抗也 不會產生顯著變化。 〃用於導電填料的叙粉可由純铭或紹合金構成。銘合金 藉由將選自銀、銅、石夕、錫、鉻、鍺及其組合中的至少一 1379315 修正曰期101年8月28日 種元素與鋁一起形成合金而得到。 根據本發明，所述組合物包括約5〜約95 wt%的導電 填料，例如約30〜約90 wt%的導電填料。如果導電填料 在組合物中的含量小於約5 wt%，則用這樣的組合物製備 的電極的導電性不足。如果組合物中導電填料的含量超過 約95 wt% ’則組合物對基板會呈現較差的黏結性和可印刷 性。 將用作導電填料的銘粉過篩(sieved)，使其粒度分佈， 即(D90 - D10)/D50的值，為約2.〇或更低，例如約〇 5〜 約1.7，同時D50在約〇.1 pm<D50彡約2〇 4爪範圍内。 結果是，根據本實施方式的電極用組合物可以在約6〇〇。〇 或更低的溫度下進行焙燒過程，即使此電極重複進行上述 培燒過程也不會引起絕對阻抗的增加和阻抗的實質變化。 通常鋁粉的粒度分佈可以用粒度分佈儀來測量或通過 掃描式電子顯微鏡(scanning electronic microscopy，SEM) 來得到。 根據本發明的一個實施方式，所述有機黏合劑為選自 纖維素（celluloses)、水溶性纖維素衍生物（λν_ s〇luble cellulose derivative)以及藉由共聚具有烯類不飽和雙鍵的 單體和羧酸類單體得到的共聚物中的至少一種。所述具有 婦類不飽和雙鍵的單體例如為丙烯酸的酯類（丙烯酸甲酯 (methyl acrylate)、曱基丙烯酸乙酯咖如㈣攸)等）' 苯乙烯（Styrene)、丙烯醯胺（acrylic amide)、丙烯腈 (acrylonitrile)等。所述羧酸類單體例如為丙烯酸、甲基丙 7 1379315 修正日期ιοί年8月28日 烯酸(methacrylic acid)、衣康酸(itac〇nic acid)等。 有機黏合劑的含量範圍為約3〜約6〇 wt%，例如約5 〜約50wt%。如果有機黏合劑含量小於約3 wt%，則组合 物會在製成漿料後呈現明顯下降的黏度，或者在印刷或^ 燥後呈現降低的黏結力。如果有機黏合劑含量超過約6〇 wt%，則組合物會含有太多的有機黏合劑，而使得這些有 機黏合劑在焙燒過程中會充分分解，造成阻抗的增加。 進而，有機黏合劑的分解溫度可為約350〜約5〇(rc， 例如約400〜約480°C。 在上述範圍内的分解溫度下，在焙燒過程中可以調節 紹粉的氧化率，使得電極具有良好的阻抗。 並且，當使用上述有機黏合劑中的具有約2〇〇c或更低 的玻璃轉化溫度(glass transition temperature)的黏結性有機 黏合劑(cohesive organic binder)時，組合物的膠版印刷會更 加容易。 在本發明的組合物中，溶劑用來溶解有機黏合劑並調 節組合物的黏度，而使其可以製成能塗敷到基板上的漿料。 上述溶劑可為選自具有約120。(：或更高的沸點且通常 用於製備電極用組合物的溶劑。根據一個實施方式，所述 溶劑為選自甲基溶纖劑(methyl cellosolve)、乙基溶纖劑 (ethyl cellosolve)、丁基溶纖劑（butyl cellosolve)、脂肪族醇 (aliphatic alcohol)、a-萜品醇（α-terpineol)、β-萜品醇 (β-terpineol)、二氫萜品醇（dihydro-terpineol)、乙二醇 (ethylene glyc〇l)、二甘醇單甲醚（diethyiene glyc〇1 8 修正日期101年8月28日 monomethyl ether)、二甘醇單乙謎（diethylene glycol monoethyl ether)、二甘醇單丙謎（diethylene glycol monopropyl ether)、二 乙二醇單丁 謎（dietherethylene glycol monobutyl ether)、二丙二醇單曱键（dipropylene glycol monomethyl ether)、丙二醇單曱謎乙酸酯(propylene glycol monomethyl ether acetate)、丙三醇(glycerol)、乙酸 丁酉旨（butyl acetate)、乙酸乙醋（ethyl acetate)、環己醇 (cyclohexanol)、丁基溶纖劑乙酸酯（butyl cellosolve acetate)、酯醇（texanol)、礦油精(mineral spirit)、有機酸、 油酸(oleic acid)及其組合中的至少一種。 由於可以調節溶劑的加入量來容易地調節黏度，溶劑 的含量可以根據具體應用來改變，可在約1〜約68 wt°/〇範 圍内。 在本發明的組合物中，玻璃膠用作一種無機黏合劑， 來改善對基板的黏結力’其加入量可以為相對於重量 份組合物加入約1〜約30重量份。 玻璃膠的例子可非限制性地包括金屬氧化物類玻璃， 包括 PbO、Bi203、Si02、b2〇3、p2〇5、Zn〇 或 Al2〇3 中的 一種或多種，並可具有約300〜約600。(：的玻璃轉化溫度1379315 Revision Date August 28, 2011 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition for an electrode and an electrode prepared using the composition. [Prior Art] For components such as resistors, ceramic capacitors, thermistors, varistors, plasma display panels, etc., the electrodes are usually printed with a composition containing silver powder as a conductive filler and printed on the screen. A pattern is formed by a screen printing method, an off-set printing method, a photolithography method, or the like, and then a firing method is used. However, the use of silver powder as a conductive filler in the formation of the electrode composition increases the production cost. The use of silver as a conductive filler also causes an electrical short between adjacent electrodes in the electrode pattern formed by the silver powder due to the migration of the silver component caused by the electron movement. This will subsequently destroy the reliability of the electrode. In order to solve these problems, efforts have been made to develop a cheaper conductive filler material to replace the silver powder. # - Kind of f filler (four) use! g as a conductive filler. However, in the air 2: ^ burning will be oxidized, resulting in a rapid decrease in the electrical conductivity of the electrode made of the composition containing the Ming filler. Since the cooking process is generally carried out in the case where the electrode is formed by the above composition, the process 2: when Ϊ2 is 2, the electrical conductivity is rapidly lowered as the degree of burning increases. In order to solve the problem of using junctions as conductive fillers, 4 the spherical powder of Ming or 18 alloys was revised on August 28, 2011. However, the use of spherical powders allows for a very high impedance of thousands of times the impedance of the electrode prepared by the silver powder, and the electrode impedance increases by 1 〇〇/0 or more during each firing. Therefore, 'I or IS alloy is included. (4) The powder has not been actually produced. SUMMARY OF THE INVENTION The present invention provides a composition for an electrode which can be subjected to a calcination process at a temperature of about 600 C or less in air, even if the above-mentioned calcination process is repeated for the composition, no absolute impedance is caused. Increase and substantial changes in impedance. According to an aspect of the invention, there is provided a composition for an electrode comprising: from about 5 to about 95 wt% of an aluminum powder having a particle size distribution represented by the following formula (1) of 2. 