200303338 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關能使電漿顯示面板（Plasma Display200303338 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a plasma display panel (Plasma Display)
Panel簡稱PDP )之正面基板形成精細的電極電路、黑色 圖案、之鹼性顯像型光硬化型組成物，以及使用其做爲具 有白黑二層構造的母線（Bus)電極的下層（黑層），而 使其正面基板形成黑色母體組織（Black Matrix)的電漿 顯示面板（PDP )。 【先前技術】 電漿顯示面板（PDP )係利用電漿放電發光，而進行 影像、實況報告之平面顯示，依面板構造、驅動方法可分 爲DC型及AC型；電漿顯示面板彩色顯示之原理是以隔牆 (Rib )使正面玻璃基板與背面玻璃基板分離，在其形成 對立的兩電極放電空間內產生電漿放電，由各放電空間封 入的氦（Helium )、氙（Xenon )等氣體放電發生紫外線 ，使背面玻璃基板內面形成之螢光體活躍起來，而產生三 原色的可視光；各放電空間，DC型電漿顯示面板係以格 子狀隔牆區分，AC型電漿顯示面板是以基板面上設置平 行排列隔牆區分，任何一種方式其放電空間之區分均以隔 牆做成。 圖1爲3電極構造之面板電方式電漿顯示面板（PDP ) 的部份構造例。 正面玻璃基板1之下面，有放電之透明電極3a、3b與 -6- (2) (2)200303338 爲降低該透明電極之線電阻的母線電極4a、4b所成對的表 示電極2a、2b，其可依所定之間距多列設置；表示電極2a 、2b之上有以印刷、燒成而形成爲積蓄電荷之用的透明誘 電體層5 (低融點玻璃），其上有蒸著而得之保護層（ MgO ) 6，保護層6是爲保護表示電極，維持放電狀態等而 設的；背面玻璃基板1 1之上有區劃放電空間線條（Stripe )狀之隔牆（Rib ) 12與各放電空間內配置的地址（Panel (PDP for short) forms a fine electrode circuit, a black pattern, a basic developing type photo-hardening composition, and a lower layer (black layer) using the same as a black and white bus electrode ), And the front substrate is formed into a plasma display panel (PDP) with a black matrix structure (Black Matrix). [Prior technology] Plasma display panel (PDP) uses plasma discharge to emit light, and performs flat display of images and live reports. It can be divided into DC type and AC type according to the panel structure and driving method; the color display of plasma display panel The principle is that the front glass substrate and the back glass substrate are separated by a partition wall. Plasma discharge is generated in the two electrode discharge spaces forming opposite electrodes. Gases such as helium (Helium) and xenon (Xenon) enclosed in each discharge space are generated. The discharge generates ultraviolet rays, which activates the phosphors formed on the inner surface of the back glass substrate to generate visible light of the three primary colors. In each discharge space, the DC type plasma display panel is distinguished by a grid-like partition wall. The AC type plasma display panel is The partition walls are arranged in parallel on the substrate surface to distinguish them. In either way, the discharge space is distinguished by partition walls. FIG. 1 is an example of a partial structure of a three-electrode panel electric plasma display panel (PDP). Under the front glass substrate 1, there are discharge transparent electrodes 3a, 3b and -6- (2) (2) 200303338 In order to reduce the line resistance of the transparent electrode, the bus bar electrodes 4a, 4b are paired with display electrodes 2a, 2b, It can be arranged in multiple rows according to a predetermined interval; it means that the transparent electromotive body layer 5 (low melting point glass) for printing and firing is formed on the electrodes 2a and 2b, and the electrode 2a and 2b are obtained by evaporation. A protective layer (MgO) 6 is provided to protect the indication electrode and maintain the discharge state; the back glass substrate 11 is provided with a partition wall (Rib) 12 in the shape of a discharge space (Stripe) and each discharge. Address configured in space (
Address )電極（資料電極）13，其可依所定之間距多列 設置；各放電空間之內部，按規則的裝配有紅（1 4a )、 藍（14b)、線（l4c)之三色螢光體膜，全顏色之顯示， 以上述紅、藍、線三原色之螢光體膜l4a、Hb、14c導入 同一畫面而構成。 形成放電空間的一對表示電極2a、2b，其兩側爲提高 畫像之反差，也同樣形成線條狀之黑色母體組織（Black Matrix ) 〇 上述構造的電漿顯示面板（PDP )，於其一對表示電 極2a、2b之間加以交流之脈衝（Pulse )電壓，可在同一 基板上的電極間放電，故稱呼爲「面放電方式」。 上述構造的電漿顯示面板，放電而發生的紫外線，使 背面基板11之螢光體膜14a、14b、14c活躍起來’產生的 可視光透過正面基板1的透明電極而顯示。 上述構造之電漿顯示面板（PDP )，其母線電極4a、 4b之形成，以往都是用鉻-銅-鉻三層蒸著或噴鍍（ Sputtering)方式成膜後，再用光微影法進行構圖。 (3) (3)200303338 但是步驟太多會使成本增高，最近有採用銀漿等導電 性糊狀物，以網版印刷後燒成之方法；或爲獲得線幅在 15 0 // m以下，而以感光性導電性糊狀物塗佈，經圖案罩曝 光、顯像、再燒成之方法。 如此電漿顯不面板的正面基板形成母線電極4a、4b，近 年來爲提升畫的反差，在母線電極形成之際，於表示側下層 (與透明電極3a、3b的接觸層）印刷上黑色糊狀物之黑層， 其上再印刷導電性銀漿之白層，以形成白黑二層構造的電極 ;此時，黑色糊狀物是以銅鐵系、銅鉻系等之黑色複合氧化 物、四氧化三鈷等之耐熱性黑色顏料配合而成樹脂組成物。 以往陰極射線管（Cathod Ray Tube簡稱CRT)顯示 、液晶顯示面板等之黑色母體組織的形成，都曾嘗試以遮 光膜形成用感光性樹脂組成物來轉用。 但是，電漿顯示面板之製造必須經過高溫燒成步驟， 此步驟會使遮光膜形成用感光性樹脂組成物中所含的碳黑 (Carbon Black )分解，以致難以形成令人滿意的黑色母 體組織。 遮光膜形成用感光性樹脂組成物中含有光聚合性組成 物、光聚合引發劑以及遮光性材料；上述遮光性材料是以 銅鐵系、銅鉻系等之黑色複合氧化物、四氧化三鈷（ Tricobalt Tetroxide)等之耐熱性黑色顏料摻合樹脂組成 物而使用。 不過，以銅鐵系、銅鉻系等之黑色複合氧化物、四氧 化三鈷等之耐熱性黑色顏料摻合之樹脂組成物，其糊狀物 -8 - (4) (4)200303338 (Paste )之保存安定性不良，特別是與光聚合性單體及 光聚合引發劑同時調配成光硬化性組成物時，光聚合性單 體開始進行聚合即發生膠化現象；因而樹脂組成物必須在 低溫下保存，而且當膠化發生、流動性下降時將會使塗佈 作業性惡化，在量產性上是個問題。 隨著形成高精細圖案的要求，耐熱性黑色顏料的粒徑 必須小徑化；不過，耐熱性黑色顏料之粒徑變小後，在糊 狀物中分散時容易引起二次凝集，進而使塗膜層突起而形 成線狀之缺陷。 【發明內容】 1 .發明所欲解決之課題 本發明之主要目的在於提供一種光硬化性組成物，其 特徵爲可以糊狀化而不會引起耐熱性黑色顏料的二次凝集 ，在乾燥、曝光、顯像、燒成之各步驟中能保持優良的安 定性，對於基板能不損及其優異的密著性、解像性、燒成 性，燒成後可形成具有充分黑色的燒成皮膜。 本發明之另外目的是提供一種使用此光硬化性組成物 ，而得高精細之黑色圖案，在正面基板形成白黑二層構造 之母線電極獲得充分的層間導電性（透明電極與母線電極 白層之層間導通）與黑色度的黑層電極電路，進而形成黑 色母體組織的電漿顯示面板（PDP )。 2.課題之解決手段 爲達成上述目的，本發明光硬化性組成物其基本的第 -9 - (5) 200303338 一種形態之特徵爲：含有（A )最大粒子徑在5 // m以下 之耐熱性黑色顏料（以四氧化三鈷黑色微粒子爲佳）均勻 分散於溶劑中而成之漿狀物，（B )有機黏結劑，（C ) 光聚合性單體，以及（D )光聚合引發劑；第二種形態之 · 特徵爲：除上述各成份外，尙含有（E)有機酸及/或（F )聚合停止劑。 本發明之光硬化性組成物，可爲糊狀形態或預先製膜 爲薄膜狀而形成乾燥薄膜之形態。 · 本發明提供以此光硬化性組成物之燒成物，形成正面 基板之電極電路（黑層）、黑色母體組織之電漿顯示面板 (PDP) 〇 3 .發明之實施形態 本發明之工作同仁，爲實現上述目的經努力不懈的探 討，終於硏究出使用最大粒徑在5 // m以下之耐熱性黑色 顏料均勻分散於溶劑中而成的漿狀物爲其特徵之所在。 本發明之光硬化性組成物，能很容易地製成不含二次 凝集物的糊狀物，其結果可提供高精細之電極電路，更能 形成黑色母體組織之電漿顯示面板（PDP )。 含有耐熱性黑色顏料等充塡劑的光硬化性組成物’不 加安定劑於室溫下即有增黏的缺點；其可能是光聚合性單 體之聚合、耐熱性黑色顏料與有機黏結劑中之羧基反應而 引起；爲抑制光硬化性組成物之膠化，長久以來都用磷酸 酯做爲安定劑，不過本發明之光硬化性組成物’使用磷酸 10· (6) (6)200303338 酯做爲安定劑時，會導致漿狀物中耐熱性黑色顏料之沉澱 ，容易引起粉體凝集；相反的，糊狀物之保存安定性會有 不良的影響。 有鑑於此，本發明的工作同仁經一再重覆硏究的結果 ，提供一種以有機酸（最好是有機酸與熱聚合停止劑摻合 使用）爲安定劑，其於室溫下具有極佳的保存安定性，可 充分供應量產之光硬化性組成物。 本發明之光硬化性組成物，使用上述四氧化三銘黑色 微粒子做爲耐熱性黑色顏料時，可形成緻密的黑色皮膜， 薄膜呈現充分黑度，經乾燥、曝光、顯像，燒成之各步驟 ，對於基板都不損及其優異的密著性、解像性、燒成性， 燒成後可得層間導電性（透明電極與母線電極白層之層間 導通）及黑度同時令人滿意之圖案。 此光硬化性組成物用爲電漿顯示面板之正面基板上以 形成白黑二層構造母線電極的黑層材料時，因母線電極之 黑層，如同三明治之構造被挾持在錫塗佈氧化銦（IT0 ) 、透明導電膜（Nesa)等之透明電極與白層之間的緣故， 使得透明電極與白層之層間導通、及由畫面側看到的黑度 都可同時獲得充分的滿意度。 本發明之光硬化性組成物，具有如上述之優良保存安 定性’而且膜厚極薄就可獲得充分的反差（Contrast)， 因此在電漿顯示面板（P D P )之量產性及低成本化上極爲 有用。 對本發明之光硬化性組成物做具體的說明如下。 •11 (7) (7)200303338 首先，最大粒徑在5 // m以下之耐熱性黑色顏料均勻 分散於溶劑中而成之漿狀物（A )，是以眾所周知的方法 將耐熱性黑色顏料均勻的分散在溶劑中調製而成；例如將 溶劑、分散劑、耐熱性黑色顏料置入球磨機等混合機中， 經充分混合、分散調製而得。 電漿顯示面板（PDP )其基板製作步驟必須在5 00〜 600 °C之高溫下燒成，因而具有高溫色調安定性之無機顏 料才能用爲耐熱性黑色顏料；具體的說，鉻、鈷、銅、鎳 、鐵、錳等之氧化物及複合氧化物都可使用，此等並無任 何限制，可單獨或兩種以上混合使用；本發明以使用銅鉻 系黑色複合氧化物、銅鐵系黑色複合氧化物、四氧化三鈷 等爲佳，其燒成後能形成緻密的黑色皮膜、色調非常優雅 〇 耐熱性黑色顏料之平均粒徑以2 // m以下爲宜，最好 以0.01 /zm〜1 /zm爲佳；平均粒子徑在2 /zm以下時， 少量添加亦不損其密著性，可形成緻密的燒成皮膜，可提 供同時獲得層間導電性（透明電極與母線電極白層之層間 導通）及黑度滿意之黑層電極用樹脂組成物；耐熱性黑色 顏料之平均粒徑大於2 // m時，燒成皮膜之緻密性不良， 所形成下層電極膜之黑色度容易下降；平均粒子徑小於 0.01 //m時，其隱蔽力降低而呈現透明感，不適宜。 耐熱性黑色顏料，以使用比表面積在1.〇〜20平方公 尺/公克之範圍的四氧化三鈷微粒子爲佳；比表面積低於 1.0平方公尺/公克時，由曝光形成電路圖案之精度會下 -12- (8) 200303338 降’線緣（Line— Edge)之直線性或燒成皮膜充分的黑度 都難以獲得；超過20平方公尺/公克時，粒子之表面積太 大’顯像之際容易發生底部切除（Undercut )現象。 漿狀物中耐熱性黑色顏料之摻合量，對有機黏結劑（ · B) 100重量份爲 1〜120重量份爲宜，調整至30〜100重 量份之範圍較佳；耐熱性黑色顏料之摻合量少於上述範圍 時’燒成後不能獲得充分的黑度；超過上述範圍時，光之 透過性不良、解像性下降、成本提高。 鲁 上述漿狀物使用之溶劑雖可任意選擇，但爲防止溶劑 衝撃（Solvent Shock)，以與糊狀物中使用之溶劑同種類 者爲佳。 漿狀物中固形份之濃度雖可任意選擇，但考慮其作業 性，以50〜8 0重量％較好；即是溶劑之摻合量對漿狀物 100重量份爲20〜50重量份之比率較適合。 上述漿狀物中使用之分散劑，能將耐熱性黑色顏料均 勻分散即可，並無特別的限制，可使用如日本油脂公司製 # 之梅里亞利姆系列產品、共榮社化學公司製之弗羅廉等高 分子分散劑。 分散劑之摻合量，對耐熱性黑色顏料1〇〇重量份以1〜 2〇重量份較爲適當；分散劑之摻合量少於上述範圍時，不 ， 能獲得充分的分散效果；超過上述範圍多量添加時，也不 能得到分散效果。 其次，上述有機黏結劑（B )，係具有羧基之樹脂； 具體的說，不管其本體爲具有乙烯性不飽和二重結合而含 -13- (9) 200303338 有羧基之感光性樹脂，以及其本體爲不具乙烯性二重結合 而含有羧基之樹脂都可以使用；適宜使用之樹脂（低級聚 合體以及聚合體均可）舉例如下。 (1 ) . ( a )不飽和羧酸與（b )具不飽和二重結合化 ] 合物，行共聚合而得之含羧基（Carboxyl )樹脂。 (2) .(a)不飽和羧酸與（b)具不飽和二重結合化 合物之共聚合體中，以側基（Pendant )方式附加乙烯性 不飽和基，而得含羧基之感光性樹脂。 · (3) .