1247195 玖、發明說明（1) 【發明所屬之技術領域】 本發明係關於一種間隙體用感光性樹脂組成物，特別 是關於一種以流延塗佈方式塗佈在液晶顯示器之大型基板 上’且在塗佈後無線形殘痕（包括水平線形殘痕及垂直線形 殘痕）、無雲狀殘痕，且塗佈在大型基板上之面内塗佈均勻 性佳、邊緣膜厚偏差值低，並可以鹼性顯影液顯影之間隙 體用感光性樹脂組成物。 【先前技術】 在液晶顯示器的技藝中，為了使兩片玻璃基板保持固 定間隔，常會在兩玻璃基板間散佈玻璃珠或塑膠珠。此種 >白头方法所政佈的珠子由於是散亂分布，故經常分布於紅 (R)、綠（G)、藍（B)晝素上，以致入射光受到散射之影響， 造成液晶顯示器對比度降低。 一。。為了改善入射光受到間隙體散射之影響，造成液晶顯 不益對比度降低等問題，一般係以黃光製程來製造感光性 〇月曰間隙體。惟此方法所製造之感光性樹脂型間隙體， 在基板顯影後會形成點狀或直條狀間隙體，上述間隙體可 以佈置在R、G、B晝素以外的區域，藉此改善散射入射光 對於液晶顯示器所造成之對比度降低的問題。此外，以此 方法製備之間隙體的厚度控制性佳，兩片玻璃間隙_ ㈣易控制，精度亦大幅提高，此對高解析度液晶顯示器 (LCD)而言極為重要。 勢 但液晶顯示器在製造上，基板大型化—直是必然的趨 攸所謂尺寸為32〇mmx 400mm的第—代基板，到尺寸 1247195 玫、發明說明（4) 驗可溶性樹脂、（B)含乙烯性不飽和基之化合物、（C)光起始 劑’以及（D)溶劑所組成。 其中’該感光性樹脂組成物於25t：所測得之黏度介於 3〜18cPs、固形份含量介於10〜35重量％、且該感光性樹 脂組成物與大型基板之接觸角21度以下。 (Λ)驗可滚性樹脂 本發明之鹼可溶性樹脂（A)係指：可溶於鹼性水溶液中 的樹脂’例如：含羧酸基之樹脂、苯酚-酚醛清漆（phenol-novolac)樹脂等，較佳係由（al)不飽和羧酸單體衍生單元、 (a2)含環氧基之不飽和單體衍生單元、（a3)其他不飽和單體 衍生單元所構成之共聚物。其中，（al)不飽和羧酸單體衍生 單元之構成比例較佳為5〜50重量份。上述不飽和羧酸單體 可舉例如下：丙烯酸、甲基丙烯酸、丁烯酸、心氯丙烯酸 乙基丙烯酸及肉桂酸等不飽和一元魏酸類；馬來酸、馬 來酸酐、富馬酸、衣康酸、衣康酸酐、檸康酸、檸康酸酐 等不飽和二元羧酸（酐）類；3價以上之不飽和多價羧酸（酐） 類等等。其中所列舉者乃以丙烯酸、甲基丙烯酸為較佳。 該等含不飽和單體可單獨或混合複數種使用。 本發明（a2)含環氧基之不飽和單體衍生單元之構成比例 較佳為10〜70重量份。上述含環氧基之不飽和單體可列舉 如下：丙烯酸環氧丙酯（glycidyl acrylate)、甲基丙稀酸環^ 丙酯（glycidyl methacrylate) 、α_乙基丙烯酸環氧丙酯 (glycidyl α-ethylacrylate)、丙烯酸 3 4_ 環氧 丁酉旨（3 心 epoxybmyl acrylate)、甲基丙烯酸6,7_環氧庚酯π: 1247195 玖、發明說明（5) epoxyheptyl methacrylate) 、a-乙基丙稀酸 6,7-環氧庚酯 (6,7-epoxyheptyl α-ethylacrylate)、鄰-乙稀基苯甲基環氧丙 醚（o-vinylbenzylglycidylether)、間-乙烯基苯甲基環氧丙醚 (m-vinylbenzylglycidylether)、對-乙稀基苯甲基環氧丙醚 (p-vinylbenzylglycidylether);以上舉例乃以甲基丙稀酸環氧 丙酯、甲基丙烯酸6,7-環氧庚酯、鄰-乙烯基苯甲基環氧丙 醚、間-乙烯基苯甲基環氧丙醚以及對_乙烯基苯曱基環氧丙 鱗較佳。 而（a3)其他不飽和單體衍生單元之構成比例較佳為 0〜70重量份。其他不飽和單體可列舉如下：甲基丙烯酸甲 酯（methyl methacrylate)、甲基丙稀酸乙酯（ethyl methacrylate)、甲基丙稀酸正 丁酉旨（n-butyl methacrylate)、 甲基丙稀酸二級丁酉旨（sec-butyl methacrylate)、甲基丙烯酸 三級丁醋（t-butyl methacrylate)等甲基丙烯酸烧醋（alkyl methacrylate);丙稀酸甲酉旨（methyl acrylate)、丙烯酸異丙酯 (isopropyl acrylate)等丙稀酸烧酯（alkyl acrylate);甲基丙稀 酸環己S旨（cyclohexyl methacrylate)、甲基丙烯酸-2-甲基環 己酯（2-methylcyclohexyl methacrylate)、曱基丙稀酸二環戊 酯（dicyclopentanyl methacrylate)、甲基丙烯酸二環戊氧基 乙酉旨（dicyclopentanyloxyethyl methacrylate)、甲基丙稀酸異 冰片醋（isobornyl methacrylate)等曱基丙烯酸環狀烧酉旨 (cyclic alkyl methacrylate);丙稀酸環己 S旨（cyclohexyl acrylate)、丙稀酸-2-甲基環己 S旨（2-methylcyclohexyl acrylate)、丙稀酸二環戊 S旨（dicyclopentanyl acrylate)、丙稀 10 1247195 玖、發明說明（6) 酸二環戊氧基乙醋（dicyclopentanyloxyethyl acrylate)等丙晞 酸環狀烧酯（cyclic alkyl acrylate);馬來酸二乙醋（diethyl maleate)、富馬酸二乙酯（diethyl fumarate)、衣康酸二乙S旨 (diethyl itaconate)等二叛酸的酉旨類（dicarboxylate);甲基丙 浠酸-2-經基乙酉旨（2-hydroxy ethyl methacrylate)、甲基丙烯 酸-2-經基丙酯（2-hydroxy propyl methacrylate)等的曱基丙烯 酸經基烧酉旨（hydroxy alkyl methacrylate);或苯乙稀（styrene) 、α_曱基苯乙烯（α-methyl styrene)、間-甲基苯乙烯（m-methyl styrene)，對-甲基苯乙烯（p-methyl styrene)、對-甲 氧基苯乙稀（p-methoxy styrene)等。其中以苯乙稀、甲基丙 烯酸三級丁酯、甲基丙烯酸二環戊酯、丙烯酸二環戊氧基 乙酯、對-甲氧基苯乙烯較佳，一般可單獨或組合使用。 本發明之鹼可溶性樹脂（A)在製造時所使用的溶劑，一 般較常用者為乙二醇丙&1 (ethylene glycol monopropyl ether) 、二甘醇二曱醚（diethylene glycol dimethyl ether)、四氫!次1 南 、乙二醇甲醚（ethylene glycol monomethyl ether)、乙二醇乙 醚（ethylene glycol monoethyl ether)、乙酸甲氧基乙酉旨 (methyl cellosolve acetate)-乙酸乙氧基乙酯（ethyl cellosolve acetate)、二甘醇一甲醚（diethylene glycol monomethyl ether)、二甘醇一乙醚（diethylene glycol monoethyl ether)、二甘醇 一丁醚（diethylene glycol monobutyl ether)、丙二醇甲醚醋酸酉旨（propylene glycol methyl ether acetate)、丙二醇乙醚醋酸醋（propylene glycol ethyl ether acetate)、丙二醇丙醚醋酸酯（propylene glycol 11 1247195 玖、發明說明（7) propyl ether acetate)、甲乙S同與丙酮，其中以二甘醇二曱醚 、丙二醇甲醚醋酸酯較佳，一般可單獨或組合使用，其中 以二甘醇二甲醚、丙二醇甲醚酸醋較佳。 鹼可溶性樹脂（A)製造時所使用之起始劑，一般為自由 基形聚合起始劑，例如 2,2’-偶氮雙異丁腈（2,2’_ azobisisobutyronitrile)、2,2’-偶氮雙（2,4-二甲基戊腈）[2,2’_ azobis-(2?4-dimethylvaleronitrile)] 、2,2’-偶氮雙（4-甲氧基-2,4-二甲 基戊腈）[2,2’-azobis-(4-methoxy-2,4-dimethylvaleronitrile)]、2,2’-偶氮雙-2_ 甲基丁腈（2,2’-azobis-2-methyl butyronitrile)等偶氮（azo)化合物、過氧化二 苯甲醯（benzoylperoxide)等之過氧化合物。 本發明之驗可溶性樹脂（A)之重量平均分子量一般為 3,000 〜100,000，較佳為 4,000 〜80,000，更佳為 5,000 〜60 ，000。鹼可溶性樹脂（A)之分子量調整，可使用單一樹脂 ，亦可使用兩種或兩種以上不同分子量之樹脂併用來達成。 (B)含乙烯性不飽和基之化合物 以100重量份鹼可溶性樹脂（A)為基準，本發明含乙烯 性不飽和基之化合物（B)的使用量較佳為5-220重量份、更 佳為50-140重量份。 