〇 or lower (particle size) Distribution), and having an organic binder of about 0.1 μm 彡 D5 (K in the range of about 20 μm; about 3 to about 6 〇 wt%; solvent: particle size distribution = (D90-D10) /D50 ------(1) where D10, D50 and D90 represent the particle diameters at the points of 10%, 50% and 90% on the cumulative curve of the particle size distribution when the total weight is 100%. D90-D10 Between 3.58 μηη and 10.42 μπι. According to another aspect of the present invention, an electrode and a plasma display panel (PDP) prepared using the above composition are provided. To make the above features and advantages of the present invention more apparent It is to be understood that the following detailed description of the embodiments and the accompanying drawings are set forth below. Some but not all embodiments of the invention. Actually The present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that the disclosure of the present invention satisfies the legal requirements of the application. The composition for an electrode includes a conductive filler, a glass frit, an organic binder, and a solvent. The conductive filler includes aluminum as a main component, and is in the form of a powder, especially having a viscosity of 2.0 or less as in the following formula (1). The spherical powder form of the indicated particle size distribution 'and has a D50 in the range of about 0.1 μηι彡D50彡 about 20 μη. Particle size distribution = (D90-D10) / D50 ______ (1) where D10, D50 and D90 represent when the total weight is Particle size at 10%, 50%, and 90% points on the cumulative curve of the particle size distribution at 100 〇/〇. Usually 'although D10, D50, and D90 can be defined as constant values, but in this embodiment, D10 And D5〇 and D9〇 are each set within a predetermined range as described above to represent the range of the present invention from the particle size of the powdery sample. Therefore, the article used as the conductive filler Particle-sized aluminum powder falling within these ranges falls within the scope of the present invention. When a composition made of a conductive filler having a particle size distribution and a particle size as described above is used to form an electrode, the obtained electrode is even After 12 burns at a temperature of about 6 ° C or lower, the impedance of the S. sinensis will not change significantly. 叙 The powder used for the conductive filler can be composed of pure or sinter alloy. The alloy is obtained by alloying at least one of 1379315 selected from the group consisting of silver, copper, shi, tin, chrome, niobium and combinations thereof with aluminum on August 28, 2011. According to the present invention, the composition comprises from about 5 to about 95% by weight of a conductive filler, for example from about 30 to about 90% by weight of a conductive filler. If the content of the electrically conductive filler in the composition is less than about 5 wt%, the electrode prepared using such a composition is insufficient in conductivity. If the content of the conductive filler in the composition exceeds about 95 wt%, the composition exhibits poor adhesion and printability to the substrate. The powder used as the conductive filler is sieved to have a particle size distribution, that is, a value of (D90 - D10) / D50 of about 2. Torr or lower, for example, about 〜5 to about 1.7, and D50 is About 11 pm < D50 彡 about 2 〇 4 claw range. As a result, the composition for an electrode according to the present embodiment may be about 6 Torr. The calcination process is carried out at a temperature of 〇 or lower, and even if the electrode is repeatedly subjected to the