(c)具環氧基與不飽和二重結合化合物與（b )具不飽和二重結合化合物之共聚合體中，加入（a)不 飽和羧酸反應，於生成的第二級羥基中，再加入（d)多 質子酸酐反應後，可得含羧基之感光性樹脂。 (4) .(e)具不飽和二重結合之酸酐與（b)具不飽 和二重結合化合物之共聚合體中，加入（f)具羥基與不 飽和二重結合化合物反應後，可得含羧基之感光性樹脂。 (5) .(g)多官能環氧化合物與（h)不飽和單羧酸 β 反應，於生成的第二級羥基中，加入（d )多質子酸酐反 應後可得含羧基之感光性樹脂。 (6) .(b)具不飽和二重結合化合物與縮水甘油甲 基丙烯酸酯（Glycidyl Methacrylate )共聚合體之環氧基 · 中，加入（i) 一分子中含一個羧基，不具乙烯性不飽和 結合之有機酸反應，於生成的第二級羥基中，再加入（d )多質子酸酐反應後，可得含羧基之樹脂。 (7) .(j)含羥基聚合體與（d)多質子酸酐反應’ -14- (10) 200303338 可得含羧基之樹脂。 (8) .(j)含羥基聚合體與（d)多質子酸酐反應， 於生成含羧基樹脂中，再加入（c)具環氧基與不飽和二 重結合化合物反應後，可得含羧基之感光性樹脂。 上述含羧基感光性樹脂以及含羧基樹脂，可單獨或混 合使用，其合計重量比率以組成物全量之10〜80重量％爲 佳；此等聚合體之摻合量較上述範圍過少時，其形成皮膜 中容易發生上述樹脂公佈不均之現象，難以獲得充分的光 硬化性及光硬化深度，選擇性的曝光、顯像而進行圖案構 成（Patterning )困難重重；摻合量過多時，容易產生圖 案扭曲、線幅收縮等現象。 上述含羧基感光性樹脂及含羧基樹脂，其重量平均分 子量以1，〇〇〇〜1 00,000爲宜，以5,000〜70,000爲佳，酸價 以50〜2 5 0毫克KOH/公克爲宜；含羧基感光性樹脂，其 二重結合當量以3 50〜2,000爲宜，最好使用400〜1，5 00者 ;上述樹脂分子量低於1，〇〇〇時，對顯像時皮膜之密著性 有不良影響；高於100, 〇〇〇時，容易產生顯像不良之情況 ;又，酸價低於50毫克KOH/公克時，鹼性水溶液溶解性 不足，易生顯像不良，高於250毫克KOH/公克時，顯像 時皮膜之密著性下降，光硬化部份（曝光部份）發生溶解 之情況，均不適宜；含羧基感光性樹脂，其二重結合當量 小於3 5 0時，燒成之際易於殘留殘渣，大於2,000時，顯像 之作業伸縮度太小，光硬化之際必須有較高之曝光量，都 不適合。 -15- (11) 200303338 本發明之光硬化性組成物中之光聚合性單體（c )， 是用來促進組成物之光硬化性，以及提昇顯像性的；此光 聚合性單體（C )可以使用如2 -羥乙基丙烯酸酯（2 -Hydroxyethyl Acrylate) 、2—羥丙基丙烯酸酯、二乙二 醇二丙稀酸酯（Diethylene Glycol Diacrylate)、三乙二 醇二丙烯酸酯、聚乙二醇二丙烯酸酯（Polyethylene Glycol Diacrylate)、聚氨酯二丙嫌酸酯（Polyurethane Diacrylate ) 、三甲醇丙烷三丙烯酸酯 （ Trimethylolpropane Triacrylate)、季戊四醇三丙儲酸酯 (Pentaerythritol Triacrylate)、季戊四醇四丙嫌酸酯、 三甲醇丙烷環氧乙烷變性三丙烯酸酯、三甲醇丙烷環氧丙 烷變性三丙烯酸酯、二季戊四醇五丙烯酸酯（Di Pentaerythritol Pentaacrylate)、二季戊四醇六丙燒酸酯 、以及上述丙烯酸酯相對應的各種甲基丙烯酸酯類；苯二 甲酸、己二酸、順丁烯二酸、衣康酸（Itaconic Acid)、 琥拍酸、偏苯三酸（Trimellitic Acid)、對苯二甲酸等之 多質子酸及羥烷基甲基丙烯酸酯（Hydroxy Alkyl metharylate)及其一、二、三或以上之聚酯等；此並無特 別的限制，可單獨或兩種以上混合使用；此光聚合性單體 ，其一分子中以具有二個以上之丙烯醯基（Acryloyl)或 甲基丙烯醯基（Methacryloyl)之多官能單體爲佳。 光聚合性單體（C )之摻合量，對上述有機黏結劑（ 含羧基感光性樹脂及/或含羧基樹脂）（B ) 1 00重量份以 20〜100重量份爲宜；光聚合性單體之摻合量較上述範圍 -16- (12) (12)200303338 少時，難得到組成物充分的硬化性；較上述範圍多時，皮 膜表面之光硬化較深部爲快，易生深淺不勻之現象。 本發明之光硬化性組成物中之光聚合引發劑（D )， 可以使用如苯偶因（Benzoin)、苯偶因甲醚（Benzoin Methyl Ether )、苯偶因乙醚、苯偶因異丙醚等之苯偶因 及苯偶因院基醚類；苯乙酮（Acetophenone) 、2，2 —二 甲氧基—2 —苯基苯乙嗣（2 ’ 2 — Dimethoxy — 2 — Phenyl Acetophenone ) 、2，2 —二乙氧基—2 —苯基苯乙酮、1， 1—二氯苯乙酮等之苯乙酮類；2—甲基一1 一 〔 4一（甲硫 基）苯基〕一 2 —嗎琳丙院一 1—醒丨2 - Methyl - 1 一〔4 —(Methylthio) Phenyl ] — 2 — Morpholine Propane — 1 —Address) electrode (data electrode) 13, which can be arranged in multiple rows according to a predetermined interval; inside each discharge space, three colors of red (1 4a), blue (14b), and line (l4c) are regularly assembled. The body film and full-color display are constituted by introducing the phosphor films 14a, Hb, and 14c of the three primary colors of red, blue, and line into the same screen. A pair of display electrodes 2a and 2b forming a discharge space are formed on both sides to improve the contrast of the image, and similarly form a black matrix structure (Linear Black Matrix). The plasma display panel (PDP) of the above structure The pulse voltage applied between the electrodes 2a and 2b can be discharged between the electrodes on the same substrate, so it is called "surface discharge method". The plasma display panel having the above-mentioned structure emits visible light through the transparent electrodes of the front substrate 1 and displays visible light generated by the ultraviolet rays generated by the discharge, activating the phosphor films 14a, 14b, and 14c of the back substrate 11. In the plasma display panel (PDP) with the above structure, the formation of the bus bar electrodes 4a and 4b has been conventionally performed by using a chromium-copper-chromium three-layer vapor deposition or sputtering method, followed by photolithography. Frame the picture. (3) (3) 200303338 However, too many steps will increase the cost. Recently, conductive pastes such as silver paste were used and fired after screen printing; or in order to obtain a line width below 15 0 // m , And the method is coated with a photosensitive conductive paste, exposed through a pattern mask, developed, and then fired. In this way, the busbar electrodes 4a and 4b are formed on the front substrate of the plasma display panel. In recent years, in order to improve the contrast of the painting, when the busbar electrodes are formed, a black paste is printed on the lower side of the display (the contact layer with the transparent electrodes 3a and 3b). The black layer of the object is printed with the white layer of conductive silver paste to form an electrode with a white and black two-layer structure. At this time, the black paste is a black composite oxide such as copper-iron and copper-chromium. And tricobalt tetroxide and other heat-resistant black pigments to form a resin composition. In the past, the formation of black matrix structures for cathode ray tube (Cathod Ray Tube, CRT) displays and liquid crystal display panels has been attempted to be converted to a photosensitive resin composition for forming a light-shielding film. However, the manufacturing of a plasma display panel must go through a high-temperature firing step. This step decomposes carbon black contained in the photosensitive resin composition for forming a light-shielding film, making it difficult to form a satisfactory black matrix structure. . The photosensitive resin composition for forming a light-shielding film contains a photopolymerizable composition, a photopolymerization initiator, and a light-shielding material. The light-shielding material is a black composite oxide such as copper-iron-based, copper-chrome-based, or tricobalt tetroxide. ) And other heat-resistant black pigments are used by blending the resin composition. However, the resin composition blended with black composite oxides such as copper-iron-based, copper-chromium-based, and heat-resistant black pigments such as tricobalt tetroxide, etc., has a paste -8-(4) (4) 200303338 (Paste). Poor stability, especially when a photocurable composition is formulated with a photopolymerizable monomer and a photopolymerization initiator at the same time, the photopolymerizable monomer starts to polymerize and gelation occurs; therefore, the resin composition must be stored at low temperature In addition, when gelation occurs and fluidity decreases, coating workability is deteriorated, which is a problem in mass productivity. With the requirements for the formation of high-definition patterns, the particle diameter of the heat-resistant black pigment must be reduced; however, as the particle size of the heat-resistant black pigment becomes smaller, it is easy to cause secondary aggregation when dispersed in a paste, and then the coating The film layer protrudes to form a linear defect. [Summary of the Invention] 1. Problems to be Solved by the Invention The main object of the present invention is to provide a photocurable composition characterized in that it can be pasted without causing secondary aggregation of a heat-resistant black pigment. It can maintain excellent stability in each step of imaging, development, and firing. It can not damage the substrate and its excellent adhesion, resolution, and firing properties. After firing, it can form a firing film with sufficient blackness. . Another object of the present invention is to provide a high-definition black pattern using the photocurable composition, and to form a white-black two-layer structured bus bar electrode on the front substrate to obtain sufficient interlayer conductivity (white layer of transparent electrode and bus bar electrode). And the black layer electrode circuit of blackness, thereby forming a plasma display panel (PDP) with a black matrix structure. 