上述含乙烯性不飽和基之化合物（B)乃具有至少一個乙 烯性不飽和基之乙稀性不飽和化合物，其中具有一個乙稀 性不飽和基之化合物舉例而言有丙烯醯胺、（甲基）丙烯醯嗎 啉、（甲基）丙烯酸-7-氨基-3,7-二曱基辛酯、異丁氧基曱基( 12 1247195 玖、發明說明（8) 曱基）丙烯醯胺、（曱基）丙烯酸異冰片基氧乙酯、（甲基）丙稀 酸異冰片酯、（甲基）丙烯酸-2-乙基己酯、乙基二甘醇（甲基) 丙烯酸酯、第三辛基（甲基）丙烯醯胺、二丙酮（甲基）丙稀畴 胺、（甲基）丙烯酸二甲氨基酯、（甲基）丙烯酸十二烷基醋、（ 甲基）丙烯酸二環戊稀氧乙酿、（曱基）丙烯酸二環戊烯酷、 N，N-二甲基（曱基）丙稀酿胺、（甲基）丙烯酸四氯苯酯、（甲基 )丙烯酸-2-四氯苯氧基乙酯、（甲基）丙烯酸四氫糠酯、（甲基 )丙烯酸四溴苯酯、（甲基）丙烯酸_2·四溴苯氧基乙酯、（曱基 )丙烯酸-2-三氯苯氧基乙酯、（甲基）丙烯酸三溴苯酯、（甲基 )丙烯酸-2-三溴苯氧基乙酯、（甲基）丙烯酸羥乙酯、（甲基 )丙烯酸-2-羥丙酯、乙烯基己内醯胺、N_乙烯基皮酪烷酮、 (甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸五氯苯酯、（甲基） 丙烯酸五溴苯酯、聚單（曱基）丙烯酸乙二醇酯、聚單（甲基） 丙烯酸丙二醇酯、（甲基）丙烯酸冰片酯。 具有2個或2個以上乙烯性不飽和基之乙烯性不飽和 化合物可舉例如下：乙二醇二（甲基）丙烯酸酯、二（曱基）丙 烯酸二裱戊烯酯、三甘醇二丙烯酸酯、四甘醇二（曱基）丙烯 酸酯、二（2-羥乙基）異氰酸酯二（甲基）丙烯酸酯、三（2_羥乙 基）異氰酸S旨三（甲基）丙烯酸酯、己内酯改質之三（2-羥乙基） 異氛酸醋三（甲基）丙烯酸酯、三（甲基）丙烯酸三羥甲基丙酯 、％氧乙烷（以下簡稱E〇)改質之三（甲基）丙烯酸三羥甲基 丙醋、壤氧丙说（以下簡稱P0)改質之三（曱基）丙烯酸三羥 曱基丙酯、三甘醇二（甲基）丙烯酸酯、新戊二醇二（曱基）丙 烯酉文酉曰、1，4-丁二醇二（甲基）丙浠酸酯、16—己二醇二（甲基） 13 1247195 玖、發明說明（9) 丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（曱基） 丙烯酸酯、聚酯二（曱基）丙烯酸酯、聚乙二醇二（甲基）丙烯 酸酯、一季戊四醇六（甲基）丙晞酸I旨、二季戊四醇五（甲基） 丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、己内酯改質之二 季戊四醇六（曱基）丙稀酸酯、己内酯改質之二季戊四醇五（ 甲基）丙烯酸酯、四（甲基）丙烯酸二三羥甲基丙酯、EO改質 之雙盼A二（甲基）丙稀酸酯、PO改質之雙紛A二（甲基）丙 烯酸酯、E0改質之氫化雙酚a二（甲基）丙烯酸酯、p〇改質 之氫化雙紛A二（甲基）丙烯酸酯、P0改質之甘油三丙酸酉旨 、EO改質之雙酚F二（曱基）丙烯酸酯、酚醛聚縮水甘油醚( 甲基）丙烯酸酯等等。 前述乙烯性不飽和化合物中，較佳者為三丙烯酸三經 甲基丙酯、E0改質之三丙烯酸三羥甲基丙酯、p〇改質之 三丙烯酸三羥甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇 四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙稀 酸酯、二季戊四醇四丙稀酸酯、己内酯改質之二季戊四醇 六丙烯酸酯、四丙烯酸二三羥曱基丙酯、P0改質之甘油三 丙酸醋。 (C)光起始齋丨 以1〇〇重量份之含乙烯性不飽和基之化合物為基準 ’本發明光起始劑（C)之使用量較佳為0.02-60重量份、更 佳為0.5-30重量份。 上述光起始劑（C)可選自：苯乙酮系化合物 14 1247195 玖、發明說明（11) 本發明之間隙體用感光性樹脂組成物中，可進一步添 加二苯曱a同（benzophenone)系化合物為光起始劑，如嗟嘲酮 (thioxanthone) 、 2,4-二乙基 °塞 °頓 酮（2,4· diethylthioxanthanone)、°塞嘲 _ -4·石風（thioxanthone-4-sulfone)、二苯曱酮（benzophenone)、4,4-雙（二甲胺）二苯 甲 ®^[4,4’-bis(dimethylamino)benzophenone]、4,4’-雙（二乙 胺）二苯甲酮[4,4’-bis(diethylamino)benzophenone]等；其他 尚有苯偶醯（benzil)、乙酸基（acetyl)等之α-二酮（α-diketone)類，二苯乙醇顚I(benzoin)等之 g同醇（acyloin)類；二 苯乙醇酮甲醚（benzoin methylether)、二苯乙醇酮乙醚 (benzoin ethylether)、二苯乙醇酮異丙醚（benzoin isopropyl ether)等之@同醇醚（acyloin ether)類；2,4,6-三曱基苯醯二苯 基膦氧化物（2,4,6-trimethyl-benzoyl diphenylphosphineoxide) 、雙-(2,6-二甲氧基苯醯）-2,4,4-三甲基苯基膦氧化物[1^3-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide]等 之醯膦氧化物（acylphosphineoxide)類；蒽 S昆（anthraquinone) 、1，4-萘酿（l，4-naphthoquinone)等之酿（quinone)類；苯酸甲 基氯（phenacyl chloride)、三溴曱基苯石風（tribromomethyl phenylsulfone)、三（三氯曱基）-3-三 口秦[tris(trichloromethyl)_ s-triazine]等之鹵化物；二-第三丁基過氧化物（di-tertbutylperoxide)等之過氧化物。其中以二苯曱酮 (benzophenone)系化合物最佳，尤以4,4’-雙（二乙胺）二苯甲 酮效果最佳。 本發明之間隙體用感光性樹脂組成物係由：鹼可溶性 16 1247195 玖、發明說明（12) 樹脂（A)、含乙稀性不飽和基之化合物（B)、及光起始劑（C) 均勻混合調製。通常本發明之間隙體用感光性樹脂組成物 須加入適當之有機溶劑予以溶解，使成溶液狀態。 (D)溶劑 本發明所使用之〉谷劑需遥用較易和其他有機成分互相 溶解之有機溶劑。該溶劑於25 〇c下飽和蒸氣壓較佳係 4.5mmHg以下，更佳為4.0mmHg以下，最佳為3 8mmHg 以下。若溶劑（D)於25°C下飽和蒸氣壓為4 5mrnHg以下時 ’間隙體用感光性樹脂組成物塗佈於大型基板後，較不易 生成雲狀殘痕。 在測定飽和蒸氣壓時，可使用一般常用的許多方法， 以本發明而言，以蒸散法（氣體流通法）較能正確測定。 以100重量份鹼可溶性樹脂（A)為基準，本發明之間隙 體用感光性樹脂組成物之溶劑（D)的使用量較佳為500-2500 重量份、更佳為550-2000重量份。 上述溶劑（D)可選自：醚類系或酯類系，其中醚類乃例 如：乙二醇丙醚（ethylene glycol monopropyl ether)、二甘醇 二甲&I (diethylene glycol dimethyl ether)、乙二醇曱醚 (ethylene glycol monomethyl ether)、乙二醇乙醚（ethylene glycol monoethyl ether)、二甘醇曱 (diethylene glycol monomethyl ether)、二甘醇乙醚（diethylene glycol monoethyl ether)、二甘醇丁醚（diethylene glycol monobutyl ether)。而 酯類系乃例如：乙酸甲氧基乙酯（methyl cellosolve acetate) 17 1247195 玖、發明說明（13 ) 、乙酸乙氧基乙S旨（ethyl cellosolve acetate)、丙二醇甲醚醋酸酯 (propylene glycol methyl ether acetate)"丙二醇乙 醋酸酉旨 (propylene glycol ethyl ether acetate)、丙二醇丙鱗醋酸酉旨（propylene glycol propyl ether acetate)。前述溶劑可一種單獨使用或併用2 種或2種以上。前述溶劑中，以二甘醇二曱、丙二醇甲 醚醋酸酯較佳。 又本發明為了提高塗佈性，可伴隨使用界面活性劑。 相對於100重量份之鹼可溶性樹脂（A)，上述界面活性劑之 使用量一般係介於〇〜6重量份，而以0〜3重量份為佳。 該界面活性劑之具體例有：聚環氧乙烷十二烷基醚、 聚環氧乙烷硬脂醯醚、聚環氧乙烷油醚等聚環氧乙烷烷基 醚類；聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚等聚環 氧乙烷烷基苯醚類；聚乙二醇二月桂酸酯、聚乙二醇二硬 脂酸酯等聚乙二醇二酯類；山梨醣醇酐脂肪酸酯類；脂肪 酸改質之聚酯類；3級胺改質之聚胺基甲酸酯類；以下為商 品名：KP(信越化學工業製）、SF-8427(Toray Dow Corning Silicon製）、普利弗隆（Polyflow，共榮社油脂化學工業製） 、愛夫多普[F-Top，得克姆普洛大庫茲製（T〇chem Products Co.，Ltd·)]、美卡夫克(Megafac ’大日本印墨化學工業製）、 弗洛多（Fluorade，住友3M製）、阿魏卡多（Asahi Guard)、 薩弗隆（Siirflon，旭硝子製）等等。此等界面活性劑可單獨或 混合複數種以上使用。 