above-described firing process, it does not cause an increase in absolute impedance and a substantial change in impedance. Usually, the particle size distribution of the aluminum powder can be measured by a particle size distribution meter or by a scanning electron microscopy (SEM). According to an embodiment of the present invention, the organic binder is selected from the group consisting of celluloses, water-soluble cellulose derivatives, and monomers copolymerized with ethylenically unsaturated double bonds. At least one of a copolymer obtained from a carboxylic acid monomer. The monomer having a pharmaceutically unsaturated double bond is, for example, an ester of acrylic acid (methyl acrylate, ethyl methacrylate or the like), styrene (styrene), acrylamide ( Acrylic amide), acrylonitrile, and the like. The carboxylic acid monomer is, for example, acrylic acid or methyl propyl 7 1379315. Amendment date 1988, methacrylic acid, itaconic acid, etc. The organic binder is present in an amount ranging from about 3 to about 6% by weight, such as from about 5 to about 50% by weight. If the organic binder content is less than about 3 wt%, the composition will exhibit a significantly reduced viscosity after being formed into a slurry, or exhibit a reduced cohesive force after printing or drying. If the content of the organic binder exceeds about 6% by weight, the composition will contain too much organic binder, and these organic binders will be sufficiently decomposed during the firing, resulting in an increase in impedance. Further, the decomposition temperature of the organic binder may be from about 350 to about 5 Torr (rc, for example, from about 400 to about 480 ° C. In the decomposition temperature within the above range, the oxidation rate of the powder can be adjusted during the calcination process, so that The electrode has a good impedance. And, when a cohesive organic binder having a glass transition temperature of about 2 〇〇 c or less is used in the above organic binder, the composition Offset printing can be easier. In the composition of the present invention, the solvent is used to dissolve the organic binder and adjust the viscosity of the composition so that it can be made into a slurry that can be applied to the substrate. A solvent having a boiling point of about 120 (or higher) and generally used for preparing an electrode composition. According to one embodiment, the solvent is selected from the group consisting of methyl cellosolve and ethyl cellosolve ( Ethyl cellosolve), butyl cellosolve, aliphatic alcohol, a-terpineol, beta-terpineol, dihydroterpineol Terpin Eol), ethylene glycol (ethylene glyc〇l), diethylene glycol monomethyl ether (diethyiene glyc〇18 modified date August 28, 101 monomethyl ether), diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, dietherethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl acetate Ether acetate), glycerol, butyl acetate, ethyl acetate, cyclohexanol, butyl cellosolve acetate, texanol At least one of mineral spirit, organic acid, oleic acid, and combinations thereof. Since the viscosity can be easily adjusted by adjusting the amount of the solvent added, the solvent content can be changed depending on the specific application. It can range from about 1 to about 68 wt ° / 。. In the composition of the present invention, the glass paste is used as an inorganic binder to improve the adhesion to the substrate. The amount of the glass paste added may be from about 1 to about 30 parts by weight based on the weight of the composition. Examples of the glass paste may include, without limitation, a metal oxide-based glass, including one or more of PbO, Bi203, SiO 2 , b 2 〇 3, p 2 〇 5, Zn 〇 or Al 2 〇 3, and may have about 300 to about 600. (: glass transition temperature