2. Means for solving the problem In order to achieve the above-mentioned object, the basic composition of the photocurable composition of the present invention is -9-(5) 200303338. One form is characterized by containing (A) a heat-resistant material having a maximum particle diameter of 5 // m or less. Black pigment (preferably black cobalt trioxide fine particles) is a slurry obtained by uniformly dispersing in a solvent, (B) an organic binder, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator; second This form is characterized in that in addition to the above-mentioned components, rhenium contains (E) an organic acid and / or (F) a polymerization stopper. The photocurable composition of the present invention may be in the form of a paste or in the form of a film formed in advance to form a dry film. · The present invention provides a fired product of the photocurable composition to form an electrode circuit (black layer) of a front substrate and a plasma display panel (PDP) with a black matrix structure. Embodiments of the invention In order to achieve the above purpose, through unremitting research, finally found out the characteristics of the use of a heat-resistant black pigment with a maximum particle size of 5 // m or less is uniformly dispersed in a solvent. The photo-curable composition of the present invention can be easily made into a paste without secondary agglomerates. As a result, it can provide a high-definition electrode circuit and can form a plasma display panel (PDP) with a black matrix structure. . The photo-hardenable composition containing fillers such as heat-resistant black pigments has the disadvantage of thickening at room temperature without stabilizers; it may be the polymerization of photopolymerizable monomers, heat-resistant black pigments and organic binders. Caused by the reaction of carboxyl groups; in order to suppress the gelation of the photocurable composition, phosphate has been used as a stabilizer for a long time, but the photocurable composition of the present invention uses phosphoric acid 10 · (6) (6) 200303338 When the ester is used as a stabilizer, it will cause the precipitation of heat-resistant black pigment in the slurry, which will easily cause the powder to agglomerate. On the contrary, the storage stability of the paste will have an adverse effect. In view of this, the working colleagues of the present invention have repeatedly researched the results, and provide an organic acid (preferably an organic acid mixed with a thermal polymerization stopper) as a stabilizer, which has excellent performance at room temperature. It has stable storage stability, and can fully supply light-curing composition for mass production. When the photocurable composition of the present invention uses the above-mentioned black oxide fine particles as a heat-resistant black pigment, it can form a dense black film, and the film exhibits sufficient blackness, and is dried, exposed, developed, and fired. In the step, the substrate is not damaged, and its excellent adhesion, resolvability, and sinterability are obtained. After the sintering, the interlayer conductivity (interlayer conduction between the transparent electrode and the white layer of the bus electrode) and the blackness are satisfactory. Of the pattern. When this photocurable composition is used as a black material for a white-black two-layer structure bus bar electrode on a front substrate of a plasma display panel, the black layer of the bus bar electrode is held in a tin-coated indium oxide as a sandwich structure. (IT0), transparent conductive film (Nesa), and the like between the transparent electrode and the white layer, so that the transparent electrode and the white layer between the conductive layer and the blackness seen from the screen side can be fully satisfied at the same time. The photocurable composition of the present invention has excellent storage stability as described above, and sufficient contrast (Contrast) can be obtained with a very thin film thickness. Therefore, it is suitable for mass production and cost reduction of a plasma display panel (PDP). Is extremely useful. The photocurable composition of the present invention is specifically described below. • 11 (7) (7) 200303338 First, a heat-resistant black pigment with a maximum particle diameter of 5 // m or less (A) is dispersed in a slurry (A), and the heat-resistant black pigment is a well-known method. It is prepared by uniformly dispersing in a solvent; for example, a solvent, a dispersant, and a heat-resistant black pigment are placed in a mixer such as a ball mill, and are obtained by thorough mixing and dispersion preparation. In the plasma display panel (PDP), the substrate manufacturing steps must be fired at a high temperature of 500 to 600 ° C, so inorganic pigments with high-temperature hue stability can be used as heat-resistant black pigments; specifically, chromium, cobalt, Oxides and composite oxides of copper, nickel, iron, manganese, etc. can be used. There are no restrictions on these, and they can be used alone or in combination of two or more. In the present invention, copper-chrome-based black composite oxides, copper-iron systems are used. Black composite oxide, tricobalt tetroxide, etc. are preferred. It can form a dense black film after firing, and its color is very elegant. The average particle diameter of the heat-resistant black pigment is preferably 2 // m or less, preferably 0.01 / zm ~ 1 / zm is preferred; when the average particle diameter is below 2 / zm, a small amount of addition does not damage its adhesion, can form a dense fired film, and can provide interlayer conductivity at the same time (between the transparent electrode and the white layer of the busbar electrode) Conductive) and resin composition for black layer electrodes with satisfactory blackness; when the average particle diameter of the heat-resistant black pigment is greater than 2 // m, the denseness of the fired film is poor, and the blackness of the formed lower electrode film is easy to decrease ; The average particle diameter of less than 0.01 // m, which reduce the hiding power presented transparent feeling, inappropriate. The heat-resistant black pigment is preferably tricobalt tetraoxide fine particles having a specific surface area in the range of 1.0 to 20 square meters per gram; when the specific surface area is less than 1.0 square meters per gram, the accuracy of the circuit pattern formed by exposure will be lower- 12- (8) 200303338 It is difficult to obtain the linearity of the line edge (Line-Edge) or the blackness of the fired film; if it exceeds 20 square meters / g, the surface area of the particles is too large. Undercut occurred. The blending amount of the heat-resistant black pigment in the paste is preferably 1 to 120 parts by weight with respect to 100 parts by weight of the organic binder (B), and the range is preferably adjusted to 30 to 100 parts by weight. When the blending amount is less than the above range, sufficient blackness cannot be obtained after firing; when it exceeds the above range, light