1258783 五、發明說明（1) 技術領域 本發明係關於爲黑色糊、及電槳顯示面板、以及其製造 方法；特別是關於一種在電漿顯示器等顯示元件之前面板 上使用，並可藉外光來控制由前面板之電極引起之反射， 而得到高對比之黑色層之黑色糊、以及對顯示對比之電漿 顯示面板及其製造方法。 背景技術 電獎顯不面板（PDP)典型上係包括一對之前面板和背面 板’該前面板和背面板係相互對向配置，藉由以一定間.隔 支撐之配置在前述板與該板間之隔室障壁，而就地訂定出 形成顯示元件之複數個隔室；於前述板內表面上挾住介電 體層位置之2個電極，係藉由其間之交流電壓而廣泛地在 隔室內放電，以使得在隔室障壁表面上形成螢光體螢幕發 光，藉由透過透明板之透過光來顯示畫像。 PDP中畫像之解析度及亮度，係端視電極之寬度、相互 接續用導體之間隔、及介電體層透明度等而定。電極及相 互接續用導體之板，係可以網版用之圖樣印刷來形成。 更且，可用來當做製得精細圖樣之方法，係有感光性糊 法。此處，感光糊即是指將具有感光性之導體糊全面塗布 在基板上，以預定之光罩曝光後、顯像，再將得到的圖樣 燒成高精細之導體圖樣所得到之物。可當做所使用的感光 性糊者，係爲含有導體粉末與感光性樹脂黏著劑之物等。 又，爲了使顯示器之顯示對比增加而於前面板上配置之 1258783 五、發明說明（2) 電極，則必須減少由電極而起之外光反射。在使該外光反 射減少方面，在_反射率的金屬性電極之前面板側上，使 形成光線透過率和反射率均低之黑色層，因此可自顯示器 前面板見到黑化電極係爲最佳之方法。 第1圖所示者係爲電漿顯示器前面板之顯示電極之構成 例。在進行電漿放電之透明顯示電極（I TO等）1之上，形 成防止外光反射以提高顯示對比之黑色層1 0，其上則形成 經減低電極電阻値之排電極7 (銀等金屬電極）。可用來當 做爲使形成該黑色層而兼備高黑色度與導電性之材料者， 例如是在特開平1 0 - 25 5 670號公報中所使用之氧化釕。 然而，雖然氧化釕是兼備高黑色度與導電性之材料，但 是其價格非常昂貴而且具有金屬光澤等所謂的困難處。本 發明即是提供一種黑色糊，其係一藉由組合具有原來那樣 黑色度與導電性之複數種材料，而形成不使用高價氧化釕 但可以顯示出優良顯示對比之黑色層之黑色糊；以及提供 一種電漿顯示面板。 發明揭示 本發明係爲一種黑色糊，其係含有無機粉末及有機成分 之糊，其特徵在於：前述之無機粉末係包括玻璃粉末及鈷 氧化物。 更且’本發明係爲一種電漿顯示面板’其特徵在於：在 具有黑色層與第1金屬電極形成之前面板、及第電極所形 成之背面板之電漿顯示面板中，其黑色層係含有鈷氧化物 1258783 五、發明說明（3) 及玻璃成分。 此外，本發明係爲一種電漿顯示面板之製造方法，其特 徵在於：在具有黑色層與第1金屬電極形成之前面板、及 第電極所形成之背面板之電漿顯示面板之製造方法中，係 使用含有鈷氧化物爲佔無機機粉末總量之10〜70重量％之 感光性糊來形成黑色層。 圖示之簡單說明 第1圖係爲本發明電漿顯示面板之前面板的製造例。第 2圖係爲本發明電漿顯示面板之前面板與背面板的構成例 。符號1爲透明電極，符號2爲編址電極，符號3爲保護 層，符號4爲隔牆，符號5爲前面玻璃基板，符號6背面 玻璃基板，符號7爲排電極，符號8爲透明介電體層，符 號9爲白色介電體層，符號10爲黑色層，符號11爲螢光 體層R，符號12爲螢光體層B，符號13爲螢光體層G。 實施發明之最佳態樣 以下，使用圖示來說明本發明之較佳的實施態樣。第2 圖所示者，係爲本發明之交流型電漿顯示面板之構成例。 於前面板中，係將透明電極1、黑色層1 0、排電極7 (金屬 電極）形成在前面玻璃基板5上，使介電體層8及保護層3 被覆該表面。但，透明電極1，在實施本發明上，其並示 爲必要之物。 又，背面板係將編址電極2形成在背面玻璃基板上。該 表面上則形成反射螢光體發光之白色介電體層9。進而， 1258783 五、 發明說明 ( 4 : ) 配 置 隔 牆 4 與螢光體層（R)ll、螢光體 層 (E 1) 1 2 螢 光 體 層 (G)l 3 >從而 ，將前面板與背面板貼 合 在 一 起 9 使 變 成 在 、r · 刖 面 板 與 背 面 板 間 所形成放電空間內 封 入 放 電 氣 體 之 構 成 Ο 該 電 漿 顯 示 面 板 係 依照以下所示之方 法 來 製 做 〇 首 先 是 前 面 板 ， 於 、r * 刖 面 玻 璃 基板5上，以離子 濺 塗 或 離 子 鍍 敷 全 面 形 成 後 使 用 光 阻 劑 以光刻法來進行等 之 製 造 ， 而 形 成 厚 0 . 12 微 米 左右 之 ITO 或Sn02之透明電極1 〇 在其 上 形 成 里 j w\ 色 層 10。該黑色層係含有 表 現 里 ^ \ w 色 之 Μ y\\\ 機 顏 料 與 玻 璃 成 分 〇 因 此，所謂的黑色係 指 對 背 景 有 視 覺 上 差 異 而 得 到 之 顯 示 里 y 1 \ \ 色對比之物，並沒 有特 別 地 限 定 爲 濃 淡 全 Μ ^ \w 之 里 y \ w 色 而 已 〇 依光透過率、反射 率 之 觀 點 來 看 5 較 宜 是 爲 濃 里 色 〇 該 里 夕1 \ Ν 色 層 之 形 成 雖然係可以使用網 版 圖 樣 印 刷 來 進 行 但依 照 可 製 得 虫主 m 細 圖樣之觀點來看， 較 宜 是 使 用 具 有 感 光 性 之 里 y \ \ \ 色 糊 0 該 里 ^ \ \ \ 色糊中係以含有無 機 顏 料 與 玻 璃 粉 末 來 做 Μ J \ ΝΝ 機 粉 末 將 之 塗布在玻璃基板上 使 燒 成 並 使 有 機 成 分 真 正 燃 燒 而 蒸 發 〇 爲此，黑色層係以 含 有 該 種 里 y \ \ \ 色 糊 之 Μ 機 粉 末 而 形 成 〇 爲 了以該無機粉末來 形 成 里 / 1 \ \ 色 層 則 有 必 要 含 有 表 現 里 ^ 1 ^ 色 之 無機顏料，同時含 有 以 低 軟 化 點 之 玻 璃 粉 末 來 做 爲 在 燒 成 中軟化燒結之結附: 劑 〇 本 發 明 所 使 用 之 並 > \ N N 機顏料係採用金屬 之 氧 化 物 〇 可 做 爲 該 金 屬 氧 化 物 者 係 有鐵、銅、錳、鈷 -6- 等 之 氧 化 物 或 其 之 1258783 五、發明說明（5) 複合氧化物；特別是依照與玻璃混合燒成時褪色少之觀點 來看，鈷氧化物係極爲優異，因而有必要以含有鈷氧化物 者來做爲本發明中之無機顏料。 可用來當做鈷氧化物類者，係有CoO :氧化鈷（Π )、 c〇2o3(h2o):氧化鈷（π )及c〇3o4 :氧化鈷（m )鈷（π )等， 但並沒有特別地限定爲某種物質。其中雖然有黑色物質， 但是已知在空氣中以3 90〜900°C加熱氧化鈷（Π )，或在真 空中以15 〇 °c加熱氧化鈷（m )將會轉化成,氧化鈷（瓜）鈷（π ) ;爲不使因本發明之熱處理而褪色之目的，以氧.化鈷（瓜） 銘（π )最爲適宜。 或者，此種鈷氧化物之平均粒徑之範圍，較宜是在 10〜100奈米者。當粒子是未滿10奈米時，則在糊中係難 以良好地分散，而在使用上具有實質困難的傾向。又，當 超過1 0 0奈米時，則由於產生光線之散亂現象以致具有黑 色度變差之傾向。 在糊中鈷氧化物之含有量，較宜是佔無機粉末總量之 1〇〜7 0重量％;在所形成之黑色層中之含有量，較宜是在 10〜70重量％。當黑色層之厚度爲1〜2微米之情況下，當不 滿1 0重量％時則不能得到完全的黑色度，當超過70重量％ 時則燒結性會變差，因而較宜是在15〜65重量％。 塗布在玻璃基板上之黑色糊，由於玻璃基板之變形少， 則較宜之燒成溫度係不滿600 °C。由於通常之無機顏料係 在不滿600°C時燒結，爲達此種燒結則玻璃粉末之軟化點 1258783 五、發明說明（6) 較宜是在400〜5 20 °C。當玻璃之軟化點是不滿400 °C時， 因在黑色層形成之際黏合樹脂會分解，則較宜是沒有在揮 發前開始軟化而妨害脫黏之情形者。又，因爲軟化點超過 5 20 °C時燒結性會變差，則較宜是沒有無機顏料等之添加 量不足之情形。 若是不滿足該軟化點之玻璃粉末時，雖然並沒有特別地 限定採用，但因爲不與電極產生反應，則較宜是採用含鉛 或鉍之硼矽氧系玻璃粉末。近年來，考量特別是在含鉛材 料之規定上日益精進，因而較宜是以氧化鉍爲主成分。玻 璃粉末之平均粒徑宜是在0.5〜5微米。在未滿〇.5微米之 場合下，則難以良好地分散；當超過5微米時，因電極之 平坦性或形狀會惡化而不宜。較佳者是1〜4微米。 此外，爲使透明電極1和排電極7間之通導良好，則在 黑色層上較宜是含有導電性粉末。可用來當做導電性粉末 者，舉例來說，係有金屬粉末或氧化金屬粉末。 可用來當做金屬粉末者，並沒有特別地限定爲某種物質 ，通吊係可使用做爲電極材料之金、銀、銅、鎳等，但依 照所謂良好之安定價數之導電性特點而言，特佳是採用鎳 〇 可用來當做氧化金屬粉末者，有氧化錫、或具有銦與錫 之合金氧化物之I TO (銦錫氧化物）等，但並沒有特別地限 定爲某種物質。爲使增加導電性，宜是在該等金屬氧化物 中進行微量元素之摻雜。例如，含有相對於氧化錫數％之 1258783 五、發明說明（7) 磷或銻將會提高其導電性。 導電性粉末之平均粒徑宜是在〇 . 1〜5微米。在導電性粉 末未滿0 . 1微米時，則難以良好地分散在黑色層中；當粉 末超過5微米時，因電極之平坦性或電極圖樣之形狀會惡 化而不宜。較佳者是〇 . 5〜4微米。 在黑色糊中導電性粉末之含有量，較宜是佔無機粉末總 量之1〜60重量％;在所形成之黑色層中導電性粉末之含有 量，較宜是在1〜60重量％。當不滿1重量％時則不能得到 完全的導電性；當超過60重量％時，則爲得到所期望之黑 色度而添加10重量％以上之鈷氧化物之情況下，其燒結性 會變差，因而較宜是在1〜50重量％。 在黑色糊中鈷氧化物與導電性粉末之含有量，其總量較 宜是佔無機粉末總量之70重量％以下；在所形成之黑色層 中鈷氧化物與導電性粉末之含有量，較宜是在70重量％以 下。當總量係超過70重量％時則燒結性會變差，因而較宜 是在15〜6 5重量％。黑色度係藉由鈷氧化物來達成；而導 電性則係藉由導電性粉末而達成。因而較宜是在60重量％ 以下。 可做爲本發明黑色糊之樹脂成分者，較宜是採用丙烯酸 系樹脂’特別是以採用光硬化型之丙烯酸系感光樹脂較佳 °可當做丙烯酸系感光樹脂，係可廣泛地採用鹼可溶性之 丙烯酸系共聚物、與多官能丙烯酸單體、和光自由基發生 齊ij與溶劑所成之物。聚合物爲具有鹼可溶性之顯像液，可 1258783 五、發明說明（8) 採用不具有環境問是之有機溶質之水溶液。另外如有必要 ，可視情況地含有可塑劑、安定劑、聚合禁止劑等較佳。 可當做丙烯酸系共聚合物者，係爲在共聚物中至少含有 丙烯酸系單體之共聚物；該丙烯酸係單體的具體實施例， 舉例來說，係有甲基丙烯酸酯、乙基丙烯酸酯、η -丙基丙 烯酸酯、異丁基丙烯酸酯、η - 丁基丙烯酸酯、第2 - 丁基丙 烯酸酯、異丁基丙烯酸酯、第3-丁基丙烯酸酯、η-戊基丙 烯酸酯、芳基丙烯酸酯、苄基丙烯酸酯、丁氧乙基丙烯酸 酯、丁氧三乙二醇基丙烯酸酯、環己基丙烯酸酯、二環戊 基丙烯酸酯、二環戊烯基丙烯酸酯、2 -乙基己基丙烯酸酯 、甘油醯基丙烯酸酯、縮水甘油基丙烯酸酯、十七碳氟代 癸基丙烯酸酯、2 -羥乙基丙烯酸酯、異萡基丙烯酸酯、2 -羥丙基丙烯酸酯、異十氧基丙烯酸酯、異辛基丙烯酸酯、 月桂基丙烯酸酯、2 ·甲氧乙二醇丙烯酸酯甲氧二乙二醇丙 烯酸酯、辛基氟戊基丙烯酸酯、酚氧基乙基丙烯酸酯、硬 脂酸基丙烯酸酯、三氟乙基丙烯酸酯、丙烯醯胺、胺乙基 丙烯酸酯、苯基丙烯酸酯、酚氧乙基丙烯酸酯、苄基硫醇 丙烯酸酯等丙烯酸酯單體，及其以甲丙烯酸酯代替丙烯酸 酯之物等。可當做丙烯酸系單體以外之共聚物者，雖可使 用具有碳-碳雙鍵之所有可能化合物，但舉例來說，較宜 是苯乙烯、Ρ -甲苯乙烯、〇 -甲苯乙烯、m -甲苯乙烯、α-甲苯乙烯、氯化甲苯乙烯、羥基甲苯乙烯等苯乙烯類；r -10- 1258783 五、發明說明（9) -甲基丙烯酸氧丙挫三甲氧矽烷、1 -苯基-2 -吡咯烷酮等。 較佳爲丙烯酸烷酯、或甲丙烯酸烷酯；更宜是至少含有甲 丙烯酸甲酯，而可製得熱分解性良好之聚合物者。爲了對 丙烯酸系共聚物賦予鹼可溶性，可添加不飽和碳酸之不飽 和酸來做爲單體。可做爲不飽和酸之具體實施例，舉例來 說，係有丙烯酸、甲丙烯酸、衣康酸、馬來酸、富馬酸、 乙酸乙烯酯、或該酸之無水物等。該等所加入的聚合物之 酸價，依照顯像性之觀點來看，較宜是在50〜1 40之範圍 〇 爲了使硬化速度增加，該聚合物至少一部分之側鏈或分 子末端上，較宜是具有碳-碳雙鍵。具有碳-碳雙鍵之基， 舉例來說，係乙烯基、芳基、丙烯醯基、甲丙烯醯基等。 就在聚合物上附加此種官能基而言，其係在相對於聚合物 中之硫醇基、胺基、經基、竣基上，使附加具有縮水甘油 基或異氰酸酯基與碳-碳雙鍵之化合物、或者附加丙烯酸 氯化合物、甲丙烯酸氯化合物或芳基氯化合物之反應方法 0 具有縮水"0油基與碳··碳雙鍵之化合物，舉例來說，係 有縮水甘油基甲丙烯酸酯、縮水甘油基甲丙烯酸酯、芳基 縮水甘油醚、縮水甘油基乙基丙烯酸酯、巴豆基縮水甘油 醚、縮水甘油基巴豆酸酯、縮水甘油基異巴豆酸酯等。具 有異氰酸基與碳-碳雙鍵之化合物，係有丙；(：希醯基異氰酸 酯、甲丙烯醯基異氰酸酯、丙烯醯基乙基異氰酸酯、甲丙 -1 1 - 1258783 五、發明說明（1〇) _醯基乙基異氰酸酯、甲丙烯醯基乙基異氰酸酯等。 可做爲多官能基單體者，係可採用1分子中具有2個以 上碳-碳雙鍵之化合物；其具體的例子有丙烯化環己基二 丙燒酸酯、1，4 - 丁院基二醇二丙嫌酸醋、1 , 3 - 丁二醇二丙 燦酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙 一醇二丙烯酸酯、聚乙二醇二丙烯酸酯、二異戊四醇基六 丙燒酸醋、二異戊四醇基單經戊基丙烯酸酯、雙三羥甲基 丙院四丙燏酸酯、甘油醯基二丙烯酸酯、甲氧化環己基二 丙烯酸酯、新戊基二醇二丙烯酸酯、丙二醇二丙烯酸酯、 聚丙二醇二丙烯酸酯、三甘油醯基二丙烯酸酯、三甲醇基 兩院丙烯酸酯、三甘油醯基二丙烯酸酯、聯苯酚A二丙烯 酸酯、聯苯酚A -環氧乙烷附加物之二丙烯酸酯、聯苯酚 A -環氧丙烷附加物之二丙烯酸酯、或以甲丙烯醯基代替上 述化合物之丙烯醯基之1部分或全部之化合物等。 