200402754 (1) 玖、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、形成電極用轉錄 薄膜及電漿顯示面板用電極，更詳細地，係關於可適用於 電漿顯示面板的電極形成之導電性糊組成物、形成電極用 轉錄薄膜以及使用該物質所得之電漿顯示面板用電極。 【先前技術】 電漿顯示面板（PDP )，由於製造製程容易、廣視 角、自發光式，顯示品質高等理由，平面顯示面板技術 中，頗受囑目，特別是彩色電漿顯示面板，作爲2 0吋以 上的大型顯示器，期待在壁掛電視等的用途成爲主流。 彩色PDP，藉由氣體放電所產生之紫外線照射於螢光 體上，可彩色顯示。因此，一般彩色PDP中，藉由紅色 發光用的螢光體部位、綠色發光用的螢光體部位、藍色發 光用的螢光體部位形成於基板上，各色發光顯示單元全部 均勻混合存在的狀態下構成。具體而言，由玻璃等組成之 基板的表面上，設置稱爲阻隔壁之絕緣性材料所構成之隔 牆，藉由該隔牆，區隔多數的顯示單元，該顯示單元的內 部成爲電漿作用的空間。於是，在該電漿作用的空間，設 置螢光體部位的同時，藉由在該螢光體部位設置產生電漿 作用之電極，以各顯示單元作爲顯示單位而構成PDP。 圖1表示交流型P D P的剖面形狀的模型化圖。於圖 中，1與2爲相對向配置之玻璃基板，3爲隔牆，藉由玻 ~ 5 _ (2) 200402754 璃基板1、玻璃基板2以及隔牆3，形成區隔單元。4爲 固定於玻璃基板1的透明電極，5係爲了降低透明電極的 阻抗，於透明電極上形成之匯流電極，6爲固定於玻璃基 板2之位址電極，7爲保持於單元內之螢光體，8爲形成 於玻璃基板1的表面上爲覆蓋透明電極4與傳遞電極5之 介電層，1 〇爲例如氧化鎂組成之保護膜。然而，直流型 PDP中，通常在電極端子（陽極端子）與電極導線（陽極 導線）之間設置阻抗體。而且，爲了提高PDP的對比， 於上述介電層8與保護膜1 〇之間等，亦有設置紅色、綠 色、藍色之彩色濾光板、黑色矩陣的情況。 作爲如此之PDP的電極圖形的製造方法，已知（1 ) 以濺鍍、蒸鍍等形成金屬薄膜，塗布光阻、曝光、顯影 後，藉由鈾刻液形成金屬薄膜圖形之蝕刻法；（2 )將含 有非感光性的無機粉末之樹脂組成物網版印刷於基板上， 獲得圖形，將其燒成之網版印刷法；（3 )含有感光性的 無機粉末之樹脂組成物的膜形成於基板上，於該膜隔著光 罩照射紫外線，藉由顯像，圖形殘留於基板上，將其燒成 之黃光微影法等。 但是’上述蝕刻法，有需要大型的真空設備，步驟上 的產出太慢等的問題。 而且’上述網版印刷法，隨面板的大型化以及高精細 化’圖形的位置精度的要求非常嚴苛，以一般的印刷無法 對準的問題。 更進一步，上述黃光微影法，形成5 μηι以上膜厚的 3Q3 - 6 - (3) (3)200402754 圖形時，含無機粉末之樹脂組成物的膜在深度方向上感度 不足，顯像時圖形易從基板界面剝離的問題。 於此，爲解決上述蝕刻法、網版印刷法以及黃光微影 法可見之問題’本發明人等，揭露藉由包含形成光阻膜與 含無機粉末之樹脂層的疊層膜於支持膜上，支持膜上所形 成之疊層膜再轉錄至基板上，使構成該疊層膜之光阻膜進 行曝光處理，形成光阻圖形的潛像，顯像該光阻膜，光阻 圖形顯現，蝕刻處理含無機粉末之樹脂層，形成對應光阻 圖形的含無機粉末之樹脂層的圖形，燒成該圖形步驟，包 含形成電極於上述基板表面的步驟之製造方法（以下稱爲 「乾膜法」）（參照日本專利特開平1 1 · 1 623 3 9與特開平 11-283495)。 但是，如此之製造方法’雖可簡便的形成高精細圖 型，具關於導電性等的電極性能不足的問題。 【發明內容】 發明所欲解決之問題 本發明的課題，在於提供一種可形成具優良導電性以 及良好密合性的電極圖型之導電性糊組成物、形成電極用 轉錄薄膜以及利用該等而得之PDP用電極。 解決課題之手段 本發明的導電性糊組成物5包含：（A )比表面積 I·5〜5.0 m2/g之導電性粉末；（B )玻璃原料混合物；以 -7- (4) (4)200402754 及（C )接合樹脂。 又本發明的導電性糊組成物，包含：（A )至少含Ag 粉末作爲導電性粉末較佳。而且，（B )作爲玻璃原料、浪 合物，至少含軟化點400〜60 0 °C的無鉛玻璃原料混合物較 佳。更進一步，（C )作爲接合樹脂，至少含羧基之甲基 丙烯酸酯樹脂較佳。 本發明的形成電極用轉錄薄膜，包含藉由塗布本發明 的導電性糊組成物所獲得之導電性樹脂層。 本發明的PDP用電極，使用本發明的導電性糊組成 物以及本發明的形成電極用轉錄薄膜而形成該電極。 【實施方式】 以下，針對本發明的導電性糊組成物、形成電極用轉 錄薄膜以及P D P用電極’加以詳細說明。 〈導電性糊組成物〉 本發明的導電性糊組成物，至少包含：（A )導電性 粉末（B )玻璃原料混合物以及（c )接合樹脂，（A )導 電性粉末的比表面積必須在1 .5〜5.〇 ni2/g。 (A)導電性粉末 本發明的導電性糊組成物所含之導電性粉末的比表面 積在1.5〜5.0 m2/g，介於1 .5〜4.0 m2/g間較佳，介於 2 · 0〜3 · 5 m2 / g間更佳。 -8- (5) (5)200402754 導電性粉末的比表面積不足1 .5m2/g的情況，使用該 導電性糊組成物所得之電極圖型的導電性不足。另一方 面，導電性粉末的比表面積超過5.0m2/g的情況，於導電 性糊組成物中，易發生粉末凝集，難以獲得安定之分散狀 態。而且，使用該導電性糊組成物所得之電極圖型，對基 板之密合性易受損壞。 而且，於此所謂比表面積，係指藉由導電性糊組成物 中的導電性粉末的B ET法，求得之平均値。 作爲本發明的導電性糊組成物中的導電性粉末，可選 擇 Ag、An、Al、Cu、Ag-Pd合金等的金屬以及合金，亦 可單獨或混合二種以上使用。該等導電性粉末中，即使於 大氣中燒成的情況下，不會產生因氧化致使導電性降低， 使用較廉價的Ag特別好。 作爲上述導電性粉末的形狀，粒狀、球狀、片狀等不 特別限定，亦可使用單獨或混合二種以上的形狀的導電性 粉末。而且，上述導電性粉末的平均粒徑，以〇 . 1〜5 μηι較 佳，可使用混合具相異粒徑的導電性粉末。 (Β )玻璃原料混合物 本發明的導電性糊組成物所含之玻璃原料混合物，適 合使用低融點的玻璃原料混合物。通常，使用軟化點65 〇 °C以下的玻璃原料混合物，使用4 0 0〜6 0 0 °C的玻璃原料混 合物較佳。玻璃原料混合物的軟化點不足400t的情況， 於燒成步驟時，在後述接合樹脂分解除去前，因玻璃原料 (6) (6)200402754 混合物開始熔融，燒成後之圖型可能殘存有機殘渣。而 且’玻璃原料混合物的軟化點超過6 0 0 °C的情況，於燒成 步驟時’玻璃原料混合物並不充分熔融，燒成後之圖型可 能密合性不足。 作爲玻璃原料混合物的組成，可選自例如：（1 )氧 化鉛、氧化硼、氧化矽系列（p b 〇 - B 2 Ο 3 - S i Ο 2系）、（2 ) 氧化鉛、氧化硼、氧化矽、氧化鋁系列（P b 〇 - Β 2 Ο 3 - S i Ο 2 -Al2〇3系）、（3 )氧化鋅、氧化硼、氧化矽系列（211〇-B203 _Si02系）、（4 )氧化鋅、氧化硼、氧化矽、氧化鋁 系列（Zn0-B2 03-Si02-Al203 系）、（5 )氧化鉛、氧化 鋅、氧化硼、氧化矽系列（Pb0-Zn0-B203-Si02系）、 (6 )氧化鉛、氧化鋅、氧化硼、氧化矽、氧化鋁系列 (Pb0-Zn0-B203 -Si02-Al203 系）、（7 )氧化鉍、氧化 硼、氧化矽系列（B i 2 Ο 3 - B 2 Ο 3 - S i Ο 2系）、（8 )氧化鉍、 氧化硼、氧化矽、氧化鋁系列（Bi203 -B203-Si02-Al203 系）、（9 )氧化鉍、氧化鋅、氧化硼、氧化矽系列 (Bi203-Zn0-B203-Si02 系）、（10)氧化鉍、氧化鋅、 氧化硼、氧化矽、氧化鋁系列（]3丨2〇3-211〇-8203 -8102- A12 Ο 3系）等。該等玻璃原料混合物中，由於環境上的問 題’使用以上述（3) 、（4) 、 （7) 、（8) 、 （9)以 及（1 0 )中g己載之無錯玻璃原料混合物較佳，其中，從導 電性糊組成物的歷久安定性的觀點而言，使用以（7 )、 (8 ) 、（ 9 )以及（1 0 )中記載之氧化鉍爲主成分之無鉛 玻璃原料混合物特別佳。 -10» (7) (7)200402754 而且，上述之玻璃原料混合物的形狀並無特別限定， 平均粒徑，以0.1〜ΙΟμιη較佳，0.5〜5μηι更佳。玻璃原料 混合物的平均粒徑不足〇· I μηι的情況，因玻璃原料混合物 的比表面積變大，於導電性糊組成物中，易發生粒子的凝 集’難以獲得安定之分散狀態，而且產生經久導電性糊組 成物增加黏度等的變化的情況。另一方面，玻璃原料混合 物的平均粒徑1 0 μπι以上的情況’難以獲得高精細的電極 圖型。 上述玻璃原料混合物，可使用具有單獨或相異之玻璃 原料混合物組成，相異之軟化點、相異之形狀、相異之平 均粒徑之玻璃原料混合物2種以上的組合。 導電性糊組成物中的玻璃原料混合物的含有量，以導 電性粉末100質量部爲基準，1〜30質量部較佳，2〜20質 量部更佳。玻璃原料混合物不足1質量部時，所得之電極 對基板的密合性恐怕不足。而且，超過3 0質量部時，所 得之電極可能導電性低，而且導電性糊組成物保存安定性 低，歷久恐產生變化。 (C )接合樹脂 作爲本發明的導電性糊組成物所含之接合樹脂，可使 用各種樹脂，使用含鹼可溶性樹脂30〜100重量％之樹脂 較佳。於此’ 「鹼可溶性」係指可藉由鹼性的蝕刻液溶 解，具有以完成蝕刻處理爲目的的程度之溶解性質。 作爲如此之鹼可溶性樹脂的具體例，例如，可選自甲200402754 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a conductive paste composition, an electrode-forming transcription film, and an electrode for a plasma display panel. More specifically, the present invention relates to an electrode suitable for a plasma. A conductive paste composition formed by electrodes of a display panel, a transcription film for an electrode, and a plasma display panel electrode obtained by using the same. [Previous technology] Plasma display panels (PDP), due to the ease of manufacturing processes, wide viewing angles, self-luminous, high display quality, etc., flat display panel technology has attracted considerable attention, especially color plasma display panels, as 2 Large displays of 0 inches or more are expected to become mainstream in applications such as wall-mounted televisions. The color PDP can be displayed in color by irradiating the phosphor with ultraviolet rays generated by gas discharge. Therefore, in a general color PDP, a phosphor portion for red light emission, a phosphor portion for green light emission, and a phosphor portion for blue light emission are formed on a substrate, and all color light emitting display units are uniformly mixed. Under the state. Specifically, a partition wall made of an insulating material called a barrier wall is provided on the surface of a substrate made of glass or the like. The partition wall separates a large number of display units, and the inside of the display unit becomes a plasma. Space for action. Therefore, in the space where the plasma is applied, a phosphor portion is provided, and an electrode which generates a plasma effect is provided in the phosphor portion, and each display unit is used as a display unit to constitute a PDP. FIG. 1 is a model view showing a cross-sectional shape of the AC-type P D P. In the figure, 1 and 2 are oppositely arranged glass substrates, and 3 is a partition wall. The glass substrate 1, glass substrate 2 and partition wall 3 are used to form a partition unit. 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode in order to reduce the impedance of the transparent electrode, 6 is an address electrode fixed to the glass substrate 2, and 7 is fluorescent light held in the cell 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the transfer electrode 5, and 10 is a protective film composed of, for example, magnesium oxide. However, in a DC type PDP, an impedance body is usually provided between an electrode terminal (anode terminal) and an electrode lead (anode lead). In addition, in order to improve the contrast of the PDP, red, green, and blue color filters and black matrices may be provided between the dielectric layer 8 and the protective film 10 described above. As a method for manufacturing an electrode pattern of such a PDP, (1) an etching method of forming a metal thin film by sputtering, vapor deposition, or the like, coating a photoresist, exposing, and developing the metal thin film pattern by using a uranium etching liquid; 2) Screen printing method of printing a resin composition containing a non-photosensitive inorganic powder on a substrate to obtain a pattern and firing it; (3) Film formation of a resin composition containing a photosensitive inorganic powder The film is irradiated with ultraviolet rays through a photomask on the substrate, and a pattern is left on the substrate through development, and a yellow light lithography method is used for firing the pattern. However, the above-mentioned etching method requires problems such as requiring large vacuum equipment, and too slow output. In addition, the above-mentioned screen printing method requires extremely strict positional accuracy of the pattern in accordance with the enlargement and high definition of the panel, and the problem of misalignment in general printing. Furthermore, when the above-mentioned yellow light lithography method is used to form a 3Q3-6-(3) (3) 200402754 pattern with a film thickness of 5 μm or more, the film of the resin composition containing inorganic powder has insufficient sensitivity in the depth direction, and the pattern is easy to develop. The problem of peeling from the substrate interface. Here, in order to solve the above-mentioned problems visible by the etching method, the screen printing method, and the yellow light lithography method, the inventors disclosed that a laminated film including a photoresist film and a resin layer containing an inorganic powder is formed on a supporting film. The laminated film formed on the supporting film is then transcribed onto the substrate, and the photoresist film constituting the laminated film is exposed to form a latent image of the photoresist pattern. The photoresist film is developed, and the photoresist pattern is developed and etched. A