transmittance is poor, resolution is reduced, and cost is increased. Although the solvent used in the above slurry can be arbitrarily selected, in order to prevent the solvent from eroding (Solvent Shock), it is better to use the same kind of solvent as the solvent used in the paste. Although the concentration of the solids in the slurry can be arbitrarily selected, considering its workability, it is preferably 50 to 80% by weight; that is, the blending amount of the solvent is 20 to 50% by weight based on 100% by weight of the slurry. The ratio is more appropriate. The dispersant used in the above slurry can disperse the heat-resistant black pigment uniformly, and there is no particular limitation. For example, the Melialim series products manufactured by Japan Oil & Fats Co., Ltd., and those manufactured by Kyoeisha Chemical Co., Ltd. can be used. Florian and other polymer dispersants. The blending amount of the dispersant is preferably 1 to 20 parts by weight based on 100 parts by weight of the heat-resistant black pigment. When the blending amount of the dispersant is less than the above range, no, a sufficient dispersion effect can be obtained; When a large amount is added in the above range, a dispersion effect cannot be obtained. Secondly, the above-mentioned organic binder (B) is a resin having a carboxyl group; specifically, whether it is a photosensitive resin containing -13- (9) 200303338 having a carboxyl group and having an ethylenically unsaturated double bond, and its Any resin containing a carboxyl group that does not have an ethylene-based double bond can be used. Examples of suitable resins (lower polymers and polymers) are as follows. (1). (A) An unsaturated carboxylic acid and (b) an unsaturated double bond compound are copolymerized to obtain a carboxyl group-containing (Carboxyl) resin. (2). (A) An unsaturated carboxylic acid and (b) an unsaturated double-bonded compound copolymer, an ethylenically unsaturated group is added in a pendant manner to obtain a carboxyl group-containing photosensitive resin. (3). (C) Epoxy and unsaturated double-bonded compound and (b) copolymer of unsaturated double-bonded compound, (a) unsaturated carboxylic acid is added to react, After adding (d) polyprotic anhydride to the secondary hydroxyl group, a photosensitive resin containing a carboxyl group can be obtained. (4). (E) An unsaturated double-bonded acid anhydride and (b) an unsaturated double-bonded compound are added to the copolymer, and (f) a hydroxyl group is reacted with the unsaturated double-bound compound to obtain Carboxyl photosensitive resin. (5). (G) The polyfunctional epoxy compound is reacted with (h) unsaturated monocarboxylic acid β, and (d) polyprotic anhydride is added to the generated secondary hydroxyl group to obtain a carboxyl-containing photosensitive resin. . (6). (B) Epoxy group of copolymer of unsaturated double-binding compound and glycidyl methacrylate (Glycidyl Methacrylate), add (i) One carboxyl group in one molecule, without ethylenic unsaturation The combined organic acid is reacted, and after adding the (d) polyprotic anhydride to the generated secondary hydroxyl group, a carboxyl group-containing resin can be obtained. (7). (J) Reaction of hydroxyl-containing polymer with (d) polyprotic anhydride '-14- (10) 200303338 A carboxyl-containing resin can be obtained. (8). (J) The hydroxyl-containing polymer is reacted with (d) polyprotic anhydride. After the carboxyl group-containing resin is formed, (c) the epoxy group is reacted with an unsaturated double-binding compound to obtain a carboxyl group. Photosensitive resin. The above carboxyl-containing photosensitive resins and carboxyl-containing resins can be used alone or in combination. The total weight ratio is preferably 10 to 80% by weight of the total composition. When the blending amount of these polymers is too small compared to the above range, they form The above-mentioned resin publication unevenness is likely to occur in the film, it is difficult to obtain sufficient light-hardening property and depth of light-hardening, and selective exposure and development to perform patterning (Patterning) are difficult; when the blending amount is too much, it is easy to produce a pattern Distortion, shrinkage, etc. The weight-average molecular weight of the carboxyl group-containing photosensitive resin and carboxyl group-containing resin is preferably 1,000 to 100,000, more preferably 5,000 to 70,000, and the acid value is preferably 50 to 250 mg KOH / g; The carboxyl photosensitive resin preferably has a double bond equivalent of 3 50 to 2,000, preferably 400 to 1,500. When the molecular weight of the resin is less than 1,000, the adhesion to the film during development It has adverse effects; when it is higher than 100,000, it is easy to produce poor imaging; and when the acid value is less than 50 mg KOH / g, the solubility of alkaline aqueous solution is insufficient and it is easy to produce poor imaging, higher than 250 When mg KOH / g, the adhesion of the film is reduced during development, and it is not suitable to dissolve the light-hardened part (exposed part); when the carboxyl-containing photosensitive resin has a double binding equivalent of less than 3 50 Residues are liable to remain during firing. When it is more than 2,000, the expansion and contraction of the image is too small, and a high exposure is required during light curing, which is not suitable. -15- (11) 200303338 The photopolymerizable monomer (c) in the photocurable composition of the present invention is used to promote the photocurability of the composition and improve the developability; the photopolymerizable monomer (C) For example, 2-Hydroxyethyl Acrylate, 2-Hydroxypropyl Acrylate, Diethylene Glycol Diacrylate, and Triethylene Glycol Diacrylate can be used. , Polyethylene Glycol Diacrylate, Polyurethane Diacrylate, Trimethylolpropane Triacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tripropylene Phosphonic acid esters, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexapropionate, and the above acrylates Corresponding various methacrylates; phthalic acid, adipic acid, maleic acid, itaconic acid ), Polyprotonic acid such as succinic acid, trimellitic acid, terephthalic acid, etc., and Hydroxy Alkyl metharylate, and one, two, three or more polyesters, etc. ; This is not particularly limited, and it can be used alone or as a mixture of two or more types. The photopolymerizable monomer has one or more of Acryloyl or Methacryloyl in one molecule. Polyfunctional monomers are preferred. The blending amount of the photopolymerizable monomer (C) is preferably 20 to 100 parts by weight based on 100 parts by weight of the organic binder (carboxyl-containing photosensitive resin and / or carboxyl-containing resin) (B); When the blending amount of the monomer is less than the above range -16- (12) (12) 200303338, it is difficult to obtain sufficient hardenability of the composition; when it is more than the above range, the light hardening on the surface of the film is faster and easier to produce depth Unevenness. As the photopolymerization initiator (D) in the photocurable composition of the present invention, for example, Benzoin, Benzoin Methyl Ether, Benzoin ethyl ether, Benzoin isopropyl ether can be used. Benzoin and benzoin ethers; acetophenone, 2,2-dimethoxy-2, phenylacetophenone (2 '2 — Dimethoxy — 2 — Phenyl Acetophenone), Acetophenones such as 2,2-diethoxy-2- 2-phenylacetophenone, 1,1-dichloroacetophenone, etc .; 2-methyl-1 1- [4-thio (methylthio) phenyl 〕 One 2 —Morin B Clinic 1—Wake 丨 2-Methyl-1 One [4 — (Methylthio) Phenyl] — 2 — Morpholine Propane — 1 —