光聚合起始劑，係可使用合適的市售之光自由基起始劑 。例如，舉例來說，有2 -苄基-2 -二甲胺基-1 - ( 4 -嗎福啉 苯基）-丁酮-1、或雙（2,4,6-三甲基苯甲醯基）-苯基礪氧 化物、2 -甲基-1 [ 4 -(甲磺）苯基]_ 2 -嗎福啉丙烷-1 -酮、 2 , 4 -二乙基硫氧化酮等。本發明所使用的光聚合起始劑系 並沒有特別地限定爲某種物質。 較佳的適合採用之溶劑，舉例來說，係有二乙二醇單乙 醚乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、2 -甲基-2, 4-戊烷二醇、3 -甲基-1,5-戊烷二醇、2 -乙基- -12- 1258783 五、發明說明（11) 1，3 -己烷二醇、松油醇、3 -甲基-3 -甲氧丁醇、r - 丁內酯 、德克撒醇、苄基醇、二丙二醇單乙醚、三丙二醇單甲醚 、丙二醇單甲醚乙酸酯等。 可以使用適合的陽離子系、陰離子系、非離子系之界面 活性劑來做爲分散劑，而且可以使用適合的酞酸二甲酯、 酞酸二乙酯、酞酸二丁酯等來做爲可塑劑。 又，可以使用1，2，3 -苯駢三偶氮酯等來做爲安定劑。 在本發明中電漿顯示面板之黑色層，其透過率較宜是在 2%以下；又自前面玻璃基板側所測定之玻璃基板與黑色層 之界面反射率，其亮度之L値較宜是在20以下。更宜是 在1 0以下。反射亮度之L値係比3 0大的場合下，自前面 玻璃基板側所見到的外光反射會變大，則會因電漿顯示面 板所顯示之對比變低而不合宜。又，反射亮度低的情況， 且透過率比2%大時，透過黑色層之光線係在黑色層和金屬 電極之界面上反射，因爲金屬電極之反射率一般係非常的 高，所以此情況下之外光反射會變大，則電漿顯示面板所 顯示之對比會變低而不合宜。 黑色糊之製作方法雖然並沒有特別地限定，但在攪拌混 合器內使溶劑、丙烯酸系共聚物、光起始劑等之有機成分 加熱溶解，以行星式混合機使之與玻璃粉末、無機顏料等 混合。採用3輥硏磨器等混練機來混練之。之後，視需要 進行過濾及消泡。在以3輥硏磨器等混練之前，混合添加 有分散劑之溶劑和無機顏料，利用雙硏磨器等分散機而製 -13- 1258783 五、發明說明（12) 做成漿液’較佳是成爲容易凝集的無機顏料之良好分散狀 能。 塗布黑色糊之方法雖然並沒有特別地限定，但較宜是網 版印刷。網版印刷係爲形成數微米至數十微米厚度之塗布 膜之適當的方法。具體而言，在塗布之後，通常以70 〜1 20 °C加熱數分鐘至1小時，以使塗布膜乾燥。以一次無 法得到所想要的厚度時，則反復作業。在非感光性之黑色 糊情況下來進行圖樣印刷，而於具有感光性之黑色糊情況 下，則全面地印刷。 爲了形成排電極7，較宜是使用感光性銀糊。同樣地在 經乾燥的黑色糊上塗布感光性銀糊，藉由使之乾燥而形成 〇 在經塗布、乾燥之黑色糊與感光性銀糊之曝光中，係透 過具有所想要的形狀之光罩來進行。曝光係藉由高壓水銀 燈等，其曝光量例如在i線_( 3 6 5奈米）之測定値，通常爲 10〜500毫焦耳/平方公分。 曝光後，藉鹼性水溶液之顯像液以除去、水洗具有未曝 光部分之感光性之黑色糊與感光性銀糊，而得到所想要的 圖樣。關於鹼性水溶液，係可以使用碳酸鈉、單乙醇胺、 二乙醇胺、三乙醇胺等之0 . 0 5〜1重量％水溶液。該顯像和 水洗雖然可以浸漬、噴霧、槳葉等來進行，但較宜是可得 到比較高解像度之噴霧顯像。顯像液之噴霧時間係從20 至2 00秒，水洗係與噴霧同時進行1〇〜60秒。 -14· 1258783 五、發明說明（1 3 ) 圖樣形成後，以電氣爐、帶式爐等來進行燒成，藉由燒 成使揮發性有機成分一同與無機成分燒結而形成黑色層1 〇 及排電極7。關於燒成之氛圍氣，其係凸在大氣中、或氮 氛圍氣下進行。燒成時較宜是保持在400〜600°C之溫度。 又’感光性黑色糊與感光性銀糊之曝光及顯像，雖然可 有效地同時進行，但個別地進行也可以。 其次，爲使形成透明的介電體層8，則可塗布含有氧化 鉛系玻璃粉末或氧化鉍系玻璃粉末之介電體糊。藉由在 550〜600 °C燒成使厚度爲10〜30微米左右。介電體玻璃層8 宜是1層，如特公平9 - 5 0 7 6 9號公報所示之2層相異軟化 點之玻璃構造也可以。 接著，形成由MgO所成之保護層3。藉CVD(化學蒸鍍） 法使厚度達1.0微米左右。 關於背面板，首先在背面玻璃基板6上，藉由光刻法使 用感光性銀糊使圖樣化，藉由燒成而形成編址電極2。 從而，藉由將塗布在其表面上之含有氧化鈦之介電體糊 予以燒成，而形成白色介電體層9。 接著，藉由光刻法使用感光性隔牆糊使圖樣化’藉由燒 成而形成隔牆4。 接著，將原來就含有紅色（R )、藍色（B )、綠色（G )之螢 光體粉末之3種螢光體糊塗布在預定位置之隔牆4間。藉 由使之乾燥而燒成’以形成螢光體R 1 1、G 1 2、B 1 3。 於是，使用封裝用之玻璃糊使前面板和背面板貼合在一 -1 5 - 1258783 五、發明說明（14) 起’在將刖面板和㈢面板與隔牆間所形成之放電空間內以 局真空（8X 1 0 ·7托利左右）予以排氣後，藉由預定壓力 ( 500〜760托利左右）將Ne〜Xe系等之放電氣體予以封入， 而製做成電漿顯示面板。 依照本發明之黑色層及製造方法，係可以製得高顯像對 比、對精密度之電漿顯示面板。 實施例 藉由以下之實施例來進一步具體地說明本發明，但本發 明並不因此而僅限定於此等實施例之事物中。又，以下之 作業，全部都是在黃色燈下進行的。 1 .感光性黑色糊之調整 (1) 20重量分之丙烯酸系共聚物（縮水甘油基甲丙烯 酸酯改性甲丙烯酸-甲丙烯酸甲酯共聚物，酸値爲1 00， 重量平均分子量爲30000 )、10重量分之多官能單體（環 氧丙烷改性三羥甲基丙烷三丙烯酸酯）、1 . 5重量分之光 聚合起始劑（2 -苄基-2 -二甲胺-1 - ( 4 -嗎福啉苯基）-丁酮 -1 )、45重量分之溶劑（二乙二醇單丁基醚乙酸酯）、1 重量分之分散劑（索爾斯巴斯20000 )、1重量分之可塑 劑（酞酸二-η - 丁酯）之有機組成，一邊在6 0 °C加熱，一 邊用馬達和攪拌槳葉使之混合、溶解。 (2 )將經溶解之有機成分溶液與以下之無機粉末以行 星式混合器預先混練之。 A .玻璃粉末 16- 1258783 五、發明說明（1 5 ) 化鋅（Ζ η 0 )所成之 玻璃粉末1軟化點：46 0 °C、平均粒徑：2微米 玻璃粉末2軟化點：49 、平均粒徑：1微米 鈷氧化物 1(C〇3〇4) 平均粒徑： 70奈米 鈷氧化物 2(Co3〇4) 平均粒徑： 100奈米 鈷氧化物 3(Co〇） 平均粒徑： 50奈米 碳黑 平均粒徑： 30奈米 導電性粉末 鎳粉末1 平均粒徑 :2微米 鎳粉末2 平均粒徑 :0 . 0 5微米 鎳粉末3 平均粒徑 :5微米 銀粉末 平均粒徑 :2微米 工TO粉末 平均粒徑 :3微米 氧化錫粉末 平均粒徑：1微米 磷摻雜品 氧化錫粉末 平均粒徑：1微米 銻摻雜品 玻璃粉末3軟化點：500°C、平均粒徑：2微米 玻璃粉末4軟化點：3 90 °C、平均粒徑：2微米 玻璃粉末5軟化點：5 3 01：、平均粒徑：2微米 玻璃粉末6軟化點：460°C、平均粒徑：〇 . 3微米 玻璃粉末7軟化點：460。(：、平均粒徑：5微米 B ·無機顏料1258783 V. INSTRUCTION DESCRIPTION (1) TECHNICAL FIELD The present invention relates to a black paste, an electric paddle display panel, and a method of manufacturing the same; in particular, to a panel used in front of a display element such as a plasma display, and can be used for external light To control the reflection caused by the electrodes of the front panel, to obtain a black paste of a high contrast black layer, and a plasma display panel for display contrast and a method of manufacturing the same. BACKGROUND OF THE INVENTION A Palladium Display Panel (PDP) typically includes a pair of front panels and a back panel. The front panel and the back panel are disposed opposite each other, and are disposed on the board and the board by a certain interval. a compartment barrier between the two, and a plurality of compartments forming the display element are defined in situ; the two electrodes on the inner surface of the panel that sandwich the position of the dielectric layer are widely separated by the alternating voltage therebetween. The indoor discharge is such that a phosphor screen is formed on the surface of the barrier, and the image is displayed by the transmitted light transmitted through the transparent plate. The resolution and brightness of the image in the PDP are determined by the width of the end view electrode, the interval between the conductors for the connection, and the transparency of the dielectric layer. The plates of the electrodes and the interconnecting conductors can be formed by printing on a pattern for the screen. Moreover, it can be used as a method of producing a fine pattern, which is a photosensitive paste method. Here, the photosensitive paste is obtained by uniformly coating a photosensitive conductor paste on a substrate, exposing it to a predetermined mask, developing the image, and then firing the obtained pattern into a high-precision conductor pattern. The photosensitive paste to be used may be a material containing a conductive powder and a photosensitive resin adhesive. Further, in order to increase the display contrast of the display and to arrange the electrodes on the front panel, it is necessary to reduce the light reflection from the electrodes. In terms of reducing the reflection of the external light, a black layer having a low light transmittance and a low reflectance is formed on the front side of the metal electrode of the reflectance, so that the blackened electrode system can be seen from the front panel of the display. The best way. The figure shown in Fig. 1 is an example of a configuration of display electrodes on the front panel of the plasma display. On the