此外，在必要時，本發明之組成物中可調合例如：填 充劑、本發明鹼可溶性樹脂（A)以外之高分子化合物、密著 18 1247195 玖、發明說明（14) 促進劑、抗氧化劑、紫外線吸收劑、防凝集劑、架橋劑、 稀釋劑等。使用量一般係〇〜1〇重量份，以〇〜6重量份較佳 ，而以0〜3重量份為最佳。 上述添加物之具體例有··玻璃、鋁之填充劑；聚乙烯 醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟丙烯酸烷酯等之 鹼可溶性樹脂（A)以外的高分子化合物；乙烯基三甲氧基矽 烷、乙烯基三乙氧基矽烷、乙烯基三（2-甲氧乙氧基）矽烷、 N (2-氨基乙基）_3_氨基丙基甲基二甲氧基石夕烧、N_(2_氨基 乙基）-3-氨基丙基三曱氧基矽烷、3_氨基丙基三乙氧基矽烷 、3-環氧丙醇丙基三曱氧基矽烷、弘環氧丙醇丙基甲基二甲 氧基矽烷、2-(3,4-環氧環己基）乙基三甲氧基矽烷、弘氯丙 基甲基二甲氧基矽烷、3_氯丙基三甲氧基矽烷、3_甲基丙烯 氧基丙基二曱氧基矽烷、3_硫醇基丙基三甲氧基矽烷等密 著促進劑·，2,2-硫代雙（4-甲基_6+丁基苯酚）、2，卜二+ 丁基 苯酚等之抗氧化劑；2-(3 +丁基-5-甲基·2-羥基苯基)-5_氯苯 基豐氮、烷氧基苯酮等紫外線吸收劑；及聚丙烯酸鈉等防 竑集劑；商品名1031S(油化Shell製）等之環氧系之化合物 或树月曰之架橋劑，商品名RE8〇l、RE8〇2(帝國Ink製）之稀 釋劑。 本發明之間隙體用感光性樹脂組成物，其黏度於室溫 下乾圍約在3〜18cps，較佳為4〜16cps，最佳為5〜14 cps。若黏 度小於3cpS，則塗佈後易產生雲狀殘痕，且面内塗佈均勻 f生不佳。若黏度大於18cps，則塗佈後易產生線形殘痕。上 述黏度之測定方式，係在25°C恆溫下，以β型旋轉黏度計 19 1247195 玖、發明說明（16) 佈方式塗布。塗佈後，以預烤（prebake)方式將溶劑去除而 形成感光性組成物層。預烤之條件，依各成分之種類、配 合比率而異’通常係在70〜90 t溫度下進行i分鐘_15分鐘 。預烤後’該⑤光性樹脂組成物層介於所指定之光罩㈣叫 間曝光’於23±2 t溫度下浸潰於顯影液％秒〜5分鐘進行 頒影’不要之部分除去而形成圖案。此時曝光使用之光線 以：g線、h線、i線等之紫外線為佳，而紫外線裝置可為( 超）高水銀燈及金屬函素燈。 上述大型基板舉例而言，有用於液晶顯示裝置等之無 鹼玻璃、鈉鈣玻璃、硬質玻璃（派勒斯玻璃）、石英玻璃及於 此等玻璃上附著透明導電膜者，或用於固體攝影裝置等之 光電變換裝置基板(㈣基板博等。此等基板—般係形成隔 離各晝素之黑色脫膜。本發明所指之大型基板係指基板之 至少-邊長為8GG釐米& _釐米以上，較佳為刪釐米 或1000釐米以上。 又前述顯影液係使用如：氫氧化鈉、氫氧化钾、碳酸 納:碳酸氫鈉、碳酸鉀、碳酸氣卸、石夕酸納、甲基石夕酸納 、風水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四曱銨、 虱氧化四乙銨、膽鹼、吡咯、哌啶、U8_二氮雜二環_ (5,4,0)-7-十一烯等鹼性化合物，顯影液之濃度在 〇.〇〇卜1〇wt%，較佳為0.01〜lwt%所構成之鹼性水溶液。且 使用此等驗性水溶液所構成之顯影液時，一般係於顯像後 再以水洗淨。其次，將壓縮空氣或壓氣將圖案風乾後 ’再以熱板或棋箱等加熱裝置作最後之加熱處理。所定加 21 1247195 玖、發明說明（19) ’冷卻後再以天平秤重’以重量差計算其固形份。單位 為重量％。 (3)接觸角：將間隙體用感光性樹腊組成物滴在大型玻璃基 板上30秒後’再以接觸角古十 司製CA-W15G型接觸角\)(協Γ界面科學股份有限公 要觸角计）、Sessile Drop Method 之 測定方式，測定角度。單位為度。 ⑷飽和蒸氣屋··使用蒸散法（氣體流通法）測定之，測定 溫度為25°C。單位為mmHg。 ：以流延塗佈方式將間隙體用感光性樹脂組成 物塗佈在蘭mmx 960mm之大型玻璃基板上， 85c溫度下預烤5分鐘’形成預烤塗膜，在納燈下，目 視檢查是否有“塗佈線形殘痕，，之現象。線形殘痕可分為 水平線形殘痕及垂直線形殘痕，其形狀如圖一所示。 〇··無線形殘痕 △ •稍微有線形殘痕，但不明顯 X:有線形殘痕 雲狀殘痕：以流延塗佈方式將間隙體用感光性樹脂組成 物塗佈在llOOrmnx 96Gmm之大型玻璃基板上然後在 85C’皿度下預烤5分鐘’形成預烤塗膜，在鈉燈下，目 視檢查是否有“塗佈雲狀殘痕,，之現象。其形狀如圖—所 0 :無雲狀殘痕 稍微有雲狀殘痕，但不明顯 X:有雲狀殘痕 24 1247195 玖、發明說明（20) 模頭相對於基板的移動方向 雲狀殘痕 1100 mm1247195 发明Invention Description (1) The present invention relates to a photosensitive resin composition for a spacer, and more particularly to a method of coating a large substrate of a liquid crystal display by a cast coating method. After coating, the wireless residual marks (including horizontal linear residual marks and vertical linear residual marks) and cloudless residual marks, and the in-plane coating uniformity coated on the large substrate is good, and the edge film thickness deviation value is low. The photosensitive resin composition for the interstitial body which can be developed by the alkaline developing solution. [Prior Art] In the art of liquid crystal display, in order to keep two glass substrates at a fixed interval, glass beads or plastic beads are often spread between the two glass substrates. Because of the scattered distribution, the beads of the whitehead method are often distributed on red (R), green (G), and blue (B) alizarin, so that the incident light is affected by scattering, resulting in a liquid crystal display. The contrast is reduced. One. . In order to improve the influence of the incident light on the scattering of the interstitial body, causing the contrast of the liquid crystal to be lowered, the photosensitive yttrium intercalated body is generally manufactured by a yellow light process. However, the photosensitive resin type spacer manufactured by this method forms a dot-like or straight strip-shaped spacer after the substrate is developed, and the spacer can be disposed in a region other than R, G, and B, thereby improving scattering incidence. The problem of reduced contrast caused by light on liquid crystal displays. In addition, the thickness of the spacer body prepared by this method is excellent, and the two glass gaps _ (four) are easy to control and the precision is also greatly improved, which is extremely important for a high-resolution liquid crystal display (LCD). However, the liquid crystal display is manufactured, and the substrate is large-sized. It is inevitable