[最佳模式] 於下文中更詳細闡述本發明。 本發明之一實施例係關於著色感光性樹脂組合物，其包含著色劑(A)、黏合劑樹脂(B)、光可聚合化合物(C)、光聚合起始劑(D)及溶劑(E)。著色劑 (A)
在本發明之一實施例中，著色劑(A)可包含黑色顏料及(若需要)有機/無機顏料。 在黑色顏料可阻擋可見光線之情形下其無具體限制。舉例而言，可使用碳黑、苯胺黑、伸苯基黑及諸如此類。黑色顏料可單獨使用或於其連同有機/無機顏料之混合物中使用。在混合物之情形中，黑色顏料可以基於著色劑總含量之5 wt%至70 wt%之量使用。若黑色顏料之量少於5 wt%，則其可減小光學密度(O.D)。若黑色顏料之量高於70 wt%，則其可過度增加相對電容率以劣化顯示器裝置之操作。 同時，有機/無機顏料可係業內已知無機顏料及有機顏料中之至少一者。 特定而言，有機/無機顏料可係在比色指數上分類為顏料之化合物(染料及色彩師學會(The Society of Dyers and Colourists))。以實例方式，化合物可係(但不限於)以下比色指數(C.I.)數值之顏料。 C.I.顏料黃13、20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、153、154、166、173、180及185； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65及71； C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、194、208、215、216、224、242、254、255及264； C.I.顏料紫14、19、23、29、32、33、36、37及38； C.I.顏料藍15 (15:3、15:4、15:6等)、21、28、60、64及76； C.I.顏料綠7、10、15、25、36、47及58； C.I顏料棕28； C.I顏料黑1及7等。 以上顏料可單獨使用或以兩者或更多者之組合使用。 隨著色劑之量增加，形成圖案，即柱狀間隔物之部分可具有增加之角度以易於保證視角。 具體而言，在著色劑以基於組合物總固體含量之30 wt%至55 wt%、較佳35 wt%至50 wt%之量存在時，可形成有效CS角度。若著色劑之量小於30 wt%，則難以獲得高解析度之產物，柱狀間隔物難以具有期望高度水準，且所形成之CS角度過小，從而使得難以保證視角。若著色劑之量高於55 wt%，則難以充分接收光，從而不利地影響圖案形成及黏附。黏合劑樹脂 (B)
在本發明之一實施例中，黏合劑樹脂(B)習用地使得著色感光性樹脂層之未曝光區域為鹼溶性且其用作著色劑之分散劑。若本發明之著色感光性樹脂組合物中所含黏合劑樹脂(B)用作著色劑(A)之黏合劑樹脂且其於鹼性顯影液中可溶，則其無限制。 舉例而言，本發明之黏合劑樹脂(B)可係含羧基單體及可與該單體共聚之其他單體之共聚物。 含羧基單體可包括不飽和羧酸，例如不飽和單羧酸或分子中具有2個或更多個羧基之不飽和多羧酸，例如不飽和二羧酸及不飽和三羧酸。 不飽和單羧酸之實例可包括丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸及肉桂酸。不飽和二羧酸之實例可包括馬來酸、富馬酸、伊康酸、檸康酸及中康酸。不飽和多羧酸可係酸酐，例如馬來酸酐、伊康酸酐及檸康酸酐。此外，不飽和多羧酸可係其單(2-甲基丙烯醯氧基烷基)酯，例如琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯及鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯。不飽和多羧酸可係二羧基聚合物在其兩端之單(甲基)丙烯酸酯，例如ω-羧基聚己內酯單丙烯酸酯及ω-羧基聚己內酯單甲基丙烯酸酯。該等含羧基之單體可單獨使用或以兩者或更多者之組合使用。 可與含羧基單體共聚之其他單體可包括(例如)芳香族乙烯基化合物，例如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基苄基甲醚、間乙烯基苄基甲醚、對乙烯基苄基甲醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、茚等；不飽和羧酸酯，例如丙烯酸甲基酯、甲基丙烯酸甲基酯、丙烯酸乙基酯、甲基丙烯酸乙基酯、丙烯酸正丙基酯、甲基丙烯酸正丙基酯、丙烯酸異丙基酯、甲基丙烯酸異丙基酯、丙烯酸正丁基酯、甲基丙烯酸正丁基酯、丙烯酸異丁基酯、甲基丙烯酸異丁基酯、丙烯酸第二丁基酯、甲基丙烯酸第二丁基酯、丙烯酸第三丁基酯、甲基丙烯酸第三丁基酯、丙烯酸2-羥基乙基酯、甲基丙烯酸2-羥基乙基酯、丙烯酸2-羥基丙基酯、甲基丙烯酸2-羥基丙基酯、丙烯酸3-羥基丙基酯、甲基丙烯酸3-羥基丙基酯、丙烯酸2-羥基丁基酯、甲基丙烯酸2-羥基丁基酯、丙烯酸3-羥基丁基酯、甲基丙烯酸3-羥基丁基酯、丙烯酸4-羥基丁基酯、甲基丙烯酸4-羥基丁基酯、丙烯酸烯丙基酯、甲基丙烯酸烯丙基酯、丙烯酸苄基酯、甲基丙烯酸苄基酯、丙烯酸環己基酯、甲基丙烯酸環己基酯、丙烯酸苯基酯、甲基丙烯酸苯基酯、丙烯酸2-甲氧基乙基酯、甲基丙烯酸2-甲氧基乙基酯、丙烯酸2-苯氧基乙基酯、甲基丙烯酸2-苯氧基乙基酯、甲氧基二乙二醇丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三甘醇丙烯酸酯、甲氧基三甘醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸異莰基酯、甲基丙烯酸異莰基酯、丙烯酸二環戊二烯基酯、甲基丙烯酸二環戊二烯基酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸降莰基酯、丙烯酸2-羥基-3-苯氧基丙基酯、甲基丙烯酸2-羥基-3-苯氧基丙基酯、單丙烯酸甘油酯、單甲基丙烯酸甘油酯等；不飽和羧酸之胺基烷基酯，例如丙烯酸2-胺基乙基酯、甲基丙烯酸2-胺基乙基酯、丙烯酸2-二甲基胺基乙基酯、甲基丙烯酸2-二甲基胺基乙基酯、丙烯酸2-胺基丙基酯、甲基丙烯酸2-胺基丙基酯、丙烯酸2-二甲基胺基丙基酯、甲基丙烯酸2-二甲基胺基丙基酯、丙烯酸3-胺基丙基酯、甲基丙烯酸3-胺基丙基酯、丙烯酸3-二甲基胺基丙基酯、甲基丙烯酸3-二甲基胺基丙基酯等；不飽和羧酸之縮水甘油酯，例如丙烯酸縮水甘油基酯、甲基丙烯酸縮水甘油基酯等；羧酸之乙烯基酯，例如乙酸乙烯基酯、丙酸乙烯基酯、丁酸乙烯基酯、苯甲酸乙烯基酯等；不飽和醚，例如乙烯基甲醚、乙烯基乙醚、烯丙基縮水甘油醚等；氰化乙烯基化合物，例如丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亞乙烯等；不飽和醯胺，例如丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等；不飽和醯亞胺，例如馬來醯亞胺、苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等；脂肪族共軛二烯，例如1,3-丁二烯、異戊二烯、氯丁二烯等；及聚苯乙烯、聚丙烯酸甲基酯、聚甲基丙烯酸甲基酯、聚丙烯酸正丁基酯、聚甲基丙烯酸正丁基酯或聚矽氧烷之聚合物鏈末端具有單丙烯醯基或單甲基丙烯醯基之大單體。以上單體可單獨使用或以兩者或更多者之組合使用。 除以上單體之外，本發明之黏合劑樹脂(B)亦可含有至少一種選自下式(I)及(II)之可共聚化合物：其中，R1
係氫或含有或不含雜原子之C1-20
烷基或環烷基；R2
係單鍵或含有或不含雜原子之C1-20
伸烷基或伸環烷基；且R1
及R2
可各自獨立地經羥基取代。 式(I)及(II)之代表性化合物可係(甲基)丙烯酸3,4-環氧基三環癸-8-基酯及(甲基)丙烯酸3,4-環氧基三環癸烷-9-基酯。 較佳地，本發明之黏合劑樹脂(B)之酸值在50至200 (KOH mg/g)範圍內。在酸值滿足此一範圍時，鹼性顯影液中之溶解性良好，抑制殘留物之產生且可改良圖案之黏附。如本文所用術語「酸值」係指以中和1 g聚合物所需之氫氧化鉀之量(mg)之形式所量測之值且通常藉由使用氫氧化鉀水溶液滴定而獲得。 此外，黏合劑樹脂較佳具有3,000至30,000、更佳5,000至20,000之聚苯乙烯轉換之重量平均分子量(Mw
)，其係藉由凝膠滲透層析(GPC)使用四氫呋喃作為溶析溶劑來量測。在分子量滿足此範圍時，塗層膜具有經改良之硬度以提供高留膜率，未曝光區域在顯影液中之溶解性優良且解析度經改良。 黏合劑樹脂(B)之分子量分佈[重量平均分子量(Mw
)/數目平均分子量(Mn
)]可為1.5至6.0、較佳1.8至4.0。在黏合劑樹脂之分子量分佈在1.5至6.0範圍內時，可顯影性可經改良。 在本發明中，黏合劑樹脂(B)可以基於著色感光性樹脂組合物之總固體含量之5 wt%至85 wt%、較佳5 wt%至70 wt%之量存在。在黏合劑樹脂(B)之量滿足此範圍時，在顯影液中之溶解性可足夠，從而使其難以於未像素化部分之基板上產生顯影殘留物，且可防止在顯影期間經曝光區域中像素化部分之膜減小，藉此容許未像素化部分之良好滲漏。光可聚合化合物 (C)
在本發明之一實施例中，光可聚合化合物(C)係如以下將闡述之可藉由光及光聚合起始劑(D)之作用聚合之化合物，且不限於其是否含有不飽和基團且具有光敏性。可聚合化合物可係單官能單體、雙官能單體或其他多官能單體。 單官能單體之實例可包括壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙基酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙基酯及N-乙烯基吡咯啶酮。 雙官能單體之實例可包括1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚及3-甲基戊二醇二(甲基)丙烯酸酯。 多官能單體之實例可包括三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯。在該等中，可較佳使用雙官能單體或多官能單體。 光可聚合化合物(C)較佳以基於著色感光性樹脂組合物之總固體含量之5 wt%至50 wt%、更佳5 wt%至30 wt%之量使用。在光可聚合化合物(C)之量滿足此範圍時，像素之強度及光滑度可經改良。光聚合起始劑 (D)