transparent display electrode (I TO or the like) 1 for performing plasma discharge, a black layer 10 which prevents reflection of external light to improve display contrast is formed, and a discharge electrode 7 which is reduced in electrode resistance is formed thereon (metal such as silver) electrode). For example, it is used as a material for forming a black layer and having a high degree of blackness and conductivity. For example, it is a cerium oxide used in Japanese Patent Publication No. Hei 10-2575670. However, although cerium oxide is a material having both high blackness and electrical conductivity, it is a so-called difficulty in that it is expensive and has a metallic luster. The present invention provides a black paste which is a black paste which can form a black layer which does not use high-priced cerium oxide but which can exhibit excellent display contrast by combining a plurality of materials having the original blackness and conductivity; A plasma display panel is provided. Disclosure of the Invention The present invention is a black paste comprising a paste of an inorganic powder and an organic component, characterized in that the inorganic powder comprises glass powder and cobalt oxide. Furthermore, the present invention relates to a plasma display panel characterized in that in a plasma display panel having a black layer and a first metal electrode before forming a front panel and a back surface formed by the first electrode, the black layer contains Cobalt oxide 1258738 V. Description of invention (3) and glass composition. Further, the present invention is a method of manufacturing a plasma display panel, characterized in that in a method of manufacturing a plasma display panel having a black layer and a first metal electrode before forming a front panel and a back surface formed by the first electrode, A black layer is formed by using a photosensitive paste containing cobalt oxide as 10 to 70% by weight based on the total amount of the inorganic machine powder. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a manufacturing example of a front panel of a plasma display panel of the present invention. Fig. 2 is a view showing an example of the configuration of the front panel and the back panel of the plasma display panel of the present invention. Symbol 1 is a transparent electrode, symbol 2 is an address electrode, symbol 3 is a protective layer, symbol 4 is a partition wall, symbol 5 is a front glass substrate, symbol 6 is a rear glass substrate, symbol 7 is a row electrode, and symbol 8 is a transparent dielectric. The bulk layer, the symbol 9 is a white dielectric layer, the symbol 10 is a black layer, the symbol 11 is a phosphor layer R, the symbol 12 is a phosphor layer B, and the symbol 13 is a phosphor layer G. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described using the drawings. The figure shown in Fig. 2 is an example of the configuration of the AC type plasma display panel of the present invention. In the front panel, a transparent electrode 1, a black layer 10, and a discharge electrode 7 (metal electrode) are formed on the front glass substrate 5, and the dielectric layer 8 and the protective layer 3 are coated on the surface. However, the transparent electrode 1 is shown to be essential in the practice of the present invention. Further, the back sheet is formed by forming the address electrodes 2 on the back glass substrate. On this surface, a white dielectric layer 9 which reflects the phosphor light is formed. Further, 1258783 V. DESCRIPTION OF THE INVENTION (4: ) Configuring the partition wall 4 and the phosphor layer (R) 11, the phosphor layer (E 1) 1 2 the phosphor layer (G) l 3 > Thus, the front panel and the back The panel is bonded together 9 to form a discharge gas in the discharge space formed between the r panel and the back panel. The plasma display panel is manufactured according to the method described below. First, the front panel is On the r* facet glass substrate 5, after ion implantation or ion plating is used, the photoresist is formed by photolithography, and the transparent ITO or Sn02 is formed to a thickness of about 0.12 μm. The electrode 1 has a jw\ color layer 10 formed thereon. The black layer contains 表现 y \\ y \\ y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y It is not particularly limited to the y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y Although it can be carried out by using the pattern printing, but according to the viewpoint of the fine pattern of the main m, it is better to use the photosensitive y \ \ \ color paste 0 in the ^ ^ \ \ color paste It is made by containing inorganic pigments and glass powders as Μ J \ 机 machine powder, which is coated on a glass substrate to be fired and the organic components are actually burned and evaporated. For this reason, the black layer contains the y \ \ \ The paste of the color paste is formed by the powder of the machine, in order to form the inner / 1 \ \ color layer with the inorganic powder. It should contain an inorganic pigment with a color of 1 ^ ^ and a glass powder with a low softening point as a binder for softening and sintering during firing: 〇 使用 used in the present invention > \ NN machine pigment system The metal oxide lanthanum can be used as the metal oxide as an oxide of iron, copper, manganese, cobalt-6- or the like or the like thereof. 