Tg。 如果玻璃膠的玻璃轉化溫度低於約3〇〇〇c，則組合物 的收縮率會過度增加’這會擴大用這種組合物形成的4極 的邊緣捲曲。相反，如果玻璃膠的玻璃轉化溫度高於約600 °c，則組合_導電成分可能不會被充錢結(sintered)， 修正日期丨01年8月28日 這會增加電極的阻抗。 如果玻璃膠的加入量少於約1重量份’則難以實現本 發明所期望的效果。相反，如果玻璃膠的加入量超過約30 重量份，則組合物中導電填料的量會相對減少’使得由此 組合物形成的電極不能實現期望水準的導電性。 另一方面，對於藉由加入玻璃膠製備的組合物，當用 雷射粒度分佈儀測量時，由於玻璃膠的影響，其粒度分佈 會輕微增加或降低。 根據本發明的一個實施方式，如果需要，為了改善組 合物的流動性和加工性及在製備過程中的穩定性，所述組 合物可進一步含有選自紫外線穩定劑（ultraviolet stabilizer)、黏度穩定劑（viscosity stabilizer)、消泡劑 (antifoaming agent)、分散劑（dispersing agent)、均化劑 (leveling agent)、抗氧化劑(anti〇xidant agent)、抗熱固化劑 (anti-heat curing agent)等及其組合中的至少一種添加劑。 這些添加劑為本領域普通技術人員所熟知，所以在此省略 其詳細舉例和說明。 在由此組合物形成電極時，可使用乾膜光阻(dry film resistor，DFR)方法、網版印刷法、膠版印刷法、塗佈法或 微影法中的至少一種方法。 根據本發明的一個實施方式，當在形成電極中使用微 影法時，此組合物進一步包括光聚合化合物和光聚合引發 劑(initiator)。 光聚合化合物為用作感光樹脂的多官能基單體或寡聚 修正日期101年8月28曰 體(oligomer)。適用於本發明的這個實施方式的光聚合化合 物非限制性地包括選自由如下物質組成的族群中的至少一 種：例如乙二醇二丙稀酸醋（ethyleneglycol diacrylate)、三 甘醇二丙稀酸 g旨(triethyleneglycol diacrylate)、1，4- 丁 二醇二 丙烯酸酷（1,4-butandiol diacrylate)、1，6-己二醇二丙烯酸醋 (l，6-hexanediol diacrylate)、新戊二醇二丙烯酸酉旨 (neopentylglycol diacrylate)、季戍四醇二丙烯酸醋 (pentaerythritol diacrylate)、季戊四醇三丙稀酸醋 (pentaerythritol triacrylate)、二季戊四醇二丙稀酸醋 (dipentaerythritol diacrylate)、二季戍四醇三丙烯酸醋 (dipentaerythritol triacrylate)、二季戊四醇五丙烯酸醋 (dipentaerythritol pentacrylate)、二季戊四醇六丙稀酸醋 (dipentaerythritol hexacrylate)、雙酴 A 二丙稀酸醋(bispenol A diacrylate)、三經甲基丙烧三丙烯酸醋（trimethylolpropane triacrylate)、盼路環氧丙烯酸醋(novolac epoxy acrylate)、 乙二醇二曱基丙稀酸酯(ethylene glycol dimethacrylate)、二 甘醇二曱基丙烯酸酯(diethylene glycol dimethacrylate)、三 甘醇二甲基丙烯酸酯(triethylene glycol dimethacrylate)、丙 二醇二甲基丙稀酸酯(propylene glycol dimethacrylate)、1，4-丁二醇二甲基丙烯酸酯（l，4-butandiol dimethacrylate)、1，6-己二醇二曱基丙烯酸酯（1，6-hexanediol dimethacrylate)等及 其組合。 相對於100重量份的上述組合物，光聚合化合物的加 入量可為約0.1〜約20重量份。如果光聚合化合物的含量 修正日期101年8月28日 =於約（U f量份’财足以發生統合，造成顯影過程 中的圖案遺漏。相反，如果光聚合化合物超過約20重量 份’則由於過量的多官能基單體或募聚體，在培燒過程中 有機物質會分解，弓丨起阻抗的增加。 進而’根據本發明的-個實施方式，任何光聚合引發 劑都可以用於上述組合物的製備，只要這種引發劑在約 200〜約400 nm的紫外線波長内呈現良好的光反應性。光 3^ 3引發劑可以疋選自由二笨曱酮(以虹叩匕⑶⑴^)、苯乙酮 (acetophenone)、三嗪類(triazine_based)化合物等及其組合 構成的組中的至少一種。 相對於100重量份的組合物，光聚合引發劑的加入量 可為約0.01〜約10重量份。 當在期望位置將上述組合物圖案化之後，在室溫下初 步乾燥組合物，然後在約100〜約20(TC的溫度下烘烤，從 而形成具有預定強度的電極圖案。 然後，在約450〜約600°C焙燒此電極圖案，從而使得 有機黏合劑和溶劑從圖案化的組合物中完全分離，而作為 無機黏合劑加入的玻璃膠則熔融來黏合導電填料。 通常培燒過程不是一次完成，而是根據後面的電介質 製程而定，重複進行例如兩次或三次。 圖1為用根據本發明的一個實施方式的組合物製備的 電漿顯示面板(plasma display panel，PDP)的示意圖。 參見圖1，根據本發明的一個實施方式，用組合物製 備電漿顯示面板10，電漿顯示面板10包括前基板100和 12 1379315 修正日期101年8月28日 後基板150。 在電聚顯示面板10中，透明電極110水平配置在面對 後基板150的前基板1〇〇表面上，並在其上具有匯流電極 112。在每個透明電極110上’形成有用於儲存由顯示面板 内部產生的電荷的第一電介質層114和用於保護第一電介 質層114並使電子釋放更容易的MgO層118。 並且’定址電極(address electrode) 117縱向形成於面對 如基板100的後基板150的上表面上。第二電介質層us 形成在具有定址電極117的後基板150的上表面上，並形 成有分隔物(partiti〇n)l20，分隔物120含有分別對應於紅 色R、綠色G和藍色B的螢光物質132，以在第二電介質 層115上定義畫素區域。 將諸如Ne+Ar、Ne+Xe等惰性氣體注入到前基板1〇〇 和後基板150之間的空間，從而當臨界值或更高^電壓被 施加到電極上時，藉由放電現象而發光。 在這樣的PDP中，匯流電極112和/或定址電極117 用根據本發明的一個實施方式的組合物形成。具體來說， 這些電極用網版印刷法、膠版印刷法、或微影法中的^種 形成。 根據本發明的一個實施方式，當這些電極用微影法彤 成時’形成這些電極的方法包括： 〜4 ’ 將根據本發明的一個實施方式的組合物塗數 板上來形成厚度為約5〜約40 μπι的組合物層； 土 在約80〜約150乞的溫度下乾燥所塗敷的級合物層約 13 1379315 修正日期丨〇丨年8月28日 20〜約60分鐘； 將乾燥的纽合物層藉由光罩暴露於紫外線； •藉由顯影從組合物層去除暴露的區域（正性）或未暴 政的區域（負性）；和 在j 5GG〜約6GGC乾燥和培燒組合物層。培燒時間不 限疋’通常為足以分解基本全部的有機物的時間。在 神m實施方式中，在約5耽或更高的溫度下 培燒時間範圍為約0.5〜約3小時，但是 限 制在此範圍内。 下面將參考實施例說明本發明，以說明根據本發明 的組合物在賊組合_成電極的過程中在約㈣β(：或更 低的溫度T可轉行轉雜，並且即使是將此組合物重 複進行培燒過程也*會引起絕對阻抗的增加和阻抗的 性變化。對於本職的普職術人員來說，本發明的詳細 情況將很明顯，所以，省略其具體描述。 1、鋁粉的製備 用仕何機器裂備球形鋁粉 並 1379315 修正日期101年8月28日 且用異丙醇作為分散劑。 表1示出了用根據本發明的一個實施方式的方法製備 的鋁粉實例的粒度分佈。 表1 A1粉 (A) A1粉 (B) A1粉 (C) A1粉 (D) A1粉 (E) A1粉 (F) A1粉 (G) A1粉 (H) A1粉 (I) A1粉 (J) DIO 1.95 4.72 5.28 2.15 2.15 3.93 5.46 1.86 1.56 3.07 D50 4 8.15 9.19 3.52 3.5 5.78 7.66 4.53 5.11 4.06 D90 6.5 12.27 13.06 5.73 7.82 14.35 10.74 8.37 14.63 11.64 D90 -D1 0 4.55 7.55 7.78 3.58 5.67 10.42 5.28 6.51 13.07 8.57 (D9 0-D 10)/ D50 1.138 0.926 0.847 1.02 1.62 1.802 0.69 1.44 2.558 2.111 2、電極用組合物的製備 (1)實施例1-8和對比例1和2 說明本發明的實施例和對比例的組合物藉由如下方法 製備：混合用作導電填料的鋁粉、玻璃膠(無鉛類Bi-Zn-B 成分，軟化點480°C，平均直徑1.5 μπι)、用作有機黏合劑 的丙稀酸類共聚物(講自Geo Myung Co.，Ltd.，SPN #30-1， 15 1379315 修正日期101年8月28曰 分解溫度447°C)、用作溶劑的酯醇（texanol)(購自Eastman Chemical Co.，Ltd.)，然後用陶竞三報研磨機(3-roll mill)捏 煉(kneading)。表2列出了這些組合物的含量比例。 表 2 (wt%) 組分 E1 E2 E3 E4 E5 E6 E7 E8 CE1 CE2 A1 粉(A) 57.5 - - A1 粉(B) - 57.5 - A1 粉(C) - - 57.5 - A1 粉(D) - - - 57.5 - - - - - - A1 粉(E) - - - - 57.5 - - - - - A1 粉(F) - - - - - 57.5 - - - - A1 粉(G) 57.5 - - - A1 粉(H) 57.5 _ - A1 粉(I) - 57.5 - A1 粉(J) 57.5 玻璃躁 9.97 9.97 9.97 9.97 9.97 9.97 9.97 9.97 9.97 9.97 有機黏合劑 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 溶劑 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 E :實施例、CE :對比例 (2)實施例9和10 16 1379315 修正曰期101年8月28曰 為了糟由微影法形成電極圖案，其他實施例的組合物 藉由以與實施例1和7不同的含量混合與實施例1和7相 同的組分來製備’同時向其中進一步加入光聚合引發劑(購 自 Shiba Co” Ltd. ’ IC369)和光聚合化合物(Satomer Co.， Ltd· ’ SR494) ’然後用陶瓷三輥研磨機捏煉。表3列出了 這些組合物的含量比例。 