在本發明之一實施例中，若光聚合起始劑(D)習用地用於感光性樹脂組合物中，則其無限制。舉例而言，其可係選自以下之至少一者：基於苯乙酮-、二苯甲酮-、三嗪-、噻噸酮-、肟-、安息香-及二咪唑-之化合物。 基於苯乙酮之化合物之實例可包括二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮及2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙-1-酮之寡聚物。 基於二苯甲酮之化合物之實例可包括二苯甲酮、鄰苯甲醯基苯甲酸甲基酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧基羰基)二苯甲酮及2,4,6-三甲基二苯甲酮。 基於三嗪之化合物之實例可包括2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪。 基於噻噸酮之化合物之實例可包括2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮。 基於肟之化合物之實例可包括 鄰乙氧基羰基-α-氧基亞胺基-1-苯基丙-1-酮及乙酮-1-[9-乙基-6-(2-甲基-4-四氫吡喃基氧基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟) (Irgacure OXE-02, Ciba)。 基於安息香之化合物之實例可包括安息香、安息香甲醚、安息香乙醚、安息香異丙醚及安息香異丁醚。 基於二咪唑之化合物之實例可包括2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基二咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基二咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)二咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)二咪唑及其中在4,4',5,5'位之苯基經烷氧羰基取代之咪唑。 光聚合起始劑之量控制著色感光性樹脂組合物中各組分之反應以改變欲自組合物形成之圖案之大小及厚度，藉此影響自圖案所給出之CS角度。因此，本發明之一實施例之著色感光性樹脂組合物以基於組合物總固體含量之0.8 wt%至3.5 wt%、較佳1.0 wt%至3.0 wt%之量包含光聚合起始劑。若光聚合起始劑之量小於0.8 wt%，則不易於形成圖案，從而可引起可靠性之問題且所形成CS角度之大小變得過小，使其難以保證視角。若光聚合起始劑之量高於3.5 wt%，則極難形成圖案且難以達成一致的CS角度。 另外，在本發明中，光聚合起始劑可與光起始佐劑一起使用以便增強著色感光性樹脂組合物之敏感性，藉此容許生產力改良。可用於本發明中之光起始佐劑包括至少一種選自由胺及羧酸組成之群之化合物。 本發明之一實施例之著色感光性樹脂組合物可進一步包含熱聚合起始劑以便促進圖案之形成。熱聚合起始劑之實例可包括3-甲基-2-丁烯基四亞甲基六氟銻酸鋶、三氟甲磺酸鐿、三氟甲磺酸釤、三氟甲磺酸鉺、三氟甲磺酸鏑、三氟甲磺酸鑭、甲磺酸四丁基鏻、乙基三苯基溴化鏻、苄基二甲胺、二甲基胺基甲基苯酚、三乙醇胺、N-正丁基咪唑及2-乙基-4-甲基咪唑。 此外，在熱聚合起始劑與光聚合起始劑一起使用時，其混合比率可影響本發明之效應。為改良CS角度，光聚合起始劑及熱聚合起始劑之比率在2:1至4:1範圍內係有利的。溶劑 (E)
在本發明之一實施例中，若溶劑(E)可有效分散或溶解著色感光性樹脂組合物中所含組份，則其無具體限制且可使用用於習用著色感光性樹脂組合物中之各種有機溶劑。 以實例方式，溶劑可包括乙二醇單烷基醚，例如乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚及乙二醇單丁醚；二乙二醇二烷基醚，例如二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚及二乙二醇二丁醚；乙二醇烷基醚乙酸酯，例如甲基賽珞蘇乙酸酯及乙基賽珞蘇乙酸酯；烷二醇烷基醚乙酸酯，例如丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙酸甲氧基丁基酯及乙酸甲氧基戊基酯；芳香族烴，例如苯、甲苯、二甲苯及均三甲苯；酮，例如甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮及環己酮；醇，例如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇及甘油；酯，例如3-乙氧基丙酸乙基酯及3-甲氧基丙酸甲基酯；及環酯，例如γ-丁內酯。 在該等中，沸點為100℃至200℃之有機溶劑在施加及乾燥方面較佳，更佳烷二醇烷基醚乙酸酯、酮、酯、甚至更佳丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己酮、3-乙氧基丙酸乙基酯及3-甲氧基丙酸甲基酯。以上溶劑可單獨使用或以兩者或更多者之組合使用。 溶劑(E)可較佳以基於本發明著色感光性樹脂組合物之總重量之60 wt%至90 wt%、更佳70 wt%至85 wt%之量存在。在溶劑(E)之量滿足此範圍時，可使用諸如輥式塗佈機、旋轉塗佈機、狹縫及旋轉塗佈機、狹縫塗佈機(亦稱為「模塗佈機」)及噴墨機等施加機器獲得良好施加。 本發明之一實施例之著色感光性樹脂組合物(若需要)可進一步包含添加劑(F)，例如黏著促進劑、顏料分散劑、填充劑、抗氧化劑、UV吸收劑、抗凝劑等。 黏著促進劑可提高與基板之黏附，且其可包括具有選自由羧基、甲基丙烯醯基、異氰酸酯、環氧基及其混合物組成之群之反應性取代基之矽烷偶合劑。矽烷偶合劑之實例可包括苯甲酸三甲氧基矽基酯、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸丙基酯三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷及β-(3,4-環氧基環己基)乙基三甲氧基矽烷。該等可單獨使用或以兩者或更多者之組合使用。 顏料分散劑可改良塗層性質且其可包括市售表面活性劑，例如基於矽-、氟-、酯-、陽離子、陰離子、非離子及兩性表面活性劑。該等可單獨使用或以兩者或更多者之組合使用。表面活性劑之實例可包括聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚乙二醇二酯、去水山梨醇脂肪酸酯、脂肪酸改性之聚酯、三級胺改性之聚胺基甲酸酯及聚乙烯亞胺。此外，以下為商標名：KP (ShinEtsu Chemical Industry)、POLYFLOW (Kyoeisha Chemical)、EF-TOP (Tochem Products)、MEGAFAC (Dai-Nippon Ink Chemical Industry)、Flourad (Sumitomo 3M)、Asahi Guard、Surflon (Asahi Glass)、SOLSPERSE 5000 (Lubrizol)、EFKA (EFKA Chemicals)及PB 821 (Ajinomoto)。 除以上顏料分散劑之外，亦可使用其他分散劑，例如DISPERBYK-161、DISPERBYK-163、DISPERBYK-164、DISPERBYK-2000、DISPERBYK-2001、DISPERBYK-130及DISPERBYK-109 (BYK Chemie)。 填充劑之實例可包括玻璃、二氧化矽及氧化鋁。 抗氧化劑之實例可包括2,2’-硫代雙(4-甲基-6-第三丁基酚)及2,6-二-第三丁基-4-甲基苯酚。 UV吸收劑之實例可包括2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并三唑及烷氧基二苯甲酮。 抗凝劑之實例可包括聚丙烯酸鈉。 本發明之一實施例之著色感光性樹脂組合物可藉由以下方法來製備。 舉例而言，將著色劑(A)與溶劑(E)混合，且使用珠粒磨機將混合物分散直至著色劑之平均直徑達到約0.2 μm或更小為止。若需要，則混合顏料分散劑或黏合劑樹脂(B)之一部分或全部。向經混合之分散物(亦稱為「碾磨基料」)中添加黏合劑樹脂(B)之剩餘部分、光可聚合化合物(C)、光聚合起始劑(D)及其他組份且(若需要)可進一步添加溶劑以便產生期望濃度，藉此製備著色感光性樹脂組合物。 本發明之一實施例係關於藉由使用以上所提及著色感光性樹脂組合物所形成之柱狀間隔物。本發明之一實施例之柱狀間隔物包含藉由以下所形成之著色層：將著色感光性樹脂組合物施加於基板上，隨後曝光至光且顯影以形成圖案。 在下文中，將詳細闡述使用本發明之著色感光性樹脂組合物形成圖案之方法。 使用本發明之著色感光性樹脂組合物來形成圖案之方法可藉由業內已知方法來實施，且習用地包含施加、曝光至光及移除之步驟。將本發明之著色感光性樹脂組合物施加於基板上，隨後光固化並顯影以形成欲用作柱狀間隔物之圖案。此外，所形成之圖案可用作黑矩陣、柱狀間隔物或柱狀間隔物-黑矩陣(黑色柱狀間隔物)。 在施加步驟中，將本發明之著色感光性樹脂組合物施加於基板(例如，玻璃，無限制)上或著色感光性樹脂組合物之預形成層上，隨後在80℃至120℃下預乾燥(預煅燒)以移除揮發性組份(例如溶劑)以產生光滑塗層膜。塗層膜較佳具有1 μm至5 μm之厚度。 在曝光至光之步驟中，將塗層膜使用遮罩在某些區域中經40 mJ/cm2
至150 mJ/cm2
之UV輻照，以用於獲得期望圖案之目的。為使用平行光線均勻輻照整個區域且將遮罩與基板正確地對準，較佳使用遮罩對準器或步進器。 在移除步驟中，使得經UV輻照固化之塗層膜與鹼性水溶液接觸以溶解並顯影未曝光區域，從而獲得期望圖案。在顯影後，(若需要)可在150℃至280℃之溫度下實施後乾燥(後煅燒)達10分鐘至60分鐘。 業內已知之任何顯影液可用於顯影。具體而言，可使用含有鹼性化合物及表面活性劑之水溶液。 鹼性化合物可係無機或有機鹼性化合物。無機鹼性化合物之實例可包括氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀及氨。有機鹼性化合物之實例可包括四甲基氫氧化銨、2-羥基乙基三甲基氫氧化銨、單甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺及乙醇胺。該等無機及有機鹼性化合物可單獨使用或以兩者或更多者之組合使用。可以基於顯影液總重量之0.01重量份至10重量份、較佳0.03重量份至5重量份之量含有鹼性化合物。 表面活性劑可選自由非離子、陰離子、陽離子表面活性劑及其混合物組成之群。非離子表面活性劑之實例可包括聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚及其他聚氧乙烯衍生物、氧乙烯/氧丙烯嵌段共聚物、去水山梨醇脂肪酸酯、聚氧乙烯去水山梨醇脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯及聚氧乙烯烷基胺。陰離子表面活性劑之實例可包括高碳數醇硫酸鹽，例如月桂基醇硫酸鈉及油醇硫酸鈉；烷基硫酸鹽，例如月桂基硫酸鈉及月桂基硫酸銨；烷基芳基磺酸鹽，例如十二烷基苯磺酸鈉及十二烷基萘磺酸鈉。陽離子表面活性劑之實例可包括胺及四級銨鹽，例如硬脂鹽酸胺及月桂基三甲基氯化銨。該等表面活性劑可單獨使用或以兩者或更多者之組合使用。表面活性劑較佳以基於顯影液總重量之0.01重量份至10重量份、更佳0.05重量份至8重量份、甚至更佳0.1重量份至5重量份之量存在。 如以上所提及，將著色感光性樹脂組合物經受施加、乾燥、曝光至光以供圖案化並顯影以於基板上形成圖案，且所形成之圖案可有效地用作用於顯示器裝置中之柱狀間隔物或黑色柱狀間隔物。 本發明之一實施例係關於液晶顯示器裝置，其具有以上所提及之柱狀間隔物或黑色柱狀間隔物。 本發明之液晶顯示器裝置具有以上所提及之柱狀間隔物或黑色柱狀間隔物，且包含業內已知之其他組份。亦即，可應用本發明之柱狀間隔物或黑色柱狀間隔物之任何液晶顯示器裝置均包括於本發明中。 藉由以下實例、比較實例及實驗實例來進一步說明本發明，此不應理解為限制本發明之範圍。製備實例 1 ：黏合劑樹脂之製備
準備配備有攪拌器、溫度計、回流冷凝器、滴液組套(dropping lot)及用於引入氮氣之管之燒瓶。為製備單體滴液組套，將40重量份之(甲基)丙烯酸3,4-環氧基三環癸烷-8-基酯及(甲基)丙烯酸3,4-環氧基三環癸烷-9-基酯(50:50, mol/mol)之混合物、50重量份之甲基丙烯酸甲酯、40重量份之丙烯酸、70重量份之乙烯基甲苯、4重量份之過氧化2-乙基己酸第三丁基酯及40重量份之丙二醇單甲醚乙酸酯(PGMEA)混合並攪拌。為製備鏈轉移劑滴液組套，將6重量份之正十二硫醇及24重量份之PGMEA混合並攪拌。然後，將395重量份之PGMEA添加至燒瓶中且將燒瓶之氣氛自空氣改變為氮氣，並在攪拌下將燒瓶之溫度提高至90℃。依序地，將單體及鏈轉移劑自滴液組套滴下。每一次滴液皆實施2小時，同時將溫度維持在90℃下。在1小時後，將溫度提高至110℃並將反應持續5小時以產生酸值為100 mg KOH/g之黏合劑樹脂。 該黏合劑樹脂經確認具有17,000之聚苯乙烯轉換之重量平均分子量(Mw
)，如藉由GPC所量測；及2.3之分子量分佈(Mw
/Mn
)。 在以下條件下使用GPC方法量測重量平均分子量(Mw
)及數目平均分子量(Mn