manufacturing method of processing a resin layer containing an inorganic powder to form a pattern of a resin layer containing an inorganic powder corresponding to a photoresist pattern, and firing the pattern, including a step of forming an electrode on the surface of the substrate (hereinafter referred to as "dry film method") ) (Refer to Japanese Patent Laid-Open Nos. 1 1 · 1 623 3 9 and Japanese Patent Laid-Open Nos. 11-283495). However, although such a manufacturing method 'can easily form a high-definition pattern, it has a problem of insufficient electrode performance such as conductivity. SUMMARY OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to provide a conductive paste composition capable of forming an electrode pattern having excellent conductivity and good adhesion, a transcription film for electrodes, and the like The electrode for PDP was obtained. Means for Solving the Problem The conductive paste composition 5 of the present invention includes: (A) conductive powder having a specific surface area of I · 5 to 5.0 m2 / g; (B) a glass raw material mixture; and -7- (4) (4) 200402754 and (C) bonding resin. The conductive paste composition of the present invention contains (A) at least an Ag-containing powder as the conductive powder. In addition, (B) as a glass raw material and a ionic compound, a lead-free glass raw material mixture containing at least a softening point of 400 to 60 ° C is preferred. Furthermore, (C) As the bonding resin, a methacrylate resin containing at least a carboxyl group is preferred. The transcription film for forming an electrode of the present invention includes a conductive resin layer obtained by applying the conductive paste composition of the present invention. The electrode for a PDP of the present invention is formed by using the conductive paste composition of the present invention and the transcription film for forming an electrode of the present invention. [Embodiment] Hereinafter, the conductive paste composition of the present invention, a film for forming an electrode, and an electrode for P D P 'will be described in detail. <Conductive Paste Composition> The conductive paste composition of the present invention includes at least: (A) conductive powder (B) glass raw material mixture and (c) bonding resin, (A) the specific surface area of the conductive powder must be 1 .5 to 5.〇ni2 / g. (A) Conductive powder The specific surface area of the conductive powder contained in the conductive paste composition of the present invention is from 1.5 to 5.0 m2 / g, preferably from 1.5 to 4.0 m2 / g, and from 2.0 to 0. ~ 3 · 5 m2 / g is better. -8- (5) (5) 200402754 When the specific surface area of the conductive powder is less than 1.5 m2 / g, the conductivity of the electrode pattern obtained by using the conductive paste composition is insufficient. On the other hand, when the specific surface area of the conductive powder exceeds 5.0 m2 / g, in the conductive paste composition, powder aggregation is likely to occur, and it is difficult to obtain a stable dispersed state. Furthermore, the electrode pattern obtained by using this conductive paste composition is liable to be damaged to the substrate. The specific surface area herein refers to the average 値 obtained by the B ET method of the conductive powder in the conductive paste composition. As the conductive powder in the conductive paste composition of the present invention, metals such as Ag, An, Al, Cu, and Ag-Pd alloys and alloys can be selected, and two or more kinds can be used alone or in combination. Among these conductive powders, even when sintered in the atmosphere, there is no reduction in conductivity due to oxidation, and it is particularly preferable to use cheaper Ag. The shape of the conductive powder is not particularly limited, such as granular, spherical, flake, and the like, and conductive powders of two or more shapes may be used alone or in combination. The average particle diameter of the conductive powder is preferably 0.1 to 5 μm, and conductive powders having different particle diameters can be used as a mixture. (B) Glass raw material mixture The glass raw material mixture contained in the conductive paste composition of the present invention is suitable for use with a low melting point glass raw material mixture. Generally, a glass raw material mixture having a softening point of 65 ° C or lower is used, and a glass raw material mixture of 400 to 600 ° C is preferably used. In the case where the softening point of the glass raw material mixture is less than 400t, during the firing step, the glass raw material (6) (6) 200402754 mixture starts to melt before the bonding resin described below is decomposed and removed, and organic residue may remain in the pattern after firing. When the softening point of the 'glass raw material mixture exceeds 600 ° C, the glass raw material mixture is not sufficiently melted during the firing step, and the pattern after firing may be insufficient in adhesion. The composition of the glass raw material mixture may be selected from, for example: (1) lead oxide, boron oxide, silicon oxide series (pb 〇- B 2 Ο 3-S i Ο 2 series), (2) lead oxide, boron oxide, oxidation Silicon, alumina series (P b 〇- Β 2 Ο 3-S i Ο 2 -Al2 03 series), (3) zinc oxide, boron oxide, silicon oxide series (211〇-B203 _Si02 series), (4) Zinc oxide, boron oxide, silicon oxide, aluminum oxide series (Zn0-B2 03-Si02-Al203 series), (5) lead oxide, zinc oxide, boron oxide, silicon oxide series (Pb0-Zn0-B203-Si02 series), (6) Lead oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide series (Pb0-Zn0-B203 -Si02-Al203 series), (7) bismuth oxide, boron oxide, silicon oxide series (B i 2 Ο 3- B 2 Ο 3-S i Ο 2 series), (8) bismuth oxide, boron oxide, silicon oxide, alumina series (Bi203 -B203-Si02-Al203 series), (9) bismuth oxide, zinc oxide, boron oxide, Silicon oxide series (Bi203-Zn0-B203-Si02 series), (10) bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide series () 3 丨 2〇3-211〇-8203 -8102- A12 〇 3 Department) etc. . Among these glass raw material mixtures, due to environmental problems, 'the above-mentioned (3), (4), (7), (8), (9), and (1 0) are contained in the error-free glass raw material mixture. Preferably, from the viewpoint of the long-term stability of the conductive paste composition, a lead-free glass raw material containing bismuth oxide as a main component described in (7), (8), (9), and (10) is used. The mixture is particularly good. -10 »(7) (7) 200402754 Moreover, the shape of the glass raw material mixture is not particularly limited, and the average particle diameter is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm. When the average particle size of the glass raw material mixture is less than 0.1 μm, the specific surface area of the glass raw material mixture becomes larger, and in the conductive paste composition, particle aggregation is likely to occur. Changes in the viscosity of the paste composition. On the other hand, when the average particle diameter of the glass raw material mixture is 10 μm or more, it is difficult to obtain a high-definition electrode pattern. The glass raw material mixture may be a combination of two or more kinds of glass raw material mixtures having separate or different glass raw material mixtures, different softening points, different shapes, and different average particle sizes. The content of the glass raw material mixture in the conductive paste composition is based on 100 parts by mass of the conductive powder, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass. If the glass raw material mixture is less than 1 part by mass, the resulting electrode may have insufficient adhesion to the substrate. In addition, when it exceeds 30 parts by mass, the resulting electrode may have low conductivity, and the conductive paste composition may have low storage stability, and may change over time. (C) Bonding resin As the bonding resin contained in the conductive paste composition of the present invention, various resins can be used, and a resin containing 30 to 100% by weight of an alkali-soluble resin is preferably used. As used herein, "alkali soluble" means that it can be dissolved by an alkaline etching solution and has a dissolving property to the extent that the etching process is completed. As a specific example of such an alkali-soluble resin, for example, it may be selected from