that the so-called size is 32〇mmx 400mm, the first generation substrate, the size is 1247195, the invention description (4) the soluble resin, (B) the ethylene The composition of the unsaturated group, (C) photoinitiator' and (D) solvent. Wherein the photosensitive resin composition was at 25t: the measured viscosity was 3 to 18 cPs, the solid content was 10 to 35 wt%, and the contact angle of the photosensitive resin composition with the large substrate was 21 or less. (Λ) Examination of Rollable Resin The alkali-soluble resin (A) of the present invention means a resin which is soluble in an alkaline aqueous solution, for example, a carboxylic acid group-containing resin, a phenol-novolac resin, or the like. Preferably, it is a copolymer composed of (al) unsaturated carboxylic acid monomer-derived unit, (a2) epoxy group-containing unsaturated monomer-derived unit, and (a3) other unsaturated monomer-derived unit. The composition ratio of the (al) unsaturated carboxylic acid monomer-derived unit is preferably 5 to 50 parts by weight. The above unsaturated carboxylic acid monomer can be exemplified as follows: unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, cardiochloroacrylic acid ethyl acrylate and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, clothing Unsaturated dicarboxylic acids (anhydrides) such as benic acid, itaconic anhydride, citraconic acid, citraconic anhydride; unsaturated polyvalent carboxylic acids (anhydrides) having a valence of three or more, and the like. Among them, acrylic acid and methacrylic acid are preferred. These unsaturated monomers may be used singly or in combination of plural kinds. The composition ratio of the epoxy group-containing unsaturated monomer-derived unit of the invention (a2) is preferably from 10 to 70 parts by weight. The above epoxy group-containing unsaturated monomer may be exemplified by glycidyl acrylate, glycidyl methacrylate, and α-glycidyl α. -ethylacrylate), acrylic acid 3 4_ epoxy butyl acrylate, methacrylic acid 6,7-epoxyheptyl π: 1247195 玖, invention description (5) epoxyheptyl methacrylate), a-ethyl acrylate 6,7-epoxyheptyl α-ethylacrylate, o-vinylbenzylglycidylether, m-vinylbenzyl glycidyl ether (m -vinylbenzylglycidylether), p-vinylbenzylglycidylether; the above examples are glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o- Vinylbenzyl epoxypropyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzoquinone epoxide are preferred. Further, the composition ratio of (a3) other unsaturated monomer-derived units is preferably from 0 to 70 parts by weight. Other unsaturated monomers can be listed as follows: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl propylene Acid methacrylate, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methyl acrylate, isopropyl methacrylate An alkyl acrylate such as isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, fluorenyl Dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, etc. Alkyl methacrylate); cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopenta acrylate Nyl acrylate), propylene 10 1247195 玖, description of the invention (6) cycloalkyl acrylate (dicyclopentanyloxyethyl acrylate) and other cyclic alkyl acrylate; diethyl maleate ), diethyl fumarate, diethyl itaconate, etc., dicarboxylate; methacrylic acid-2-transformyl (2) -hydroxy ethyl methacrylate), hydroxyalkyl methacrylate such as 2-hydroxy propyl methacrylate; or styrene, α_曱--methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene Wait. Among them, styrene, butyl methacrylate, dicyclopentanyl methacrylate, dicyclopentyloxyethyl acrylate, and p-methoxystyrene are preferred, and they may be used singly or in combination. The solvent used in the production of the alkali-soluble resin (A) of the present invention is generally more commonly used as ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, and four. Hydrogen! 