)。經量測之重量平均分子量對經量測之數目平均分子量之比率係指分子量分佈(Mw
/Mn
)。 儀器：HLC-8120GPC (Tosoh Corporation) 管柱：TSK-GELG4000HXL + TSK-GELG2000HXL (串聯) 管柱溫度：40℃ 溶析溶劑：四氫呋喃 流量：1.0 ml/min 注射體積：50 μl 檢測器：RI 試樣濃度：0.6 wt% (溶劑：四氫呋喃) 用於校正之標準品材料：TSK STANDARD POLYSTYRENE F-40、F-4、F-1、A-2500、A-500 (Tosoh Corporation)實例 1 至 11 及比較實例 1 至 4 ： 著色感光性樹脂組合物之製備
藉由將比率列示於下表1至3 (單位：wt%)中之組份混合來製備著色感光性樹脂組合物。表 1 表 2 表 3
R194：顏料紅194 (Wonil) B15:6：顏料藍15:6 (DIC) PBk7 (Carbon Black、MA-8，Mitsubishi) 黏合劑樹脂：製備實例1 光可聚合化合物：二新戊四醇六丙烯酸酯(KAYARAD DPHA, Nippon Kayaku) 光聚合起始劑：乙酮-1-[9-乙基-6-(2-甲基-4-四氫吡喃基氧基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟) (Irgacure OXE-02, Ciba) 熱聚合起始劑：VH-096 (Wako) 添加劑1：DiperBYK-163 (BYK) 添加劑2：Solsperse 5000 (Lubrizol) 溶劑：丙二醇單甲醚乙酸酯實驗實例 1 ：
實例1至11及比較實例1至4中所製備之著色感光性樹脂組合物用於製備圖案層。特定而言，使用中性清潔劑及水洗滌5 cm×5 cm大小之玻璃基板(Corning)並乾燥，將著色感光性樹脂組合物中之每一者藉助旋塗施加於其上以使得最終膜厚度變為3.5 μm，且將玻璃基板在80℃至120℃下乾燥(預煅燒) 1分鐘至2分鐘，以移除所用溶劑。隨後，將各膜使用含有g、h及i光線中之每一者之1 KW高壓汞燈在40 mJ/cm2
至150 mJ/cm2
下經受UV輻照，藉此形成圖案且藉由使用KOH (pH 10.5)之水溶液作為顯影液來移除未曝光區域。然後，在200℃至250℃下實施後煅燒達10分鐘至30分鐘。＜CS 角度之量測 ＞
將如上形成於基板上之圖案量測其CS角度。使用SNU (SIS-1200, SNU precision)藉由量測上部圖案之底部與對應於自上部圖案之底部高度達到80%之點之間之角度來實施量測，如圖1中所示。因此，根據著色感光性樹脂組合物中之著色劑之量之CS角度值顯示於表4中，根據光聚合起始劑之量之CS角度值顯示於表5中，且根據光聚合起始劑及熱聚合起始劑之比率之CS角度值顯示於表6中。表 4 表 5 表 6
如表4至6中所示，本發明實例1至11之著色感光性樹脂組合物以規定量包含著色劑及光聚合起始劑以展現相較於比較實例1至4經改良之CS角度值。此外，在其中進一步使用熱聚合起始劑之實例中，獲得更改良之CS角度。具體而言，在其中光聚合起始劑及熱聚合起始劑之比率在2:1至4:1範圍內之實例8至10中，獲得較佳結果。 儘管已顯示並闡述本發明之具體實施例，但熟習此項技術者將理解，不意欲將本發明限於較佳實施例，且熟習此項技術者將明瞭，可在不背離本發明之精神及範圍之情形下作出各種改變及修改。 因此，本發明之範圍係藉由隨附申請專利範圍及其等效內容界定。[Best Mode] The present invention is explained in more detail below. An embodiment of the present invention relates to a colored photosensitive resin composition, which includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E ). Colorant (A) In an embodiment of the present invention, the colorant (A) may include black pigments and (if necessary) organic/inorganic pigments. There is no specific limitation in the case where the black pigment can block visible light. For example, carbon black, aniline black, phenylene black, and the like can be used. The black pigment can be used alone or in a mixture of organic/inorganic pigments. In the case of a mixture, the black pigment can be used in an amount of 5 wt% to 70 wt% based on the total content of the colorant. If the amount of black pigment is less than 5 wt%, it can reduce the optical density (OD). If the amount of the black pigment is higher than 70 wt%, it may excessively increase the relative permittivity to deteriorate the operation of the display device. Meanwhile, the organic/inorganic pigment can be at least one of the known inorganic pigments and organic pigments in the industry. Specifically, organic/inorganic pigments can be compounds classified as pigments on the color index (The Society of Dyers and Colourists). By way of example, the compound may be (but not limited to) pigments with the following color index (CI) values. CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149 , 166, 168, 176, 177, 180, 192, 194, 208, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; CI Pigment Brown 28; CI Pigment Black 1 and 7 etc. The above pigments can be used alone or in combination of two or more. As the amount of the toner increases, the pattern, that is, the portion of the columnar spacer may have an increased angle to easily ensure the viewing angle. Specifically, when the colorant is present in an amount of 30 wt% to 55 wt%, preferably 35 wt% to 50 wt% based on the total solid content of the composition, an effective CS angle can be formed. If the amount of the colorant is less than 30 wt%, it is difficult to obtain a high-resolution product, it is difficult for the columnar spacer to have the desired height, and the formed CS angle is too small, making it difficult to ensure the viewing angle. If the amount of the colorant is higher than 55 wt%, it is difficult to receive light sufficiently, thereby adversely affecting pattern formation and adhesion. Binder resin (B) In an embodiment of the present invention, the binder resin (B) conventionally makes the unexposed area of the colored photosensitive resin layer alkali-soluble and it is used as a dispersant for the colorant. If the binder resin (B) contained in the colored photosensitive resin composition of the present invention is used as the binder resin of the colorant (A) and it is soluble in an alkaline developer, it is not limited. For example, the binder resin (B) of the present invention may be a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer. The carboxyl group-containing monomer may include unsaturated carboxylic acids, such as unsaturated monocarboxylic acids or unsaturated polycarboxylic acids having two or more carboxyl groups in the molecule, such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acids. Examples of unsaturated monocarboxylic acids may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids may include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, such as maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polycarboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, such as