One丨、2 -苯甲基—2 —二甲基氨基—1 一（4 —嗎啉苯基 )丁院—1—酮 〔2—Benzyl—2—DimethylAmino—l — (4 — Morpholine Phenyl) Butane — 1— One〕等之氣基苯 乙酮類；2 —甲基蒽酯（2 — Methyl Anthraguinone) 、2 — 乙基蒽酯、2 -特一丁基蒽醌、1 一氯蒽醌等之蒽醌類；2 ，4—二甲基硫雜蒽酮（2，4 — Dimethyl Thioxanthone) 、2，4一二乙基硫雜蒽酮、2-氯硫雜蒽酮、2，4一二異 丙基硫雜蒽酮等之硫雜蒽酮類；苯乙酮二甲基縮酮（ Acetophenone Dimethyl Ketal)、苯甲基二甲基縮酮等之 縮酮類；二苯甲酮（Benzophenone)等之二苯甲酮類；氧 雜蒽酮類（Xanthone) ; (2，6 -二甲氧基苯醯）—2，4 ，4 —戊基鱗氧化物〔（2，6 — Dimethoxy Benzoyl) — 2 ，4，4 — Pentyl Phosphine Oxide )、雙（2，4，6—二甲 -17- (13) (13)200303338 基苯醯）一苯基膦氧化物、2，4，6-三甲基苯醯二苯基 膦氧化物、乙基- 2，4，6-三甲基苯醯苯基膦氧化物等 之膦氧化物類；各種過氧化物等等；此等眾所周知的光聚 合引發劑可以單獨或兩種以上混合使用，光聚合引發劑（ D )之摻合比率，對有機黏結劑（含羧基感光性樹脂及/ 或含羧基樹脂）（B) 100重量份以1〜30重量份爲宜，最 好是5〜20重量份。 上述光聚合引發劑（D)可加入一種或兩種以上之光 增感劑，光增感劑可用如下之第三級胺類，N，N -二甲 胺基安息香酸乙基酯（Ethyl N，N — Dimethyl Amino Benzoate ) 、N，N —二甲胺基安息香酸異戊酯（Ieoamyl N，N — Dimethyl Amino Benzoate) 、4 —二甲胺基安息香 酸戊酯、三乙基胺（Tri Ethyl Amine )、三乙醇胺（Tri Ethanol Amine )等等。 要求光硬化深度較深時，可混合使用CIBA SPECIALITY CHE MI CALS公司製造的依爾卡丘亞—784等 之鈦系光聚合引發劑、白色（Leuco)染料等硬化助劑。 本發明之光硬化性組成物，摻合多量無機充塡劑、玻 璃粉末時，所得組成物之保存安定性會下降、膠化、流動 性降低，使塗佈作業性有惡化之傾向； 爲使本發明光硬化性組成物之保存安定性提高，以添 加具有能使無機充塡劑、玻璃粉末成份之金屬或氧化物粉 末形成錯體化或鹽類效果之化合物（即安定劑’如有機酸 (E))爲佳；有機酸（E)可使用者如丙二酸（Malonic -18- (14) 200303338One 丨, 2-benzyl-2-dimethylamino-1, 1- (4-morpholinylphenyl) butan-1-one [2-Benzyl-2—DimethylAmino—l — (4 — Morpholine Phenyl) Butane — 1—One] and other gas-based acetophenones; 2—Methyl Anthraguinone, 2—Ethyl Anthraguinone, 2—Tetrabutylanthraquinone, 1—Chloroanthraquinone, etc. Anthraquinones; 2,4-Dimethyl Thioxanthone (2,4-Dimethyl Thioxanthone), 2,4-Diethyl Thianthone, 2-Chloothanthone, 2, 4-Diiso Thiazantrones such as propylthioanthone; Acetophenone Dimethyl Ketal, Acetophenone, etc .; Benzophenone, etc. Benzophenones; Xanthone; (2,6-dimethoxyphenylhydrazone) —2,4,4—pentyl scale oxide [(2,6 — Dimethoxy Benzoyl) — 2,4,4—Pentyl Phosphine Oxide), bis (2,4,6-dimethyl-17- (13) (13) 200303338 phenylphenylhydrazone) monophenylphosphine oxide, 2,4,6-trimethyl Phenylhydrazone diphenylphosphine oxide, ethyl-2,4,6- Phosphine oxides such as methylphenylphosphonium phenylphosphine oxide; various peroxides, etc .; these well-known photopolymerization initiators can be used alone or in combination of two or more, and the photopolymerization initiator (D) is blended The ratio is preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the organic binder (carboxyl-containing photosensitive resin and / or carboxyl-containing resin). The above photopolymerization initiator (D) may be added with one or two or more kinds of photosensitizers. The photosensitizers may be used in the following tertiary amines, N, N-dimethylaminobenzoic acid ethyl ester (Ethyl N , N — Dimethyl Amino Benzoate), N, N — Dimethyl Amino Benzoate, Ieoamyl N, N — Dimethyl Amino Benzoate, 4 — Dimethyl Amino Benzoate, Tri Ethyl Amine), Tri Ethanol Amine, and the like. When deep photo-hardening is required, a titanium photopolymerization initiator such as Ilkachua-784 manufactured by CIBA SPECIALITY CHE MI CALS company, and hardening assistants such as white (Leuco) dye can be mixed and used. When the photocurable composition of the present invention is blended with a large amount of an inorganic filler and glass powder, the storage stability of the obtained composition will decrease, gelation, and fluidity will decrease, which will tend to deteriorate the coating workability; The storage stability of the photocurable composition of the present invention is improved to add a compound (ie, a stabilizer, such as an organic acid) that has the effect of distorting or salting the metal or oxide powder of the inorganic filler and glass powder component. (E)) is preferred; organic acids (E) can be used by users such as malonic acid (Malonic -18- (14) 200303338
Acid )、己二酸、甲基、醋酸、檸檬酸、乙醯醋 Aceto Acetic Acide )、硬脂酸、順丁 燒二酸、反丁 酸、苯二甲酸等；可單獨或兩種以上混合使用；有機 摻合量，對上述玻璃粉末、無機微粒子1 0 0重量份以< 1 0重量份爲宜。 以往做爲鈷安定劑使用之磷酸酯，對四氧化三鈷 充分之效果。 本發明光硬化性組成物中，加入光聚合性單體所 成物之保存安定性不良、膠化、流動性降低，使塗佈 性有惡化之傾向；爲使本發明組成物之保存安定性提 以添加光聚合性單體之熱聚合停止劑（F )爲佳；熱 停止劑（F)可以使用如吩噻嗪（Phenothiazine)、 二酣（Hydroquinone) 、N —苯基萘（基）胺）（ Phenyl Naphthyl Amine )、氯酿（Chloranil)、焦掊 Pyrogallol)、苯醌（Benzoquinone)、特—丁基鄰 酚（t— Butyl Catechol)等等，可單獨或兩種以上混 用；熱聚合停止劑（F )之摻合量，對上述有機黏結 B) 100重量份，以0.01〜1重量份爲佳。 在不損及本發明光硬化性組成物特性之情況下， 添加適量的玻璃粉末、導電性粉末，其軟化點在400 -°C之間。 爲提高燒成後導體電浴的密著性，可添加適量玻 末，其摻合量對四氧化三鈷黑色微粒子等耐熱性黑色 1〇〇重量份，以200重量份以下爲宜，150重量份以下 酸（ 烯二 酸之 不具 得組 作業 局， 聚合 對苯 N - 酚（ 苯二 合使 劑（ 可以 -600 璃粉 顏料 較佳 -19- (15) (15)200303338 ;玻璃粉末之玻璃轉移點（Tg)以300〜500 °c爲宜，玻璃 軟化點（Ts )以400〜600 °C爲宜；從解像度來看，平均粒 徑在20 // m以下，最好在5 // m以下之玻璃粉末較適合 使用。 光硬化性組成物添加玻璃粉末，使曝光、顯像後之皮 膜容易在600 °C以下燒成；但是，本發明組成物採用燃燒 性良好之有機黏者成份，其於玻璃粉末熔融之前就已完全 脫除，玻璃粉末之軟化點低於400 °C時，發生低溫熔融易 將有機黏結劑包圍住，而殘存之有機黏結劑會分解，使組 成物容易產生氣孔（Blister)。 玻璃粉末以使用氧化鉛、氧化鉍、或氧化鋅等爲主成 份之非結晶性玻璃料（Ffit )較佳。 本發明組成物糊狀化之稀釋劑或各種塗佈步驟調整粘 度之稀釋劑可以使用如甲乙酮、環己酮等之酮類；甲苯、 二甲苯、四甲基苯等之芳香族烴類；賽璐素（Cello solve )、甲基賽璐素、卡必醇（Carbitol )、甲基卡必醇、丁 基卡必醇、丙二醇甲醚、二丙二醇甲醚、二丙二醇乙醚、 三乙二醇乙醚等之乙二醇醚類、醋酸乙酯、醋酸丁酯、醋 酸賽璐素、醋酸丁基賽璐素、醋酸卡必醇、醋酸丁基卡必 醇、醋酸丙二醇甲醚等之醋酸酯類；乙醇、丙醇、乙二醇 、丙二醇、萜品醇（Terpineol)等之醇類；辛烷、癸烷（ Decane )等之脂肪族烴；石油醚、石油精（Naphtha )、 氫化石油精、溶劑石油精等之石油系溶劑等之，可單獨或 兩種以上混合使用。 -20- (16) (16)200303338 本發明之光硬化性組成物，因應需要可以添加矽氧系 、丙烯腈系等之消泡、平滑劑、提高皮膜密著性之矽烷偶 合劑等；也可以添加眾所周知的氧化防止劑、燒成時與基 板之結合成份，如金屬氧化物、矽氧化物、硼氧化物等之 微粒子。 本發明之光硬化性組成物，如爲已成膜之薄膜狀時， 可直接置於基板上形成層壓製品（Laminate);爲糊狀（ Paste )時，可用網版（Screen )印刷法、棒桿塗佈（Bar Coat )、刮板（Blade )塗佈等適當方法塗佈於基板上， 如塗佈於玻璃基板而成電漿顯示面板（PDP )之正面基板 :其次，爲獲得指觸乾燥性，將塗佈後基板經熱風循環式 乾燥爐、遠紅外線乾燥爐等，在60〜120 °C下5〜40分鐘乾 燥，使有機溶劑蒸發而得無壓感塗膜；其後行選擇曝光、 顯像、燒成、而形成所定圖案的電極電路。 曝光步驟中，使用具有所定曝光圖案之負片罩（ Negative Mask)即可進行接觸曝光以及非接觸曝光；曝 光光源可使用鹵素燈、高壓水銀燈、雷射光、鹵化金屬燈 、黑燈、無電極燈等，曝光量以50〜1000mJ/cm2爲佳。 顯像步驟可使用噴霧法、浸漬法等；顯像液可以使用 氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉等之金屬 鹼性水溶液；乙醇胺、二乙醇胺、三乙醇胺等之胺水溶液 ;特別以1 . 5重量％以下濃度之稀鹼水溶液最適用，組成 物中含羧基樹脂之羧基會膠化，未硬化部份（未曝光部份 )可除去；上述之顯像液沒有限制；顯像後之廢棄顯像液 -21 - (17) 200303338 ，可以水洗或酸中和除去。 燒成步驟是將顯像後之基板，置於空氣或氮氣大氣中 400〜600 °C下行加熱處理，形成所定之黑色圖案；此時之 昇溫速度以20 °C/分鐘爲宜。 【實施方式】 〔實施例〕 以下列實施例及比較例來具體說明本發明；本發明下 記實施例並無任何限制； 〔合成例1〕 於裝置有溫度計、攪拌機、滴液漏斗、以及迴流冷却 器之燒瓶中，將甲基丙烯酸甲酯（Methyl Methacrylate) 與甲基丙儲酸（Methacrylic Acid)依0.76: 0.24之分子比 加入之，再注入溶媒二丙二醇甲醚及觸媒偶氮二異丁腈（ Azobisisobutyronitrile)，在氮氣大氣中80 °C下攪拌2〜6 小時，可得樹脂溶液；樹脂溶液冷却後加入聚合停止劑甲 基對苯二酣（Methyl Hydroquinone)、觸媒溴化四丁基鱗 (Tetrabutyl Phosphonium Bromide)、縮水甘油甲基丙嫌 酸酯（Glycidyl Methacrylate);對上述樹脂之羧基1分子 ，附加分子比爲0.1 2分子；在95〜105 °C下進行附加反應 1 6小時，冷却後取出，即爲生成之有機黏結劑A ;此有機 黏結劑A的樹脂，其重量平均分子量約10,000、酸價59毫 克KOH/公克、二重結合當量爲950 ;所得共聚合樹脂之 -22- (18) (18)200303338 重量平均分子量，是使用島津製作所製之PUMP LC- 6AD 及昭和電工製 Column Shodex KF — 804、KF — 803、KF — 802三支連繋之高速液體色層分析儀測定。 〔合成例2〕 甲基丙烯酸甲酯與甲基丙烯酸之加入分子比更改爲 0.87: 0.13，不進行縮水甘油甲基丙烯酸酯之附加反應， 其他都和合成例1相同，即生成有機黏結劑B :此有機黏結 劑B的樹脂，其重量平均分子量約1 0,000、酸價74毫克 KOH/公克。 將上述所得之有機黏結劑A或B，依下述組成比調配 組成物，以攪拌機攪拌後，經三滾輪機滾練成糊狀、滾練 條件爲試樣1公斤在室溫下滾練3 0分鐘。 如上所述，將最大粒子徑在5 // m以下之耐熱性黑色 顏料均勻分散於溶劑中而成漿狀物（A );本實施例係將 最大粒徑在5 /zm以下，平均粒徑爲0.2 //m之四氧化三 鈷黑色微粒子，加入三丙二醇甲醚（簡稱TPM )中，濃度 70%左右；分散劑之摻合量，對黑色微粒子100重量份爲 1 〇重量份；以球磨機均勻分散調製之（漿狀物中的溶劑濃 度爲漿狀物100重量份，溶劑23重量份）；使用日本油脂 公司製之高分子分散劑AKM — 0531，其漿狀物以（A— 1 )表示，使用共榮社化學公司製之高分子分散劑DOP A -15B，其形成之漿狀物以（A - 2)表示。 玻璃粉末係將氧化鉛（PbO ) 60%、氧化硼（B2〇3 ) -23- (19) (19)200303338 20%、二氧化矽（Si02) 15%、三氧化二鋁（Al2〇3) 5% 混合粉碎即得；其熱膨脹係數爲α 70 X 10 - 7/ t， 玻璃轉移點爲4 4 5 °C，平均粒徑爲1 . 