201111910 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種在彩色液晶顯示裝置或彩色攝像 元件等所使用的彩色濾光片之製造上所使用之彩色濾光片 用著色組成物、及使它之彩色濾光片。 【先前技術】 液晶顯示裝置係藉由被2片偏光板夾住的液晶層，控 制通過第1片偏光板的光線之偏光程度，且控制通過第2 片偏光板的光量，來進行顯示之顯示裝置，藉由在2片偏 光板之間設置彩色濾光片而能夠彩色顯示。 彩色濾光片係在玻璃等的透明基板的表面，將2種以 上不同色相的微細帶（條紋）狀的過濾片區段平行或交叉配 置而成者，或是將微細過濾片區段以縱向橫向一定的配列 配置而成者。過濾片區段係微細至數μηι〜數百μπι，而且 係每色相以規定配列整齊地配置而成。 通常，於彩色液晶顯示裝置中，用以驅動液晶的透明 電極係藉由蒸鍍或濺鍍來形成於彩色濾光片上，而且在其 上面形成用以使液晶以一定方向配向之配向膜。爲了充分 地得到該等透明電極及配向膜的性能，通常，在200°C以 上、較佳是23 0°C以上的高溫進行該等的形成係必要的。因 此，目前以彩色濾光片之製造方法而言，將耐光性、耐熱 性優良的顏料作爲著色劑之稱爲顏料分散法之方法係成爲 主流。 以彩色濾光片被要求的品質項目而言，可舉出對比及 亮度。使用對比低的彩色濾光片時，會擾亂液晶所控制的 201111910 偏光程度，且必須隔離光線時（OFF狀態）會產生漏光，或 是必須透射光線時（ON狀態）會產生透射光衰減，致使成爲 模糊不清的畫面。因此，爲了實現高品質的液晶顯示裝置， 高對比化係不可缺少的。 又，若使用亮度低的彩色濾光片，則因爲光的透射率 低，致使畫面變暗，爲了成爲明亮的畫面，增加光源亦即 背光的數目係必要的。因此，從抑制消耗電力的增加之觀 點，彩色濾光片的高亮度化係成爲趨勢。 通常，爲了達成彩色濾光片的高亮度、高對比化，係 進行顏料的微細化處理，必須製造接近極限地接近一次粒 子之顏料分散體。藉此，因爲能夠抑制顏料引起之光線的 散射，且藉由提升分散體的透明度，能夠使分散體的分光 光譜具有高透射率，能夠製造高亮度、高對比的彩色濾光 片。 彩色濾光片基板的3原色（紅、綠、藍；RGB)之一的綠 色，通常係使用鹵化銅酞菁顏料（例如C.I.顔料綠36或C.I. 顏料綠7)作爲主顏料。但是只要是使用鹵化銅酞菁顏料， 會有難以兼具髙對比及高亮度之情形。 爲了解決該等問題，係使用鹵化鋅酞菁顏料作爲發揮 鮮明的色調及廣闊的顏色顯示區域且具有高著色力之綠色 顔料，該鹵化鋅酞菁顏料係從目前的鹵化銅酞菁顔料將中 心金屬取代成爲鋅而成（例如參照專利文獻〗）。 但是，相較於鹵化銅酞菁顔料，鹵化鋅酞菁顏料係酸 性度高。由於該高酸性度的影響，相較於其他顏料種類， 因爲顯示高溶解性，對於在彩色濾光片層上所積層的液晶 201111910 相亦容易被溶解、萃取。因此，會造成電壓保持率的低落' 發生顯示不均、產生配向不良等，而成爲作爲液晶顯示元 件的性能低落之原因。 目前，相對於使用其他顏料時電壓保持率爲9 5%以 上，鹵化鋅酞菁顏料時係止於90%以下而希望能夠改善。 將電壓保持率低落的彩色濾光片組入而成之液晶顯示裝 置，在畫面會產生顯示不均或影像被固定而產生影像永不 變化亦即影像持續殘留之現象，乃是不佳》 因此，爲了提升電壓保持率，製造使用鹵化鋅酞菁顏 料作爲綠色顏料之彩色濾光片係成爲重大課題。 又，由於該高酸性度，相較於其他顏料種類，鹵化鋅 酞菁顏料係難以確保分散安定性，在經時保存狀態中，能 夠觀察到產生結晶異物之現象。該結晶異物產生時，無法 形成良好的塗膜，作爲著色組成物係不合格。就使用先前 所使用的鹵化鋅酞菁顏料以外的顏料而言，作爲電壓保持 率的改善法，在專利文獻2揭示添加含環氧基的化合物、 或含氧雜環丁烷環的化合物等之各種化合物的方法。 但是，相較於鹵化銅酞菁顏料，酸性度高的鹵化鋅酞 菁顏料係非常難以得到電壓保持率良好且不會發生顯示不 均、配向不良而且經時分散安定性良好之彩色濾光片用感 光性著色組成物。 [先前技術文獻] [專利文獻] [專利文獻1]特開2004-70342號公報 [專利文獻2]特開2000-292920號公報 201111910 【發明內容】 本發明之目的係提供一種彩色濾 成物、具備它之彩色濾光片、及具備 顯示裝置，該彩色濾光片用感光性著 使用由鹵化鋅酞菁顏料所構成的綠色 晶顯示裝置的電壓保持率低落，同時 [解決課題之手段] 依照本發明的第1態樣時，係提 感光性著色組成物，其係至少含有含 色著色劑、光聚合性單體、樹脂、光 成之感光性著色組成物，其特徵爲該 官能胺基甲酸乙酯丙烯酸酯以該感光 成分作爲基準在15重量％以上、45 有，或是將二新戊四醇五丙烯酸酯及 酯以該感光性著色組成物的固體成分 以上、25重量％以下的範圍含有，該 丙烯酸酯係具有（甲基）丙烯醯基之f 0.7xl0_3mol/g以上、雙鍵基數爲4·5χ 多官能異氰酸酯對具有羥基的（甲基 到。而且，該感光性著色組成物，係 色組成物而得到的彩色濾光片之液晶 率爲90%以上。 依照本發明的第2態樣時，係提 感光性著色組成物，其係至少含有含 色著色劑、光聚合性單體、樹脂、環 光片用感光性著色組 該彩色濾光片之液晶 色組成物能夠改善在 顏料時成爲問題之液 顯示優良的亮度》 供一種彩色濾光片用 鹵化鋅酞菁顏料的綠 聚合起始劑及溶劑而 光聚合性單體係將多 性著色組成物的固體 重量％以下的範圍含 二新戊四醇六丙烯酸 作爲基準在1 0重量％ 多官能胺基甲酸乙酯 丨安基甲酸乙酯基數爲 l(T3mol/g以上且係使 :)丙烯酸酯反應而得 具備使用該感光性著 顯示元件的電壓保持 供一種彩色濾光片用 鹵化鋅酞菁顏料的綠 氧化合物、光聚合起 201111910 始劑及溶劑而成之感光性著色組成物，其特徵爲該環氧化 合物係將該感光性著色組成物中的鹵化鋅酞菁顏料之重量 設爲100重量份時，含有10〜3 00重量份且係100〜500的 環氧當量（g/eq:每1個環氧基的分子量=分子量+環氧基 數），而且，該感光性著色組成物，係具備使用該感光性著 色組成物而得到的彩色濾光片之液晶顯示元件的電壓保持 率爲90%以上。 [發明之效果] 依照本發明，能夠製造較使用鹵化銅酞菁顔料作爲綠 色顏料時更高亮度的彩色濾光片。又，因爲同時能夠降低 從綠色著色層溶出至液晶之綠色顏料成分，能夠達成得到 —種彩色濾光片用感光性著色組成物，其係改善了以往使 用鹵化鋅酞菁顏料時成爲問題之液晶顯示裝置的電壓保持 率低落。 【實施方式】 以下，說明本發明的各種實施形態。 關於本發明的第1實施形態之彩色濾光片用著色組成 物係含有含鹵化鋅酞菁顏料的綠色著色劑、光聚合性單 體、非感光性樹脂及/或感光性樹脂、聚合起始劑及溶劑。 以下，說明該彩色濾光片用著色組成物之各構成成分。 <綠色著色劑> 關於本發明的第1實施形態之彩色濾光片用感光性著 色組成物係以使用含有鹵化鋅酞菁顏料的綠色著色劑作爲 特徵之一。 將代表性的鹵化鋅酞菁顏料以染料索引（C.I.)號數表 201111910 示時，可舉出C.I.顏料綠58等。藉由鹵化鋅酞菁顏料能 夠得到其他綠色顏料所無法得到的高亮度。 以鹵化鋅酞菁顏料而言’能夠使用藉由眾所周知的製 方法所得到者。特別是能夠使用藉由記載於色材67[9]、 547-554(19 94年）的方法所製造之使用正己胺作爲鹼性物 質測定時’顏料表面的酸性官能基較佳爲1〇〇pm〇1/g以上、 更佳爲200pmol/g以上者。 又’因爲鹵化鋅酞菁顏料係顯示高酸性度，且相較於 其他顏料種’溶解性高，所以電壓保持率容易低落而且難 以確保顏料分散安定性。因此，在含有鹵化鋅酞菁顏料的 感光性著色組成物混合其他物質，顏料分散系亦容易變爲 不安定，且鹵化鋅酞菁顏料容易結晶析出，尤其是含有鹼 性的物質時’由於與顯示高酸性度的鹵化鋅酞菁顏料之鹽 會以異物的形式析出等而成爲問題。 如以上，就製造使用鹵化鋅酞菁顏料而成之彩色濾光 片而言，在抑制發生結晶異物之同時能夠謀求提升電壓保 持率係成爲課題。 綠色著色劑係不只是鹵化鋅酞菁顏料，爲了調整顏色 或補色之目的，亦可並用其他綠色顏料或黃色顔料。 就能夠並用的其他綠色顏料而言，可舉出C.I.顔料綠 7、10、36、37等。又，能夠並用的其他黃綠色顏料，可 舉出 C.I.顏料黃 1、2、3、4、5、6、10、12、13、14、15、 16、17、18、24、31、32、34、35、35:1、36、36:1、37、 37:1、 40、 42、 43、 53、 55、 60、 61、 62、 63、 65、 73、 74、 77、 81、 83、 93、 94、 95、 97、 98、 100、 101、 1〇4 201111910 106、 108、 109、 110、 113、 114、 115、 116、 117、 118、 119、 120、 123、 126、 127、 128、 129、 13 8' 139、 14 7、 150、 15 1、 152、 153' 154、 15 5> 156、 16 1、 162、 164 ' 166、 167、 168、 169、 170、 171、 172、 173、 174、 175、 176、 177、 178、 179、 180、 18 1、 182、 18 5、 187、 18 8、 193、194、198、199、213、214 等。其中，以使用 C.I.顏 料黃 138、139、150、185 爲較佳。 在本實施形態之感光性著色組成物的總不揮發成分中 之較佳顔料成分的含量，從得到充分的色再現性之觀點， 爲10〜90重量％，以15〜85重量％爲較佳，以20〜80重 量％爲最佳。顏料成分的含量小於1 〇重量％時，難以得到 充分的色再現性，大於90重量％時顏料載體的含量變低， 致使著色組成物的安定性有變差之傾向》 較佳顏料比率係以顏料成分之總重量作爲基準，鹵化 鋅酞菁顏料爲20〜100重量％，鹵化銅酞菁顏料爲〇〜80 重量％，黃色顏料爲〇〜5 0重量％。 更佳顏料比率係以顔料成分作爲基準，鹵化鋅酞菁顏 料爲50〜90重量％，鹵化銅酞菁顏料爲5〜45重量％，黃 色顏料爲5〜45重量％。藉由此種顔料的構成比率，能夠 擴大色度區域。 使用鹵化鋅酞菁顏料之關於本實施形態的感光性著色 組成物，係以成爲與使用鹵化銅酞菁顏料之感光性著色組 成物同樣的色度的方式塗布於玻璃基板等，且測定塗膜的 透射率時，在45 Onm附近至53 Otim附近，顯示透射率比使 用銅酞菁顏料而成之著色組成物的塗膜高。特別是在透射 -10- 201111910 率的尖峰，透射率約高5 %左右亦即顯示約90%的値。因此， 藉由在彩色液晶顯示裝置組合通常所使用的背光，能夠得 到使用C.I.顏料綠36或C.I.顏料綠7等鹵化銅酞菁顏料之 感光性著色組成物所無法得到的高亮度。 在本實施形態之感光性著色組成物所使用的顏料，以 使用進行鹽磨處理來微細化而成之物爲佳。