_ 11 - (8) 200402754 基丙烯酸酯系樹脂、羥基苯乙烯樹脂、諾瓦 脂、聚酯樹脂等。 如此之鹼可溶性樹脂中，較佳之例，可選 體（I)與單體（III)的共聚合體，單體（ (II)與單體（III)的共聚合體等的含羧基的 酯樹脂。 單體（I):含羧基的單體類 丙烯酸、甲基丙烯酸、順丁烯二酸、反-2 · 丁烯酸、亞甲基丁二酸、甲基順丁烯二酸、 二酸、肉桂酸、丁二酸單2 -甲基丙烯氧基乙 聚己內酯單甲基丙烯酸酯等。 單體（Π ):含OH的單體類 甲基丙烯酸2 -羥基乙酯、甲基丙烯酸2 -甲基丙烯酸3 -羥基丙酯等的含羥基的單體類； 烯、m ·羥基苯乙烯、p -羥基苯乙烯等酚性含羥 等。 單體（ΙΠ ):其他可能共聚合之單體類 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基 酯、甲基丙烯酸正十二酯、甲基丙烯酸苯甲酯 酸環氧丙酯、甲基丙烯酸二環戊酯等的單體 甲基丙烯酸酯；苯乙烯、α-甲基苯乙烯等的芳 系單體；丁二烯、·異戊-間-二烯等共軛二烯類 烯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、 酸苯甲酯等的聚合鏈的一側末端含甲基 拉克酚醛樹 擇以下的單 I )、單體 甲基丙烯酸 丁烯二酸、 甲基反丁烯 酯、ω -羧基 羥基丙酯、 〇-羥基苯乙 基的單體類 丙烯酸正丁 、甲基丙烯 (I )以外的 香族乙烯基 ;於聚苯乙 聚甲基丙烯 :丙烯醯基 -12- (9) (9)200402754 (methacryloyl )等的聚合性不飽和基的巨單體類： 上述單體（Ο與單體（III)的共聚合體以及單體 (I)、單體（II)與單體（III)的共聚合體，因存在由 單體（I)共聚合成分，可成爲鹼可溶性。其中單體 (I)、單體（II)與單體（III)的共聚合體，由（Α)導 電性粉末、（Β )玻璃原料混合物的分散安定性以及後述 對鹼顯影液的溶解性的觀點而言，特別佳。該共聚合體中 由單體（I)的共聚合成分的含有率，5〜60質量％較佳， 10〜40質量％特別佳，由單體（π )的共聚合成分的含有 率，1〜50質量％較佳，5〜30質量％特別佳。 作爲構成導電性糊組成物之鹼可溶性樹脂的分子量， 以 GPC聚苯乙烯換算的重量平均分子量（以下稱之爲 「Mw」），5,000〜5,000,000 較佳，1 0,000 〜3 00,000 更 佳。 本發明的導電性糊組成物中（C )接合樹脂的使用比 例，以對（A )導電性粉末100質量部計，5〜50質量部的 比例較佳。接合樹脂的含有量，不足5質量部的情況，導 電性糊組成物中易產生粉末凝集，難以獲得安定的分散狀 態，而且，塗布該導電性糊組成物形成之電極形成用薄膜 的可撓性、轉錄性顯著降低。此外，接合樹脂的含有量， 超過5 0質量部的情況，在電極形成步驟中的燒成處理步 驟，圖形的收縮有變大的傾向，可能引起圖形的變形。 (D )溶劑 -13· (10) (10)200402754 本發明的導電性糊組成物，通常含有溶劑。作爲上述 溶劑，與（A )導電性粉末與（B )玻璃原料混合物的親 和性以及與（C )接合樹脂的溶解性良好，對導電性糊組 成物可具適當黏性，藉由乾燥可輕易蒸發去除較佳。 如此的溶劑的具體例，例如：3-戊酮、2-己酮、4-庚 酮、環己酮等酮類；正-戊醇、4 -甲基-2 -戊醇、環己醇、 二丙酮醇等的醇類；2-甲氧基乙醇、2-乙氧基乙醇、丁氧 基乙醇、丙二醇單甲醚、丙二醇單乙醚等醚系醇類；乙酸 正丁酯、乙酸戊酯等的飽和脂肪族單羧酸烷酯類；乳酸乙 酯、乳酸正丁酯等的乳酸酯類；乙酸甲基乙氧基乙酯、乙 酸乙基乙氧基乙酯、乙酸甲氧基丙酯、3 -乙氧基丙酸乙酯 等的醚系酯類等。使用該等單獨或2種以上組合皆可。 導電性糊組成物中溶劑的含有比例，在可獲得良好的 膜形成性（流動性或可塑性）的範圍內，可適當選擇，通 常，以對（A)導電性粉末100質量部計，可爲1〜1〇,〇〇〇 質量部，以10〜1，〇〇〇質量部較佳。 於導電性糊組成物，除上述成分外，其他無機粉末、 可塑劑、顯像促進劑、接合助劑、保存安定性、消泡劑、 氧化防止劑、紫外線吸收劑、分散劑、交鏈劑、光聚合起 始劑、光酸產生劑、熱聚合起始劑、熱酸產生劑等各種添 加劑，可含有任意成分。 特別是導電性糊組成物，爲了保持本發明的形成電極 用轉錄薄膜的良好的可撓性以及轉錄性，使用可塑劑較 佳。作爲用於導電性糊組成物之可塑劑，可使用各種化合 -14- (11) (11)200402754 物，例如：己二酸二丁酯、己二酸二異丁酯、己二酸二 2 -乙基己酯、壬二酸二2 -乙基己酯、癸二酸二丁酯、癸二 酸二丁基二乙二酯、十二酸羥丙酯、油酸羥丙酯、鄰苯二 甲酸二2 -乙基己酯的等化合物，乙二醇、丙二醇等的烷 二醇的二甲基丙烯酸酯類；聚乙二醇、聚丙二醇等的聚烷 二醇的二甲基丙烯酸酯類；丙三醇、1，2,4-丁三醇、三羥 甲基烷類、四羥甲基烷類、異戊四醇、二異戊四醇等的三 價以上的多價醇的聚甲基丙烯酸酯類，以及該等的二羧酸 變成物；三價以上的多價醇的聚烷二醇附加物的聚甲基丙 烯酸酯類等的分子中，至少含一甲基丙烯醯基之甲基丙烯 酸酯化合物較佳。 導電性糊組成物中可塑劑的含量，以對（A )導電性 粉末1 〇 〇質量部計，含〇 · 5〜3 0質量部的比例較佳，以 1〜2 0質量部更佳。 而且，本發明的導電性糊組成物，亦可含具感光性的 物質，於該情形，利用添加構成後述之鹼顯像型放射線性 光阻組成物的感放射線性成分，以賦予感光性。於導電性 糊組成物賦予感光性的情況，不利用光阻組成物，可形成 電極圖形。 導電性糊組成物’上述（A )接合樹脂以及依據需要 的上述之任意有機成分溶解成爲媒液後，與上述（A )導 電性粉末、（B )玻璃原料混合物以及依據需要的上述任 意無機粉末混合，藉由使用如滾輪捏合機、混合機、乳化 混合機、球磨機、玻璃珠磨機等的捏合機進行捏和，可調 -15- (12) 200402754 製而成。 如上述調製之導電性糊組成物，具有適於塗布之流動 性的糊組成物，其黏度，通常爲100〜 1 00,000 cp，u 5 0 0〜1 0,000 cp 較佳。 〈形成電極用轉錄薄膜〉_ 11-(8) 200402754 based acrylic resins, hydroxystyrene resins, Nova resins, polyester resins, etc. Among such alkali-soluble resins, preferred examples include copolymers of the monomer (I) and the monomer (III), carboxyl-containing ester resins such as the copolymer of the monomer ((II) and the monomer (III)). Monomer (I): carboxyl-containing monomers acrylic acid, methacrylic acid, maleic acid, trans-2 · butenoic acid, methylene succinic acid, methyl maleic acid, diacid, Cinnamic acid, succinic acid mono 2-methacryloxyethylene polycaprolactone monomethacrylate, etc. Monomer (Π): OH-containing monomers 2-hydroxyethyl methacrylate, methacrylic acid Hydroxyl-containing monomers such as 2-hydroxypropyl methacrylate; phenolic hydroxyl-containing monomers such as olefins, m-hydroxystyrene, and p-hydroxystyrene. Monomers (ΙΠ): Others which may be copolymerized Monomer monomers such as methyl methacrylate, ethyl methacrylate, methyl ester, n-dodecyl methacrylate, glycidyl methacrylate, dicyclopentyl methacrylate, etc. Methacrylic esters; aromatic monomers such as styrene and α-methylstyrene; conjugated diene olefins such as butadiene, isoprene-m-diene, and polymethylpropene One end of the polymer chain, such as methyl ester, polyethyl methacrylate, and benzyl acid, contains methyl lacqueraldehyde, the following monomers (I), monomers of methacrylic acid, butadiene methacrylate Alkenyl esters, ω-carboxyhydroxypropyl esters, 0-hydroxyphenethyl monomer-based acrylic n-butyl, aromatic vinyl groups other than methacrylic acid (I); polyphenylene polymethacrylic acid: allyl- 12- (9) (9) 200402754 (methacryloyl) and other polymerizable unsaturated macromonomers: the above-mentioned monomer (copolymer of monomer 0 and monomer (III), monomer (I), monomer (II) ) The copolymer with monomer (III) can be alkali-soluble due to the copolymerization of monomer (I). Among them, the copolymer of monomer (I), monomer (II) and monomer (III), From the viewpoints of dispersion stability of (A) conductive powder, (B) glass raw material mixture, and solubility to an alkali developer, which will be described later, it is particularly preferable. The copolymer is composed of a copolymerized component of monomer (I). The content rate is preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass. The content rate of the copolymerized component from the monomer (π) is 1 It is preferably 50% by mass, and particularly preferably 5 to 30% by mass. As the molecular weight of the alkali-soluble resin constituting the conductive paste composition, the weight average molecular weight in terms of GPC polystyrene (hereinafter referred to as "Mw"), 5,000 It is more preferably ∼5,000,000, and more preferably 10,000 to 30,000,000. The proportion of the (C) bonding resin in the conductive paste composition of the present invention is calculated based on 100 parts by mass of (A) conductive powder, and 5 to 50 parts by mass. When the content of the bonding resin is less than 5 parts by mass, powder aggregation is likely to occur in the conductive paste composition, and it is difficult to obtain a stable dispersed state. In addition, a thin film for electrode formation formed by applying the conductive paste composition The flexibility and transcription are significantly reduced. When the content of the bonding resin exceeds 50 parts by mass, the shrinkage of the pattern tends to increase in the firing process step in the electrode formation step, which may cause the pattern to deform. (D) Solvent -13 · (10) (10) 200402754 The conductive paste composition of the present invention usually contains a solvent. As the above-mentioned solvent, it has good affinity with (A) conductive powder and (B) glass raw material mixture, and good solubility with (C) bonding resin. It can have appropriate viscosity for conductive paste composition, and can be easily dried by drying. Evaporation removal is preferred. Specific examples of such solvents include, for example, ketones such as 3-pentanone, 2-hexanone, 4-heptanone, and cyclohexanone; n-pentanol, 4-methyl-2-pentanol, cyclohexanol, Alcohols such as diacetone alcohol; ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, butoxyethanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; n-butyl acetate, pentyl acetate, etc. Saturated aliphatic monocarboxylic acid alkyl esters; lactates such as ethyl lactate and n-butyl lactate; methyl ethoxy ethyl acetate, ethyl ethoxy ethyl acetate, methoxy propyl acetate, Ether-based esters such as ethyl 3-ethoxypropionate. These may be used alone or in combination of two or more. The content ratio of the solvent in the conductive paste composition may be appropriately selected within a range in which good film formation properties (flowability or plasticity) can be obtained. Generally, it can be calculated as 100 mass parts of (A) conductive powder. A mass fraction of 1 to 10,000 is preferably a mass fraction of 10 to 1,000. In the conductive paste composition, in addition to the above components, other inorganic powders, plasticizers, development accelerators, joining aids, storage stability, antifoaming agents, oxidation inhibitors, ultraviolet absorbers, dispersants, and cross-linking agents , Various additives such as a photopolymerization initiator, a photoacid generator, a thermal polymerization initiator, and a thermal acid generator, and may contain optional components. In particular, the conductive paste composition is preferably a plasticizer in order to maintain the good flexibility and transcription of the transcription film for electrode formation of the present invention. As the plasticizer for the conductive paste composition, various compounds can be used. For example: 14- (11) (11) 200402754, such as dibutyl adipate, diisobutyl adipate, and di2 adipate -Ethylhexyl ester, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl diethylene sebacate, hydroxypropyl dodecanoate, hydroxypropyl oleate, o-benzene Compounds such as di2-ethylhexyl diformate; dimethacrylates of alkanediols such as ethylene glycol and propylene glycol; dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol Types; glycerol, 1,2,4-butanetriol, trimethylolane, tetramethylolane, isopentaerythritol, diisopentaerythrol, etc. Polymethacrylates and their dicarboxylic acid derivatives; polymethacrylates of polyalkylene glycol additions of polyvalent alcohols of trivalent or higher, and at least one methacrylic acid A methacrylate compound is preferred. The content of the plasticizer in the conductive paste composition is preferably from 0.5 to 30 mass parts, and more preferably from 1 to 20 mass parts, based on 100 mass parts of the conductive powder (A). Further, the conductive paste composition of the present invention may contain a photosensitive material. In this case, a photosensitive component is added to constitute a later-described alkali-developing radiation photoresist composition to impart photosensitivity. When the conductive paste composition imparts photosensitivity, an electrode pattern can be formed without using a photoresist composition. Conductive paste composition 'The above-mentioned (A) bonding resin and any of the above-mentioned organic components as required are dissolved into a vehicle solution, and then mixed with the above-mentioned (A) conductive powder, (B) glass raw material mixture, and the above-mentioned optional inorganic powder. Mixing is performed by using a kneader such as a roller kneader, a mixer, an emulsifying mixer, a ball mill, a glass bead mill, and the like, which can be adjusted to -15- (12) 200402754. The conductive paste composition prepared as described above has a paste composition suitable for coating, and its viscosity is usually 100 to 100,000 cp, preferably u 50 to 0,000 cp. <Formation of electrode transcription film>