6 // m。 [白層電極（上層）用導電糊狀物（Paete)] 有機黏結劑A 1 0 0.0重量份 季戊四醇三丙烯酸酯 5 0.0重量份 2-苯甲基-2-二甲氨基-1-(4-嗎啉苯基）-丁烷-1-酮 5.0重量份 三丙二醇甲醚 8 0.0重量份 銀粉 450.0重量份 玻璃粉末 22.0重量份 磷酸酯 1 .〇重量份 (20) 200303338 [黑層電極（下層）用糊狀物] (組成物例1) 有機黏結劑B 季戊四醇三丙烯酸酯 2-苯甲基-2- 一^甲氨基-1-(4 -嗎琳本基）-丁院-1-嗣 三丙二醇甲醚 漿狀物（A - 1) (組成物例2) 有機黏結劑B 季戊四醇三丙烯酸酯 2-甲基-1-[-4-(甲硫基）苯基]-2-嗎啉丙烷）-1-酮 2,4一二乙基硫雜蒽酮 三丙二醇甲醚 漿狀物（A — 1) 100.0重量份 50.0重量份 5.0重量份 40.0重量份 5 0.0重量份 1 0 0.0重量份 5 0.0重量份 7.5重量份 1.0重量份 40.0重量份 50.0重量份 -25 200303338 (21) (組成物例3) 有機黏結劑B 1 0 0.0重量份 季戊四醇三丙烯酸酯 50.0重量份 2-甲基-1-[-4-(甲硫基）苯基]-2-嗎啉丙烷）-1-酮 7.5重量份 2,4 一二乙基硫雜蒽酮 1. 〇重量份 三丙二醇甲醚 4 0.0重量份 漿狀物（A— 1) 5 0.0重量份 丙二酸 1.0重量份 (組成物例4) 有機黏結劑B 1 0 0.0重量份 季戊四醇三丙烯酸酯 5 0.0重量份 2-甲基-1-[-4·(甲硫基）苯基]-2·嗎啉丙烷）-1-酮 7.5重量份 2,4— _^乙基硫雜葱醒 1.0重量份 三丙二醇甲醚 40.0重量份 漿狀物（A— 1) 50.0重量份 丙二酸 1.0重量份 吩噻嗪 0.1重量份Acid), adipic acid, methyl, acetic acid, citric acid, Aceto Acetic Acide), stearic acid, maleic acid, fumaric acid, phthalic acid, etc .; can be used alone or in combination of two or more The organic blending amount is preferably < 10 parts by weight to 100 parts by weight of the glass powder and the inorganic fine particles. Phosphate used in the past as a cobalt stabilizer has a sufficient effect on cobalt tetroxide. In the photocurable composition of the present invention, the storage stability of the product formed by adding a photopolymerizable monomer is poor, the gelation, and the fluidity are reduced, so that the coating property tends to be deteriorated; in order to make the storage stability of the composition of the present invention A thermal polymerization stopper (F) added with a photopolymerizable monomer is preferred; as the thermal stopper (F), for example, phenothiazine, hydroquinone, and N-phenylnaphthyl (amine) amine can be used. ) (Phenyl Naphthyl Amine), Chloranil, Pyrogallol, Benzoquinone, t-Butyl Catechol, etc., can be used alone or in combination of two or more; thermal polymerization stopped The blending amount of the agent (F) is preferably 0.01 to 1 part by weight based on 100 parts by weight of the organic bond B). Without impairing the characteristics of the photocurable composition of the present invention, an appropriate amount of glass powder or conductive powder is added, and its softening point is between 400-° C. In order to improve the adhesiveness of the conductor electric bath after firing, an appropriate amount of glass frit can be added, and its blending amount is 100 parts by weight of heat-resistant black such as tricobalt tetraoxide black particles, preferably 200 parts by weight or less, 150 parts by weight or less acid (Adipic acid does not have a working group, polymerized p-benzene N-phenol (benzene diene agent (may be -600 glass powder pigment is better -19- (15) (15) 200303338; glass powder transfer point of glass powder ( Tg) is preferably 300 ~ 500 ° c, and glass softening point (Ts) is preferably 400 ~ 600 ° C; from the perspective of resolution, the average particle size is below 20 // m, preferably below 5 // m Glass powder is more suitable for use. Adding glass powder to the light-hardening composition makes it easy to burn the film after exposure and development below 600 ° C; however, the composition of the present invention uses organic sticky ingredients with good flammability. The glass powder has been completely removed before melting. When the softening point of the glass powder is lower than 400 ° C, low temperature melting will easily surround the organic binder, and the remaining organic binder will decompose, making the composition prone to pores (Blister ). Glass powder so that A non-crystalline glass frit (Ffit) containing lead oxide, bismuth oxide, or zinc oxide as a main component is preferred. The diluent for pasting the composition of the present invention or the diluent for adjusting the viscosity in various coating steps can use methyl ethyl ketone, for example. , Ketones such as cyclohexanone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; Cello solve, methylcellulose, Carbitol, methylcarbidine Glycol ethers such as alcohols, butyl carbitol, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, triethylene glycol ether, ethyl acetate, butyl acetate, celluloid acetate, butyl acetate Cellulose, carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and other acetates; ethanol, propanol, ethylene glycol, propylene glycol, terpineol and other alcohols; octane , Decane (Decane) and other aliphatic hydrocarbons; petroleum ether, petroleum spirit (Naphtha), hydrogenated petroleum spirit, solvent petroleum spirit and other petroleum solvents, etc., can be used alone or in combination of two or more. -20- (16 ) (16) 200303338 The photocurable composition of the present invention, upon request It can be added with defoaming and smoothing agents such as siloxane and acrylonitrile, and silane coupling agents to improve film adhesion. It can also add well-known oxidation inhibitors and binding components such as metal oxides during firing. Fine particles of silicon, silicon oxide, boron oxide, etc. When the photocurable composition of the present invention is in the form of a film, it can be directly placed on a substrate to form a laminate (Laminate); ), It can be coated on the substrate by appropriate methods such as screen printing, bar coating, and blade coating. For example, it can be applied to a glass substrate to form a plasma display panel ( PDP) front substrate: Secondly, in order to obtain the touch-drying property, the coated substrate is dried in a hot air circulation drying oven, a far-infrared drying oven, etc. at 60 to 120 ° C for 5 to 40 minutes to evaporate the organic solvent. Thus, a pressure-free coating film is obtained; subsequently, an electrode circuit of a predetermined pattern is formed by selecting exposure, development, and firing. In the exposure step, a negative mask with a predetermined exposure pattern (Negative Mask) can be used for contact exposure and non-contact exposure; the exposure light source can be a halogen lamp, high-pressure mercury lamp, laser light, metal halide lamp, black lamp, electrodeless lamp, etc. , The exposure is preferably 50 ~ 1000mJ / cm2. The imaging step can be performed by spraying, dipping, etc .; the imaging solution can be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, etc .; metal alkaline aqueous solutions; ethanolamine, diethanolamine, triethanolamine, etc. Amine aqueous solution; especially dilute alkali aqueous solution with a concentration of 1.5% by weight or less is most suitable. The carboxyl group containing carboxyl resin in the composition will gel, and the unhardened part (unexposed part) can be removed. Restriction; discarded developer solution -21-(17) 200303338 after development, which can be removed by washing with water or neutralization with acid. The firing step is to place the developed substrate in an air or nitrogen atmosphere at a temperature of 400 ~ 600 ° C and heat it down to form a predetermined black pattern; the heating rate at this time is preferably 20 ° C / min. [Embodiments] [Examples] The following examples and comparative examples are used to explain the present invention in detail; the examples of the present invention are not limited in the following; [synthesis example 1] The apparatus includes a thermometer, a stirrer, a dropping funnel, and reflux