1258783 5. Inventive Description (5) Composite oxide; especially in accordance with glass In view of the fact that the fading is small at the time of firing, the cobalt oxide is extremely excellent, and it is necessary to use the cobalt oxide as the inorganic pigment in the present invention. It can be used as a cobalt oxide, such as CoO: cobalt oxide (Π), c〇2o3 (h2o): cobalt oxide (π) and c〇3o4: cobalt oxide (m) cobalt (π), etc., but not It is specifically defined as a substance. Although there is a black substance, it is known that heating cobalt oxide (Π) in air at 3 90 to 900 ° C, or heating cobalt oxide (m ) at 15 ° C in a vacuum will be converted into cobalt oxide (melon). Cobalt (π); for the purpose of not discoloring by the heat treatment of the present invention, cobalt (melon) (π) is most suitable. Alternatively, the range of the average particle diameter of such a cobalt oxide is preferably from 10 to 100 nm. When the particles are less than 10 nm, it is difficult to disperse well in the paste, and there is a tendency to be substantially difficult in use. Further, when it exceeds 100 nm, there is a tendency that the blackness is deteriorated due to the scattering of light. The content of the cobalt oxide in the paste is preferably from 1 to 70% by weight based on the total amount of the inorganic powder; and more preferably from 10 to 70% by weight in the black layer formed. When the thickness of the black layer is 1 to 2 μm, the complete blackness cannot be obtained when less than 10% by weight, and the sinterability is deteriorated when it exceeds 70% by weight, so it is preferably 15 to 65. weight%. The black paste applied to the glass substrate has a lower firing temperature of 600 ° C because the glass substrate has less deformation. Since the usual inorganic pigment is sintered at less than 600 ° C, the softening point of the glass powder is 1258783 for this sintering. 5. The invention (6) is preferably 400 to 5 20 °C. When the softening point of the glass is less than 400 °C, since the binder resin decomposes when the black layer is formed, it is preferable that the glass is not softened before the volatilization to hinder the debonding. Further, since the sinterability is deteriorated when the softening point exceeds 5 20 °C, it is preferred that the amount of addition of inorganic pigment or the like is insufficient. In the case of a glass powder which does not satisfy the softening point, it is not particularly limited, but since it does not react with the electrode, it is preferred to use a boron-oxygen-based glass powder containing lead or antimony. In recent years, consideration has been made, especially in the regulation of lead-containing materials, and it is preferable to use cerium oxide as a main component. The average particle diameter of the glass powder is preferably from 0.5 to 5 μm. In the case where the thickness is less than 5 μm, it is difficult to disperse well; when it exceeds 5 μm, the flatness or shape of the electrode may be deteriorated. Preferably it is 1 to 4 microns. Further, in order to make the conduction between the transparent electrode 1 and the row electrode 7 good, it is preferable to contain a conductive powder on the black layer. It can be used as a conductive powder, for example, a metal powder or an oxidized metal powder. It can be used as a metal powder, and is not particularly limited to a certain substance. The hanging system can use gold, silver, copper, nickel, etc. as electrode materials, but according to the conductivity characteristics of the so-called good security pricing. It is particularly preferable that nickel ruthenium is used as the oxidized metal powder, and there is tin oxide or I TO (indium tin oxide) having an alloy oxide of indium and tin, but is not particularly limited to a certain substance. In order to increase the conductivity, it is preferred to dope the trace elements in the metal oxides. For example, it contains 1258783% relative to tin oxide. 5. Inventive Note (7) Phosphorus or antimony will increase its conductivity. The average particle diameter of the conductive powder is preferably 〇 1 to 5 μm. When the conductive powder is less than 0.1 μm, it is difficult to disperse well in the black layer; when the powder exceeds 5 μm, the flatness of the electrode or the shape of the electrode pattern may be deteriorated. The preferred one is 〇 5 to 4 microns. The content of the conductive powder in the black paste is preferably from 1 to 60% by weight based on the total amount of the inorganic powder; and the content of the conductive powder in the black layer formed is preferably from 1 to 60% by weight. When the content is less than 1% by weight, complete conductivity cannot be obtained. When the amount is more than 60% by weight, in the case where cobalt oxide of 10% by weight or more is added to obtain a desired degree of blackness, the sinterability is deteriorated. Therefore, it is preferably from 1 to 50% by weight. The content of the cobalt oxide and the conductive powder in the black paste is preferably 70% by weight or less based on the total amount of the inorganic powder; and the content of the cobalt oxide and the conductive powder in the formed black layer, More preferably, it is 70% by weight or less. When the total amount is more than 70% by weight, the sinterability is deteriorated, so that it is preferably 15 to 65 % by weight. Blackness is achieved by cobalt oxide; electrical conductivity is achieved by conductive powder. Therefore, it is preferably 60% by weight or less. It can be used as the resin component of the black paste of the present invention, and it is preferable to use an acrylic resin. In particular, it is preferably a photo-curable acrylic photosensitive resin. It can be used as an acrylic photosensitive resin, and can be widely used as an alkali-soluble one. An acrylic copolymer, a polyfunctional acrylic monomer, and a photoradical, which are formed by a solvent. The polymer is an alkali-soluble imaging solution, which can be used as an aqueous solution which does not have an environmentally friendly organic solute. Further, if necessary, it may preferably contain a plasticizer, a stabilizer, a polymerization inhibiting agent, and the like. As the acrylic copolymer, a copolymer containing at least an acrylic monomer in the copolymer; a specific example of the acrylic