本發明的形成電極用轉錄薄膜，必須含有藉由塗布本 發明的導電性糊組成物所獲得之導電性樹脂層。 本發明的形成電極用轉錄薄膜，通常由支持薄膜，以 及至少含有藉由塗布本發明的導電性糊組成物所獲得之導 電性樹脂層的轉錄層所構成，係爲用於乾膜法的電極形成 步驟之複合材料。 構成本發明的形成電極用轉錄薄膜之支持薄膜，具耐 熱性以及耐溶劑性，同時具可撓性的樹脂薄膜較佳。藉由 支持薄膜具可撓性，可利用滾筒塗布機、刀片塗布機、狹 縫塗布機等，塗布本發明的導電性糊組成物，導電性樹脂 層以滾筒狀捲回的狀態保存且可提供使用。作爲形成支持 薄膜的樹脂，可選擇例如聚乙烯對苯二甲酯、聚酯、聚乙 烯、聚丙烯、聚苯乙烯、聚亞醯胺、聚乙烯醇、聚氯乙 烯、聚氟乙烯等含氟樹脂、尼龍、纖維素等。作爲支持薄 膜的厚度，可例如爲2 〇〜1 〇 〇 μηι。 此外，於上述支持薄膜的表面，施行脫型處理較佳。 因此，朝基板的轉錄步驟’易進行支持薄膜的剝離操作。 構成本發明的形成電極用轉錄薄膜之導電性樹脂層， -16- (13) (13)200402754 藉由塗布本發明的導電性糊組成物、乾燥塗膜、除去溶劑 的一部分或全部而可形成。 作爲塗布導電性糊組成物的方法，膜厚的均勻性佳之 膜厚大小（例如1 μηι以上）的塗膜，可有效率形成較 佳’具體而言，可選擇藉由滾筒塗布機之塗布方法，藉由 刀片塗布機之塗布方法，藉由狹縫塗布機之塗布方法，藉 由帷幕塗布機之塗布方法，藉由網印塗布機之塗布方法， 藉由凸板印刷塗布機之塗布方法較佳。 塗膜的乾燥條件，以50〜l5〇°C溫度0.5〜30分鐘，乾 燥後的溶劑的殘留比例（導電性樹脂層中的含有率）通常 以2質量％以下。 如上述形成之導電性樹脂層的膜厚，通常在 1〜ΙΟΟμιη，介於3〜50μηι較佳，介於5〜40μπι更佳。 而且’於本發明的形成電極用轉錄薄膜，亦可設置保 護膜與轉錄層的表面接觸。保護膜，可使用與支持薄膜相 同之材料。而且，通常在保護膜的表面進行脫型處理，保 曰蒦0吴的剝離強度’必須比支持薄膜的剝離強度小。 本發明的形成電極用轉錄薄膜，於支持薄膜上形成光 阻層外’導電性樹脂層，亦可疊層形成。藉由轉錄該疊層 於基板上，可獲得導電性樹脂層上形成光阻層的疊層膜。 而且，本發明的形成電極用轉錄薄膜 (A- 1 )藉由塗布本發明的導電性糊組成物所獲得之 導電性樹脂層，以及（A - 2 )含有至少含著色顏料的無機 -17- (14) (14)200402754 粉末以及接合樹脂之著色樹脂層疊層而得較佳。於著色樹 脂層’作爲無機粉末，更含有上述之導電性粉末以及玻璃 原料混合物較佳。 使用該疊層膜時，由導電性樹脂層與著色樹脂層構成 的疊層電極，可一塊形成，而且，與基板的密合性、導電 性優、外反射光少，可適用於PDP用匯流電極之電極形 成。 更進一步，本發明的形成電極用轉錄薄膜，於支持薄 膜上形成光阻層上，該導電性樹脂層與著色樹脂層，順序 β層形成亦可。藉由轉錄該疊層膜於基板上，於著色樹脂 層上形成導電性樹脂層，更進一步，於其上形成光阻層， 可得疊層膜。 該著色樹脂層與光阻層，與該導電性樹脂層相同，塗 布含後述的著色顏料之糊組成物以及光阻組成物，乾燥塗 膜、除去溶劑的一部分或全部而可形成。 如此形成之著色樹脂層的膜厚，通常爲1〜20 μηι， 3〜15 μιη較佳，5〜10 μηι更佳。 而且，光阻層的膜厚，通常爲1〜20 μηι，3〜15 μηι較 佳，5〜1 0 μ m更佳。 含著色顏料之糊組成物 爲了形成著色樹脂層所使用的含著色顏料之糊組成 物，含有至少含著色顏料的無機粉末以及接合樹脂。 含著色顏料之糊組成物中所含的著色顏料，因爲防止 所得之電極的外反射而添加之物質，例如，可選擇Co、The transcription film for forming an electrode of the present invention must contain a conductive resin layer obtained by applying the conductive paste composition of the present invention. The transcription film for forming an electrode of the present invention is generally composed of a support film and a transcription layer containing at least a conductive resin layer obtained by coating the conductive paste composition of the present invention, and is an electrode used in the dry film method. Forming step of the composite material. The support film constituting the transcription film for forming an electrode of the present invention is preferably a resin film having heat resistance and solvent resistance and having flexibility. The support film is flexible, and the conductive paste composition of the present invention can be applied by a roll coater, a blade coater, a slit coater, or the like. The conductive resin layer is stored in a roll-shaped state and can be provided. use. As the resin forming the supporting film, for example, fluorine-containing materials such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyvinyl fluoride can be selected. Resin, nylon, cellulose, etc. The thickness of the supporting film may be, for example, 20 to 100 μm. In addition, it is preferable to perform a release treatment on the surface of the support film. Therefore, the substrate-side transcription step 'facilitates the peeling operation of the supporting film. The conductive resin layer constituting the electrode-forming transcription film of the present invention may be formed by coating the conductive paste composition of the present invention, drying the coating film, and removing a part or all of the solvent. . As a method for applying the conductive paste composition, a coating film having a good film thickness uniformity (for example, 1 μm or more) can be formed efficiently. Specifically, a coating method using a roll coater can be selected. The coating method by the blade coater, the coating method by the slit coater, the coating method by the curtain coater, the coating method by the screen printing coater, and the coating method by the convex printing coater are good. The drying conditions of the coating film are at a temperature of 50 to 150 ° C for 0.5 to 30 minutes. The residual ratio of the solvent after drying (the content of the conductive resin layer) is usually 2% by mass or less. The film thickness of the conductive resin layer formed as described above is usually 1 to 100 μm, preferably 3 to 50 μm, and more preferably 5 to 40 μm. Further, in the electrode-forming transcription film of the present invention, a protective film may be provided in contact with the surface of the transcription layer. The protective film can be made of the same material as the supporting film. Moreover, the release film is usually subjected to a release treatment on the surface of the protective film, and it is necessary that the peel strength of the film is smaller than the peel strength of the supporting film. The transcription film for forming an electrode of the present invention may be formed by laminating a conductive resin layer on the support film with a conductive resin layer outside the photoresist layer. By laminating the laminate on a substrate, a laminated film in which a photoresist layer is formed on a conductive resin layer can be obtained. Further, the electrode-forming transcription film (A-1) of the present invention is a conductive resin layer obtained by coating the conductive paste composition of the present invention, and (A-2) contains an inorganic-17- containing at least a coloring pigment. (14) (14) 200402754 Powder and coloring resin laminated layer of bonding resin are better. In the colored resin layer ', as the inorganic powder, it is preferable to further contain the above-mentioned conductive powder and a glass raw material mixture. When this laminated film is used, a laminated electrode composed of a conductive resin layer and a colored resin layer can be formed as a single body. In addition, it has excellent adhesion to the substrate, excellent conductivity, and low external reflection light, and is suitable for PDP bus Electrode formation. Furthermore, the electrode-forming transcription film of the present invention forms a photoresist layer on the supporting film, and the conductive resin layer and the colored resin layer may be formed in the order of β layers. A laminated film can be obtained by transcribing the laminated film on a substrate, forming a conductive resin layer on the colored resin layer, and further forming a photoresist layer thereon. The colored resin layer and the photoresist layer can be formed by coating a paste composition containing a coloring pigment and a photoresist composition described later, and drying the coating film and removing a part or all of the solvent, similarly to the conductive resin layer. The film thickness of the colored resin layer thus formed is usually 1 to 20 μm, preferably 3 to 15 μm, and more preferably 5 to 10 μm. Moreover, the film thickness of the photoresist layer is usually 1 to 20 μm, more preferably 3 to 15 μm, and more preferably 5 to 10 μm. Colored pigment-containing paste composition The colored pigment-containing paste composition used to form the colored resin layer contains an inorganic powder containing at least a colored pigment and a bonding resin. The colored pigment contained in the colored pigment-containing paste composition is added to prevent external reflection of the obtained electrode. For example, Co,
-18- (15) (15)200402754-18- (15) (15) 200402754