表3 組分 實施例9 實施例10 Α1 粉(Α) 58 Α1 粉(G) 58 玻璃膠 6.2 6.2 有^黏合劑 21 21 溶劑 6.3 6.3 光聚合引發劑 1.5 1.5 光聚合化合物 7 L 7 3、用這些組合物形成厚膜電極 用購自Tester Sangyo Co.，Ltd.的ΡΙ1210塗佈機將實施 例1〜8和對比例1和2的組合物塗敷到具有高溶點的1〇 cm X 1〇 cm的玻璃基板上。然後，乾燥塗佈的組合物，並 在110°C下烘烤’然後從輸入到輸出在一個半小時内在帶 式爐(belt furnace)中於560°C培燒15分鐘的峰值保持時間 (peak holding time)。然後，形成電極的25 μιη的圖案，並 測量電極的阻抗。測量結果列於表4中。 17 修正日期101年8月28曰 電極藉由如下方法形成：分·實施例9和1()的組合 。’、^到基板上’來形成厚度為25 μιη的組合物層；在110 C乾燥所^的組合物層約2G分鐘；將錢的組合物層藉 由光罩暴路於紫外線；藉由顯影從組合物層去除暴露的區 域或未暴露的區域；在56〇ΐ焙燒組合物層。 測量這些電極的阻抗並將結果列於表4中。 4、測量重複焙燒的電極的阻抗變化 測量了用實施例1〜1〇以及對比例i和2的組合物形 成的電極的初始阻抗之後，將電極圖案進行額外的一次或 兩次焙燒，然後測量電極的阻抗變化。測量結果列於表4 中0 表4Tg. If the glass transition temperature of the glass paste is less than about 3 〇〇〇 c, the shrinkage of the composition will increase excessively. This will enlarge the edge curl of the 4 pole formed by this composition. Conversely, if the glass transition temperature of the glass paste is higher than about 600 ° C, the combined _ conductive component may not be sintered, corrected date 8 August 28, 2001, which increases the impedance of the electrode. It is difficult to achieve the desired effect of the present invention if the glass gum is added in an amount of less than about 1 part by weight. On the contrary, if the glass gum is added in an amount exceeding about 30 parts by weight, the amount of the conductive filler in the composition is relatively reduced, so that the electrode formed by the composition cannot achieve a desired level of conductivity. On the other hand, for the composition prepared by adding the glass paste, when measured by a laser particle size distribution meter, the particle size distribution thereof slightly increases or decreases due to the influence of the glass paste. According to an embodiment of the present invention, the composition may further contain, if necessary, an ultraviolet stabilizer, a viscosity stabilizer, in order to improve fluidity and processability of the composition and stability during preparation. (viscosity stabilizer), antifoaming agent, dispersing agent, leveling agent, anti-xidant agent, anti-heat curing agent, etc. At least one additive in its combination. These additives are well known to those skilled in the art, so detailed examples and illustrations thereof are omitted herein. When the electrode is formed of the composition, at least one of a dry film resistor (DFR) method, a screen printing method, an offset printing method, a coating method, or a lithography method can be used. According to an embodiment of the present invention, when a lithography method is used in forming an electrode, the composition further includes a photopolymerizable compound and a photopolymerization initiator. The photopolymerizable compound is a polyfunctional monomer or oligomer used as a photosensitive resin. The date of August 28, 2010 is an oligomer. The photopolymerizable compound suitable for use in this embodiment of the invention includes, without limitation, at least one selected from the group consisting of ethyleneglycol diacrylate, triethylene glycol diacrylic acid g (triethyleneglycol diacrylate), 1,4-butandiol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol Neopentylglycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, diquaternary tetraol triacrylate (dipentaerythritol triacrylate), dipentaerythritol pentacrylate, dipentaerythritol hexacrylate, bispenol A diacrylate, trimethoprim triacetate (trimethylolpropane triacrylate), novolac epoxy acrylate Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethyl propylene Propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. And their combinations. The photopolymerizable compound may be added in an amount of from about 0.1 to about 20 parts by weight based on 100 parts by weight of the above composition. If the content of the photopolymerizable compound is corrected on August 28, 2011 = about (the amount of U f is sufficient to cause integration, causing pattern omission during development. Conversely, if the photopolymerizable compound exceeds about 20 parts by weight) Excessive polyfunctional monomer or polymerizer, the organic substance will decompose during the calcination process, and the impedance will increase. Further, according to an embodiment of the present