mono(2-methacryloyloxyethyl) succinate, mono(2-methacrylic acid) Acetoxyethyl) ester, phthalic acid mono(2-propenoxyethyl) ester, and phthalic acid mono(2-methacryloxyethyl) ester. Unsaturated polycarboxylic acids can be mono(meth)acrylates with dicarboxyl polymers at both ends, such as ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used alone or in combination of two or more. Other monomers that can be copolymerized with carboxyl-containing monomers can include, for example, aromatic vinyl compounds, such as styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro Styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-ethylene Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene, etc.; unsaturated carboxylic acid esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate Ester, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate , Isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2- Hydroxyethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate , 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate Hydroxybutyl ester, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, methyl Phenyl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methyl methacrylate Oxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxy Propylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, methyl Dicyclopentadienyl acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-methacrylate 3-phenoxypropyl ester, glycerol monoacrylate, glycerol monomethacrylate, etc.; amino alkyl esters of unsaturated carboxylic acids, such as 2-aminoethyl acrylate, 2-amino methacrylate Ethyl ester, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-Dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethacrylate Methylaminopropyl ester, 3-dimethylaminopropyl methacrylate, etc.; glycidyl esters of unsaturated carboxylic acids, such as glycidyl acrylate Esters, glycidyl methacrylate, etc.; vinyl esters of carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.; unsaturated ethers, such as vinyl Methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.; cyanide vinyl compounds, such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylene cyanide, etc.; unsaturated amides, such as acrylonitrile Amine, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide, etc.; unsaturated amides, such as maleic amides Imine, benzyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc.; aliphatic conjugated dienes, such as 1,3-butadiene, isoprene Diene, chloroprene, etc.; and polymerization of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate or polysiloxane Macromonomers with monoacrylic acid group or monomethacrylic acid group at the end of the chain. The above monomers can be used alone or in combination of two or more. In addition to the above monomers, the adhesive resin (B) of the present invention may also contain at least one copolymerizable compound selected from the following formulas (I) and (II): Wherein, R 1 or a hydrogen-based with or without hetero atoms C 1-20 alkyl group or cycloalkyl group; R 2 lines with or without a single bond or C 1-20 alkylene hetero atoms or cycloalkyl extension ; And R 1 and R 2 may each independently be substituted by a hydroxyl group. The representative compounds of formula (I) and (II) can be 3,4-epoxytricyclodecyl-8-yl (meth)acrylate and 3,4-epoxytricyclodecyl (meth)acrylate Alk-9-yl ester. Preferably, the acid value of the adhesive resin (B) of the present invention is in the range of 50 to 200 (KOH mg/g). When the acid value meets this range, the solubility in the alkaline developer is good, the generation of residues is suppressed, and the adhesion of the pattern can be improved. The term "acid value" as used herein refers to a value measured in the form of the amount of potassium hydroxide (mg) required to neutralize 1 g of polymer and is usually obtained by titration using an aqueous potassium hydroxide solution. In addition, the binder resin preferably has a polystyrene conversion weight average molecular weight (M w ) of 3,000 to 30,000, more preferably 5,000 to 20,000, which is obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent Measure. When the molecular weight meets this range, the coating film has an improved hardness to provide a high film retention rate, the unexposed area has excellent solubility in the developer and the resolution is improved. The molecular weight distribution [weight average molecular weight (M w )/number average molecular weight (M n )] of the binder resin (B) can be 1.5 to 6.0, preferably 1.8 to 4.0. When the molecular weight distribution of the binder resin is in the range of 1.5 to 6.0, the developability can be improved. In the present invention, the binder resin (B) may be present in an amount of 5 wt% to 85 wt%, preferably 5 wt% to 70 wt% based on the total solid content of the colored photosensitive resin composition. When the amount of the binder resin (B) satisfies this range, the solubility in the developer solution can be sufficient, making it difficult to generate development residues on the substrate of the non-pixelated portion, and can prevent the