所謂鹽磨處理 係將顏料、水溶性無機鹽及水溶性有機溶劑之混合物，使 用捏合機、二輥磨機、三輥磨機、球磨機、立式球磨機、 砂磨機等的捏合機，邊加熱邊機械性捏合後，藉由水洗來 除去水溶性無機鹽及水溶性有機溶劑之處理。水溶性無機 鹽其作用係作爲粉碎助劑，認爲鹽磨時利用無機鹽的高硬 度來將顏料粉碎，藉此生成活性面而產生結晶成長。因此， 捏合時係顏料的粉碎及結晶成長同時產生，所得到的顏料 之一次粒徑依照捏合條件而不同。 藉由加熱來促進結晶成長，加熱溫度以40〜150°C爲 佳。加熱溫度小於40°C時，因爲結晶成長的產生不充分， 顔料粒子的形狀係接近無定形，乃是不佳。另一方面，加 熱溫度大於150°C時，因爲結晶成長過度進展，顔料之一次 粒徑變大’不適合作爲彩色濾光片用著色組成物的著色 料。從鹽磨處理顏料的一次粒子的粒徑分布與鹽磨處理所 需要費用的平衡而言，鹽磨處理的捏合時間以2〜24小時 爲佳。 藉由將鹽磨處理顏料時的條件最佳化，一次粒徑係非 常微細，又’能夠得到具有分布幅度狹窄且尖銳的粒徑分 布之顏料。 -11- 201111910 在本實施形態之感光性著色組成物所含有的綠色顏料 之使用TEM(透射型電子顯微鏡）所求得的一次粒徑，以20 〜100 nm的範圍爲佳。一次粒徑小於20 nm時，難以分散在 有機溶劑中，又，大於lOOnm時，難以得到充分的對比》 以25〜85 nm的範圍爲特佳。 鹽磨處理所使用的水溶性無機鹽，能夠使用氯化鈉、 氯化鋇、氯化鉀、硫酸鈉等，從價格而言，以使用氯化鈉（食 鹽）爲佳。從處理效率及生產效率兩方面而言，水溶性無機 鹽係將顏料成分的總重量作爲基準，以使用50〜2000重量 %爲佳，以使用300〜1000重量％爲最佳。 鹽磨處理所使用的水溶性有機溶劑其作用係將顏料及 水溶性無機鹽潤濕，只要是可溶解（混合）於水且實質上不 溶解所使用的水溶性無機鹽者，沒有特別限定。但是，因 爲在鹽磨處理時溫度會上升而成爲溶劑容易蒸發的狀態， 從安全性的觀點，以沸點爲1 2(TC以上的高沸點溶劑爲佳。 水溶性有機溶劑的具體例，可使用例如2-甲氧基乙 醇、2-丁氧基乙醇、2-(異戊氧基）乙醇、2-(己氧基）乙醇、 二乙二醇、二乙二醇單乙基醚、二乙二醇單丁基醚、三乙 二醇、三乙二醇單甲基醚、液狀的聚乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、二丙二醇、二丙二醇單甲基醚、 二丙二醇單乙基醚、或液狀的聚丙二醇等。水溶性有機溶 劑係將顏料成分的總重量作爲基準，以在5〜1 000重量％ 的範圍使用爲佳，以在50〜500重量％的範圍使用爲最佳。 鹽磨處理時亦可按照需要添加樹脂。所使用的樹脂之 種類係沒有特別限定，能夠使用天然樹脂、改質天然樹脂、 -12- 201111910 合成樹脂或使用天然樹脂改質而成之合成樹脂。所使用的 樹脂以在室溫爲固體且係不溶於水爲佳，而且一部分可溶 於上述水溶性有機溶劑爲特佳。樹脂的使用量係將顏料成 分的總重量作爲基準，以在5〜200重量％的範圍爲佳。 <色素衍生物> 在本實施形態之彩色濾光片用著色組成物，爲了改善 顏料的分散性之目的，能夠使用色素衍生物。以色素衍生 物而言，可舉出在有機顔料、蒽醌、吖啶酮或三阱導入具 有鹼性取代基 '酸性取代基或取代基亦可之酞醯亞胺甲基 而成之化合物。 該等化合物之中，以通式P-Lm所表示的有機顏料衍生 物爲佳。 在通式P-Lm中，P係有機顔料殘基，L係具有鹼性取 代基、酸性取代基或取代基亦可之酞醯亞胺甲基，111係i 〜4的整數。 有機顏料衍生物可使用例如特開昭63-305173號公 報、特公昭57-15620號公報 '特公昭59-40172號公報、 特公昭63-17102號公報或特公平5-9469號公報等所記載 者’該等可單獨或混合2種類以上而使用。 有機顔料衍生物的混合量係相對於1〇〇重量份顏料， 以1〜50重量份爲佳’以3〜3〇重量份爲更佳，以5〜25 重量份爲最佳。相對於1〇〇重量份顏料，顏料衍生物小於 1重量份時’會有分散性變差之情形，大於5〇重量份時， 會有耐熱性、耐光性變差之情形^ 在通式P-Lm中，構成P的有機顏料殘基之有機顏料， -13- 201111910 可舉出如以下者，例如二酮吡咯并吡咯系顔料偶氮、雙 偶氮及多偶氮等的偶氮系顔料：銅酞菁、鹵化銅酞菁及無 金屬酞菁等的酞菁系顏料；胺基蒽醌、二胺基二惠醌、葱 嘧啶、黃士酮、蒽嵌蒽酮、靛蒽酮、皮蒽酮及紫蒽酮等的 蒽醌系顏料；喹吖酮系顏料；二噚哄系顔料；紫環酮 (perinone)系顔料；茈系顏料；硫靛藍系顏料：異卩引哄滿系 顔料：異吲哚滿酮系顏料；喹啉黃系顏料：士林（threne) 系顏料：及金屬錯合物系顏料等。 在本發明的彩色濾光片用感光性著色組成物中，爲了 改善顏料的分散性之目的，使用色素衍生物亦佳。 <光聚合性單體> 所謂光聚合性單體，係藉由自由基來誘發聚合之單 體。特別是意指藉由對著色組成物照射紫外線進行硬化來 生成透明樹脂之具有乙烯性不飽和雙鍵的化合物，光聚合 性單體亦包含通常被稱爲低聚物之平均分子量爲1 000左 右的低聚物且具有乙烯性不飽和雙鍵者。 使用光聚合性單體時之混合量係將綠色著色劑的總量 作爲基準，以10〜3 0 0重量％爲佳，從光硬化性及顯影性 之觀點，以1 0〜2 0 0重量％爲更佳。 光聚合性單體的具體例，可舉出（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸 2-羥基丙酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸β-羧基乙 酯及（甲基）丙烯酸三環癸酯等的單官能（甲基）丙烯酸酯 類；聚乙二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙烯 酸酯、三乙二醇二（甲基）丙烯酸酯及三丙二醇二（甲基）丙烯 -14- 201111910 酸酯等的二官能（甲基）丙烯酸酯類；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、二新戊四醇六（甲基）丙烯酸酯及二新戊四醇五 (甲基）丙烯酸酯等三官能以上的多官能（甲基）丙烯酸酯： 1，6_己二醇二環氧丙基醚、及雙酚A二環氧丙基醚、新戊 二醇二環氧丙基醚、及苯酚酚醛清漆樹脂等的環氧化合物 與（甲基）丙烯酸之反應物亦即環氧（甲基）丙烯酸酯；將聚 酯 '聚胺基甲酸乙酯、異三聚氰酸酯、羥甲基化三聚氰胺 等改質而成之各種（甲基）丙烯酸酯類；及（甲基）丙烯酸、苯 乙烯、乙酸乙烯酯、羥乙基乙烯基醚、乙二醇二乙烯基醚、 新戊四醇三乙烯基醚、（甲基）丙烯醯胺、N-羥甲基（甲基） 丙烯醯胺、N-乙烯基甲醯胺、丙烯腈等（甲基）丙烯酸酯以 外的單體，該等可單獨或混合2種類以上而使用，但是未 必限定於該等。 作爲本實施形態之感光性組成物能夠使用的其他光聚 合性單體，可舉出使多官能異氰酸酯對具有羥基的（甲基） 丙烯酸酯反應而得到之具有（甲基）丙烯醯基之多官能胺基 甲酸乙酯丙烯酸酯，或是含有二新戊四醇五丙烯酸酯及二 新戊四醇六丙烯酸酯之丙烯酸酯。另外，具有羥基的（甲基） 丙烯酸酯與多官能異氰酸酯的組合係任意而沒有特別限 定。又，可將含有1種的多官能胺基甲酸乙酯或二新戊四 醇五丙烯酸酯及二新戊四醇六丙烯酸酯之丙烯酸酯單獨使 用，亦可組合2種以上而使用。 在此，具有羥基的（甲基）丙烯酸酯，可舉出（甲基）丙烯 酸2-羥基乙酯、（甲基）丙烯酸4-羥基丁酯、三羥甲基丙烷 -15- 201111910 二（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、雙三羥甲 基丙烷三（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、 二新戊四醇環氧乙烷改質五（甲基）丙烯酸酯、二新戊四醇 環氧丙烷改質五（甲基）丙烯酸酯、二新戊四醇己內酯改質 五（甲基）丙烯酸酯、甘油丙烯酸酯甲基丙烯酸酯、甘油二 甲基丙烯酸酯、2-羥基-3·丙烯醯基丙基甲基丙烯酸酯、含 環氧基的化合物與羧基（甲基）丙烯酸酯之反應物、含羥基 的多元醇聚丙烯酸酯等》 又’多官能異氰酸酯，可舉甲苯二異氰酸酯、六亞甲 基二異氰酸酯、二苯基亞甲基二異氰酸酯、異佛酮二異氰 酸酯、聚異氰酸酯等。 在本實施形態之感光性組成物能夠使用的光聚合性單 體，係除了含有上述多官能胺基甲酸乙酯丙烯酸酯，或是 二新戊四醇五丙烯酸酯及二新戊四醇六丙烯酸酯之丙烯酸 酯以外’亦可含有具有雙鍵基的成分作爲其他單體，該具 有雙鍵基係在使多官能異氰酸酯對具有羥基的（甲基）丙烯 酸酯反應時，具有（甲基）丙烯醯基之多官能胺基甲酸乙酯 丙烯酸酯無法得到者。 另外，上述的多官能胺基甲酸乙酯丙烯酸酯，以胺基 甲酸乙酯基數爲 0.7χ 10_3mol/g以上，雙鍵基數爲 4.5xl(T3m〇l/g以上爲佳。多官能胺基甲酸乙酯丙烯酸酯的 胺基甲酸乙酯基數小於0.7 xlO _3 mo Ι/g時，硬化後的感光性 組成物容易因藥品或溶劑而膨潤，在感光性組成物層上所 形成的透明電極（ITO)會產生裂痕，或是在感光性組成物層 所積層的液晶相亦容易被萃取。因此，會造成電壓保持率 -16- 201111910 低落，且發生顯示不均、產生配向不良等，致使作爲液晶 顯示元件的性能低落，而且使顯示品質大幅度地降低》又， 雙鍵基數小於4.5x1 (T3mol/g時，因爲曝光敏感度低落，且 解像性變差，任一情況都不佳。 <聚合起始劑> 在本實施形態之彩色濾光片用著色組成物，爲了藉由 紫外線照射該組成物來硬化，或是爲了使用微影法來形成 過濾片區段，添加了光聚合起始劑。光聚合起始劑的混合 量係將顏料的總量作爲基準，以5〜200重量％爲佳’從光 硬化性及顯影性的觀點，以1〇〜150重量％爲更佳。 作爲光聚合起始劑，可使用〇苯氧基二氯乙醯苯、4-三級丁基-二氯乙醯苯、二乙氧基乙醯苯、1-(4-異丙基苯 基）-2-羥基-2-甲基丙烷-1-酮、1-羥基環己基苯基酮、2-苄 基-2-二甲胺基-1-(4-味啉苯基）-丁烷-1-酮、及 2-甲基 -1-[4-(甲硫基）苯基]-2-味啉丙烷-1-酮等的乙醯苯系光聚合 起始劑；苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻 異丙基醚、及苄基二甲基縮酮等的苯偶姻系光聚合起始 劑；二苯基酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、 4-苯基二苯基酮、羥基二苯基酮、丙烯酸化二苯基酮、及 4-苯甲醯基-4，-甲基二苯基硫醚等的二苯基酮系光聚合起 始劑；9-氧硫卩山卩星、2-氯-9-氧硫卩山唱、2-甲基-9-氧硫卩山嗤、 異丙基-9-氧硫妯唱及2,4-二異丙基9-氧硫卩[1]卩星等的9-氧硫 D山嘎系光聚合起始劑；2,4,6-三氯-s-三畊、2-苯基- 4,6-雙（三 氯甲基）-s-三哄、2-(對甲氧基苯基）-4,6-雙（三氯甲基）-s-三阱、2-(對甲苯基）-4,6-雙（三氯甲基）-s-三阱、2-胡椒基 -17- 201111910 -4,6-雙（三氯甲基）-s-三阱、2,4-雙（三氯甲基）-6-苯乙烯基 -S·二哄、2-(萘甲醯-1-基）-4,6-雙（三氯甲基）-S-三哄、2-(4-甲氧基-萘甲醯-1-基）-4,6-雙（三氯甲基）_5_三畊、2,4-三氯 甲基-(胡椒基）-6-三阱、及2,4-三氯甲基（4，-甲氧基苯乙烯 基）-6 -三阱等的三阱系光聚合起始劑：硼系光聚合起始劑； 咔唑系光聚合起始劑；咪唑系光聚合起始劑；及肟酯系光 聚合起始劑等。 