invention, any photopolymerization initiator can be used for the above. The composition is prepared as long as the initiator exhibits good photoreactivity in the ultraviolet wavelength of from about 200 to about 400 nm. The light 3^3 initiator may be selected from the group consisting of dicuminone (to rainbow trout (3) (1) ^) And at least one of the group consisting of acetophenone, triazine-based compound, and the like, and a combination thereof. The photopolymerization initiator may be added in an amount of from about 0.01 to about 10 with respect to 100 parts by weight of the composition. After the above composition is patterned at a desired position, the composition is preliminarily dried at room temperature, and then baked at a temperature of about 100 to about 20 (TC) to form an electrode pattern having a predetermined strength. Then, the electrode pattern is fired at about 450 to about 600 ° C, so that the organic binder and the solvent are completely separated from the patterned composition, and the glass paste added as an inorganic binder is melted to bond the conductive filler. The firing process is not completed in one pass, but is repeated, for example, two or three times depending on the subsequent dielectric process. Fig. 1 is a plasma display panel prepared by using the composition according to an embodiment of the present invention. Schematic of PDP) Referring to Figure 1, a plasma display panel 10 is prepared from a composition according to one embodiment of the present invention. The plasma display panel 10 includes a front substrate 100 and 12 1379315. The substrate 150 is modified after August 28, 2011. In the electro-polymer display panel 10, the transparent electrode 110 is horizontally disposed on the front substrate 1 surface facing the rear substrate 150, and has a bus electrode 112 thereon. On each of the transparent electrodes 110, 'is formed for storage by A first dielectric layer 114 that displays charges generated inside the panel and an MgO layer 118 for protecting the first dielectric layer 114 and making electrons easier to release. An address electrode 117 is formed longitudinally on the upper surface facing the rear substrate 150 such as the substrate 100. A second dielectric layer us is formed on the upper surface of the rear substrate 150 having the address electrodes 117, and is formed with a spacer The spacer 120 contains phosphors 132 corresponding to red R, green G, and blue B, respectively, to define a pixel region on the second dielectric layer 115. Such as Ne+Ar, Ne+ An inert gas such as Xe is injected into the space between the front substrate 1A and the rear substrate 150, so that when a threshold value or a higher voltage is applied to the electrodes, light is emitted by the discharge phenomenon. In such a PDP, the bus electrode 112 and/or the address electrode 117 are formed with a composition according to an embodiment of the present invention. Specifically, these electrodes are formed by a screen printing method, an offset printing method, or a lithography method. According to one embodiment of the present invention, when the electrodes are formed by lithography, the method of forming the electrodes includes: ~4' The composition according to one embodiment of the present invention is coated on the number of plates to form a thickness of about 5~ a layer of the composition of about 40 μm; the soil is dried at a temperature of about 80 to about 150 Torr. The layer of the applied layer is about 13 1379315. The date of revision is August 28, 20 to about 60 minutes; The conjugate layer is exposed to ultraviolet light by means of a reticle; • the exposed area (positive) or the undynched area (negative) is removed from the composition layer by development; and the combination of drying and cultivating at j 5GG~about 6GGC Layer of matter. The burning time is not limited to 'time is usually enough time to decompose substantially all of the organic matter. In the embodiment of the god m, the firing time is from about 0.5 to about 3 hours at a temperature of about 5 Torr or higher, but is limited to this range. The invention will now be described with reference to the examples to illustrate that the composition according to the invention