Cr、Cu、Fe、Μη、Ni、Ti、Zn等的金屬以及其氧化物、 複合氧化物、碳化物、氮化物、硫化物、矽化物、硼化 物、碳黑、石墨等的無機粉末，可使用單獨或混合2種以 上。其中作爲較佳之著色顏料，可選自Co、Cr、Cu、 Fe、Μη、Ni、Ti組成的群之金屬粉末、金屬氧化物以及 複合氧化物粉末（例如，可選擇Ni粉末、C〇304粉末、 Fe3〇4粉末、Cu-Cr複合氧化物粉末、Cu-Fe-Mn複合氧化 物粉末、Cu-Cr-Mn複合氧化物粉末、Co-Fe-Mn複合氧化 物粉末等）。藉由使用該等著色顏料，可得例如黑色、灰 色等的含著色顏料糊組成物。 上述著色顏料的平均粒徑，1 μιη以下較佳，0.0 1〜0.5 μηι更佳。使用著色顏料的平均粒徑超過1 μπι之含無機粉 末的樹脂組成物的情況，難以獲得足夠防止外光反射效果 的電極。著色顏料的平均粒徑不足〇 · 〇 1 μιη的情況，因著 色顏料的比表面積變大，含著色顏料之糊組成物中易發生 粉末的凝集，難以獲得安定分散狀態。 於上述含著色顏料之糊組成物，作爲無機粉末，含著 色顏料較佳，更進一步，含有導電性粉末以及玻璃原料混 合物更佳。導電性粉末與著色顏料的含有比例，導電性粉 末：著色顏料的値，以7 5 : 2 5〜2 5 : 7 5的比例較佳。上述 含有比例，藉由使用含導電性粉末與著色顏料的含著色顏 料之糊組成物，可具有足夠外光反射防止效果，而且具有 形成作爲電極機能的導電性之PDP用匯流電極。而且， 玻璃原料混合物的含有比例，相對用於含著色顏料之糊組 -19- (16) (16)200402754 成物的全部無機粉末，50質量％以下，以1〜30質量％較 佳。 含著色顏料之糊組成物中，作爲導電性粉末，可選擇 Ag、Au、Al、Cu、Ag-Pd合金等的金屬以及合金，可使 用單獨或2種以上混合。於該等導電性粉末中，即使於大 氣中燒成的情況下亦不因氧化而產生導電性降低，以使用 較廉價的Ag特別好。 上述導電性粉末的形狀，可爲粒狀、球狀、片狀等不 特別限定，可使用單獨或2種以上的形狀的導電性粉末混 合。而且，上述導電性粉末的平均粒徑，〇· 1〜5 μηι較 佳，可使用混合相異粒徑的導電性粉末。 而且，含著色顏料之糊組成物中，較佳的玻璃原料混 合物，可使用與本發明的導電性糊組成物相同的玻璃原料 混合物。 上述含著色顏料之糊組成物所含之接合樹脂，可選擇 與本發明的導電性糊組成物相同的接合樹脂。 而且，上述含著色顏料之糊組成物，與本發明的導電 性糊組成物相同，可含有溶劑以及上述以外的無機粉末、 可塑劑、顯像促進劑、接合助劑、保存安定性、消泡劑、 氧化防止劑、紫外線吸收劑、分散劑、交鏈劑、光聚合起 始劑、光酸產生劑、熱聚合起始劑、熱酸產生劑等各種添 加劑，可含有任意成分。 含者色顏料之糊組成物’可與本發明的導電性糊組成 物相同方式調製。 -20- (17) (17)200402754 如上述所調製之含著色顏料之糊組成物，具有適於塗 布的流動性之糊組成物，其黏度’通常爲100〜丨⑼^00 cp，5 0 0〜1 0,000 cp 較佳。 光阻組成物 爲了形成光阻層所使用之光阻組成物，可使用例如， 鹼顯像型感放射線性光阻組成物，有機溶劑顯像型感放射 線性光阻組成物，水性顯像型感放射線性光阻組成物等， 較佳可使用鹼顯像型感放射線性光阻組成物。本發明所謂 之「放射線」，係指包含可見光、紫外線、遠紫外線、電 子線、X線等。 鹼顯像型感放射線性光阻組成物，含有鹼可溶性樹脂 與感放射線成分爲必要成分。構成鹼顯像型感放射線性光 阻組成物之鹼可溶性樹脂，可選擇例如構成含無機粉末的 樹脂組成物的鹼可溶性樹脂。 構成鹼顯像型感放射線性光阻組成物之感放射線成 分，例如（a )反應性單體與光聚合起始劑的組合，（b ) 三聚氰胺樹脂與由放射線照射形成酸之光酸產生劑的組合 較佳，上述（a )的組合中，特別以甲基丙烯酸酯化合物 與光聚合起始劑的組合更佳。 構成感放射線成分之甲基丙烯酸酯化合物的具體例， 可選擇··乙二醇、丙二醇等的烷二醇的甲基丙烯酸二酯 類；聚乙二醇、聚丙二醇等聚烷二醇的甲基丙烯酸二酯 類；兩末端爲羥基的聚丁二烯、兩末端爲羥基的聚異戊二 -21 - (18) (18)200402754 烯、兩末端爲羥基的聚己內酯等的兩末端羥基化聚合體的 甲基丙烯酸二酯類；丙三醇、1，2，4 - 丁三醇、三羥甲基烷 類、四羥甲基烷類、異戊四醇、二異戊四醇等的三價以上 的多價醇的聚甲基丙烯酸酯類；三價以上的多價醇的聚烷 二醇附加物的聚甲基丙烯酸酯類；1，4-環己二醇、1，4-苯 二醇類等的環狀聚醇的聚甲基丙烯酸酯類；聚酯甲基丙烯 酸酯、環氧甲基丙烯酸酯、胺基甲酸乙酯樹脂甲基丙烯酸 酯、醇酸樹脂甲基丙烯酸酯、矽樹脂甲基丙烯酸酯、螺環 樹脂甲基丙烯酸酯等的寡聚甲基丙烯酸酯類等，可使用該 等單獨或二種以上組合。 而且，構成感放射線成分之光聚合起始劑的具體例， 苯甲基、二苯乙醇酮、二苯丙酮、樟腦醌、2-羥基-2-甲 基-1-苯基-2-丙酮、1-羥基環己基苯基酮、2，2 -二甲基- 2-苯基苯乙酮、2-甲基-[4’-(甲硫基）]-2·嗎啉-1-丙酮、2-苯 甲基-2-二甲基胺基-1-(4-嗎啉苯基）-1-丁酮等的羰基化合 物；過氧化二苯甲醯、過氧化二第三丁烷、第三丁基過氧 化氫、氫過氧異丙苯、對過氧化甲烷等的有機過氧化物； 1,3-bis (三氯甲基）-5-(2’-氯苯基）-1，3,5-三畊、2-[2-(2-呋 喃）乙炔基]-4,6-bis(2-氯苯基）-1，3,5-三畊等的三鹵甲烷 類；2,2’-bis(2-氯苯基）4,5,4’，5’-四苯基-1，2’-二咪唑等的 咪唑的二聚物，可使用該等單獨或二種以上混合。 該鹼顯像型感放射線性光阻組成物之感放射線成分的 含有比例，以鹼可溶性樹脂爲1 0 0質量部，通常爲1〜3 0 0 質量部，以1 〇〜2〇〇質量部較佳。 -22- (19) 200402754 而且，鹼顯像型感放射線性光阻組成物中，爲了賦予 良好的膜形成性，含有適當的有機溶劑較佳。如此之有機 溶劑，可選擇構成含無機粉末的樹脂組成物中列舉之溶 劑。 於光阻組成物，除上述成分外，含有顯像促進劑、接 合助劑、保存安定性、消泡劑、氧化防止劑、紫外線吸收 劑、均勻劑等各種添加劑亦可。Cr, Cu, Fe, Mn, Ni, Ti, Zn and other metals, and its oxides, complex oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, graphite and other inorganic powders, can be Use alone or in combination. Among them, as a preferred coloring pigment, metal powders, metal oxides, and composite oxide powders selected from the group consisting of Co, Cr, Cu, Fe, Mn, Ni, and Ti (for example, Ni powder, Co304 powder can be selected). , Fe304 powder, Cu-Cr composite oxide powder, Cu-Fe-Mn composite oxide powder, Cu-Cr-Mn composite oxide powder, Co-Fe-Mn composite oxide powder, etc.). By using these coloring pigments, for example, a coloring pigment paste-containing composition such as black or gray can be obtained. The average particle diameter of the color pigment is preferably 1 μm or less, and more preferably 0.0 1 to 0.5 μm. When an inorganic powder-containing resin composition having an average particle diameter of more than 1 μm is used, it is difficult to obtain an electrode having a sufficient effect of preventing external light reflection. When the average particle diameter of the coloring pigment is less than 0.1 μm, the specific surface area of the coloring pigment becomes larger, and aggregation of the powder tends to occur in the paste composition containing the coloring pigment, making it difficult to obtain a stable dispersion state. In the above-mentioned color pigment-containing paste composition, as the inorganic powder, it is preferable to include the color pigment, and further, it is more preferable to include a conductive powder and a glass raw material mixture. The content ratio of the conductive powder and the coloring pigment, and the conductive powder: the tincture of the coloring pigment, is preferably 7 5: 2 5 to 2 5: 7 5. The above-mentioned content ratio, by using a colored pigment-containing paste composition containing a conductive powder and a colored pigment, can have a sufficient effect of preventing external light reflection, and also has a conductive bus electrode for PDP that functions as an electrode. In addition, the content ratio of the glass raw material mixture is preferably 50% by mass or less, and preferably 1 to 30% by mass, relative to all inorganic powders used in the paste group containing colored pigments. In the paste composition containing colored pigments, as the conductive powder, metals and alloys such as Ag, Au, Al, Cu, and Ag-Pd alloys can be selected, and they can be used alone or in combination of two or more. Among these conductive powders, even when sintered in the atmosphere, there is no reduction in conductivity due to oxidation, and it is particularly preferable to use cheaper Ag. The shape of the conductive powder is not particularly limited, and the shape may be granular, spherical, flake, or the like. The conductive powder may be used alone or in combination of two or more shapes. The average particle diameter of the conductive powder is preferably from 0.1 to 5 μm, and conductive powders having different particle diameters can be used. Further, in the paste composition containing a colored pigment, a preferable glass raw material mixture may be the same glass raw material mixture as the conductive paste composition of the present invention. As the bonding resin contained in the coloring pigment-containing paste composition, the same bonding resin as the conductive paste composition of the present invention can be selected. The color pigment-containing paste composition may be the same as the conductive paste composition of the present invention, and may contain a solvent and inorganic powder other than the above, a plasticizer, a development accelerator, a bonding aid, storage stability, and defoaming. Various additives, such as agents, oxidation inhibitors, ultraviolet absorbers, dispersants, cross-linking agents, photopolymerization initiators, photoacid generators, thermal polymerization initiators, and thermal acid generators, may contain optional components. The paste composition of the pigment containing pigment can be prepared in the same manner as the conductive paste composition of the present invention. -20- (17) (17) 200402754 The paste composition containing colored pigments prepared as above, has a paste composition suitable for coating fluidity, and its viscosity is usually 100 ~ 丨 ⑼ ^ 00 cp, 50 0 ~ 1 0,000 cp is preferable. Photoresist composition To form a photoresist composition for use in a photoresist layer, for example, an alkali imaging type radiation sensitive photoresist composition, an organic solvent imaging type radiation sensitive photoresist composition, and an aqueous imaging type may be used. The radiation-sensitive photoresist composition and the like are preferably an alkali imaging type radiation-sensitive photoresist composition. The "radiation" referred to in the present invention means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like. The alkali imaging type radiation-sensitive photoresist composition contains an alkali-soluble resin and a radiation-sensitive component as essential components. As the alkali-soluble resin constituting the alkali imaging type radiation-sensitive photoresist composition, for example, an alkali-soluble resin constituting a resin composition containing an inorganic powder can be selected. Radiation-sensitive components constituting an alkali-imaging type radiation-sensitive photoresist composition, such as (a) a combination of a reactive monomer and a photopolymerization initiator, and (b) a melamine resin and a photoacid generator that forms an acid by radiation irradiation The combination of P is preferably, and the combination of (a) above is particularly preferably a combination of a methacrylate compound and a photopolymerization initiator. Specific examples of the methacrylate compound constituting the radiation-sensitive component include methacrylate diesters of alkanediols such as ethylene glycol and propylene glycol, and methyl formate of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Acrylic acid diesters; polybutadiene with hydroxyl groups at both ends, polyisoprene with hydroxyl groups at both ends-21-(18) (18) 200402754 ene, polycaprolactone with hydroxyl groups at both ends, etc. Methacrylic diesters of hydroxylated polymers; glycerol, 1,2,4-butanetriol, trimethylolane, tetramethylolane, isoprene tetraol, diisopentaerythritol Polymethacrylates such as polyvalent alcohols of trivalent or higher; polymethacrylates of polyalkylene glycol additions of polyvalent alcohols of trivalent or higher; 1,4-cyclohexanediol, 1, Polymethacrylates of cyclic polyols such as 4-benzenediols; polyester methacrylates, epoxy methacrylates, urethane resin methacrylates, alkyd resin methyl Oligomethacrylates such as acrylate, silicone methacrylate, and spiro resin methacrylate, etc. The like, alone or in combination of two or more. Specific examples of the photopolymerization initiator constituting the radiation-sensitive component