以上的光聚合起始劑可單獨或混合2種以上而使用。 亦可並用α -醯氧基酯、醯基氧化膦、乙醛酸甲基苯酯、二 苯乙二酮、9, 10 -菲醌、樟腦醌、乙基蒽醌、4,4，-二乙基異 酞基苯酮、3,3’，4,4’-四（三級丁基過氧化羰基）二苯基酮、 及4，4’-二乙基胺基二苯基酮等的化合物作爲敏化劑。 使用敏化劑時，敏化劑的混合量係將光聚合起始劑作 爲基準’以3〜60重量％爲佳，從光硬化性、顯影性的觀 點，以5〜5 0重量％爲更佳。 <溶劑> 本實施形態之彩色濾光片用著色組成物係含有溶劑， 用以使顔料充分地分散在顏料載體且使在玻璃基板等的透 明基板上以乾燥膜厚度爲0.2〜5μηι的方式塗布來形成過 濾片區段變爲容易。 以溶劑而言，可舉出1，2,3-三氯丙烷、1，3-丁二醇 (l，3-butanediol)、 1,3-丁二醇（1,3-butylene glycol)、 1，3-丁二醇二乙酸酯、1,4 -二噚烷、2 -庚酮' 2 -甲基-1，3 -丙二醇、 3,5,5-三甲基-2-環己燃-1-1-酮、3,3,5 -三甲基環己酮、3-乙氧基丙酸乙酯、3 -甲基-1,3-丁二醇、3 -甲氧基-3-甲基-1- 201111910 丁醇、3-甲氧基-3-乙酸甲基丁酯、3-甲氧基丁醇、3-乙酸 甲氧基丁酯、4-庚酮、間二甲苯、間二乙苯、間二氯苯' N，N-二甲基乙醯胺、N，N_二甲基甲醯胺、正丁醇、正丁苯、 乙酸正丙酯、N -甲基吡咯啶酮、鄰二甲苯、鄰氯甲苯、鄰 二乙苯、鄰二氯苯、對氯甲苯、對二乙苯、二級丁基苯、 三級丁基苯、γ-丁內酯、異丁醇、異佛酮、乙二醇二乙基 醚、乙二醇二丁基醚、乙二醇單異丙基醚、乙二醇單乙基 醚、乙二醇單乙基醚乙酸酯、乙二醇單三級丁基醚、乙二 醇單丁基醚、乙二醇單丁基醚乙酸酯、乙二醇單丙基醚、 乙二醇單己基醚、乙二醇單甲基_、乙二醇單甲基醆乙酸 酯、二異丁基酮、二乙二醇二乙基醚、二乙二醇二甲基醚、 二乙二醇單異丙基醚、二乙二醇單乙基醚乙酸酯、二乙二 醇單丁基醚、二乙二醇單丁基醚乙酸酯、二乙二醇單甲基 醚、環己醇、環己醇乙酸酯、環己酮、二丙二醇二甲基醚、 二丙二醇甲基醚乙酸酯、二丙二醇單乙基醚、二丙二醇單 丁基醚、二丙二醇單丙基醚、二丙二醇單甲基醚、二丙酮 醇、甘油三乙酸酯、三丙二醇單丁基醚、三丙二醇單甲基 酸、丙二醇二乙酸酯、丙二醇苯基醚、丙二醇單乙基醚、 汽二醇單乙基醚乙酸酯、丙二醇單丁基醚、丙二醇單丙基 酸、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單 甲基醚丙酸酯、苄醇、甲基異丁基酮、甲基環己醇、乙酸 正戊酯、乙酸正丁酯、乙酸異戊酯、乙酸異丁酯、乙酸丙 醋、二元酸酯等，該等可單獨或混合2種以上而使用。 <環氧化合物> 在本實施形態之彩色濾光片用著色組成物，亦可混合 -19- 201111910 環氧化合物。 所謂環氧化合物係指具有環氧基的化合物’在彩色濾 光片製程之煆燒時，環氧基產生熱硬化反應來將塗膜表 面、內部交聯，具有抑制來自鹵化鋅酞菁顏料或鹵化鋅酞 菁顏料的不純物往液晶相溶出之作用。環氧化合物可以是 低分子化合物亦可以是高分子化合物，代表例可舉出雙酚 A系環氧樹脂、氫化雙酚A系環氧樹脂、雙酚F系環氧樹 脂、氫化雙酚F系環氧樹脂、酚醛清漆型環氧樹脂、環式 脂肪族系環氧樹脂、雜環式環氧樹脂、環氧丙酯系樹脂、 環氧丙基胺系樹脂、環氧化油等的環氧樹脂；前述環氧樹 脂的溴化衍生物、或參（環氧丙基苯基）甲烷、三環氧丙基 異三聚氰酸酯等。其中，就膜的硬化密度高且對著色組成 物的顯影性之不良影響較少而言，以雙酚A系環氧樹脂、 氫化雙酚A系環氧樹脂、酚醛清漆型環氧樹脂、環式脂肪 族系環氧樹脂、環氧丙酯系樹脂 '環氧丙基胺系樹脂、參（環 氧丙基苯基）甲烷爲佳。 在本實施形態能夠使用之較佳市售環氧化合物的例子 可舉出 NAGASECHEMTEX 公司製 EX1U、EX2(U、EX411、 EX901 ' 曰本化藥公司製 EPPN501H、JAPAN EPOXYRESIN 公司製JER1 52等。 環氧化合物係將感光性著色組成物中的鹵化鋅酞菁顏 料設作1〇〇重量份時’添加10〜3〇〇重量份。小於10重量 份的添加量時，膜的硬化密度低落’且電壓保持率改善效 果變小。大於300重量份時’光聚合性單體或光聚合起始 劑等的添加量受到限制’除了無法確保充分的顯影性以 -20- 201111910 外，經時安定性亦成爲問題。 又，所謂環氧當量係指從環氧化合物的化學式計算所 求得之依據「分子量+環氧基數：單位g/eq」所定義之値， 亦即每1個環氧基的分子量。在本發明，以100〜500的範 圍爲佳，以100〜250的範圍爲更佳。環氧當量小於1〇〇時， 硬化性高且膜的交聯密度太高，致使硬化時收縮變大而無 法得到膜的平坦性。環氧當量大於500時，硬化性不足且 電壓保持率的改善效果變小。 而且’爲了促進環氧化合物的硬化，亦可並用環氧硬 化劑。代表性的環氧硬化劑可舉出酸酐系硬化劑及胺系硬 化劑之2種’就胺系硬化劑係反應速度快' 單成分而具有 難以使其安定之缺點而言，及就若被液晶相萃取電壓保持 率有變差之可能性而言’以及與鋅酞菁顏料的相容性差而 難以確保分散安定性而言，在本發明係以酸酐系硬化劑爲 理想。酸酐系硬化劑可舉出順丁烯二酸、酞酸、四氫酞酸、 六氫酞酸、焦蜜石酸 '二苯基酮四羧酸、聯苯基四羧酸、 聯苯基醚四羧酸 '二苯基碉四羧酸的酸酐等。其中，從能 夠構築緻密的交聯構造之觀點，以在1分子中具有2個以 上的酐基者爲佳’又，從能夠將短波長的透射良好等的光 學特性或液晶的電壓保持率保持爲較高之觀點，以環己院 四羧酸二酐等的飽和烴系的多官能酸酐爲更佳。 <樹脂> 本實施形態之著色組成物係含有樹脂。藉由含有樹 脂’本發明的感光性著色組成物的分散安定性變爲更良 好’使用該著色組成物來形成彩色濾光片的有色材料層 -21 - 201111910 時，能夠得到顏料凝聚物少且顯影性、圖案形狀亦良好的 有色材料層。 樹脂以將熱塑性樹脂、熱硬化性樹脂、含酸性基的乙 烯性不飽和單體共聚合而成之鹼可溶性乙烯系樹脂、及具 有乙烯性不飽和活性雙鍵之能量線硬化性樹脂爲佳，在可 見光區域之400〜7〇Onm的全波長區域中之分光透射率，以 8 0%以上爲佳，以95 %以上的樹脂爲更佳。 熱塑性樹脂可舉出例如丁縮醛樹脂、苯乙烯-順丁烯二 酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚胺基甲酸乙酯系樹 脂、聚酯樹脂、乙烯系樹脂、醇酸樹脂、聚苯乙烯樹脂、 聚醯胺樹脂、橡膠系樹脂、環化橡膠系樹脂、纖維素類、 聚乙烯（HDPE、LDPE)、聚丁二烯及聚醯亞胺樹脂等。 又，熱硬化性樹脂可舉出例如苯胍阱樹脂、松香改質 順丁烯二酸樹脂、松香改質反丁烯二酸樹脂、三聚氰胺樹 脂、脲樹脂及酚樹脂等。 將本實施形態之彩色濾光片用感光性著色組成物以鹼 顯影型著色光阻的形態使用時，以使用將（甲基）丙烯酸等 的含酸性基的乙烯性不飽和單體共聚合而成之鹼可溶性乙 烯系樹脂作爲黏合劑樹脂爲佳。 又，作爲黏合劑樹脂，亦能夠使用具有乙烯性不飽和 活性雙鍵之能量線硬化性樹脂。該樹脂的製造方法有例如 準備具有羥基、羧基、胺基等反應性的取代基之線型高分 子作爲樹脂的前驅物，並使具有異氰酸酯基、醛基、環氧 基等反應性取代基之（甲基）丙烯酸化合物或桂皮酸反應， -22- 201111910 來得到將（甲基）丙烯醯基、苯乙烯基等的光交聯性基導入 該線型高分子而成之樹脂的方法；或/及將含苯乙烯-順丁 烯二酸酐共聚物或α-烯烴-順丁烯二酸酐共聚物等的酸酐 之線型高分子使用（甲基）丙烯酸羥基烷酯等具有羥基之（甲 基）丙烯酸化合物半酯化之方法等。 在黏合劑樹脂之中，兼具鹼可溶性能與能量線硬化性 能者，能夠作爲具有鹼可溶性乙烯系樹脂與具有乙烯性不 飽和活性雙鍵的能量線硬化性樹脂之兩方的性能者來使 用。 爲了使顏料良好地分散，樹脂的重量平均分子量（Mw) 以5,000〜100,000的範圍爲佳，以5,000〜80,000的範圍 爲較佳，以5,000〜30,000的範圍爲更佳。又，數量平均分 子量（Μη)以5,000〜5 0,000的範圍爲佳，Mw/Mn的値以10 以下爲佳。 若樹脂的重量平均分子量（Mw)大於1 00,000以上時因 爲樹脂間的相互作用變強、感光性著色組成物的黏度變 高，致使處理易於變爲困難。又，重量平均分子量（Mw) 小於若5,000以下時，在顯影性或對玻璃等的基板之黏附 性，會有產生問題之情形。 樹脂係將綠色著色劑的總重量作爲基準，能夠以0〜 500重量份的量使用。以30〜500重量份爲佳，小於30重 量份時，顯影性、成膜性及各種耐性易於變爲不充分，大 於500重量份時，顏料濃度變低而無法顯示顏色特性。 又，從顏料分散性、顯影性及耐熱性的觀點，用作顏 料吸附基及顯影時的鹼可溶性基之羧基、用作顏料載體及 -23- 201111910 對溶劑的親和性基之脂肪族基及芳香族基之平衡，對於顏 料分散性、顯影性、進而耐久性係重要的，因此樹脂的酸 價以 20〜3 00mgKOH/g 的範圍爲佳。酸價以 50〜 15 0mgKOH/g的範圍爲更佳。酸價小於20mgKOH/g時，對 顯影液之溶解性差而難以形成微細圖案。大於3 00mgKOH/g 時，會有微細圖案未留存之情形。 而且，酸價爲50〜150mgKOH/g的範圍時，感光性著 色組成物的分散安定性變爲良好且結晶異物的抑制變爲更 良好。 <調平劑> 爲了使在透明基板上之組成物的調平性良好，本實施 形態之著色組成物，以添加調平劑爲佳。調平劑以在主鏈 具有聚醚構造或聚酯構造之二甲基矽氧烷爲佳。在主鏈具 有聚醚構造之二甲基矽氧烷的具體例可舉出 TORAY-DOWCORNING 公司製 FZ-2122、BYK-Chemie 公司 製 BYK-3 3 3 等。 在主鏈具有聚酯構造之二甲基矽氧烷的具體例，可舉 出BYK-Chemie公司製BYK-310、BYK-370等。亦可並用 在主鏈具有聚醚構造之二甲基矽氧烷及在主鏈具有聚酯構 造之二甲基矽氧烷。調平劑的含量一般係將著色組成物的 總重量作爲基準（100重量％)爲0.003〜0.5重量％。 作爲調平劑較佳之物可舉出在分子內具有疏水基及親 水基之所謂界面活性劑的—種。