exposed area during development The film of the middle pixelated part is reduced, thereby allowing good leakage of the non-pixelated part. Photopolymerizable compound (C) In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator (D) as described below, and does not It is limited to whether it contains unsaturated groups and has photosensitivity. The polymerizable compound may be a monofunctional monomer, a difunctional monomer, or other multifunctional monomers. Examples of monofunctional monomers may include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate And N-vinylpyrrolidone. Examples of bifunctional monomers may include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate (Meth) acrylate, bis(acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate. Examples of multifunctional monomers may include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentaerythritol Penta (meth) acrylate and dineopentaerythritol hexa (meth) acrylate. Among them, a bifunctional monomer or a multifunctional monomer can be preferably used. The photopolymerizable compound (C) is preferably used in an amount of 5 wt% to 50 wt%, more preferably 5 wt% to 30 wt% based on the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerizable compound (C) satisfies this range, the intensity and smoothness of the pixel can be improved. Photopolymerization initiator (D) In one embodiment of the present invention, if the photopolymerization initiator (D) is conventionally used in the photosensitive resin composition, it is not limited. For example, it can be at least one selected from the group consisting of acetophenone-, benzophenone-, triazine-, thioxanthone-, oxime-, benzoin- and diimidazole-based compounds. Examples of acetophenone-based compounds may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1 -[4-(2-Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthienyl) -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one and 2-hydroxy-2-methyl The oligomer of -1-[4-(1-methylvinyl)phenyl]propan-1-one. Examples of benzophenone-based compounds may include benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzophenone-4'-methylbenzophenone Sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone. Examples of triazine-based compounds may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-Bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2- (3,4-Dimethoxyphenyl)vinyl]-1,3,5-triazine. Examples of thioxanthone-based compounds may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1. -Chloro-4-propoxythioxanthone. Examples of oxime-based compounds may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and ethyl ketone-1-[9-ethyl-6-(2-methyl -4-Tetrahydropyranyloxybenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE-02, Ciba). Examples of benzoin-based compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of diimidazole-based compounds may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy Phenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)diimidazole and 4,4', Imidazole in which the phenyl group at the 5,5' position is substituted with an alkoxycarbonyl group. The amount of the photopolymerization initiator controls the reaction of each component in the colored photosensitive resin composition to change the size and thickness of the pattern to be formed from the composition, thereby affecting the CS angle given from the pattern. Therefore, the colored photosensitive resin composition of an embodiment of the present invention contains the photopolymerization initiator in an amount of 0.8 wt% to 3.5 wt%, preferably 1.0 wt% to 3.0 wt% based on the total solid content of the composition. If the amount of the photopolymerization initiator is less than 0.8 wt%, it is not easy to form a pattern, which may cause reliability problems and the size of the formed CS angle becomes too small, making it difficult to ensure the viewing angle. If the amount of the photopolymerization initiator is higher than 3.5 wt%, it is extremely difficult to form a pattern and it is difficult to achieve a consistent CS angle. In addition, in the present invention, a photopolymerization initiator can be used together with a photoinitiator adjuvant in order to enhance the sensitivity of the colored photosensitive resin composition, thereby allowing productivity improvement. The photoinitiating adjuvant that can be used in the present invention includes at least one compound selected from the group consisting of amines and carboxylic acids. The colored photosensitive resin composition of an embodiment of the present invention may further include a thermal polymerization initiator to promote pattern formation. Examples of the thermal polymerization initiator may include 3-methyl-2-butenyltetramethylene hexafluoroantimonate, ytterbium triflate, samarium triflate, erbium triflate, Dysprosium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, tetrabutylphosphonium methanesulfonate, ethyltriphenylphosphonium bromide, benzyldimethylamine, dimethylaminomethylphenol, triethanolamine, N -N-butylimidazole and 2-ethyl-4-methylimidazole. In addition, when