include benzyl, benzophenone, diphenylacetone, camphorquinone, 2-hydroxy-2-methyl-1-phenyl-2-acetone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethyl-2-phenylacetophenone, 2-methyl- [4 '-(methylthio)]-2 · morpholine-1-acetone, Carbonyl compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinyl) -1-butanone; benzophenone peroxide, di-tert-butane, Organic peroxides such as tributyl hydroperoxide, cumene hydroperoxide, p-peroxide, etc .; 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -1, Trihalomethanes such as 3,5-trigon, 2- [2- (2-furan) ethynyl] -4,6-bis (2-chlorophenyl) -1,3,5-trigon; 2 Dimers of imidazoles such as 2,2'-bis (2-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-diimidazole, etc. These can be used alone or in combination mixing. The content ratio of the radiation-sensitive components of the alkali-imaging type radiation-sensitive photoresist composition is 100 parts by mass of alkali-soluble resin, usually 1 to 300 parts by mass, and 100 to 200 parts by mass. Better. -22- (19) 200402754 In addition, in the alkali imaging type radiation-sensitive photoresist composition, it is preferable to contain a suitable organic solvent in order to provide good film forming properties. As such an organic solvent, the solvents listed in the resin composition containing the inorganic powder can be selected. The photoresist composition may contain various additives such as a development accelerator, a bonding aid, storage stability, an antifoaming agent, an oxidation inhibitor, an ultraviolet absorber, and a leveling agent in addition to the above components.
光阻組成物，藉由均勻溶解上述鹼可溶性樹脂、感放 射線性成分以及依據需要之上述任意成分，可調製而成。 如上述所調製的光阻組成物，具有適於塗布的流動性 之糊組成物，其黏度，通常爲10〜1 0,000 cp，100〜1，000 cp較佳。 〈電極的形成方法〉 本發明的PDP用電極的形成方法，使用本發明的形 成電極用轉錄薄膜較佳，包含：〔1〕導電性樹脂層的轉 錄步驟；〔2〕光阻膜的形成步驟；〔3〕光阻膜的曝光步 驟；〔4〕光阻膜的顯像步驟；〔5〕導電性樹脂層的蝕刻 步驟；〔6〕圖形的燒成步驟。而且，〔1〕導電性樹脂層 的轉錄步驟，使用導電性樹脂層與著色樹脂層的疊層膜較 佳。 〔1〕導電性樹脂層的轉錄步驟 導電性樹脂層，使用本發明的形成電極用轉錄薄膜， -23- (20) (20)200402754 轉錄構成該轉錄薄膜的導電性樹脂層於基板上而形成。此 時，支持薄膜上有導電性樹脂層，於該導電性樹脂層上使 用有著色樹脂層的轉錄薄膜，轉錄導電性樹脂層與著色樹 脂層的疊層膜較佳。 轉錄步驟的一例表示如下所述。根據需要使用之形成 電極用轉錄薄膜的保護膜剝離後，於基板上，如與導電性 樹脂層（疊層膜的情況則是著色樹脂層）表面接觸般重疊 轉錄薄膜，藉由加熱滾筒熱壓接該轉錄薄膜，將支持薄膜 從導電性樹脂層剝離除去。如此，轉錄導電性樹脂層至基 板上，成爲密合狀態。而且，於疊層膜的情況，著色樹脂 層形成於基板上，於其上，形成導電性樹脂層，成爲密合 狀態。 於此，轉錄的條件，例如，加熱滾筒的表面溫度在 2 0〜140°C，於加熱滾筒上滾筒的壓力爲1〜5 kg/cm2，加熱 滾筒的移動速度爲 0.1〜10.0 m/分。而且，亦可預熱基 板，預熱的溫度可例如爲40〜100°C。 〔2〕光阻膜的形成步驟 該步驟’係形成光阻膜於導電性樹脂層的表面。 光阻膜’可藉由網版印刷法、滾輪塗布法、旋轉塗布 法、流延塗布法等塗布上述之光阻組成物後，乾燥塗膜而 可形成。 而且’於支持薄膜上所形成光阻膜，藉由轉錄至導電 性樹脂層的表面亦可，如前述般，使用具光阻層與導電性 -24- (21) (21)200402754 樹S曰層的疊層膜之轉錄薄膜，或者具光阻層、導電性樹脂 層與著色樹脂層的疊層膜之轉錄薄膜，一起進行轉錄亦 可。根據如此之形成方法，步驟可簡化外，同時可預期所 形成之電極的膜厚均勻性。 〔3〕光阻膜的曝光步驟 該步驟，係於光阻膜的表面，隔著曝光用光罩，以紫 外線等的放射線選擇性的曝光，形成光阻圖形的潛像。 於此’作爲放射線照射裝置，使用前述微影術所使用 的紫外線照射裝置，製造半導體以及液晶顯示裝置時所使 用之曝光裝置等，並無特別限制。 〔4〕光阻膜的顯像步驟 該步驟，藉由對已曝光之光阻膜進行顯像處理，將光 阻圖形（潛像）顯現。 於光阻膜的顯像步驟中，使用之顯影液，根據光阻膜 (光阻組成物）的種類，可適當選擇。具體而言，鹼顯像 型感放射線性光阻組成物，可使用鹼顯影液於光阻膜。 作爲鹼顯影液的有效成分’可選擇例如：氫氧化鋰、 氫氧化鈉、氫氧化鉀、磷酸氫鈉、磷酸氫二銨、磷酸氫二 鉀、磷酸氫二鈉、磷酸二氫銨、磷酸二氫鉀、磷酸二氫 鈉、矽酸鋰、矽酸鈉、矽酸鉀、碳酸鋰、碳酸鈉、碳酸 鉀、硼酸鋰、硼酸鈉、硼酸鉀、氨等的無機鹼性化合物； 氫氧化四甲基銨、氫氧化三甲基羥乙基銨、甲基胺、二甲 -25- (22) (22)200402754 基胺、三甲基胺、乙基胺、二乙基胺、三乙基胺、異丙基 胺、二異丙基胺、乙醇胺等的有機鹼性化合物。 於光阻膜的顯像步驟，使用之鹼顯影液，前述鹼性化 合物的1種或2種以上溶解於水中’可調製而成。於此鹼 顯影液中的鹼性化合物的濃度，通常爲〇 · 〇 〇 1〜1 〇重量％， 0 · 0 1〜5重量％較佳。而且，由驗顯影液進行顯像處理後， 通常施行水洗處理。 於此，顯像處理的條件，根據光阻膜，可選擇適當之 顯影液的種類·組成·濃度、顯像時間、顯像溫度、顯像 方法（例如浸泡法、搖動法、沖淋法、噴灑法、混拌 法）、顯像裝置等。 藉由該顯像步驟，形成由光阻殘留部與光阻除去部構 成的光阻圖形（對應曝光用光罩的圖形）。 該光阻圖形，於下一步驟（蝕刻步驟）中，作爲蝕刻 遮罩作用，光阻殘留部的構成材料，必須比導電性樹脂層 與著色樹脂層的構成材料，對蝕刻液之溶解度小。 〔5〕導電性樹脂層的蝕刻步驟 該步驟，導電性樹脂層（以及著色樹脂層）進行蝕刻 處理，形成對應光阻圖形之導電性樹脂層（以及著色樹脂 層）的圖形。 亦即導電性樹脂層中，光阻圖形之光阻除去部所對應 的部分，溶解於蝕刻液，選擇性的除去。因此，若持續進 行蝕刻處理，導電性樹脂層（以及著色樹脂層）上光阻除 -26- (23) (23)200402754 去部所對應的部分，露出基板表面。 導電性樹脂層的蝕刻步驟所使用之蝕刻液，鹼性溶液 較佳。因此，導電性樹脂層（以及著色樹脂層）所含之鹼 可溶性樹脂可輕易溶解而除去。 而且，導電性樹脂層（以及著色樹脂層）所含之無機 粉末，因鹼可溶性樹脂均勻分散，藉由鹼性溶液溶解具結 合劑的鹼可溶性樹脂並洗淨之，亦可同時除去無機粉末。 於此，作爲蝕刻液使用之鹼性溶液，與顯影液相同組 成的溶液更佳。 蝕刻液，藉由顯像步驟中使用之顯影液相同溶液，可 連續進行顯像步驟與鈾刻步驟，可簡化步驟。 而且，由鹼性溶液進行蝕刻處理後，通常施行水洗處 理。而且，必要時蝕刻處理後，亦可包含於導電性樹脂層 (以及著色樹脂層）圖形側面以及基板露出部上殘存不要 部分擦拭取出的步驟。 於此，可選擇適當之蝕刻液的種類·組成·濃度、處 理時間、處理溫度、處理方法（例如浸泡法、搖動法、沖 淋法、噴灑法、混拌法）、處理裝置等。 而且，蝕刻處理後，光阻殘留部的一部分或全部，即 使殘留，該光阻殘留部在下一燒成步驟中除去。 〔6〕圖形的燒成步驟 該步驟，對導電性樹脂層（以及著色樹脂層）的圖 形，進行燒成處理，形成電極。因此，樹脂層殘留部中的 -27- (24) (24)200402754 有機物質燒失，於基板表面上，可獲得形成圖形（疊層膜 時爲疊層圖形）之電極。 於此，燒成處理的溫度，必須到達使樹脂層殘留部中 的有機物質燒失的溫度，通常大氣中，400〜600 °C。而 且，燒成時間通常爲10〜90分鐘之間。 {實施例} 以下，說明本發明的實施例，本發明不因此限定。而 且，以下「質量部」以「部」表示。 而且，Mw爲東受公司（TOSOH)製凝膠滲透色譜分 析儀（GPC)(商品名HLC- 8 02A)測定之聚苯乙烯換算 的重量平均分子量。 〈實施例1〉 (1 )導電性糊組成物的調製 (A)以比表面積1.8m2/g的Ag粉100部，作爲導電 性粉末；（B )平均粒徑3 μηα的Bi203 -B203-Si02系的玻 璃原料混合物（不定形，軟化點5 20 1： ) 1 0部，作爲玻璃 原料混合物；（C )甲基丙烯酸2-乙基己酯/甲基丙烯酸 3·羥基丙酯/甲基丙烯酸/ 丁二酸單2-甲基丙烯氧基乙酯 =60/20/20/20 (質量 ％ )共聚合體（Mw = 5 0,000 ) 2 0 部，作爲接合樹脂；油酸1部、壬二酸二2-乙基己酯1 〇 部’作爲其他任意成分；以及丙二醇單甲醚1 〇〇部，作爲 溶劑；以玻璃珠磨機捏合後，用不鏽鋼網（5 0 0網目，25 -28- (25) 200402754 μηι直徑）過濾後，導電性糊組成物調製而成。 (2 )鹼顯像型感放射線性光阻組成物的調製 以甲基丙烯酸苯甲酯/甲基丙烯酸；75/25 (質 共聚合體（Mw = 3 0,0 00 ) 6 0部，作爲鹼可溶性樹月旨 二丙烯酸三丙烯乙二酯40部，作爲多官能基單體（ 射線性成分）；以 2-苯甲基-2-二甲基胺基-1-(4_嗎 基）-1 · 丁酮5部，作爲光聚合起始劑（感放射線 分）；以乙酸甲氧基丙酯1 〇 〇部，作爲溶劑；捏合後 由匣式濾器（2 μιη直徑）過濾，鹼顯像型感放射線 阻組成物（以下稱爲「光阻組成物」）調製而成。 (3 )轉錄薄膜的製作 藉由以下（i )與（Π )的操作，順序疊層光阻 及導電性樹脂層，成爲之疊層膜’形成於支持薄膜上 作成本發明的形成電極用轉錄薄膜。 (i )以（2 )調製成光阻組成物，利用刀片塗布 塗布於膜厚38 μ+m的PET膜所成的支持薄膜上，以 °C、3分鐘乾燥塗膜，除去溶劑’於支持薄膜上’形 度8 μηι的光阻膜。 (ii )以（1 )調製成之導電性糊組成物，利用 塗布機，塗布於（i )所製成的光阻膜上，以1 0 0 °C、 鐘乾燥塗膜，除去溶劑，形成厚度2 5 μηι的導電性樹 於光阻膜上，具有光阻膜與導電性樹脂層之疊層膜’ ：% ) ;以 感放 啉苯 性成 ，藉 性光 膜以 ，製 機， 100 成厚 刀片 5分 脂層 形成 -29- (26) (26)200402754 於支持薄膜上，製作成形成電極用轉錄薄膜。 (4 )疊層膜的轉錄步驟 於玻璃基板表面，如同與由（3 )製成之形成電極用 轉錄薄膜的導電性樹脂層表面接觸，重疊轉錄薄膜，以加 熱滾筒，熱壓接該轉錄薄膜。於此，作爲壓接條件，以加 熱滾筒的表面溫度lOOt、滾筒壓力2.5 kg/cm、加熱滾 筒的移動速度〇 · 5 m/分。因此，轉錄薄膜轉錄至玻璃基板 表面，成爲密合狀態。 (5 )光阻膜的曝光步驟·顯像步驟 上述（4 )中於玻璃基板形成之疊層膜中的光阻膜， 從支持薄膜上隔著曝光光罩（1 00 μηι寬的條狀圖形以及 四邊5 cm的圖形），藉由超高壓水銀燈，以400mJ/cm2 照射i線（波長3 6 5 nm的紫外光）。剝離光阻膜上的支持 薄膜，然後，對曝光後之光阻膜，以0.5質量％的碳酸鈉 水溶液（3 0 °C )作爲顯影液，藉由沖淋法3 0秒，進行光 阻膜的顯像處理。 因此’除去未受紫外光照射的未硬化的光阻，形成光 阻圖形。 (6 )導電性樹脂層的蝕刻步驟 連續上述步驟，以 0.5質量％的碳酸鈉水溶液（3 0 °C )作爲蝕刻液，藉由沖淋法60秒，進行導電性樹脂層 -30- (27) (27)200402754 的蝕刻處理。 然後，用超純水進行水洗處理，以及乾燥處理。因 此，形成導電性樹脂層殘留部與導電性樹脂層除去部構成 的圖形。 (7 )圖形的燒成步驟 形成導電性樹脂層圖形之玻璃基板，於燒成爐內大氣 壓下，以5 9 (TC 3 0分鐘進行燒成處理。因此，於玻璃基板 表面上，形成膜厚8 μηι的電極圖形。 (8 )電極圖形的導電性評價 所得之電極圖形（四邊5 cm的圖形）的阻抗率，以 四點探針測定，2 · 9 μ Ω · c m，表示具有不到 3.0 μ Ω · c m 的優良導電性。 (9 )電極圖形的密合性評價 所得之電極圖形（1 〇〇 μηι寬的條狀圖形）上，貼上 依據 JIS Ζ 1 5 22的規定賽璐仿（cellophane )黏著膠，依 照JIS K5400膠帶法，進行密合性評價。其結果，無法剝 離電極圖形，表示具有良好的密合性。 〈實施例2〜4〉 實施例1中作爲導電性粉末（A )，使用如表1中的 比表面積的Ag粒子，此外具有與實施例1相同之導電性 -31 - 928 (28) (28)200402754 糊組成物的調製、形成電極用轉錄薄膜的製作、形成電極 圖形以及進行電極圖形的評價。 電極圖形的評價結果，表示於表1中。 〈實施例5〉 進行實施例2中（1 )導電性糊組成物的調製’（2 ) 鹼顯像型感放射線性光阻組成物的調製’更進一步’以 (1 ’）進行以下的含著色顏料糊組成物的調製。 (1’）含著色顏料糊組成物的調製 以平均粒徑1 μιη的Ag粉60部，作爲導電性粉末； 以平均粒徑0.6 μιη的Cu-Fe-Mn複合氧化物粉末40部， 作爲著色顏料；平均粒徑3 μηι的Bi2〇3-B2〇3-Si02系的 玻璃原料混合物（不定形，軟化點5 20。(：）；! 〇部，作爲玻 璃原料混合物；（C )甲基丙烯酸2-乙基己酯/甲基丙烯 酸3 -經基丙酯/甲基丙烯酸/ 丁二酸單2_甲基丙烯氧基 乙醋=60/20/20/20 (質量 ％ )共聚合體（Mw = 5 0,0 00 ) 2 0部’作爲接合樹脂；油酸1部、壬二酸二2 -乙基己酯 1 0部’作爲其他任意成分；以及丙二醇單甲醚〗〇 〇部， 作爲Ϊ容劑；以玻璃珠磨機捏合後，用不鏽鋼網（5〇〇網 目’ 25 μηι直徑）過濾後，含著色顏料糊組成物調製而 成。 貫施例2中（3 )轉錄薄膜的製作，與實施例2相同 的製成轉錄薄膜之後， (Hi)實施例2中（Π)製成之轉錄薄膜的導電性樹 -32- (29) (29)200402754 脂層上，利用刀片塗布機，塗布（Γ )調製成的含著色顏 料糊組成物，以100°c、5分鐘乾燥塗膜，除去溶劑，形 成厚度5 μηι的導電性樹脂層於光阻膜上，具有光阻膜、 導電性樹脂層與含著色顏料的樹脂層之疊層膜’形成於支 持薄膜上，製作成本發明的形成電極用轉錄薄膜，與實施 例2相同，形成電極圖形以及進行電極圖形的評價。電極 圖形的評價結果，表示於表1中。 〈比較例1〜3〉 實施例1中作爲導電性粉末（A )，使用如表1中的 比表面積的A g粒子，此外具有與實施例1相同之導電性 糊組成物的調製、形成電極用轉錄薄膜的製作、形成電極 圖形以及進行電極圖形的評價。 電極圖形的i平價結果’表不於表1中。 〈比較例4〉 實施例5中作爲導電性粉末（A )，使用如表1中的 比表面積的Ag粒子，此外具有與實施例5相同之導電性 糊組成物的調製、形成電極用轉錄薄膜的製作、形成電極 圖形以及進行電極圖形的評價。 電極圖形的評價結果，表示於表1中。 發明的效果 根據本發明的導電性糊組成物以及形成電極用轉錄薄 -33- (30) (30)200402754 膜’可形成不僅具有優良的導電性，而且具有良好的密合 性之電極圖形。本發明的導電性糊組成物以及形成電極用 轉錄薄膜，可適合使用於電漿顯示器（PDP )的電極形 成。 【圖示簡單說明】 圖1表示說明用的一般Ρ 〇 P的剖面圖 主要元件對照表 1 :玻璃基板 2 :玻璃基板 3 :隔牆 4 :透明電極 5 z匯流電極 6 :位址電極 7 :螢光體 8 :介電層 9 :介電層 1 〇 :保護膜 -34-The photoresist composition can be prepared by uniformly dissolving the alkali-soluble resin, the radiation-sensitive component, and any of the above-mentioned optional components as needed. The photoresist composition prepared as described above has a paste composition suitable for coating fluidity, and its viscosity is usually 10 to 10,000 cp, preferably 100 to 1,000 cp. <Method for Forming Electrode> The method for forming an electrode for PDP of the present invention, preferably using the transcription film for forming an electrode of the present invention, includes: [1] a transcription step of a conductive resin layer; [2] a photoresist film formation step [3] Photoresist film exposure step; [4] Photoresist film development step; [5] Conductive resin layer etching step; [6] Pattern firing step. [1] The transcription step of the conductive resin layer is preferably a laminated film using a conductive resin layer and a colored resin layer. [1] Transcription step of conductive resin layer The conductive resin layer is formed by using the transcription film for forming an electrode of the present invention. -23- (20) (20) 200402754 The conductive resin layer constituting the transcription film is transcribed and formed on a substrate. . In this case, a conductive resin layer is provided on the supporting film, and a transcription film having a colored resin layer is used on the conductive resin layer. A laminated