monomer, for example, a methacrylate or an ethyl acrylate Η-propyl acrylate, isobutyl acrylate, η-butyl acrylate, 2 - butyl acrylate, isobutyl acrylate, 3-butyl acrylate, η-pentyl acrylate, Aryl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-B Hexyl acrylate, glyceryl methacrylate, glycidyl acrylate, heptafluorocarbon methacrylate, 2-hydroxyethyl acrylate, isodecyl acrylate, 2-hydroxypropyl acrylate, iso Decaoxy acrylate, isooctyl acrylate, lauryl acrylate, 2 · methoxy ethylene glycol acrylate methoxy diethylene glycol acrylate, octyl fluoropentyl acrylate, phenolic ethyl acrylate Stearic acid Acrylate monomers such as enoate, trifluoroethyl acrylate, acrylamide, amine ethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl thiol acrylate, and the like The ester replaces the acrylate or the like. As the copolymer other than the acrylic monomer, although all possible compounds having a carbon-carbon double bond can be used, for example, styrene, fluorene-methylstyrene, fluorene-methylstyrene, m-toluene are preferred. Styrene such as ethylene, α-methylstyrene, styrene chloride, hydroxymethylstyrene; r -10- 1258783 V. Description of the invention (9) - oxypropylene trimethomethacrylate, 1-phenyl-2 - Pyrrolidone and the like. Preferably, it is an alkyl acrylate or an alkyl methacrylate; more preferably, it contains at least methyl methacrylate, and a polymer having good thermal decomposition property can be obtained. In order to impart alkali solubility to the acrylic copolymer, an unsaturated acid of unsaturated carbonic acid may be added as a monomer. Specific examples of the unsaturated acid can be used, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetate, or an anhydride of the acid. The acid value of the polymer to be added is preferably in the range of 50 to 140 in terms of development, in order to increase the rate of hardening, at least a part of the side chain or the molecular end of the polymer. It is preferred to have a carbon-carbon double bond. The group having a carbon-carbon double bond is, for example, a vinyl group, an aryl group, an acrylonitrile group, a propylene group or the like. Insofar as the functional group is added to the polymer, it is attached to the thiol group, the amine group, the trans group, the fluorenyl group in the polymer to have an additional glycidyl group or an isocyanate group and a carbon-carbon double. Reaction of a compound of a bond, or an additional chlorinated chloro compound, a methacrylic acid chloro compound or an aryl chloride compound, has a compound which has a shrinkage "0 oil-based and carbon-carbon double bond, for example, a glycidyl group Acrylate, glycidyl methacrylate, aryl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, glycidyl isocrotate, and the like. a compound having an isocyanato group and a carbon-carbon double bond, which is a C; (: thiol isocyanate, propylene propylene isocyanate, acryl decyl ethyl isocyanate, methyl propyl-1 1 - 1258783 5. Description of the invention ( 1〇) _mercaptoethyl isocyanate, propylene propylene ethyl isocyanate, etc. As a polyfunctional monomer, a compound having two or more carbon-carbon double bonds in one molecule can be used; Examples are propylene cyclohexyl dipropionate, 1,4-butanyl glycol dipropylene vinegar, 1,3-butanediol dipropanoate, ethylene glycol diacrylate, diethylene Alcohol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, diisoamyl alcohol hexapropanoic acid vinegar, diisopentaerythritol mono-pentyl acrylate, ditrimethylol丙院四丙燏, glyceryl decyl diacrylate, Cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerin decyl diacrylate , trimethylol-based two-yard acrylate, triglyceryl decyl diacrylic acid a diacrylate of diphenol A diacrylate, a biphenol A-ethylene oxide addenda, a diacrylate of a biphenol A-propylene oxide addenda, or a propylene fluorenyl group substituted with a propylene fluorenyl group as the above compound A part or all of the compound, etc. As the photopolymerization initiator, a suitable commercially available photoradical initiator can be used. For example, for example, 2-benzyl-2-dimethylamino-1 - (4-norfosphenylphenyl)-butanone-1, or bis(2,4,6-trimethylbenzylidene)-phenylindole oxide, 2-methyl-1 [4- ( Methanesulfonate phenyl]-2-pyroline propane-1-one, 2,4-diethylthio oxy ketone, etc. The photopolymerization initiator used in the present invention is not particularly limited to a certain substance. Preferred solvents are, for example, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 2-methyl-2 , 4-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl--12- 1258783 V. Description of the invention (11) 1,3-hexanediol, terpineol , 3-methyl-3-methoxybutanol, r-butyrolactone, texaol Benzyl alcohol, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. A suitable cationic, anionic or nonionic surfactant can be used as a dispersing agent, and can be used. Suitable dimethyl phthalate, diethyl phthalate, dibutyl phthalate, etc. as a plasticizer. Further, 1,2,3-benzoquinone triazoate can be used as a stabilizer. In the black layer of the plasma display panel of the present invention, the transmittance is preferably less than 2%; and the interface reflectance of the glass substrate and the black layer measured from the side of the front glass substrate is preferably L 20 or less. More preferably below 10. When the L 値 of the reflected brightness is larger than 30, the external light reflection seen from the front glass substrate side becomes large, which is unsuitable because the contrast displayed by the plasma display panel becomes low. Further, when the reflection brightness is low and the transmittance is larger than 2%, the light transmitted through the black layer is reflected at the interface between the black layer and the metal electrode, because the reflectance of the metal electrode is generally very high, so in this case, Outside the light reflection will become larger, the contrast displayed by the plasma display panel will be lower and not suitable. Although the method of producing the black paste is not particularly limited, the organic component such as a solvent, an acrylic copolymer, or a photoinitiator is heated and dissolved in a stirring mixer, and is mixed with a glass powder or an inorganic pigment by a planetary mixer. Wait for mixing. A mixing machine such as a 3-roll honing machine is used for mixing. After that, filter and defoam as needed. Before mixing by a three-roll honing machine or the like, a solvent and an inorganic pigment to which a dispersing agent is added are mixed, and a dispersing machine such as a double honing machine is used to prepare a-13-1258783. 