the thermal polymerization initiator and the photopolymerization initiator are used together, the mixing ratio thereof can affect the effect of the present invention. In order to improve the CS angle, it is advantageous for the ratio of the photopolymerization initiator and the thermal polymerization initiator to be in the range of 2:1 to 4:1. Solvent (E) In one embodiment of the present invention, if the solvent (E) can effectively disperse or dissolve the components contained in the colored photosensitive resin composition, it is not specifically limited and can be used for conventional colored photosensitive resins Various organic solvents in the composition. By way of example, the solvent may include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ether Ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; glycol alkyl ether acetates, such as methyl serosol Acetate and ethyl cyloxe acetate; alkyl glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy acetate Methyl butyl ester and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl Base ketones and cyclohexanone; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters, such as ethyl 3-ethoxypropionate and 3-methoxy Methyl propionate; and cyclic esters, such as γ-butyrolactone. Among them, an organic solvent with a boiling point of 100°C to 200°C is preferable in terms of application and drying, more preferably alkyl ether acetate, ketone, ester, and even more preferably propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. The above solvents can be used alone or in combination of two or more. The solvent (E) may preferably be present in an amount of 60 wt% to 90 wt%, more preferably 70 wt% to 85 wt% based on the total weight of the colored photosensitive resin composition of the present invention. When the amount of solvent (E) satisfies this range, such as roll coater, spin coater, slit and spin coater, slit coater (also called "die coater") can be used And application machines such as inkjet machines achieve good application. The colored photosensitive resin composition (if necessary) of an embodiment of the present invention may further include additives (F), such as adhesion promoters, pigment dispersants, fillers, antioxidants, UV absorbers, anticoagulants and the like. The adhesion promoter can improve the adhesion to the substrate, and it can include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryl group, an isocyanate group, an epoxy group and a mixture thereof. Examples of silane coupling agents may include trimethoxysilyl benzoate, γ-methacryloxypropyltrimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-iso Propyl cyanate triethoxysilane, γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. These can be used alone or in combination of two or more. The pigment dispersant can improve coating properties and it can include commercially available surfactants, such as based on silicon-, fluorine-, ester-, cationic, anionic, nonionic and amphoteric surfactants. These can be used alone or in combination of two or more. Examples of surfactants can include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified Polyurethane and polyethyleneimine. In addition, the following are trade names: KP (ShinEtsu Chemical Industry), POLYFLOW (Kyoeisha Chemical), EF-TOP (Tochem Products), MEGAFAC (Dai-Nippon Ink Chemical Industry), Flourad (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), SOLSPERSE 5000 (Lubrizol), EFKA (EFKA Chemicals) and PB 821 (Ajinomoto). In addition to the above pigment dispersants, other dispersants can also be used, such as DISPERBYK-161, DISPERBYK-163, DISPERBYK-164, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-130 and DISPERBYK-109 (BYK Chemie). Examples of fillers may include glass, silica, and alumina. Examples of antioxidants may include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol. Examples of UV absorbers may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. Examples of anticoagulants may include sodium polyacrylate. The colored photosensitive resin composition of an embodiment of the present invention can be prepared by the following method. For example, the colorant (A) and the solvent (E) are mixed, and the mixture is dispersed using a bead mill until the average diameter of the colorant reaches about 0.2 μm or less. If necessary, part or all of the pigment dispersant or binder resin (B) is mixed. Add the remaining part of the binder resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and other components to the mixed dispersion (also known as the "mill base") and If necessary, a solvent may be further added to produce a desired concentration, thereby preparing a colored photosensitive resin composition. One embodiment of the present invention relates to a columnar spacer formed by using the above-mentioned coloring photosensitive resin composition. The columnar spacer of an embodiment of the present invention includes a coloring layer formed by applying a colored photosensitive resin composition on a substrate, and then exposing to light and developing to form a