該調平劑雖然具有親水 基，但是對水的溶解性小’因此添加在著色組成物時具有 其表面張力降低性能低之特徵。而且’在此種調平劑中’ -24- 201111910 以儘管表面張力降低性能低，但是對玻璃板的濕潤性良好 者爲有用，且以使用在未出現起泡引起的塗膜缺陷之添加 量中，能夠充分地抑制帶電性者爲佳。 調平劑以使用具有聚環氧烷單位之二甲基聚矽氧烷爲 佳。聚環氧烷單位有聚環氧乙烷單位、聚環氧丙烷單位， 二甲基聚矽氧烷亦可同時具有聚環氧乙烷單位及聚環氧丙 烷單位。 又，聚環氧烷單位之與二甲基聚矽氧烷的鍵結形態， 係以下任一者均可，包含：聚環氧烷單位係鍵結於二甲基 聚矽氧烷的重複單位中而成之側接型；鍵結於二甲基聚矽 氧院的末端之末端改質型；及與二甲基聚矽氧烷交替地重 複鍵結而成之直鏈狀的嵌段共聚物型。 具有聚環氧烷單位之二甲基聚矽氧烷，可舉出由 TORAY-DOWCORNING股份公司在市場上銷售之例如 FZ-2110、 FZ-2122、 FZ-2130、 FZ-2166' FZ-219卜 FZ-2203 ' FZ-2207,但是不被該等限定》 在調平劑，亦可輔助性地添加陰離子性、陽離子性、 非離子性或兩性的界面活性劑。界面活性劑係混合2種以 上而使用亦無妨。 在調平劑輔助性地添加之陰離子性界面活性劑可舉出 聚氧乙烯烷基醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯 酸共聚物的鹼金屬鹽（alkali salt)、烷基萘磺酸鈉、烷基二 苯基醚二磺酸鈉' 月桂基硫酸單乙醇胺、月桂基硫酸三乙 醇胺、月桂基硫酸銨、硬脂酸單乙醇胺、硬脂酸鈉、月桂 基硫酸鈉、苯乙烯-丙烯酸共聚物的單乙醇胺、聚氧乙烯烷 -25- 201111910 基醚磷酸酯等》 在調平劑輔助性地添加之陽離子性界面活性劑可舉出 烷基4級銨鹽或該等的環氧乙烷加成物。 在調平劑輔助性地添加之非離子性界面活性劑可舉出 聚氧乙烯油醯基醚、聚氧乙烯月桂基醚、聚氧乙烯壬基苯 基醚、聚氧乙烯烷基醚磷酸酯、聚氧乙烯山梨醇酐單硬脂 酸酯、聚乙二醇單月桂酸酯等；亦可舉出烷基二甲基胺基 乙酸甜菜鹼、烷基咪唑啉等的兩性界面活性劑、及氟系或 聚矽氧系的界面活性劑。 <其他成分> 爲了使組成物的經時黏度安定化，在本實施形態之著 色組成物，能夠使其含有儲存安定劑。又，爲了提高與透 明基板的黏附性，亦能夠使其含有矽烷偶合劑等的黏附提 升劑。 儲存安定劑可舉出例如苄基三甲基氯化物、二乙基羥 基胺等的4級氯化銨：乳酸、草酸等的有機酸及其甲基醚； 三級丁基兒茶酚；四乙基膦、四苯基膦等的有機膦；亞磷 酸鹽等。儲存安定劑係相對於著色組成物中的色素100重 量份，能夠使用〇. 1〜1 〇重量份的量。 黏附提升劑可舉出乙烯基參（β-甲氧基乙氧基）矽烷、乙 烯基乙氧基矽烷、乙烯基三甲氧基矽烷等的乙烯基矽烷 類；γ-甲基丙烯醢氧基丙基三甲氧基矽烷等的（甲基）丙烯醯 基矽烷類；β-(3,4 -乙氧基環己基）乙基三甲氧基矽烷、 β-(3,4-環氧環己基）甲基三甲氧基矽烷、β-(3,4-環氧環己基） 乙基三乙氧基矽烷、β_(3,4-環氧環己基）甲基三乙氧基矽 -26- 201111910 院、γ-環氧丙氧基丙基三甲氧基砂院、γ_環氧丙氧基丙基 二乙氧基砂院等的環氧基砂垸類；Ν-β(胺乙基）γ -胺丙基三 甲氧基矽烷、Ν-β (胺乙基）γ-胺丙基三乙氧基矽烷、Ν_ρ (胺 乙基）γ-胺丙基甲基二乙氧基砂院、γ-胺丙基三乙氧基砂 烷、γ -胺丙基三甲氧基矽烷、Ν -苯基-γ -胺丙基三甲氧基矽 烷、Ν-苯基-γ-胺丙基三乙氧基矽烷等的胺基矽烷類；丫_氫 硫基丙基三甲氧基砂院、γ -氫硫基丙基三乙氧基砂院等的 硫矽烷類等。矽烷偶合劑係相對於著色組成物中的色素1〇〇 重量份’較佳爲以0.01〜10重量份，更佳爲以0.05〜5重 量份的量來使用。 本實施形態之感光性著色組成物能夠將至少含有鹵化 鋅酞菁顏料的綠色著色劑，較佳是與色素衍生物及/或分散 助劑一同在樹脂及有機溶劑等的著色劑載體中，使用三輥 磨機、二輥磨機、砂磨機、捏合機、立式球磨機等各種分 散手段而微細地分散來製造。又，本實施形態之感光性著 色組成物，亦可將在著色劑載體中各自分散數種類的著色 劑而成者進行混合來製造。 <分散助劑> 使著色劑分散在著色劑載體中時，能夠適當地使用樹 脂型分散劑、界面活性劑等的分散助劑。分散助劑對著色 劑的分散優良且防止分散後之著色劑的再凝集之效果大， 因此所使用的感光性著色組成物係使用分散助劑來將著色 劑分散在著色劑載體中而構成時，能夠得到分光透射率高 的彩色濾光片。 -27- 201111910 樹脂型分散劑具有：著色劑親和性部位，其具有吸附 於著色劑之性質；及與著色劑載體具有相溶性的部位；其 作用係吸附於著色劑而安定化著色劑至著色劑載體的分 散。作爲樹脂型分散劑，具體上，能夠使用聚胺基甲酸乙 酯、聚丙烯酸酯等的聚羧酸酯、不飽和聚醯胺、聚羧酸、 聚羧酸（部分）胺鹽、聚羧酸銨鹽、聚羧酸烷基胺鹽、聚矽 氧烷、長鏈聚胺基醯胺磷酸鹽、含羥基的聚羧酸酯或該等 的改質物、聚（低級伸烷基亞胺）與具有游離之羧基的聚酯 反應所形成的醯胺或其鹽等的油性分散劑、（甲基）丙烯酸-苯乙烯共聚物、（甲基）丙烯酸-(甲基）丙烯酸酯共聚物、苯 乙烯-順丁烯二酸共聚物、聚乙烯醇、聚乙烯基吡咯啶酮等 的水溶性樹脂或水溶性高分子化合物、聚酯系、改質聚丙 烯酸酯系、環氧乙烷/環氧丙烷加成化合物、磷酸酯系等， 該等可單獨或混合2種以上而使用。 界面活性劑可舉出月桂基硫酸鈉、聚氧乙烯烷基醚硫 酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物的鹼金屬 鹽（alkali salt)、硬脂酸鈉、烷基萘磺酸鈉、烷基二苯基 醚二磺酸鈉、月桂基硫酸單乙醇胺、月桂基硫酸三乙醇胺、 月桂基硫酸銨、硬脂酸單乙醇胺、苯乙烯-丙烯酸共聚物的 單乙醇胺、聚氧乙烯烷基醚磷酸酯等的陰離子性界面活性 劑；聚氧乙烯油醯基醚、聚氧乙烯月桂基醚、聚氧乙烯壬 基苯基醚、聚氧乙烯烷基醚磷酸酯、聚氧乙烯山梨醇酐單 硬脂酸酯、聚乙二醇單月桂酸酯等的非離子性界面活性 劑；烷基4級銨鹽或該等的環氧乙烷加成物等的陽離子性 界面活性劑；烷基二甲基胺基乙酸甜菜鹼等的烷基甜菜 -28- 201111910 鹼；烷基咪唑啉等的兩性界面活性劑。該等可單獨或混合 2種以上而使用。 (粗大粒子的除去） 含有上述所說明的各成分之著色組成物，能夠以凹版 膠版用印刷油墨、無水膠版印刷油墨、絲綢網版印刷用油 墨、溶劑顯影型或鹼顯影型著色光阻的形態來調製。另外， 著色光阻係使著色劑分散在含有透明樹脂及單體、光聚合 起始劑、有機溶劑之組成物中而成者。 本發明實施形態之著色組成物係以使用離心分離、燒 結過濾器、膜濾器等手段來進行較佳是5μπι以上的粗大粒 子、更佳是Ιμιη以上的粗大粒子、再更佳是0.5 μηι以上的 粗大粒子及混入的塵埃之除去爲理想。 如此，本實施形態之著色組成物以實質上不含有0.5 μιη 以上的粒子爲佳。以粒徑爲0.3 μιη以下爲更佳（依照S EM 之粒徑）。 接著，說明本發明的第2實施形態之彩色濾光片。 使用以上說明的第1實施形態之著色組成物，使用印 刷法或微影法能夠製造本發明的第2實施形態之彩色濾光 片。 使用印刷法來形成過濾片區段係因爲只要重複進行以 印刷油墨的形式調製而成的著色組成物之印刷及乾燥即能 夠圖案化，作爲彩色濾光片的製造方法，係低成本且大量 生產性優良。而且，由於印刷技術的發展而能夠進行具有高 尺寸精確度及平滑度的微細圖案之印刷。爲了進行印刷， 著色組成物的組成以在印刷版上或膠布上油墨不會乾燥、 -29- 201111910 固化爲佳。又，控制在印刷機上的流動性亦是重要的，亦 能夠使用分散劑或體質顏料來調整油墨的黏度。 使用微影法來形成過濾片區段時，係將上述以溶劑顯 影型或鹼顯影型著色光阻的形式調製而成之著色組成物， 使用噴霧塗布或旋轉塗布、狹縫塗布、輥塗布等的塗布方 法並以乾燥膜厚度爲0.2〜5 μιη的方式塗布在透明基板 上。按照需要透過以與該膜接觸或不接觸狀態設置且具有 規定圖案的光罩來進行紫外線曝光。隨後，藉由浸漬在溶 劑或鹼性顯影液或使用噴霧器等噴灑顯影液而除去未硬化 部’來形成需要的圖案後，對於其他顏色亦重複同樣的操 作，而能夠製造彩色濾光片。而且，爲了促進著色光阻的 聚合’亦可按照需要施行加熱。使用微影法時，能夠製造 精確度比上述印刷法高的彩色濾光片。 在顯影時，可使用碳酸鈉、氫氧化鈉等的水溶液作爲 鹼性顯影液，亦可以使用二甲基苄胺、三乙醇胺等的有機 鹼。又，亦可在顯影液添加消泡劑或界面活性劑。 又，爲了提升紫外線曝光敏感度，在塗布上述著色光 阻並乾燥後，亦可塗布水溶液或鹼性水溶性樹脂、例如聚 乙烯醇或水溶性丙烯酸樹脂等並乾燥來形成防止氧引起的 聚合阻礙之膜後，進行紫外線曝光。 本實施形態之彩色濾光片，係除了上述方法以外，亦 可使用電極沈積法、轉印法等來製造，上述著色組成物能 夠使用任一方法。而且，電極沈積法係利用在基板上所形 成的透明導電膜並藉由膠體粒子的電泳在透明導電膜上電 極沈積形成各顏色的過濾片區段，來製造彩色濾光片。又， -30- 201111910 轉印法係在剝離性的轉印基片的表面，預先形成過濾片區 段’並將該過濾片區段轉印至需要的基板之方法。 本實施形態之彩色濾光片具備至少一紅色過濾片區 段、至少一藍色過濾片區段及至少一綠色過濾片區段，前 述至少一綠色過濾片區段係使用上述本發明的第1實施形 態之彩色濾光片用著色組成物來形成。 紅色過濾片區段能夠使用一般的紅色著色組成物來形 成。紅色著色組成物可使用例如C . I.顏料紅 7、1 4、4 1、 48:1、 48:2、 48:3、 48:4、 57:1、 81、 81:1、 81:2、 81:3、 81:4、 122、 146、 168、 177、 178、 184、 185、 187、 200、 202 ' 208、 210、 246 ' 254、 255、 264' 270、 272、 279 等 的紅色顏料。 在紅色著色組成物，亦可並用C.I.顏料橙43、71、73 等的橙色顏料及/或C.I.顏料黃1、2、3' 4、5、6、10、12、 13、 14、 15、 16、 17、 18、 24、 31、 32、 34、 35、 35:1、 36、36:1、37、37:1、40、42、43、53、55、60、61、62、 63、 65' 73、 74、 77、 81、 83、 93、 94、 95、 97、 98、 100、 101、 104、 106、 108、 109、 110、 113、 114、 115、 116、 117、 118、 119、 120、 123、 126、 127、 128、 129、 138、 139、 147 ' 150、 151、 152、 153、 154、 155、 156、 161、 162、 164、 166、 167、 168、 169、 170、 171、 172、 173、 174、 175、 176、 177、 179、 180、 181、 182、 185、 187、 188、193、194、198、199、213、214 等的黃色顏料。 