5. The invention (12) is made into a slurry. It is a good dispersing energy of an inorganic pigment which is easy to aggregate. The method of applying the black paste is not particularly limited, but is preferably screen printing. Screen printing is a suitable method for forming a coating film having a thickness of several micrometers to several tens of micrometers. Specifically, after coating, it is usually heated at 70 to 1 20 ° C for several minutes to 1 hour to dry the coating film. When the desired thickness cannot be obtained at one time, the work is repeated. Pattern printing is carried out in the case of a non-photosensitive black paste, and in the case of a photosensitive black paste, it is printed in its entirety. In order to form the discharge electrode 7, it is preferred to use a photosensitive silver paste. Similarly, a photosensitive silver paste is applied onto the dried black paste, and dried to form a crucible in the exposed and dried black paste and the photosensitive silver paste, and transmitted through the light having a desired shape. The cover is coming. The exposure is measured by a high-pressure mercury lamp or the like, for example, in the measurement of i-line (36 5 nm), and is usually 10 to 500 mJ/cm 2 . After the exposure, a photosensitive black paste having an unexposed portion and a photosensitive silver paste were removed by a developing solution of an aqueous alkaline solution to obtain a desired pattern. As the alkaline aqueous solution, a 0.5 to 1% by weight aqueous solution of sodium carbonate, monoethanolamine, diethanolamine or triethanolamine can be used. Although the development and washing can be carried out by dipping, spraying, paddle, etc., it is preferably a spray image which can obtain a relatively high resolution. The spraying time of the developing liquid is from 20 to 200 seconds, and the washing system and the spraying are performed simultaneously for 1 to 60 seconds. -14· 1258783 V. DESCRIPTION OF THE INVENTION (1 3) After the pattern is formed, it is fired in an electric furnace or a belt furnace, and the volatile organic component is sintered together with the inorganic component by firing to form a black layer 1 and Row electrode 7. Regarding the atmosphere of the firing, it is carried out in the atmosphere or under a nitrogen atmosphere. It is preferred to maintain the temperature at 400 to 600 ° C during firing. Further, the exposure and development of the photosensitive black paste and the photosensitive silver paste can be carried out individually, but may be carried out individually. Next, in order to form the transparent dielectric layer 8, a dielectric paste containing a lead oxide-based glass powder or a cerium oxide-based glass powder can be applied. The thickness is 10 to 30 μm by firing at 550 to 600 °C. The dielectric glass layer 8 is preferably one layer, and a glass structure of two layers of different softening points as disclosed in Japanese Patent Publication No. Hei 9-565A. Next, a protective layer 3 made of MgO is formed. The thickness is about 1.0 μm by CVD (Chemical Vapor Deposition). Regarding the back sheet, first, a photosensitive silver paste is patterned on the back glass substrate 6 by photolithography, and the address electrode 2 is formed by firing. Thus, the white dielectric layer 9 is formed by firing a dielectric paste containing titanium oxide coated on the surface thereof. Next, patterning is performed by photolithography using a photosensitive partition paste, and the partition wall 4 is formed by firing. Next, three kinds of phosphor pastes which originally contain red (R), blue (B), and green (G) phosphor powders are applied between the partition walls 4 at predetermined positions. It is fired by drying it to form phosphors R 1 1 , G 1 2, and B 1 3 . Thus, the front panel and the back panel are bonded together using a glass paste for packaging in a -1 5 - 1258783. 5. The invention (14) is used in the discharge space formed between the panel and the panel. After the partial vacuum (about 8×10 −7 Torr) is exhausted, a discharge gas such as Ne to Xe is sealed by a predetermined pressure (about 500 to 760 Torr) to prepare a plasma display panel. According to the black layer and the manufacturing method of the present invention, a plasma display panel of high development contrast and precision can be obtained. EXAMPLES The present invention will be specifically described by the following examples, but the present invention is not limited thereto but limited thereto. Also, all of the following operations were performed under a yellow light. 