pattern. Hereinafter, the method of forming a pattern using the colored photosensitive resin composition of the present invention will be described in detail. The method for forming a pattern using the colored photosensitive resin composition of the present invention can be implemented by a method known in the industry, and conventionally includes the steps of applying, exposing to light, and removing. The colored photosensitive resin composition of the present invention is applied on a substrate, and then photocured and developed to form a pattern to be used as a columnar spacer. In addition, the formed pattern can be used as a black matrix, a column spacer or a column spacer-black matrix (black column spacer). In the application step, the colored photosensitive resin composition of the present invention is applied on a substrate (for example, glass, without limitation) or a pre-formed layer of the colored photosensitive resin composition, and then pre-dried at 80°C to 120°C (Pre-calcined) to remove volatile components (such as solvent) to produce a smooth coating film. The coating film preferably has a thickness of 1 μm to 5 μm. In the step of exposure to light, the coating film is irradiated with 40 mJ/cm 2 to 150 mJ/cm 2 of UV in certain areas using a mask for the purpose of obtaining the desired pattern. In order to irradiate the entire area uniformly with parallel light and correctly align the mask with the substrate, a mask aligner or stepper is preferably used. In the removing step, the coating film cured by UV radiation is brought into contact with an alkaline aqueous solution to dissolve and develop unexposed areas, thereby obtaining a desired pattern. After development, post-drying (post-calcining) can be carried out at a temperature of 150°C to 280°C (if necessary) for 10 minutes to 60 minutes. Any developer known in the industry can be used for development. Specifically, an aqueous solution containing a basic compound and a surfactant can be used. The basic compound may be an inorganic or organic basic compound. Examples of inorganic alkaline compounds may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, carbonic acid Sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate and ammonia. Examples of organic basic compounds may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine and ethanolamine. These inorganic and organic basic compounds can be used alone or in a combination of two or more. The basic compound may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on the total weight of the developer. The surfactant can be selected from the group consisting of nonionic, anionic, cationic surfactants and mixtures thereof. Examples of nonionic surfactants may include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers and other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, and Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine. Examples of anionic surfactants may include high carbon number alcohol sulfates, such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates, such as sodium lauryl sulfate and ammonium lauryl sulfate; alkyl aryl sulfonates , Such as sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate. Examples of cationic surfactants may include amines and quaternary ammonium salts, such as stearyl amine hydrochloride and lauryl trimethyl ammonium chloride. These surfactants can be used alone or in combination of two or more. The surfactant is preferably present in an amount of 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 8 parts by weight, even more preferably 0.1 parts by weight to 5 parts by weight based on the total weight of the developer. As mentioned above, the colored photosensitive resin composition is subjected to application, drying, exposure to light for patterning and development to form a pattern on a substrate, and the formed pattern can be effectively used as a pillar in a display device Spacers or black columnar spacers. One embodiment of the present invention relates to a liquid crystal display device, which has the above-mentioned columnar spacer or black columnar spacer. The liquid crystal display device of the present invention has the above-mentioned columnar spacer or black columnar spacer, and contains other components known in the industry. That is, any liquid crystal display device to which the columnar spacer or the black columnar spacer of the invention can be applied is included in the invention. The following examples, comparative examples and experimental examples are used to further illustrate the present invention, which should not be construed as limiting the scope of the present invention. Preparation Example 1 : Preparation of Binder Resin A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a tube for introducing nitrogen was prepared. In order to prepare the monomer dripping set, 40 parts by weight of 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclic (meth)acrylate Mixture of decane-9-yl ester (50:50, mol/mol), 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of peroxide 2 -Tert-butyl ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) are