1 South, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate - ethyl cellosolve Acetate), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate Methyl ether acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate (propylene glycol 11 1247195 玖, invention description (7) propyl ether acetate), methyl ethane S and acetone, of which diethylene glycol Dimethyl ether and propylene glycol methyl ether acetate are preferred, and can be used singly or in combination, in which diglyme is used. The propylene glycol methyl ether vinegar is preferred. The initiator used in the manufacture of the alkali-soluble resin (A) is generally a radical-type polymerization initiator such as 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile), 2,2' -Azobis(2,4-dimethylvaleronitrile)[2,2'_ azobis-(2?4-dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4 -2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2_methylbutyronitrile (2,2'-azobis- A peroxy compound such as an azo compound such as 2-methyl butyronitrile or a benzoylperoxide. The weight average molecular weight of the soluble resin (A) of the present invention is generally from 3,000 to 100,000, preferably from 4,000 to 80,000, more preferably from 5,000 to 60,000. The molecular weight of the alkali-soluble resin (A) can be adjusted by using a single resin or by using two or more resins of different molecular weights. (B) Compound Containing Ethylenic Unsaturated Group The compound (B) containing the ethylenically unsaturated group of the present invention is preferably used in an amount of 5 to 220 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Preferably it is 50-140 parts by weight. The above ethylenically unsaturated group-containing compound (B) is an ethylenically unsaturated compound having at least one ethylenically unsaturated group, wherein a compound having an ethylenically unsaturated group is exemplified by acrylamide, (A) Acetyl morpholine, (meth)acrylic acid-7-amino-3,7-dimercaptooctyl ester, isobutoxy fluorenyl (12 1247195 玖, invention description (8) fluorenyl) acrylamide, (fluorenyl) isobornyl oxyethyl acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diglycol (meth) acrylate, third Octyl (meth) acrylamide, diacetone (meth) propyl domain amine, dimethyl amino (meth) acrylate, dodecyl methacrylate (meth) acrylate, dicyclopentyl (meth) acrylate Dilute oxygen, (cyclo)acrylic acid dicyclopentene, N,N-dimethyl(fluorenyl) acrylamide, tetrachlorophenyl (meth)acrylate, (meth)acrylic acid-2- Tetrachlorophenoxyethyl ester, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2·tetrabromobenzene (meth)acrylate Oxyethyl ester, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, (methyl) Hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinyl tyrosone, phenoxyethyl (meth) acrylate, (meth) acrylate Pentachlorophenyl ester, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, borneol (meth)acrylate. The ethylenically unsaturated compound having 2 or more ethylenically unsaturated groups can be exemplified as follows: ethylene glycol di(meth)acrylate, dinonylpentenyl bis(decyl)acrylate, triethylene glycol diacrylate Ester, tetraethylene glycol bis(indenyl) acrylate, bis(2-hydroxyethyl)isocyanate di(meth) acrylate, tris(2-hydroxyethyl)isocyanate S tris(meth)acrylate , caprolactone modified tris(2-hydroxyethyl) isocyanate tri(meth)acrylate, tris(meth)acrylic acid trimethylolpropyl ester, % oxyethane (hereinafter referred to as E〇) Modified tris(meth)acrylic acid trimethylol propyl vinegar, oxypropyl propylene (hereinafter referred to as P0) modified tris(mercapto)acrylic acid trishydroxypropyl propyl ester, triethylene glycol di(meth)acrylic acid Ester, neopentyl glycol di(indenyl) propylene hydrazine, 1,4-butanediol di(methyl)propionate, 16-hexanediol di(methyl) 13 1247195 玖, description of the invention (9) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetrakis(yl) acrylate, polyester di(decyl) acrylate Polyethylene glycol di(meth)acrylate, pentaerythritol hexa(methyl)propionic acid I, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra(meth) acrylate, caprolactone modification Dipentaerythritol