cooling In the flask of the device, Methyl Methacrylate and Methacrylic Acid were added in a molecular ratio of 0.76: 0.24, and then the solvent dipropylene glycol methyl ether and the catalyst azodiisobutyl were injected. Nitrile (Azobisisobutyronitrile), stirred at 80 ° C in a nitrogen atmosphere for 2 to 6 hours to obtain a resin solution; after the resin solution is cooled, the polymerization stopper Methyl Hydroquinone and the catalyst tetrabutyl bromide are added. Tetrabutyl Phosphonium Bromide, Glycidyl Methacrylate; 1 molecule of the carboxyl group of the above resin, the additional molecular ratio is 0.1 2 molecules; the additional reaction is performed at 95 ~ 105 ° C for 16 hours, Take out after cooling, it is the generated organic binder A; the resin of this organic binder A has a weight average molecular weight of about 10,000, an acid value of 59 mg KOH / g, and a double weight The combined equivalent weight was 950; the weight average molecular weight of the obtained copolymer resin was -22- (18) (18) 200303338, and PUMP LC-6AD manufactured by Shimadzu Corporation and Column Shodex KF — 804, KF — 803, KF — manufactured by Showa Denko were used. 802 three linked high-speed liquid chromatography analysis. [Synthesis Example 2] The added molecular ratio of methyl methacrylate and methacrylic acid was changed to 0.87: 0.13, and no additional reaction of glycidyl methacrylate was performed. Everything else was the same as that in Synthesis Example 1, and an organic binder B was formed. : The resin of this organic binder B has a weight average molecular weight of about 10,000 and an acid value of 74 mg KOH / g. The organic binder A or B obtained above was prepared according to the following composition ratio, stirred by a mixer, and then rolled into a paste by a three-roller machine, and the rolling conditions were 1 kg of the sample at room temperature. 3 0 minutes. As described above, the heat-resistant black pigment having a maximum particle diameter of 5 // m or less is uniformly dispersed in a solvent to form a slurry (A); in this embodiment, the maximum particle diameter is 5 / zm or less, and the average particle diameter is 0.2 micrometers of black cobalt trioxide microparticles, added to tripropylene glycol methyl ether (TPM for short) at a concentration of about 70%; the blending amount of the dispersant is 100 parts by weight to 100 parts by weight of the black microparticles; uniformly prepared by a ball mill (The concentration of the solvent in the slurry is 100 parts by weight of the slurry and 23 parts by weight of the solvent); a polymer dispersant AKM-0531 manufactured by Nippon Oil & Fats Co., Ltd. is used, and the slurry is represented by (A-1) and used The polymer dispersant DOP A -15B manufactured by Kyoeisha Chemical Co., Ltd., and the resulting slurry is represented by (A-2). The glass powder is made of 60% lead oxide (PbO), boron oxide (B203) -23- (19) (19) 200303338 20%, silicon dioxide (Si02) 15%, and aluminum oxide (Al203) It can be obtained by 5% mixing and crushing; its thermal expansion coefficient is α 70 X 10-7 / t, the glass transition point is 4 4 5 ° C, and the average particle size is 1.6 / m. [Conductive paste (Paete) for white layer electrode (upper layer)] Organic binder A 1 0 0.0 parts by weight pentaerythritol triacrylate 5 0.0 parts by weight 2-benzyl-2-dimethylamino-1- (4- Morpholine phenyl) -butane-1-one 5.0 parts by weight tripropylene glycol methyl ether 8 0.0 parts by weight silver powder 450.0 parts by weight glass powder 22.0 parts by weight phosphoric acid ester 1.0 parts by weight (20) 200303338 [Black layer electrode (lower layer) Paste] (Composition Example 1) Organic binder B Pentaerythritol triacrylate 2-benzyl-2-monomethylamino-1- (4-morpholinyl) -Dingyuan-1- 嗣 三Propylene glycol methyl ether slurry (A-1) (Composition example 2) Organic binder B Pentaerythritol triacrylate 2-methyl-1-[-4- (methylthio) phenyl] -2-morpholine propane ) -1-one 2,4-diethylthioxanthone tripropylene glycol methyl ether slurry (A — 1) 100.0 parts by weight 50.0 parts by weight 5.0 parts by weight 40.0 parts by weight 5 0.0 parts by weight 1 0 0.0 parts by weight 5 0.0 parts by weight 7.5 parts by weight 1.0 parts by weight 40.0 parts by weight 50.0 parts by weight -25 200303338 (21) (Composition Example 3) Organic binder B 1 0 0.0 parts by weight pentaerythritol triacrylate 50.0 parts by weight 2 -Methyl-1-[-4- (methylthio) phenyl] -2-morpholine propane) -1-one 7.5 parts by weight 2,4-diethylthioanthone 1. 0 parts by weight tripropylene glycol Methyl ether 4 0.0 parts by weight of slurry (A-1) 5 0.0 parts by weight of malonic acid 1.0 part by weight (Composition Example 4) Organic binder B 1 0 0.0 parts by weight pentaerythritol triacrylate 5 0.0 parts by weight 2-formyl Propyl-1-[-4 · (methylthio) phenyl] -2 · morpholine propane) -1-one 7.5 parts by weight 2,4- ^ ethylthionine 1.0 parts by weight tripropylene glycol methyl ether 40.0 Parts by weight (A-1) 50.0 parts by weight Malonic acid 1.0 parts by weight Phenothiazine 0.1 parts by weight
-26- (22) 200303338 (組成物例5) 100.0重量份 5 0.0重量份 7.5重量份 1. 〇重量份 4 0.0重量份 5 0.0重量份 1. 〇重量份 〇. 1重量份-26- (22) 200303338 (Composition Example 5) 100.0 parts by weight 5 0.0 parts by weight 7.5 parts by weight 1.0 part by weight 4 0.0 parts by weight 5 0.0 parts by weight 1.0 part by weight 0.1 part by weight
有機黏結劑B 季戊四醇三丙烯酸酯 2-甲基甲硫基）苯基]-2-嗎啉丙烷）-1-酮 2,4 一二乙基硫雜蒽酮 三丙二醇甲醚 漿狀物（A - 2) 丙二酸 吩噻嗪Organic binder B pentaerythritol triacrylate 2-methylmethylthio) phenyl] -2-morpholine propane) -1-one 2,4 diethylthioanthrone tripropylene glycol methyl ether slurry (A -2) Phenothiazine malonate
(比較組成物例1) 有機黏結劑B 100.0重量份 季戊四醇三丙烯酸酯 50.0重量份 2-苯甲基-2-二甲氨基-1--(4-嗎啉苯基）丁烷-1-酮 5.0重量份 三丙二醇甲醚 80.0重量份 四氧化三鈷 平均粒徑0.2 //m 3 5.0重量份 磷酸酯 1.0重量份 -27- (23) (23)200303338 由上述組成物例1〜5及比較組成物例1所得之各糊狀 物（Paste )，進行四氧化三鈷之最大粒徑、燒成後之線 狀、糊狀物安定性、比電阻値、層間導通、L*値等之評定 ;其評定方法如下。 〔四氧化三鈷之最大粒徑〕 上述組成所得之黑層電極（下層）用糊狀物，以範圍 爲5〜25 //m、單位爲2.5 /zm之硏磨計（Grind Gauge) 測定四氧化三鈷之最大粒徑。 〔糊狀物安定性〕 將組成物例3、4、比較組成物例1之糊狀物，各取300 公克置入密閉容器中，於40 °C下放置一個月，評定其增粘 率（％ )。 〔燒成後之線狀〕 在附著ITO (錫塗佈氧化銦）膜之玻璃基板上，將評 定用糊狀物以3 00篩目之聚酯網版全面塗佈，於熱風循環 式乾燥爐9〇°C下經20分鐘之乾燥，形成指觸乾燥性良好的 皮膜；於此皮膜上將白層電極（上層）用導電性糊狀物， 以3 00篩目之聚酯網版全面塗佈，經熱風循環式乾燥爐9〇 °C下2 0分鐘之乾燥，形成指觸乾燥性良好的白黑兩層之皮 膜；之後以鹵化金屬燈爲光源、線與空間之比=50/ 100 //m的負片罩（Negative Mask)、組成物上的積算光量爲 -28- (24) 200303338 300 mJ/平方公分，使圖案曝光；在液溫25 °C下以5重量％ 之碳酸鈉水溶液進行顯像、水洗；最後在大氣下以5 °C / 分—之昇溫速度’於550C下經30分鐘之燒成，製成圖案 燒成基板；上述比電阻評定時，同樣製成圖案燒成基板。 - 所得的燒成基板，用顯微鏡觀察其圖案，評定其線狀 有無不規則的分佈、扭曲等等。 〔比電阻値、層間導通〕 · 以圖案尺寸0.4公分X 10公分之負片罩曝光之外，與 上述相同製成試驗基板。 所得之試驗基板，以毫歐計測定燒成皮膜之電阻其次 用薩弗塗覆機測定燒成皮膜之膜厚，可算出燒成皮膜之比 電阻値。 以檢測器確認燒成皮膜之白層電極（上層）與錫塗佈 氧化銦（ITO )膜之導通情況，可導通以〇表示，不能導 通以X表示。 ® 〔L*値〕 以圖案尺寸3公分X 10公分之負片罩曝光之外，與上 述相同製成試驗基板。 · 所得之試驗基板，用色彩色差計（MINOLTA CAMERA公司製CR — 221 )依ji S — Z - 8 7 2 9之規定測定 L*a*b*表色系之値；以明度表示指數L*，做爲黑色度之指 標，予以評定；L *値愈小表示黑色度愈優異。 -29 - (25) 200303338 評定結果如表1。 組成物例__ 比較組 1 2 3 4 5 成物例1 最大粒徑（// m) 5以下 5以下 5以下 5以下 5以下 12.5 糊狀物增粘率(％) 10 5 5 10 燒成後之線狀 赃 4π£. 無 ffi 有 層間導通 〇 〇 〇 〇 〇 〇 .........