film of the transcription conductive resin layer and the colored resin layer is preferred. An example of the transcription step is shown below. After the protective film forming the transcription film for electrodes is peeled off as needed, the transcription film is superimposed on the substrate as it is in contact with the surface of the conductive resin layer (colored resin layer in the case of a laminated film), and is heated and pressed by a heating roller. The transcription film was attached, and the support film was peeled off from the conductive resin layer. In this way, the conductive resin layer is transcribed onto the substrate and brought into a close state. Further, in the case of a laminated film, a colored resin layer is formed on a substrate, and a conductive resin layer is formed thereon to be in an adhered state. Here, the conditions of transcription, for example, the surface temperature of the heating drum is 20 to 140 ° C, the pressure of the drum on the heating drum is 1 to 5 kg / cm2, and the moving speed of the heating drum is 0.1 to 10.0 m / min. Furthermore, the substrate may be preheated, and the preheating temperature may be, for example, 40 to 100 ° C. [2] Step of forming photoresist film This step 'is to form a photoresist film on the surface of the conductive resin layer. The photoresist film 'can be formed by applying the above-mentioned photoresist composition by a screen printing method, a roll coating method, a spin coating method, a cast coating method, or the like, and then drying the coating film. Moreover, the photoresist film formed on the supporting film can be transcribed to the surface of the conductive resin layer. As mentioned above, a photoresist layer and conductivity are used. -24- (21) (21) 200402754 Tree S A transcription film of a laminated film of a plurality of layers, or a transcription film of a laminated film of a photoresist layer, a conductive resin layer, and a colored resin layer may be transcribed together. According to such a forming method, the steps can be simplified, and at the same time, the thickness uniformity of the formed electrode can be expected. [3] Exposure step of the photoresist film This step is to form a latent image of a photoresist pattern by selectively exposing the surface of the photoresist film with radiation such as ultraviolet rays through an exposure mask. Here, as the radiation irradiation device, the ultraviolet irradiation device used in the aforementioned lithography is used, and the exposure device used when manufacturing semiconductors and liquid crystal display devices is not particularly limited. [4] Development step of photoresist film In this step, a photoresist pattern (latent image) is developed by developing the exposed photoresist film. The developing solution used in the development step of the photoresist film can be appropriately selected according to the type of the photoresist film (photoresist composition). Specifically, for an alkali imaging type radiation-sensitive photoresist composition, an alkali developing solution can be used for the photoresist film. As an active ingredient of the alkali developing solution, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, diammonium phosphate, and diphosphate may be selected. Inorganic alkaline compounds such as potassium hydrogen, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia, etc .; tetramethyl hydroxide Ammonium, trimethylhydroxyethylammonium hydroxide, methylamine, dimethyl-25- (22) (22) 200402754 baseamine, trimethylamine, ethylamine, diethylamine, triethylamine Organic basic compounds such as isopropylamine, diisopropylamine, ethanolamine, etc. In the developing step of the photoresist film, one or two or more of the aforementioned alkaline compounds are dissolved in water as an alkali developing solution to be prepared. The concentration of the basic compound in the alkali developing solution is usually from 0 to 0% by weight, and preferably from 0 to 0 to 5% by weight. In addition, after the development processing is performed with the developer solution, water washing processing is usually performed. Here, according to the conditions of the development process, an appropriate type, composition, concentration, development time, development temperature, and development method (for example, immersion method, shaking method, shower method, Spraying method, mixing method), developing device, etc. Through this developing step, a photoresist pattern (a pattern corresponding to an exposure mask) composed of a photoresist remaining portion and a photoresist removing portion is formed. In the next step (etching step), the photoresist pattern serves as an etching mask, and the constituent material of the photoresist remaining portion must be less soluble in the etchant than the constituent materials of the conductive resin layer and the colored resin layer. [5] Step of etching conductive resin layer In this step, the conductive resin layer (and the colored resin layer) is etched to form a pattern of the conductive resin layer (and the colored resin layer) corresponding to the photoresist pattern. That is, the portion of the conductive resin layer corresponding to the photoresist removal portion of the photoresist pattern is dissolved in the etching solution and selectively removed. Therefore, if the etching process is continued, the photoresist on the conductive resin layer (and the colored resin layer) is removed. The corresponding portion of the removed portion is exposed to the surface of the substrate. The etching solution used in the etching step of the conductive resin layer is preferably an alkaline solution. Therefore, the alkali-soluble resin contained in the conductive resin layer (and the colored resin layer) can be easily dissolved and removed. Furthermore, the inorganic powder contained in the conductive resin layer (and the colored resin layer) is uniformly dispersed in the alkali-soluble resin, and the alkali-soluble resin with a binder is dissolved and washed in an alkaline solution to remove the inorganic powder at the same time. Here, the alkaline solution used as the etching solution is preferably a solution having the same composition as the developing solution. The etching solution can continuously perform the developing step and the uranium etching step by using the same solution of the developing solution used in the developing step, and the steps can be simplified. After the etching treatment is performed with an alkaline solution, a water washing treatment is usually performed. In addition, after the etching process, if necessary, a step of removing unnecessary portions remaining on the side of the pattern of the conductive resin layer (and the colored resin layer) and the exposed portion of the substrate may be included. Here, you can choose the type, composition, concentration, processing time, processing temperature, processing method (such as immersion method, shaking method, shower method, spray method, mixing method), and processing equipment of the appropriate etching solution. After the etching treatment, if a part or all of the photoresist residual portion remains, the photoresist residual portion is removed in the next firing step. [6] Pattern firing step In this step, the pattern of the conductive resin layer (and the colored resin layer) is subjected to firing treatment to form an electrode. Therefore, the -27- (24) (24) 200402754 organic matter in the residual portion of the resin layer was burned out, and an electrode forming a pattern (a laminated pattern in the case of a laminated film) was obtained on the substrate surface. Here, the temperature of the firing process must reach a temperature at which the organic substances in the residual portion of the resin layer are burned out, and usually 400 to 600 ° C in the atmosphere. The firing time is usually between 10 and 90 minutes. {Examples} Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, the following "quality department" is represented by "department". In addition, Mw is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) (trade name HLC-8 02A) manufactured by Tosoh Corporation. <Example 1> (1) Preparation of conductive paste composition (A) 100 parts of Ag powder having a specific surface area of 1.8 m2 / g were used as conductive powder; (B) Bi203 -B203-Si02 with an average particle diameter of 3 μηα System glass raw material mixture (indefinite shape, softening point 5 20 1: 1 :) 10 parts as glass raw material mixture; (C) 2-ethylhexyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid / 2-methacryloxyethyl succinate = 60/20/20/20 (mass%) copolymer (Mw = 5 0,000) 2 parts as the bonding resin; 1 oleic acid, azelaic acid Diethyl 2-ethylhexyl ester 100 parts as other optional ingredients; and propylene glycol monomethyl ether 100 parts as a solvent; after kneading with a glass bead mill, use a stainless steel mesh (500 mesh, 25 -28- (25) 200402754 μm diameter) After filtration, the conductive paste composition is prepared. (2) The base imaging type radiation-sensitive photoresist composition is prepared by using benzyl methacrylate / methacrylic acid; 75/25 (mass copolymer (Mw = 3 0, 00)) 60 parts as the base 40 parts of soluble tree tripropylene ethylene diacrylate as polyfunctional monomer (radiation component); 2-benzyl-2-dimethylamino-1- (4_morphyl)- 1. 