can be converted to about (4) β (or lower temperature T) during the thief combination-forming electrode, and even if the composition is repeated The firing process also causes an increase in absolute impedance and a change in impedance. The details of the present invention will be apparent to the general practitioner of the present application, and therefore, a detailed description thereof will be omitted. Spherical aluminum powder was spun with a machine and 1379315, dated August 28, 101, and isopropyl alcohol was used as a dispersing agent. Table 1 shows the particle size of an example of aluminum powder prepared by the method according to one embodiment of the present invention. Table 1 A1 powder (A) A1 powder (B) A1 powder (C) A1 powder (D) A1 powder (E) A1 powder (F) A1 powder (G) A1 powder (H) A1 powder (I) A1 Powder (J) DIO 1.95 4.72 5.28 2.15 2.15 3.93 5.46 1.86 1.56 3.07 D50 4 8.15 9.19 3.52 3.5 5.78 7.66 4.53 5.11 4.06 D90 6.5 12.27 13.06 5.73 7.82 14.35 10.74 8.37 14.63 11.64 D90 -D1 0 4.55 7.55 7.78 3.58 5.67 10.42 5.28 6.51 13.07 8.57 (D9 0-D 10)/ D50 1.138 0.926 0.847 1.02 1. 62 1.802 0.69 1.44 2.558 2.111 2. Preparation of Electrode Composition (1) Examples 1-8 and Comparative Examples 1 and 2 The compositions of the examples and comparative examples of the present invention were prepared by the following method: mixing for use as a conductive Filled aluminum powder, glass glue (lead-free Bi-Zn-B component, softening point 480 ° C, average diameter 1.5 μπι), acrylic copolymer used as organic binder (speaking from Geo Myung Co., Ltd. , SPN #30-1, 15 1379315 Amendment date August 28, 2011, decomposition temperature 447 ° C), ester alcohol (texanol) (purchased from Eastman Chemical Co., Ltd.), and then used Tao Jingsan 3-roll mill kneading. Table 2 lists the content ratio of these compositions. Table 2 (wt%) Component E1 E2 E3 E4 E5 E6 E7 E8 CE1 CE2 A1 Powder (A) 57.5 - - A1 powder (B) - 57.5 - A1 powder (C) - - 57.5 - A1 powder (D) - - - 57.5 - - - - - - A1 powder (E) - - - - 57.5 - - - - - A1 powder (F) - - - - - 57.5 - - - - A1 powder (G) 57.5 - - - A1 powder (H) 57.5 _ - A1 powder (I) - 57.5 - A1 powder (J) 57.5 glass crucible 9.97 9.97 9.97 9.97 9.97 9 .97 9.97 9.97 9.97 9.97 Organic binder 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 19.11 Solvent 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 13.42 E: Examples, CE: Comparative Example (2) Examples 9 and 10 16 1379315 Amendment In order to form an electrode pattern by lithography for the sake of the smear, the composition of the other examples was prepared by mixing the same components as those of Examples 1 and 7 at different contents from those of Examples 1 and 7. At the same time, a photopolymerization initiator (purchased from Shiba Co" Ltd. 'IC369) and a photopolymerizable compound (Satomer Co., Ltd. 'SR494)' were further added thereto and then kneaded by a ceramic three-roll mill. Table 3 lists the content ratios of these compositions. Table 3 Component Example 9 Example 10 Α1 powder (Α) 58 Α1 powder (G) 58 Glass glue 6.2 6.2 with adhesive 21 21 Solvent 6.3 6.3 Photopolymerization initiator 1.5 1.5 Photopolymerization compound 7 L 7 3. These compositions formed thick film electrodes. The compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were applied to 1 〇cm X 1 having a high melting point using a ΡΙ1210 coater available from Tester Sangyo Co., Ltd. 〇cm on the glass substrate. Then, the coated composition was dried and baked at 110 ° C and then peaked from the input to the output in a belt furnace at 560 ° C for 15 minutes. Holding time). Then, a pattern of 25 μm of the electrode was formed, and the impedance of the electrode was measured. The measurement results are shown in Table 4. 17 Revised date August 28, 2011 Electrodes are formed by the following method: a combination of Examples 9 and 1 (). ', ^ onto the substrate' to form a layer of composition having a thickness of 25 μm; drying the composition layer at 110 C for about 2 G minutes; the composition layer of money is violently exposed to ultraviolet rays by a photomask; The exposed or unexposed areas are removed from the composition layer; the composition layer is fired at 56 Torr. The impedance of these electrodes was measured and the results are shown in Table 4. 4. Measurement of impedance change of repeatedly fired electrode After measuring the initial impedance of the electrode formed by the compositions of Examples 1 to 1 and Comparative Examples i and 2, the electrode pattern was subjected to additional one or two baking, and then measured. The impedance of the electrode changes. The measurement results are listed in Table 4 0 Table 4