又，藍色過濾片區段能夠使用一般的藍色著色組成物 來形成。藍色著色組成物可使用例如C.I.顏料藍15、15:1、 -31- 201111910 15:2、15:3、15:4、15:6、16、22、60、64 等的藍色顏料。 又，在藍色著色組成物，亦可並用C.I.顏料紫丨、19、23、 27、29、30、32、37、40、42、50 等的紫色顏料。 在透明基板或反射基板上形成過濾片區段之前，若預 先形成黑色矩陣，能夠進一步提高液晶顯示面板的對比。 黑色矩陣能夠使用將鉻或鉻/氧化鉻的多層膜、氮化鈦等的 無機膜或將遮光劑分散而成的樹脂膜，但是不被該等限定。 又，亦可在前述透明基板或反射基板上，預先形成薄 膜電晶體（TFT)，隨後，形成過濾片區段。藉由在TFT基板 形成過爐片區段’能夠提高液晶顯不面板的開口率，並使 亮度提高。 在彩色濾光片上，可按照需要形成保護膜或柱狀間隔 物、透明導電膜、液晶配向膜等。 使用密封劑將彩色濾光片與對向基板貼合，並從在密 封部所設置的注入口注入液晶後，將注入口密封，且按照 需要藉由在基板的外側貼合偏光膜或相位差膜，能夠製造 液晶顯示面板。 如此液晶顯示面板，能夠使用於扭曲向列（TN; Twisted Nematic)、超扭曲向列（STN; Super Twisted Nematic)、面 內切換（IPS; In-Plane Switching)、垂直配向（VA; Vertically Aligned)、光學補償彎曲（OCB ; Optically Compensatory Bend)等使用彩色濾光片來進行彩色化之液晶顯示模式。 [實施例] 以下，具體地說明作爲光聚合性單體之多官能丙烯酸 酯的合成例、調製含有各種光聚合性單體之著色感光性組 -32- 201111910 成物而成之實施例及比較例，但是本發明不被該等實施例 限定’在未脫離本發明的宗旨之範圍能夠實施各種變更。 又’在實施·例之「份」係表示「重量份」。又，Mw及Μη 係各自意味著數量平均分子量及重量平均分子量。 (合成例1) 在內容量爲1L的5 口反應容器，添加623g二新戊四 醇六丙烯酸酯（東亞合成（股）製）、44 g六亞甲基二異氰酸 酯，並在60 °C使其反應8小時，來得到含有多官能丙烯酸 酯（1)之產物，該多官能丙烯酸酯（1)具有（甲基）丙烯醯基且 胺基甲酸乙酯基數爲 1.64xl(T3mol/g、雙鍵基數爲 8.22xl(T3m〇l/g。產物中，多官能丙烯酸酯（1)的佔有比率 爲45重量％，剩餘部分係由其它的光聚合性單體佔有。另 外，依照IR分析，確認在反應產物中不存在異氰酸酯基。 (合成例2) 在內容量爲1L的5 口反應容器，添加142g甲基丙烯 酸環氧丙酯、77g丙烯酸、0.2g甲氧基苯酚、3g三苯基膦， 並在80°C使其反應12小時，來得到2-羥基-3-丙烯醯基丙 基甲基丙烯酸酯。 進一步在此添加490g三羥甲基丙烷的六亞甲基二異 氰酸酯力13 成物[CORONATE HL(曰本 POLYURETHANE(股） 製）]，並在60 °C使其反應8小時，來得到含有多官能丙烯 酸酯（2)之產物，該多官能丙烯酸酯（2)具有（甲基）丙烯醯基 且胺基甲酸乙酯基數爲 4.82xl(T3mol/g、雙鍵基數爲 4.52xl(T3m〇l/g。產物中，多官能丙烯酸酯（2)的佔有比率 爲1 00重量％。又，依照IR分析，確認在反應產物中不存 •33- 201111910 在異氰酸酯基。 (丙烯酸樹脂A的合成及其溶液的調製） 在反應容器添加800份環己酮，並邊注入氮氣至容器 邊加熱至100 °C，且在同溫度以1小時滴入80.0份苯乙烯、 40.0份甲基丙烯酸、85.0份N，N-甲基丙烯酸甲酯、95.0份 甲基丙烯酸正丁酯及10.0份偶氮雙異丁腈的混合物來進行 聚合反應。 滴入後，進而在100 °C使其反應3小時後，添加使用 50份環己酮使2.0份偶氮雙異丁腈溶解而成之物，進而在 1 〇 〇 °C使其繼續反應1小時，來得到重量平均分子量爲約 3 0000、酸價爲87mgKOH/g之丙烯酸樹脂A的環己酮溶液。 冷卻至室溫後，將樹脂溶液取樣約2g，並在180 °C加 熱乾燥20分鐘且測定非揮發性成分，並將在前面所合成的 樹脂溶液以非揮發性成分成爲2 0重量％的方式添加乙二醇 單甲基醚乙酸酯來調製丙烯酸樹脂A溶液。 (丙烯酸樹脂B〜E的合成及該溶液的調製） 依照下述表1所表示的單體組成、起始劑（偶氮雙異丁 腈）及其量（重量份）且使用與上述丙烯酸樹脂A的合成方法 同樣地進行丙烯酸樹脂B〜E之合成，來調製該等的溶液。 又’所合成的樹脂之酸價、重量平均分子量係如下述表1 所表示。 [表1] 丙烯酸 樹脂溶液 苯乙烯 MA MMA nBMA A1BN 酸價 "----- 分子量 A 80.0 40.0 85.0 95.0 2.0 87 3000Π~~~ B 80.0 25.3 100.0 95.0 6.0 55 1¾ C 80.0 56.1 101.0 95.0 3.5 122 21900 D 80.0 9.7 115.0 95.0 1.5 21 3820(Ρ~ E 80.0 75.0 106.0 95.0 1.7 1 163 35〇m' 201111910 但是，上述表1中的簡碼等係各自如以下。 MA :甲基丙烯酸 ΜΜΑ :甲基丙烯酸甲酯 ηΒΜΑ:甲基丙烯酸正丁酯 ΑΙΒΝ :偶氮雙異丁腈 (樹脂型分散劑溶液1的調製） 使用市售的樹脂型分散劑亦即日本LUBRIZOL公司製 SOLSPERSE 56000及乙二醇單甲基醚乙酸酯並調製成爲非 揮發性成分爲40重量％之溶液，且使用作爲樹脂型分散劑 溶液1。 (樹脂型分散劑溶液2的調製） 使用市售的樹脂型分散劑亦即CIBA JAPAN公司製 「EFKA4 3 00」及乙二醇單甲基醚乙酸酯並調製成爲非揮發 性成分爲40重量％之溶液，且使用作爲樹脂型分散劑溶液 2 ° [實施例1] 將11.0份鹵化鋅酞菁系綠色顏料（C.I.顏料綠58)、2.5 份上述樹脂型分散劑溶液、40·0份上述丙烯酸樹脂A溶液 及46.5份乙二醇單甲基醚乙酸酯的混合物均勻地攪拌混合 後’使用直徑〇.5mm的氧化锆珠粒並藉由艾格爾碾磨機 (Eiger mill)(EIGER JAPAN 公司製「MINIMODEL M-250 MKII」）分散5小時後，使用5·0μιη的過濾機過濾來製造綠 色顏料分散體。 隨後’將40.0份上述綠色顏料分散體、22.4重量份丙 烯酸樹脂Α溶液、2.9重量份作爲光聚合性單體之於合成 -35- 201111910 例1所合成的多官能丙烯酸酯（1)、0.2份光聚合起始劑 (CIBA JAPAN 公司製「IRGACURE OXE-02」）、34.5 份環 己酮、乙二醇單甲基醚乙酸酯及乙基-3-乙氧基丙酸酯的混 合溶液之混合物均勻地攪拌混合後，使用直徑1 . 〇 μΐΏ的過 濾機過濾而得到鹼顯影型綠色光阻材1。 [實施例2 ' 3] 與實施例1同樣地使用多官能丙烯酸酯（1)作爲光聚合 性單體，除了將添加量變更爲下述表1所表示的量以外， 與實施例1同樣地進行，來製造下述表1所表示組成之鹼 顯影型綠色光阻材2、3。 [實施例4] 除了將綠色顏料分散體減量爲20.0份以外，與實施例 2同樣地進行，來製造下述表1所表示組成之驗顯影型綠 色光阻材4。 [實施例5] 除了將綠色顏料分散體增量爲5 0 · 0份以外，與實施例 2同樣地進行，來製造下述表1所表示組成之驗顯影型綠 色光阻材5。 [實施例6] 除了將光聚合性單體變更爲在合成例2所合成的多官 能丙烯酸酯（2)以外，與實施例1同樣地進行，來製造下述 表1所表示組成之鹼顯影型綠色光阻材6。 [實施例7〜8 ] 除了使用多官能丙烯酸酯（2)作爲光聚合性單體，並將 添加量變更爲下述表1所記載的量以外，與實施例6同樣 -36- 201111910 地進行，來製造下述表1所表示組成之鹼顯影型綠色光阻 材7〜8。 [實施例9] 除了將上述綠色顔料分散體減量爲20.0份以外，與實 施例7同樣地進行，來製造下述表1所表示組成之鹼顯影 型綠色光阻材9。 [實施例10] 除了將上述綠色顏料分散體增量爲50.0份以外，與實 施例7同樣地進行，來製造下述表2所表示組成之鹼顯影 型綠色光阻材1 0。 [實施例1 1 ] 除了將光聚合性單體變更爲含有二新戊四醇五丙烯酸 酯及二新戊四醇六丙烯酸酯之單體（東亞 '合成公司製 「ARONIX M-402」）以外，與實施例1同樣地進行，來製 造下述表1所表示組成之鹼顯影型綠色光阻材11。 [實施例12、13] 除了使用含有二新戊四醇五丙烯酸酯及二新戊四醇六 丙烯酸酯之單體（東亞合成公司製「ARONIXM-402」）作爲 光聚合性單體，並將添加量變更爲下述表1所記載的量以 外，與實施例11同樣地進行，來製造下述表1所表示組成 之鹼顯影型綠色光阻材12、13。 [實施例14] 除了將上述綠色顔料分散體減量爲2 0.0份以外，與實 施例1 2同樣地進行，來得到鹼顯影型綠色光阻材1 4。詳 細的組成係如下述表1所表示。 -37- 201111910 [實施例15] 除了將上述綠色顏料分散體增量爲50.0份以外，與實 施例1 2同樣地進行，來得到下述表2所表示組成之鹼顯影 型綠色光阻材1 5。 -38- 201111910 Μ 實施例 15 PG58 經 线gg r癍 M-402 OXE-02 環己酮 /PGMAc/ EEP ο 窆 ο 式 00 rn cs d Ο cs (N 100.0 29.3% 1 辑2 卹 PG58 丙烯酸 樹脂A M-402 OXE-02 環己酮 /PGMAc/ EEP ο 异 ο ON CS o o； VO 100.0 29.3% 實施例 13 PG58 裝sg M-402 ΌΧΕ-02 環己酮 /PGMAc/ EEP ο ο ο r^* 00 cn rs o p 100.0 29.3% 實施例 12 PG58 趦< KM M-402 OXE-02 環己酮 /PGMAc/ EEP ο ο ο 〇\ o (N 〇 00 100.0 式 29.3% 實施例 11 PG58 經c 裝Sg KM M-402 OXE-02 1 環己酮 /PGMAc/ EEP ο ο VO (S <N 〇 00 100.0 〇 29.3% 實施例 _10 ；PG58 趦c ΐε艇 多官能 丙烯酸 酯(2) OXE-02 | 環己酮 /PGMAc/ EEP ο 佘 oo 00 v〇 CN 〇 cs 寸 100.0 36.7% 實施例 9 PG58 丙烯酸 樹脂A 多官能 丙烯酸 酯(2) OXE-02 | 環己酮 /PGMAc/ EEP ο o m o K (N d 00 100.0 14.7% 實施例 8 PG58 趑< K癍 多官能 丙烯酸 酯(2) OXE-02 環己酮 /PGMAc/ EEP ρ ο o d ό (N 〇 σί 100.0 ! 