1. Adjustment of photosensitive black paste (1) 20 parts by weight of acrylic copolymer (glycidyl methacrylate modified methacrylic acid-methyl methacrylate copolymer, acid hydrazine is 100, weight average molecular weight is 30,000) , 10 parts by weight of a polyfunctional monomer (propylene oxide modified trimethylolpropane triacrylate), 1.5 parts by weight of a photopolymerization initiator (2-benzyl-2-dimethylamine-1 - (4-ofoline phenyl)-butanone-1), 45 parts by weight of solvent (diethylene glycol monobutyl ether acetate), 1 part by weight of dispersant (Sols Bass 20000), The organic component of 1 part by weight of a plasticizer (di-n-butyl phthalate) was mixed and dissolved by a motor and a stirring blade while being heated at 60 °C. (2) The dissolved organic component solution and the following inorganic powder are preliminarily kneaded by a planetary mixer. A. Glass powder 16- 1258783 V. Description of the invention (1 5 ) Glass powder formed by zinc (Ζ η 0 ) 1 softening point: 46 0 ° C, average particle diameter: 2 μm glass powder 2 softening point: 49 Average particle size: 1 micron cobalt oxide 1 (C〇3〇4) Average particle size: 70 nm cobalt oxide 2 (Co3〇4) Average particle size: 100 nm cobalt oxide 3 (Co〇) Average grain Diameter: 50 nm carbon black Average particle size: 30 nm conductive powder nickel powder 1 Average particle size: 2 micron nickel powder 2 Average particle size: 0. 0 5 micron nickel powder 3 Average particle size: 5 micron silver powder average Particle size: 2 micron TO powder average particle size: 3 micron tin oxide powder average particle size: 1 micron phosphorus dopant tin oxide powder average particle size: 1 micron erbium doped glass powder 3 softening point: 500 ° C, Average particle size: 2 micron glass powder 4 Softening point: 3 90 ° C, average particle diameter: 2 micron glass powder 5 softening point: 5 3 01:, average particle diameter: 2 micron glass powder 6 softening point: 460 ° C, Average particle size: 〇. 3 micron glass powder 7 softening point: 460. (:, average particle size: 5 μm B · inorganic pigment
I258783 五、發明說明（16 ) 粉末之平均粒徑係以雷射繞射散亂法粒度分布計（ 微多拉克HRA)來測定其D50(50%通過時之平均粒徑） 〇 (3 )將所得到的預先混練物以3輥硏磨器混練之’而 製得感光性糊。 2 ·圖樣加工 (1 )在形成有透明電極（I TO)之前面玻璃基板之全面 上，以網版印刷（網版PET#420 )感光性黑色糊，於85°C 乾燥1 0分鐘。經乾燥後之厚度爲2 . 5微米。 (2) 在其上，以網版印刷（網版PET#3 50 )感光性銀糊 ，於85 °C乾燥40分鐘。經乾燥後與黑色層合計之厚度 爲10微米。 (3) 用高壓水銀燈，透過光罩來進行曝光（ 3 00毫無 耳/平方公分）。光罩係採用內加光罩。 (4 )播用鹼性顯像液（碳酸鈉0 . 4重量％之水溶液）’ 使曝光後之基板噴霧顯像，之後以水浴沖洗之。 (5 )採用電氣爐將所得到的圖樣，於大氣中、以2小 時由室溫昇溫至580°C，之後在58(TC保持20分鐘，於 爐中自然冷卻，燒成後之厚度，黑色層和銀電極合計爲 5微米（內黑色層爲1.5微米）。 變化在形成黑色層之感光性黑色糊中之黑色顏料、玻 璃粉末、導電性粉末之組成，其實施結果係示於第1表 、第2表中。黑色度係以比色計（除去正反射模式）來測 -18- 1258783 五、發明說明（17) 定，反射度之L値在1 0以下表示爲◎(優）、在： 表示爲〇（良）、在21〜30表示爲△(可）、而在31 則表示爲X (不可）。導電性係以測定儀確定導電， 阻値在1 0毫Ω以下爲◎(優）、在1 〇以上爲〇（良： 導電爲X (不可）。網版印刷性係以印刷容易度來表 ◎(優）> 〇（良）> △(可）>X (不可）。吸樣加工性乃圖 線蝕刻及表面突起在5微米以下係表示爲◎(優） 6〜10微米表示爲〇（良）、在丨丨微米以上表不爲八 。燒結性乃當爲完全燒結之物時以◎(優）’當燒結 脫黏劑低之物則以△表示。該結果係示於第1表、 表中（表中之單位爲重量分）。 1〜20 以上 其電 、不 示： 樣之 、在 (可） 性比 第2 -19- 1258783 五、發明說明（18) 第1表 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 實施 例7 玻 璃 粉 末 1 (軟化點：460°c、 平均粒徑：2微米） 60 60 60 60 60 2 (軟化點：490°C、 平均粒徑：1微米） 30 3 (軟化點：500°C、 平均粒徑：2微米） 80 Μ /\\\ 機 顏 料 鈷氧化物1 (平均粒徑：70奈米） 35 65 15 40 35 鈷氧化物2 (平均粒徑：100奈米） 35 鈷氧化物3 (平均粒徑：50奈米） 35 導 電 性 粉 末 鎳粉末1 (平均粒徑：2微米） 5 5 5 5 5 銀粉末 (平均粒徑：2微米） 5 評 量 結 果 糊之網版印刷性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 糊之圖樣加工性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 580°C之燒結性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 580°C燒成後之黑色度 ◎ ◎ ◎ ◎ 〇 〇 〇 58〇°C燒成後之色彩 黑色 黑色 黑色 黑色 黑色 褐色 黑色 導電性 ◎ ◎ ◎ 〇 ◎ ◎ ◎ -20- 1258783 五、發明說明（19) 第2表I258783 V. INSTRUCTIONS (16) The average particle size of the powder is determined by the laser diffraction scattering particle size distribution meter (micro-Doraq HRA) to determine its D50 (average particle size at 50% pass) 〇(3) The obtained pre-kneaded product was kneaded by a 3-roll honing machine to obtain a photosensitive paste. 2. Pattern processing (1) On the entire surface of the glass substrate before the formation of the transparent electrode (I TO ), the photosensitive black paste was screen printed (screen PET #420) and dried at 85 ° C for 10 minutes. The thickness after drying is 2.5 microns. (2) On this, a photosensitive silver paste was screen printed (screen PET #3 50) and dried at 85 ° C for 40 minutes. The thickness after drying with the black layer was 10 μm. (3) Expose through a reticle with a high-pressure mercury lamp (3 00 without ear/cm 2 ). The reticle is a built-in reticle. (4) The alkaline imaging solution (aqueous solution of sodium carbonate 0.4% by weight) was used for the purpose of spraying the exposed substrate, followed by rinsing with a water bath. (5) Using an electric furnace, the obtained pattern was heated from room temperature to 580 ° C in the atmosphere for 2 hours, then at 58 (TC for 20 minutes, naturally cooled in the furnace, thickness after firing, black) The total of the layer and the silver electrode is 5 μm (the inner black layer is 1.5 μm). The composition of the black pigment, the glass powder, and the conductive powder in the photosensitive black paste forming the black layer is shown in Table 1. In the second table, the blackness is measured by a colorimeter (excluding the specular reflection mode) -18 - 1258783. 5. The invention (17) is determined, and the L 反射 of the reflectance is expressed as ◎ (excellent) at 10 or less. In the case of: 〇 (good), 21 to 30 is represented by Δ (may), and 31 is represented by X (not). Conductivity is determined by a measuring instrument, and the resistance is less than 10 mΩ. (Excellent), 1 〇 or more is 〇 (good: Conductive is X (not available). Screen printing is based on ease of printing ◎ (Excellent) > 〇 (good) > △ (可) > X (not available). The sample processing property is the line etching and the surface protrusion is expressed as ◎ (excellent) at 6 micrometers or less. Good), not more than 丨丨μm. The sinterability is ◎ (excellent) when it is completely sintered, and it is represented by △ when the sintered debonding agent is low. The result is shown in Table 1. In the table (the unit in the table is the weight). 1~20 or more of the electricity, not shown: the sample, the (ability) ratio 2-19-1258783 5. The invention (18) The first table embodiment 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Glass powder 1 (softening point: 460 ° C, average particle diameter: 2 μm) 60 60 60 60 60 2 (softening point: 490 ° C , Average particle size: 1 μm) 30 3 (softening point: 500 ° C, average particle size: 2 μm) 80 Μ /\\\ Machine pigment cobalt oxide 1 (average particle size: 70 nm) 35 65 15 40 35 Cobalt Oxide 2 (Average Particle Size: 100 nm) 35 Cobalt Oxide 3 (Average Particle Size: 50 nm) 35 Conductive Powder Nickel Powder 1 (Average Particle Size: 2 μm) 5 5 5 5 5 Silver Powder (Average particle diameter: 2 μm) 5 Evaluation result paste screen printing property ◎ ◎ ◎ ◎ ◎ ◎ ◎ paste ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 580 ° C after the black degree of burning ◎ ◎ ◎ ◎ 〇 58 〇 ° C after the color black Black black black black brown black conductivity ◎ ◎ ◎ ◎ ◎ ◎ -20- 1258783 V. Description of invention (19) Table 2