—----— 比電阻値 3.2 3-3 3.2 3.2 3.2 3.4 (X ΙΟ-8 Ω cm) L*値 8.1 8.4 8.3 8.2 8.1 9.7(Comparative composition example 1) Organic binder B 100.0 parts by weight pentaerythritol triacrylate 50.0 parts by weight 2-benzyl-2-dimethylamino-1-(4-morpholinyl) butane-1-one 5.0 parts by weight tripropylene glycol methyl ether 80.0 parts by weight tricobalt tetraoxide average particle size 0.2 // m 3 5.0 parts by weight phosphate 1.0 parts by weight -27- (23) (23) 200303338 The above composition examples 1 to 5 and comparative composition examples Each obtained paste (Paste) was evaluated for the maximum particle size of tricobalt tetroxide, the linear shape after firing, the stability of the paste, the specific resistance 値, the interlayer conduction, L * 値, etc .; the evaluation method is as follows. [Maximum particle size of tricobalt tetroxide] The paste for the black layer electrode (lower layer) obtained from the above composition was measured with a grind gauge (Grind Gauge) ranging from 5 to 25 // m and a unit of 2.5 / zm. path. [Stability of Paste] Put the pastes of Composition Examples 3 and 4 and Comparative Composition Example 1 into sealed containers, and place them in a closed container at 40 ° C for one month to evaluate the viscosity increase ( %). [Line shape after firing] On a glass substrate to which an ITO (tin-coated indium oxide) film is attached, the evaluation paste is fully coated with a polyester screen having a mesh size of 300, and is heated in a hot-air circulation drying furnace After 20 minutes of drying at 90 ° C, a film with good finger-drying properties was formed. On this film, a white layer electrode (upper layer) was coated with a conductive paste and coated with a polyester screen of 300 mesh. The cloth is dried in a hot-air circulating drying oven at 90 ° C for 20 minutes to form a film with white and black layers with good finger-drying properties. The metal halide lamp is used as the light source, and the ratio of line to space is 50/100. // m negative mask (Negative Mask), the accumulated light on the composition is -28- (24) 200303338 300 mJ / cm2, the pattern is exposed; at a liquid temperature of 25 ° C, a 5% by weight sodium carbonate aqueous solution Image development and water washing; finally, firing at 550C for 30 minutes in the atmosphere at a temperature increasing rate of 5 ° C / min- to produce a pattern firing substrate; in the above specific resistance evaluation, pattern firing is also made Substrate. -Obtain the obtained fired substrate, observe the pattern with a microscope, and evaluate the linear distribution for irregular distribution, distortion, etc. [Specific resistance 値, interlayer conduction] · A test substrate was fabricated in the same manner as described above, except that the pattern was exposed with a negative size of 0.4 cm x 10 cm. The obtained test substrate was measured in milliohms for the resistance of the fired film. Secondly, the thickness of the fired film was measured with a Saffer coating machine to calculate the specific resistance 値 of the fired film. The detector is used to confirm the continuity of the white layer electrode (upper layer) of the fired film and the tin-coated indium oxide (ITO) film. The continuity is indicated by 0, and the continuity is not indicated by X. ® [L * 値] A test substrate was made in the same manner as described above, except that it was exposed with a negative cover with a pattern size of 3 cm x 10 cm. · The obtained test substrate was measured with a color difference meter (CR — 221, manufactured by Minolta Camera, Inc.) in accordance with the specifications of ji S — Z-8 7 2 9. , As an index of blackness, to be evaluated; the smaller the L * 表示, the better the blackness. -29-(25) 200303338 The evaluation results are shown in Table 1. Composition example __ Comparative group 1 2 3 4 5 Product example 1 Maximum particle size (// m) 5 or less 5 or less 5 or less 5 or less 5 or less 12.5 Paste thickening rate (%) 10 5 5 10 Firing The following linear shape is 4π £. Without ffi, there is inter-layer conduction......... ---------- Specific resistance 値 3.2 3-3 3.2 3.2 3.2 3.4 (X ΙΟ-8 Ω cm) L * 値 8.1 8.4 8.3 8.2 8.1 9.7
由表1之結果可知，本發明之光硬化性組成物’其糊 狀物中四氧化三鈷的最大粒徑很小可均勻分散。 使用本發明之光硬化性組成物，燒成後之線狀沒有不 規則分佈及扭曲之情況，可形成高精細度之電極電路。 使用本發明之光硬化性組成物，不僅能形成高精細度 的燒成圖案，其保存安定性也很優良，燒成後可形成同時 滿足充分層間導通及黑色度之黑層電極（下層）；摻合使 用有機酸以及聚合停止劑時，其保存安定性特別優異。 上述評定用糊狀物，於燒成後密著性之評定沒問題； 此密著性之評疋’是以玻璃紙粘著膠帶（Cellophane Tape )進行剝離（Peeling )試驗，評定圖案有無剝離情況。 -30- (26) (26)200303338 〔發明之功效〕 如上所述，使用本發明之光硬化性組成物，可以糊狀 化而不會引起耐熱性黑色顏料之二次凝集；保存安定性優 異，經乾燥、曝光、顯像、燒成之各步驟，也不損及對基 板之優良密著性、解像性、燒成性；燒成後能形成具有充 分黑色度的燒成皮膜。 使用本發明之光硬化性組成物，在電漿顯示面板（ PDP )的正面基板上形成白黑二層構造的母線電極，同時 獲得充分層間導電性（透明電極與母線電極白層之層間導 通）與黑色度的黑層電極電路，可提供高精細度的黑色圖 案。 本發明之光硬化性組成物，可提高糊狀物之生產性、 保存安定性優異、極薄之膜厚也能獲得充分的反差，對電 漿顯示面板之量產性及低成本化很有幫助。 【圖式簡單說明】 圖1爲面放電方式AC型電漿顯示面板（PDP )之部份 分解透視圖。 〔符號說明〕 1 :正面玻璃基板 2a，2b :表示電極 3a，3b:透明電極 4 a，4 b :母線電極 -31 - (27) (27)200303338 5 :透明誘電體層 6 :保護層 1 〇 :黑色母體組織 1 1 :背面玻璃基板 - 1 2 :隔牆 1 3 :地址電極 14a，14b，14c:螢光體膜 •From the results in Table 1, it can be seen that the maximum particle diameter of tricobalt tetraoxide in the paste of the photocurable composition of the present invention is small and can be uniformly dispersed. By using the photocurable composition of the present invention, there is no irregular distribution or distortion of the linear shape after firing, and a high-definition electrode circuit can be formed. Using the photocurable composition of the present invention can not only form a high-definition firing pattern, but also have excellent storage stability. After firing, a black layer electrode (lower layer) that satisfies sufficient interlayer conduction and blackness can be formed; When an organic acid and a polymerization stopper are blended, the storage stability is particularly excellent. The above-mentioned evaluation paste has no problem in evaluation of adhesiveness after firing. The evaluation of this adhesiveness' is a peeling test using a cellophane tape to evaluate whether the pattern is peeled. -30- (26) (26) 200303338 [Effect of the invention] As described above, the photocurable composition of the present invention can be pasted without causing secondary aggregation of the heat-resistant black pigment; excellent storage stability After drying, exposing, developing, and firing, the excellent adhesion, resolution, and firing properties to the substrate are not impaired; a firing film with sufficient blackness can be formed after firing. Using the photocurable composition of the present invention, a white-black two-layer bus electrode is formed on the front substrate of a plasma display panel (PDP), and sufficient interlayer conductivity is obtained (interlayer conduction between the transparent electrode and the white layer of the bus electrode) The black layer electrode circuit with blackness can provide a high-definition black pattern. The photocurable composition of the present invention can improve the productivity of the paste, has excellent storage stability, and can obtain sufficient contrast even with an extremely thin film thickness, which is very useful for the mass productivity and cost reduction of the plasma display panel. help. [Brief description of the drawings] FIG. 1 is an exploded perspective view of a surface discharge type AC plasma display panel (PDP). [Description of Symbols] 1: front glass substrates 2a, 2b: indicating electrodes 3a, 3b: transparent electrodes 4a, 4b: busbar electrodes-31-(27) (27) 200303338 5: transparent electrophoretic layer 6: protective layer 1 : Black matrix structure 1 1: Back glass substrate-1 2: Partition wall 1 3: Address electrodes 14a, 14b, 14c: Phosphor film
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