hexa(indenyl) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, tetrakis (meth) acrylate ditrimethylol propyl ester, EO modified double expectation A Di(meth)acrylic acid ester, PO modified double A (di) (meth) acrylate, E0 modified hydrogenated bisphenol a di(meth) acrylate, p 〇 modified hydrogenated double A Di(meth)acrylate, P0 modified glycerol propionate, EO modified bisphenol F bis(indenyl) acrylate, phenolic polyglycidyl ether (meth) acrylate, and the like. Among the above ethylenically unsaturated compounds, preferred are trimethyl methyl acrylate, E0 modified trimethylol propyl triacrylate, p 〇 modified trimethylol propyl triacrylate, and pentaerythritol. Acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetrapropyl acrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrihydroxy decyl acrylate Ester, P0 modified glycerol triacetate. (C) Photoinitiation is preferably based on 1 part by weight of the ethylenically unsaturated group-containing compound. The photoinitiator (C) of the present invention is preferably used in an amount of 0.02 to 60 parts by weight, more preferably 0.5 to 30 parts by weight. The photoinitiator (C) may be selected from the group consisting of: acetophenone-based compound 14 1247195 玖, and the invention (11) The photosensitive resin composition for a spacer of the present invention may further contain benzophenone. The compound is a photoinitiator, such as thioxanthone, 2,4-diethyl thiophene ketone (2,4·diethylthioxanthanone), ° 嘲 _ _ 4 · stone wind (thioxanthone -4- Sulfone), benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamine) Benzene [4,4'-bis(diethylamino)benzophenone], etc.; other α-diketones such as benzil, acetoxy, etc., diphenylethanol oxime I (benzoin) and the like acyloin; benzoin methylether, benzoin ethylether, benzoin isopropyl ether, etc. @ Acylloether ether; 2,4,6-trimethyl-benzoyl diphenylphosphine oxide, bis-(2,6-di Neodymium phosphine oxide, such as oxybenzoquinone)-2,4,4-trimethoxy-benzoyl-2,4,4-trimethylbenzyl phosphineoxide (acylphosphineoxide); 蒽S Kun (anthraquinone), 1,4-naphthoquinone (quinone), phenacyl chloride, tribromopyrene stone (tribromomethyl phenylsulfone), tris(trichloromethyl)-3-trimethyl (trichloromethyl) s-triazine, etc.; per-oxidation of di-tertbutylperoxide Things. Among them, the benzophenone-based compound is the best, and the 4,4'-bis(diethylamine)benzophenone is the best. The photosensitive resin composition for a spacer of the present invention is composed of: alkali soluble 16 1247195 玖, invention description (12) resin (A), ethylenically unsaturated group-containing compound (B), and photoinitiator (C) ) Evenly mix modulation. In general, the photosensitive resin composition for a spacer of the present invention is dissolved in a suitable organic solvent to be in a solution state. (D) Solvents The granules used in the present invention require an organic solvent which is relatively easy to dissolve with other organic components. The saturated vapor pressure of the solvent at 25 〇c is preferably 4.5 mmHg or less, more preferably 4.0 mmHg or less, and most preferably 3 8 mmHg or less. When the solvent (D) has a saturated vapor pressure of not more than 45 mrnHg at 25 ° C, the photosensitive resin composition for a spacer is applied to a large substrate, and it is difficult to form a cloud-like residue. In the measurement of the saturated vapor pressure, many methods which are generally used can be used, and in the case of the present invention, the evapotranspiration method (gas flow method) can be accurately measured. The solvent (D) used in the photosensitive resin composition for a spacer of the present invention is preferably used in an amount of from 500 to 2500 parts by weight, more preferably from 550 to 2000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). The solvent (D) may be selected from the group consisting of ethers or esters, wherein the ethers are, for example, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether (diethylene glycol