實施 例8 實施 例9 實施 例10 實施 例11 實施 例12 實施 例13 實施 例14 實施 例15 比較 例1 玻 璃 粉 末 1 (軟化點：460°C、 平均粒徑：2微米） 90 15 60 60 60 4 (軟化點：390°C、 平均粒徑：2微米） 60 5 (軟化點：530(TC、 平均粒徑：2微米） 60 6 (軟化點：460°C、 平均粒徑：0.3微米） 60 7 (軟化點·· 460°C、 平均粒徑：5微米） 60 Μ j\ \\ 機 顏 料 鈷氧化物1 (平均粒徑：70奈米） 5 80 35 35 35 35 35 35 碳黑 (平均粒徑：30奈米） 35 導 電 性 粉 末 鎳粉末1 (平均粒徑：2微米） 5 5 5 5 5 5 5 鎳粉末2 (平均粒徑：0.05微米） 5 鎳粉末3 (平均粒徑：5微米） 5 評 量 結 果 糊之網版印刷性 ◎ 〇 ◎ ◎ Δ 〇 Δ 〇 ◎ 糊之圖樣加工性 ◎ 〇 ◎ ◎ 〇 Δ 〇 Δ ◎ 58〇°C之燒結性 ◎ Δ Δ Δ ◎ ◎ ◎ ◎ ◎ 580°C燒成後之黑色度 Δ 〇 〇 〇 ◎ ◎ ◎ ◎ X - 21 - 1258783 五、發明說明（20) 在實施例1〜3中，其黑色層所形成之圖樣、黑色度、 色彩、導電性等任一項均得到優異之結果。在實施例4中 ’因爲沒有添加導電性粉末而使得其導電性比實施例1〜3 者低。在實施例5中，由於使用比較大的平均粒徑之鈷氧 化物’而使得其黑色度比實施例1〜3低。在實施例6中， 其黑色度係比實施例1〜4要來得低，而色彩也呈褐色。在 實施例7中，銀之光澤度係比鎳更容易影響黑色度，使得 其黑色度係比實施例1〜4低。 在實施例8中，因鈷氧化物之含量低，故黑色度也變得 比較低。在實施例9中，因鈷氧化物之含量高，故燒結性 也變得比較低。在實施例1 0中，因玻璃之軟化點低，爲 了使包括在有機物全部分解飛散之前玻璃即軟化之有機物 殘留，則燒結性變得比較低。在實施例1 1中，由於玻璃 之軟化點高，在含有鈷氧化物和金屬粉末狀態之下，燒結 性會變低。在實施例1 2、1 4中，由於玻璃粉末或導電性 粉末粒度均小之糊特性，使得網版印刷上變得比較低。在 實施例1 3、1 5中，由於玻璃粉末或導電性粉末粒度均大 ，使得平坦性或圖樣加工性變得比較低。在比較例1中， 金屬氧化物系之無機顏料並不是一般的黑色顏料上所使用 之碳黑，會因燒成而分解、燒成後全部都不殘留，以致黑 色度變得非常低而不可行。 產業上利用之可能性 本發明之黑色糊由於係含有鈷氧化物’燒成後可以安定 -22- 1258783 五、發明說明（21) 地得到比較高黑色度之膜。又且，本發明之電漿顯示面板 因爲在黑色層上係含有鈷氧化物，可以安定地得到比較高 之黑色度、比較良好的顯示對比。此外，本發明之電漿顯 示面板之製造方法，乃藉由使用含有鈷氧化物之感光性黑 色糊，於燒成後可以比較容易地、安定地得到由比較高黑 色度所成之高精密度的黑色層之圖樣。 符號說明Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 1 Glass powder 1 (softening point: 460 ° C, average particle diameter: 2 μm) 90 15 60 60 60 4 (softening point: 390 ° C, average particle diameter: 2 μm) 60 5 (softening point: 530 (TC, average particle diameter: 2 μm) 60 6 (softening point: 460 ° C, average particle diameter: 0.3 μm) 60 7 (softening point · 460 ° C, average particle size: 5 μm) 60 Μ j\ \\ Machine pigment cobalt oxide 1 (average particle size: 70 nm) 5 80 35 35 35 35 35 35 Carbon black ( Average particle size: 30 nm) 35 Conductive powder nickel powder 1 (average particle diameter: 2 μm) 5 5 5 5 5 5 5 Nickel powder 2 (average particle diameter: 0.05 μm) 5 Nickel powder 3 (average particle diameter: 5 μm) 5 Measured result paste screen printing property ◎ 〇 ◎ ◎ Δ 〇 Δ 〇 ◎ paste pattern processing ◎ 〇 ◎ ◎ 〇 Δ 〇 Δ ◎ 〇 〇 C C Δ Δ Δ Δ ◎ ◎ ◎ ◎ ◎ Blackness after firing at 580 °C Δ 〇〇〇 ◎ ◎ ◎ ◎ X - 21 - 1258783 V. DESCRIPTION OF THE INVENTION (20) In Examples 1 to 3, any of the patterns, blackness, color, and conductivity formed by the black layer was excellent. In Example 4, the conductivity was lower than that of Examples 1 to 3 because no conductive powder was added. In Example 5, the blackness ratio was achieved by using a relatively large average particle diameter of the cobalt oxide. Examples 1 to 3 were low. In Example 6, the blackness was lower than that of Examples 1 to 4, and the color was also brown. In Example 7, the gloss of silver was more susceptible to blackness than nickel. The blackness is lower than those of Examples 1 to 4. In Example 8, since the content of cobalt oxide is low, the blackness is also relatively low. In Example 9, the content of cobalt oxide is high. In the case of Example 10, since the softening point of the glass is low, the sinterability is relatively low in order to cause the organic substance which is softened by the glass before the organic matter is completely decomposed and scattered, and the sinterability is relatively low. In Example 1 1, because the softening point of the glass is high, Cobalt oxide and a metal powder under the state, the sinterability becomes low. In Example 1 2,1 4, since the glass powder and conductive powder of small average particle size of the paste characteristics, becomes relatively low so that the screen printing. In Examples 1 3 and 15 , since the glass powder or the conductive powder had a large particle size, flatness or pattern processability became relatively low. In Comparative Example 1, the metal oxide-based inorganic pigment is not a carbon black used in a general black pigment, and is decomposed by firing, and does not remain after firing, so that the blackness becomes extremely low. Row. Industrial Applicability The black paste of the present invention contains a cobalt oxide. After firing, it can be stabilized. -22- 1258783 V. Inventive Note (21) A film having a relatively high degree of blackness is obtained. Further, since the plasma display panel of the present invention contains cobalt oxide on the black layer, it is possible to stably obtain a relatively high blackness and a relatively good display contrast. Further, in the method for producing a plasma display panel of the present invention, by using a photosensitive black paste containing a cobalt oxide, high precision by relatively high blackness can be obtained relatively easily and stably after firing. The pattern of the black layer. Symbol Description
1 透 明 電 極 2 編 址 電 極 3 保 護 層 4 隔 牆 5 玻 璃 基 板 6 背面 玻 璃 基 板 7 排 電 極 8 透 明 介 電 體 層 9 白 色 介 電 體 層 10 里 y I \ \ 色 層 11 螢 光 體 層 R 12 螢 光 體 層 Β 13 螢 光 體 層 G 23-1 transparent electrode 2 addressing electrode 3 protective layer 4 partition wall 5 glass substrate 6 back glass substrate 7 row electrode 8 transparent dielectric layer 9 white dielectric layer 10 y I \ \ color layer 11 phosphor layer R 12 phosphor layer Β 13 phosphor layer G 23-