5 parts of methyl ethyl ketone, used as photopolymerization initiator (radiation sensitive component); 1,000 parts of methoxypropyl acetate, used as solvent; filtered by a cassette filter (2 μm diameter) after kneading, and alkali developed Modified radiation-resistance composition (hereinafter referred to as "photoresist composition"). (3) Production of transcription film The following operations (i) and (Π) are used to sequentially stack photoresist and conductive resin. The laminated film is formed on a supporting film as the transcription film for electrode formation according to the present invention. (I) A photoresist composition is prepared by (2), and is coated on a PET film having a thickness of 38 μ + m with a blade. On the support film formed by the film, dry the coating film at ° C for 3 minutes, and remove the photoresist 'on the support film' with a shape of 8 μηι (Ii) The conductive paste composition prepared in (1) is applied to the photoresist film prepared in (i) using a coater, and the coating film is dried at 100 ° C for 10 minutes to remove the solvent. Form a conductive tree with a thickness of 2 5 μm on the photoresist film, a laminated film with a photoresist film and a conductive resin layer ':%); made of photo-reactive benzene and made of photoresist film, 100 thick blades were formed with a 5 fat layer. -29- (26) (26) 200402754 was formed on a supporting film to form a transcription film for electrodes. (4) The transcription step of the laminated film is on the surface of the glass substrate as if it is in contact with the surface of the conductive resin layer made of (3) to form an electrode transcription film, and the transcription film is overlapped to heat a roller to thermally bond the transcription film . Here, as the crimping conditions, the surface temperature of the heating roller was 100 t, the roller pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. Therefore, the transcription film is transcribed onto the surface of the glass substrate and becomes in a close state. (5) Exposure step and development step of the photoresist film The photoresist film in the laminated film formed on the glass substrate in the above (4) is provided with an exposure mask (a 100 μm wide stripe pattern) across the support film. And 5 cm on all sides), i-rays (ultraviolet light with a wavelength of 3 65 nm) were irradiated with 400 mJ / cm2 by an ultra-high pressure mercury lamp. The support film on the photoresist film was peeled off, and then the exposed photoresist film was treated with a 0.5 mass% sodium carbonate aqueous solution (30 ° C) as a developing solution, and the photoresist film was subjected to a shower method for 30 seconds. Imaging processing. Therefore, 'uncured photoresist which is not irradiated with ultraviolet light is removed to form a photoresist pattern. (6) The step of etching the conductive resin layer is continued from the above steps, and the conductive resin layer is subjected to a shower method for 30 seconds by using a 0.5% by mass sodium carbonate aqueous solution (30 ° C) as an etching solution. ) (27) 200402754 Etching. Then, water-washing treatment and drying treatment are performed with ultrapure water. Therefore, a pattern consisting of a conductive resin layer remaining portion and a conductive resin layer removing portion is formed. (7) Pattern firing step The glass substrate that forms the pattern of the conductive resin layer is fired at 59 (TC 30 minutes) under atmospheric pressure in the firing furnace. Therefore, a film thickness is formed on the surface of the glass substrate. 8 μηι electrode pattern. (8) The resistivity of the electrode pattern (a pattern of 5 cm on four sides) obtained by evaluating the conductivity of the electrode pattern, measured with a four-point probe, 2 · 9 μ Ω · cm, indicating that it has less than 3.0 Excellent electrical conductivity of μ Ω · cm. (9) The electrode pattern (100 μηι wide stripe pattern) obtained by evaluating the adhesion of the electrode pattern is affixed with a celluloid pattern in accordance with JIS ZE 1 5 22 ( cellophane) Adhesive was evaluated for adhesion in accordance with JIS K5400 tape method. As a result, the electrode pattern could not be peeled off, indicating good adhesion. <Examples 2 to 4> In Example 1, the conductive powder (A ), Using Ag particles having specific surface areas as shown in Table 1, and having the same conductivity as in Example 1 -31-928 (28) (28) 200402754 Preparation of paste composition, formation of electrode transcription film, formation Electrode pattern and Evaluation of polar pattern. The evaluation result of the electrode pattern is shown in Table 1. <Example 5> (1) Modification of the conductive paste composition in Example 2 ('2) Alkali-type radiation-sensitive photoresist (1 ') The following preparation of the coloring pigment paste-containing composition was performed (1'). (1 ') The coloring pigment paste-containing composition was prepared with 60 parts of Ag powder having an average particle diameter of 1 μm. Conductive powder; 40 Cu-Fe-Mn composite oxide powders with an average particle diameter of 0.6 μm as color pigments; a mixture of glass raw materials of Bi2 03-B2 03-Si02 series (indefinite shape) with an average particle diameter of 3 μm , Softening point 5 to 20. (:); 〇 part, as a glass raw material mixture; (C) 2-ethylhexyl methacrylate / methacrylic acid 3-propylpropyl / methacrylic acid / succinic acid mono 2_methacryloxyethyl acetate = 60/20/20/20 (mass%) copolymer (Mw = 5 0,00) 2 0 'as a bonding resin; 1 oleic acid, 2 azelaic acid di 2 -10 parts of ethylhexyl ester as other optional components; and propylene glycol monomethyl ether as a compatibilizer; glass beads After kneading with a mill, it was filtered through a stainless steel mesh (500 mesh '25 μηι diameter) and prepared with a color pigment paste-containing composition. (3) Production of a transcription film in Example 2 was the same as in Example 2. After the transcription film is made, (Hi) the conductive tree of the transcription film made in (Π) of Example 2 -32- (29) (29) 200402754 was coated on the lipid layer using a blade coater to prepare (Γ) The pigment-containing pigment paste composition was dried at 100 ° C for 5 minutes, and the solvent was removed to form a conductive resin layer having a thickness of 5 μm on the photoresist film. The photoresist film, the conductive resin layer, and the pigment containing pigment were formed. The laminated film 'of the resin layer was formed on a support film, and a transcription film for forming an electrode according to the present invention was produced. In the same manner as in Example 2, an electrode pattern was formed and an electrode pattern was evaluated. The evaluation results of the electrode patterns are shown in Table 1. <Comparative Examples 1 to 3> In Example 1, as the conductive powder (A), Ag particles having a specific surface area as shown in Table 1 were used, and the same conductive paste composition as in Example 1 was used to prepare and form electrodes. Production of the transcription film, formation of an electrode pattern, and evaluation of the electrode pattern were performed. The results of i-parity of the electrode pattern are shown in Table 1. <Comparative Example 4> In Example 5, Ag particles having a specific surface area as shown in Table 1 were used as the conductive powder (A), and the conductive paste composition prepared in Example 5 was used to form a transcription film for electrodes. Production, formation of electrode patterns, and evaluation of electrode patterns. The evaluation results of the electrode pattern are shown in Table 1. ADVANTAGE OF THE INVENTION The conductive paste composition according to the present invention and the electrode-forming transcription sheet -33- (30) (30) 200402754 film 'can form an electrode pattern having not only excellent conductivity but also good adhesion. The conductive paste composition and the transcription film for forming an electrode of the present invention can be suitably used for electrode formation of a plasma display (PDP). [Brief description of the diagram] Fig. 1 shows the cross-section of a general PO for the main components. Table 1: Glass substrate 2: Glass substrate 3: Partition wall 4: Transparent electrode 5 z Bus electrode 6: Address electrode 7: Phosphor 8: Dielectric layer 9: Dielectric layer 1 0: Protective film -34-