29.3% 實施例 7 PG58 趦c 跋Sg 1E艇 多官能 丙烯酸 酯(2) Γ〇ΧΕ-02 | 環己酮 /PGMAc/ EEP ο ο V〇 〇s <N 〇 rn 寸 100.0 29.3% 實施例 6 PG58 趙<1 KU 多官能 丙烯酸 酯(2) OXE-02 環己酮 /PGMAc/ EEP ρ ο 00 oi (N rn fS d «η m 100.0 Ό 29.3% 實施例 5 PG58 趙C 跋S5 1E® 多官能 丙烯酸 酯(1) OXE-02 環己酮 /PGMAc/ EEP ο 戋 o 卜 vri CN d 100.0 36.8% 實施例 4 PG58 m< 跋鹊 多官能 丙烯酸 酯⑴ OXE-02 環己酮 /PGMAc/ EEP ο 异 q ΓΛ 卜 CN o 100.0 14.7% 實施例 3 PG58 經<ί ^gg KM 多官能 丙烯酸 酯⑴ OXE-02 環己酮 /PGMAc/ EEP ο 专 〇 寸 00 n d 〇\ 100.0 1 29.3% : 1 實施例 2 PG58 經<c 跋sg E靼 多官能 丙烯酸 酯⑴ OXE-02 I 環己酮 /PGMAc/ EEP ο ο 卜 <s o σ> μ 100.0 29.3% 實施例 1 PG58 經c 缑Sg KM- 多官能 丙烯酸 酯⑴ OXE-02 環己酮 /PGMAc/ EEP ο ο 寸 cs Os CS <N 〇 yr) 100.0 -1 29.3% 1 顏料種 透明樹脂 m 4niS 光聚合起始劑 有機溶劑 顔料 分散體 透明樹脂 光聚合性 單體 光聚合 起始劑 有機溶劑 合計 fr 豳 固體成分中 顔料量 画[Technical Field] The present invention relates to a coloring composition for a color filter used in the manufacture of a color filter used in a color liquid crystal display device, a color image sensor, or the like. And the color filter that makes it. [Prior Art] The liquid crystal display device controls the display of the light passing through the first polarizing plate by controlling the degree of polarization of the light passing through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. The device can be displayed in color by providing a color filter between two polarizing plates. The color filter is formed on the surface of a transparent substrate such as glass, and two or more different types of fine-grained (striped) filter segments are arranged in parallel or in a crosswise manner, or the fine filter segments are fixed in the longitudinal direction. The configuration of the distribution is the same. The filter segments are finely divided to several μηι to several hundreds μπι, and each color phase is arranged neatly in a predetermined arrangement. Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of the transparent electrode and the alignment film, it is usually necessary to carry out the formation at a high temperature of 200 ° C or higher, preferably 23 ° C or higher. Therefore, in the current method for producing a color filter, a method in which a pigment excellent in light resistance and heat resistance is used as a colorant is called a pigment dispersion method. For the quality items required for color filters, comparison and brightness can be cited. When using a low contrast color filter, it will disturb the degree of polarization of the 201111910 controlled by the liquid crystal, and when light is isolated (OFF state), light leakage occurs, or when light must be transmitted (ON state), transmitted light is attenuated. Become a blurry picture. Therefore, in order to realize a high-quality liquid crystal display device, a high contrast system is indispensable. Further, when a color filter having a low luminance is used, since the transmittance of light is low, the screen is darkened, and in order to obtain a bright screen, it is necessary to increase the number of backlights, that is, the number of backlights. Therefore, from the viewpoint of suppressing an increase in power consumption, the high luminance of the color filter tends to be. In general, in order to achieve high brightness and high contrast of the color filter, it is necessary to produce a pigment dispersion which is close to the primary particle in a near-limit manner. Thereby, the scattering of the light by the pigment can be suppressed, and by increasing the transparency of the dispersion, the spectral spectrum of the dispersion can be made to have a high transmittance, and a high-intensity, high-contrast color filter can be produced. The green color of one of the three primary colors (red, green, blue; RGB) of the color filter substrate is usually a copper phthalocyanine pigment (for example, C.I. Pigment Green 36 or C.I. Pigment Green 7) as a main pigment. However, as long as a copper halide phthalocyanine pigment is used, it may be difficult to have both contrast and high brightness. In order to solve such problems, a zinc halide phthalocyanine pigment is used as a green pigment which exhibits vivid color tone and a broad color display region and has high coloring power, and the zinc halide phthalocyanine pigment is centered from the current copper halide phthalocyanine pigment. The metal is replaced by zinc (see, for example, the patent literature). However, the zinc halide phthalocyanine pigment has a higher acidity than the copper halide phthalocyanine pigment. Due to the high acidity, the liquid crystal 201111910 