mixed and stirred. To prepare the chain transfer agent drop set, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were mixed and stirred. Then, 395 parts by weight of PGMEA was added to the flask and the atmosphere of the flask was changed from air to nitrogen, and the temperature of the flask was increased to 90°C under stirring. Sequentially, the monomer and chain transfer agent are dropped from the dropping set. Each drop was performed for 2 hours while maintaining the temperature at 90°C. After 1 hour, the temperature was increased to 110°C and the reaction was continued for 5 hours to produce a binder resin with an acid value of 100 mg KOH/g. The binder resin was confirmed to have a polystyrene-converted weight average molecular weight (M w ) of 17,000, as measured by GPC; and a molecular weight distribution (M w /M n ) of 2.3. The GPC method was used to measure the weight average molecular weight (M w ) and number average molecular weight (M n ) under the following conditions. The ratio of the measured weight average molecular weight to the measured number average molecular weight refers to the molecular weight distribution (M w /M n ). Instrument: HLC-8120GPC (Tosoh Corporation) Column: TSK-GELG4000HXL + TSK-GELG2000HXL (in series) Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Injection volume: 50 μl Detector: RI sample Concentration: 0.6 wt% (solvent: tetrahydrofuran) Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (Tosoh Corporation) Examples 1 to 11 and comparison example 1-4: preparation of colored photosensitive resin composition by a ratio listed in table 1 to 3 (unit: wt%) of the ingredients were mixed to prepare colored photosensitive resin composition. Table 1 Table 2 Table 3 R194: Pigment Red 194 (Wonil) B15:6: Pigment Blue 15:6 (DIC) PBk7 (Carbon Black, MA-8, Mitsubishi) Binder resin: Preparation Example 1 Photopolymerizable compound: Dineopentaerythritol hexaacrylic acid Ester (KAYARAD DPHA, Nippon Kayaku) Photopolymerization initiator: ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzoyl)-9H- Carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE-02, Ciba) Thermal polymerization initiator: VH-096 (Wako) Additive 1: DiperBYK-163 (BYK) Additive 2: Solsperse 5000 (Lubrizol) Solvent: Propylene Glycol Monomethyl Ether Acetate Experimental Example 1 : The colored photosensitive resin composition prepared in Examples 1 to 11 and Comparative Examples 1 to 4 was used to prepare the pattern layer. Specifically, a glass substrate (Corning) with a size of 5 cm × 5 cm is washed with a neutral detergent and water and dried, and each of the colored photosensitive resin compositions is applied on it by spin coating to make the final film The thickness becomes 3.5 μm, and the glass substrate is dried (pre-calcined) at 80°C to 120°C for 1 minute to 2 minutes to remove the solvent used. Subsequently, each film was subjected to UV irradiation at 40 mJ/cm 2 to 150 mJ/cm 2 using a 1 KW high pressure mercury lamp containing each of g, h, and i rays, thereby forming patterns and using An aqueous solution of KOH (pH 10.5) is used as a developer to remove unexposed areas. Then, post-calcination is performed at 200°C to 250°C for 10 minutes to 30 minutes. < Measurement of CS angle > Measure the CS angle of the pattern formed on the substrate as above. Use SNU (SIS-1200, SNU precision) to measure the angle between the bottom of the upper pattern and the point corresponding to the height of 80% from the bottom of the upper pattern, as shown in Figure 1. Therefore, the CS angle value according to the amount of the coloring agent in the colored photosensitive resin composition is shown in Table 4, and the CS angle value according to the amount of the photopolymerization initiator is shown in Table 5, and according to the photopolymerization initiator The CS angle value of the ratio to the thermal polymerization initiator is shown in Table 6. Table 4 Table 5 Table 6 As shown in Tables 4 to 6, the colored photosensitive resin compositions of Examples 1 to 11 of the present invention contain a colorant and a photopolymerization initiator in prescribed amounts to exhibit improved CS angle values compared to Comparative Examples 1 to 4 . In addition, in the example in which the thermal polymerization initiator is further used, a better CS angle is obtained. Specifically, in Examples 8 to 10 in which the ratio of the photopolymerization initiator and the thermal polymerization initiator was in the range of 2:1 to 4:1, better results were obtained. Although the specific embodiments of the present invention have been shown and described, those skilled in the art will understand that it is not intended to limit the present invention to the preferred embodiments, and those skilled in the art will understand that they can do without departing from the spirit and spirit of the present invention. Various changes and modifications are made under the circumstances of the scope. Therefore, the scope of the present invention is defined by the scope of the attached patent application and its equivalent content.