El E2 E3 E4 E5 E6 m) △R(%) m) △R(%) _ △R(%) R(fl) △R(%) △R(%) R(H) △R(%) PF 0.18 - 0.15 - 0.25 - 0.16 - 0.18 - 0.17 - SF 0.18 0 0.16 6.7 0.24 -4 0.16 0 0.19 5.5 0.18 5.9 TF 0.19 5.5 0.16 6.7 0.22 -12 0.16 0 0.19 5.5 0.20 11.8 E7 E8 E9 E10 CE1 CE2 R(n) AR(%) R(Q) △R(0/〇) ΙΙ(Ω) △R(%) m) △R(%) R(Q) △R(%) 聊 △R(%)· PF 0.19 0.17 - 0.2 - 0.14 - 0.42 - 0.38 - SF 0.21 10.1 0.18 5.9 0.22 10 0.15 7.1 0.49 16.7 0.46 21 * TF 0.20 5.3 0.18 5.9 0.2 0 0.14 0 0.55 30.9 0.53 39.5 PF :初次焙燒(560°C)後 SF :第二次焙燒(560°C)後 11379315 修正日期101年8月28日 TF :第三次焙燒(560°C)後 E :實施例 CE :對比例 由表4可見’由實施例1〜1〇的具有約2 〇或更低的 粒度分佈（(D90-D10)/D50)的組合物製備的電極具有比用 對比例1和2的組合物製備的電極低得多的初始阻抗。 由於實施例1的D50為4’而對比例2的D50為4.06, 這些例子在D50方面非常相似。但是，由表4可見，這此 例子根據其粒度分佈在初始阻抗和後續再焙燒阻抗方面呈 現出非常顯著的區別。 並且，對於實施例6，當(D90-D10)/D50超過1.7時， 根據重複焙燒的阻抗變化大於由(D90-D10)/D50在1.7或 更低的組合物製成的電極。 結果是，這些實施例說明根據本發明僅僅藉由調節用 作導電填料的鋁粉的D50，並調節其粒度分佈（即 (D90-D10)/D50)至約2.0或更低，即使是焙燒和重複焙燒 之後，也可以得到較低的初始阻抗和不顯著的阻抗變化二 雖然本發明已以實施例揭露如上，然其並非用以限定 本發明，任何所屬技術領域中具有通常知識者，在不脫二 本發明之精神和範圍内，當可作些許之更動與潤鄭，故本 發明之保s蒦範圍當視後附之申請專利範圍所界定者為 【圖式簡單說明】 ‘^ ° 實施方式的Μ合物製備的 圖1為用根據本發明的一個 電聚顯示幕的示意圖。 1379315 修正日期101年8月28日 【主要元件符號說明】 10 :電漿顯示面板 100 :前基板 110 :透明電極 112 :匯流電極 114 :第一電介質層 115 :第二電介質層 117 :定址電極 118 : MgO 層 120 :分隔物 132 :螢光物質 150 :後基板 20El E2 E3 E4 E5 E6 m) △R(%) m) △R(%) _ △R(%) R(fl) △R(%) △R(%) R(H) △R(%) PF 0.18 - 0.15 - 0.25 - 0.16 - 0.18 - 0.17 - SF 0.18 0 0.16 6.7 0.24 -4 0.16 0 0.19 5.5 0.18 5.9 TF 0.19 5.5 0.16 6.7 0.22 -12 0.16 0 0.19 5.5 0.20 11.8 E7 E8 E9 E10 CE1 CE2 R(n) AR(%) R(Q) △R(0/〇) ΙΙ(Ω) △R(%) m) △R(%) R(Q) △R(%) Chat △R(%)· PF 0.19 0.17 - 0.2 - 0.14 - 0.42 - 0.38 - SF 0.21 10.1 0.18 5.9 0.22 10 0.15 7.1 0.49 16.7 0.46 21 * TF 0.20 5.3 0.18 5.9 0.2 0 0.14 0 0.55 30.9 0.53 39.5 PF : SF: second after initial calcination (560 ° C) After sub-baking (560 ° C) 11379315 Revised date August 28, 2011 TF: Third calcination (560 ° C) after E: Example CE: Comparative example can be seen from Table 4 'by Example 1~1〇 The electrode prepared with the composition having a particle size distribution of about 2 Torr or less ((D90-D10) / D50) had a much lower initial impedance than the electrode prepared with the compositions of Comparative Examples 1 and 2. Since the D50 of Example 1 is 4' and the D50 of Comparative Example 2 is 4.06, these examples are very similar in terms of D50. However, as can be seen from Table 4, this example shows a very significant difference in initial impedance and subsequent re-baking resistance depending on its particle size distribution. Also, with respect to Example 6, when (D90-D10) / D50 exceeds 1.7, the impedance change according to the repeated firing is larger than that of the electrode made of the composition of (D90-D10) / D50 of 1.7 or lower. As a result, these examples illustrate that according to the present invention, only by adjusting the D50 of the aluminum powder used as the conductive filler, and adjusting its particle size distribution (i.e., (D90-D10)/D50) to about 2.0 or lower, even if calcined and After the repeated firing, a lower initial impedance and an insignificant impedance change can also be obtained. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art does not In the spirit and scope of the present invention, the scope of the invention is defined as the scope of the patent application as defined in the attached patent application. [^ ° Implementation Figure 1 of the present invention is a schematic view of an electropolymer display screen in accordance with the present invention. 1379315 Revised date August 28, 2011 [Description of main component symbols] 10: Plasma display panel 100: Front substrate 110: Transparent electrode 112: Bus electrode 114: First dielectric layer 115: Second dielectric layer 117: Address electrode 118 : MgO layer 120 : separator 132 : fluorescent substance 150 : rear substrate 20