phase which is deposited on the color filter layer is easily dissolved and extracted because it exhibits high solubility compared to other pigment types. Therefore, the voltage holding rate is lowered, and display unevenness occurs, and misalignment occurs, which is a cause of deterioration in performance as a liquid crystal display element. At present, the voltage retention ratio is more than 9 5% with respect to the use of other pigments, and the zinc halide phthalocyanine pigment is desirably 90% or less and is expected to be improved. A liquid crystal display device in which a color filter having a low voltage holding ratio is incorporated, which causes uneven display or a fixed image, and the image never changes, that is, the image continues to remain, which is not good. In order to increase the voltage holding ratio, it has become a major issue to manufacture a color filter system using a zinc halide phthalocyanine pigment as a green pigment. Further, due to the high acidity, it is difficult to ensure dispersion stability of the zinc halide phthalocyanine pigment compared to other pigment types, and a phenomenon in which crystal foreign matter is generated can be observed in the state of storage over time. When the crystal foreign matter was generated, a favorable coating film could not be formed, and the coloring composition was unacceptable. In the case of using a pigment other than the above-mentioned zinc halide phthalocyanine pigment, as a method for improving the voltage holding ratio, Patent Document 2 discloses the addition of an epoxy group-containing compound or an oxetane ring-containing compound. Methods for various compounds. However, compared with a copper halide phthalocyanine pigment, a zinc halide phthalocyanine pigment having a high acidity is very difficult to obtain a color filter having a good voltage holding ratio and exhibiting unevenness in alignment, poor alignment, and good dispersion stability over time. The composition is colored by photosensitivity. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2004-70342 (Patent Document 2) JP-A-2000-292920A No. 201111910 SUMMARY OF THE INVENTION The object of the present invention is to provide a color filter, A color filter having the same, and a display device having a low voltage holding ratio using a green crystal display device comprising a zinc halide phthalocyanine pigment, and a method for solving the problem In the first aspect of the present invention, a photosensitive coloring composition containing at least a coloring coloring agent, a photopolymerizable monomer, a resin, and a photoactive photosensitive coloring composition, which is characterized by the functional amine group, is provided. The ethyl formate acrylate is 15% by weight or more and 45 or more, and the dipentaerythritol pentaacrylate and ester are more than 25% by weight of the solid content of the photosensitive coloring composition. In the range, the acrylate has a (meth) propylene fluorenyl group of f 0.7xl0_3mol/g or more, and the double bond group number is 4·5 χ. The polyfunctional isocyanate group has a hydroxyl group (methyl group. Moreover, The color filter of the coloring composition and the color filter has a liquid crystal ratio of 90% or more. According to the second aspect of the present invention, the photosensitive coloring composition is provided to contain at least a coloring coloring. The photosensitive coloring group of the coloring agent, the photopolymerizable monomer, the resin, and the ring light sheet can improve the brightness of the liquid which is a problem in the case of the pigment, and the halogen color is used for the color filter. A green polymerization initiator and a solvent of a zinc phthalocyanine pigment, and a photopolymerizable single system in which a solid weight% or less of a polychromatic coloring composition contains dipentaerythritol hexaacrylic acid as a reference at 10% by weight of a polyfunctional amine The ethyl carbureate ethyl benzoate has a base number of 1 (T3 mol/g or more and is:) acrylate, and has a voltage holding using the photosensitive display element for a color filter for a zinc halide phthalocyanine A green coloring compound of a pigment, a photopolymerizable photosensitive coloring composition obtained by photopolymerization from 201111910, and a solvent, characterized in that the epoxy compound is a zinc halide phthalocyanine in the photosensitive coloring composition. When the weight is 100 parts by weight, it contains 10 to 300 parts by weight and an epoxy equivalent of 100 to 500 (g/eq: molecular