monobutyl ether). The ester type is, for example, methyl cellosolve acetate 17 1247195 玖, invention description (13), ethyl cellosolve acetate, propylene glycol methyl acetate (propylene glycol methyl ether) Ether acetate) "propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate. These solvents may be used alone or in combination of two or more. Among the above solvents, diethylene glycol dioxime and propylene glycol methyl ether acetate are preferred. Further, in order to improve the coatability, the present invention can be used in conjunction with a surfactant. The surfactant is generally used in an amount of from 〇 to 6 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and preferably from 0 to 3 parts by weight. Specific examples of the surfactant include polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ethers such as oxyethylene octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate, polyethylene glycol distearate, etc. Glycol diesters; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; the following trade names: KP (Shin-Etsu Chemical Co., Ltd.), SF- 8427 (manufactured by Toray Dow Corning Silicon), Plyflulon (Polyflow, Co., Ltd.), Evdop [F-Top, Dekamp Co., Ltd. (T〇chem Products Co.) ,Ltd·)], Mekafac (made by Dainippon Chemical Industry), Frodo (Sumitomo 3M), Asahi Guard, Siirflon, Asahi Glass )and many more. These surfactants may be used singly or in combination of plural kinds or more. Further, when necessary, the composition of the present invention may be adjusted, for example, a filler, a polymer compound other than the alkali-soluble resin (A) of the present invention, a coating of 18 1247195 玖, an invention (14) accelerator, an antioxidant, UV absorbers, anti-agglomerating agents, bridging agents, thinners, etc. The amount used is generally 〇1 to 1 part by weight, preferably 〇6 parts by weight, and most preferably 0 to 3 parts by weight. Specific examples of the above additives include glass and aluminum fillers; polymer compounds other than alkali-soluble resins (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. ; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxyethoxy) decane, N (2-aminoethyl) 3 - aminopropyl methyl dimethoxy Burning, N_(2_aminoethyl)-3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxy decane, Hong epoxy Propyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, chloropropyl methyl dimethoxy decane, 3-chloropropyl trimethoxy Adhesion promoter such as decane, 3-methacryloxypropyl dimethoxy decane, 3-thiol propyl trimethoxy decane, 2,2-thiobis(4-methyl _6 Antioxidant such as +butylphenol), 2, di-dibutylphenol; 2-(3 + butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl nitrogen, alkoxy UV absorbers such as benzophenone; and sodium polyacrylate A sputum-collecting agent; an epoxy-based compound such as 1031S (manufactured by Oiled Shell) or a bridging agent of Shuyueyu, and a diluent of the trade name RE8〇l, RE8〇2 (manufactured by Imperial Ink). The photosensitive resin composition for a spacer of the present invention has a viscosity of about 3 to 18 cps at a room temperature, preferably 4 to 16 cps, preferably 5 to 14 cps. If the viscosity is less than 3 cps, cloud-like residuals are likely to occur after coating, and the in-plane coating is uniform and poor. If the viscosity is more than 18 cps, linear defects are likely to occur after coating. The above-mentioned viscosity measurement method is applied at a constant temperature of 25 ° C by a β-type rotational viscosity meter 19 1247195 玖 and a description of the invention (16). After coating, the solvent was removed by a prebake method to form a photosensitive composition layer. The conditions for pre-baking vary depending on the type of the components and the compounding ratio, and are usually carried out at a temperature of 70 to 90 t for 1 minute to 15 minutes. After pre-baking, the 5 light-sensitive resin composition layer is interposed between the specified photomask (4) and the exposure is performed at a temperature of 23±2 t. The developer is immersed in the developer for 1 second to 5 minutes for the filming. Form a pattern. At this time, the light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-mercury lamp and a metal element lamp. Examples of the large-sized substrate include an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, and a transparent conductive film attached to the glass, or a solid-state film. a photoelectric conversion device substrate such as a device ((4) substrate, etc. These substrates generally form a black release film for isolating each halogen. The large substrate referred to in the present invention means that at least a side length of the substrate is 8 GG cm & _ More than a centimeter, preferably cm or more than 1000 cm. Further, the developer is used such as: sodium hydroxide, potassium hydroxide, sodium carbonate: sodium hydrogencarbonate, potassium carbonate, carbonic acid gas, sodium sulphate, methyl Sodium sulphate, feng shui, ethylamine, diethylamine, dimethylethanolamine, tetraammonium hydroxide, tetraethylammonium hydride, choline, pyrrole, piperidine, U8_diazabicyclo_ (5, a basic compound such as 4,0)-7-undecene, an aqueous solution having a concentration of the developer of 1% by weight, preferably 0.01 to 1% by weight, and using such an assay. In the case of a developer composed of an aqueous solution, it is usually washed with water after development. After the air or air is compressed, the pattern is air-dried, and then the heating device such as a hot plate or a chess box is used for the final heat treatment. The addition is 21 1247195 玖, the invention description (19) 'after cooling, the balance is weighed' with the difference in weight Calculate the solid content. The unit is % by weight. (3) Contact angle: After the gap body is dripped on the large glass substrate with the photosensitive tree wax composition for 30 seconds, the contact angle of the CA-W15G type contact angle is also adopted. \) (Xieyi Interface Science Co., Ltd.) The method of measuring the Sessile Drop Method and measuring the angle. The unit is degrees. (4) Saturated vapor house··Measured by the evapotranspiration method (gas flow method), the measurement temperature was 25 °C. The unit is mmHg. : Applying the photosensitive resin composition of the gap body to a large glass substrate of lan mmx 960 mm by a cast coating method, pre-baking for 5 minutes at 85 c' to form a pre-baked coating film, and visually checking whether it is under a nano lamp. There is a phenomenon of "coating linear residual marks, and the linear residual marks can be divided into horizontal linear residuals and vertical linear residuals, and their shapes are as shown in Fig. 1. 〇··Wireless residual △ • slightly linear residuals However, it is not obvious that X: a linear residue of a linear shape: a photosensitive resin composition is coated on a large glass substrate of llOOrmnx 96Gmm by a cast coating method and then pre-baked at 85 C'. Minutes 'formed a pre-baked film, and under the sodium lamp, visually check whether there is a phenomenon of "coating cloud-like residue." Its shape is as shown in the figure - 0: no cloud-like residuals have a slight cloud-like residue, but not obvious X: there are cloud-like residuals 24 1247195 玖, invention description (20) the movement direction of the die relative to the substrate is cloud-like Trace 1100 mm
開始端 圖一 (7)面内塗佈均勻性：以流延塗佈方式將間隙體用感光性樹 脂組成物塗佈在llOOmmx 960mm之大型玻璃基板上， 然後在85°C溫度下預烤5分鐘，形成預烤塗膜，以 Tencor a-step觸針式測定儀量測膜厚，測定點如下列圖 二所示。 1100mm 流延塗佈方向 y 開始端 OmmStarting point Figure 1 (7) In-plane coating uniformity: The gap body is coated with a photosensitive resin composition on a large glass substrate of llOOmmx 960mm by a cast coating method, and then pre-baked at a temperature of 85 ° C. Minutes, a pre-baked film was formed, and the film thickness was measured with a Tencor a-step stylus meter. The measurement points are shown in Figure 2 below. 1100mm cast coating direction y start end Omm
末端 Omm 960mm 圖二 25End Omm 960mm Figure 2 25