weight per one epoxy group = molecular weight + number of epoxy groups), and the photosensitive property The liquid crystal display element having a color filter obtained by using the photosensitive coloring composition has a voltage holding ratio of 90% or more. [Effect of the Invention] According to the present invention, it is possible to manufacture a copper bismuth halide. A cyanine pigment is a color filter having a higher brightness as a green pigment. Further, since the green pigment component eluted from the green colored layer to the liquid crystal can be reduced at the same time, a photosensitive coloring composition for a color filter can be obtained. The voltage holding ratio of the liquid crystal display device which has been a problem in the conventional use of a zinc halide phthalocyanine pigment has been lowered. [Embodiment] Hereinafter, various embodiments of the present invention will be described. The coloring composition for a color filter according to the first embodiment of the present invention contains a green coloring agent containing a zinc halide phthalocyanine pigment, a photopolymerizable monomer, a non-photosensitive resin, and/or a photosensitive resin, and an polymerization initiation. Agent and solvent. Hereinafter, each constituent component of the coloring composition for a color filter will be described. <Green coloring agent> The photosensitive coloring composition for a color filter according to the first embodiment of the present invention is characterized in that a green coloring agent containing a zinc halide phthalocyanine pigment is used. When a representative zinc halide phthalocyanine pigment is shown by the dye index (C.I.) number table 201111910, C.I. Pigment Green 58 or the like can be given. High brightness which cannot be obtained by other green pigments can be obtained by the zinc halide phthalocyanine pigment. In the case of a zinc halide phthalocyanine pigment, it can be obtained by a well-known production method. In particular, when the hexylamine is used as a basic substance produced by the method described in the color materials 67 [9] and 547-554 (19 94), the acidic functional group on the surface of the pigment is preferably 1 Å. More than pm 〇 1 g, more preferably 200 pmol / g or more. Further, since the zinc halide phthalocyanine pigment exhibits high acidity and has high solubility compared to other pigment species, the voltage holding ratio is liable to be low and it is difficult to ensure pigment dispersion stability. Therefore, when a photosensitive coloring composition containing a zinc halide phthalocyanine pigment is mixed with another substance, the pigment dispersion system is liable to become unstable, and the zinc halide phthalocyanine pigment is easily crystallized, especially when it contains a basic substance. It is a problem that a salt of a zinc halide phthalocyanine pigment having a high acidity is precipitated as a foreign matter. As described above, in the production of a color filter using a zinc halide phthalocyanine pigment, it is a problem to suppress the occurrence of crystal foreign matter and to increase the voltage holding ratio. The green colorant is not only a zinc halide phthalocyanine pigment, but also other green pigments or yellow pigments for the purpose of adjusting color or complementary color. Other green pigments which can be used in combination include C.I. Pigment Green 7, 10, 36, 37 and the like. Further, other yellow-green pigments that can be used in combination include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 1〇4 201111910 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 13 8' 139, 14 7, 150, 15 1, 152, 153' 154, 15 5 > 156, 16 1 , 162, 164 ' 166, 167, 168, 169, 170, 171, 172, 173, 174 , 175, 176, 177, 178, 179, 180, 18 1, 182, 18 5, 187, 18 8, 193, 194, 198, 199, 213, 214, and the like. Among them, it is preferred to use C.I. pigment yellow 138, 139, 150, 185. The content of the preferred pigment component in the total nonvolatile component of the photosensitive coloring composition of the present embodiment is preferably from 10 to 90% by weight, preferably from 15 to 85% by weight, from the viewpoint of obtaining sufficient color reproducibility. It is preferably 20 to 80% by weight. When the content of the pigment component is less than 1% by weight, it is difficult to obtain sufficient color reproducibility, and when the content is more than 90% by weight, the content of the pigment carrier becomes low, and the stability of the colored composition tends to be deteriorated. The zinc halide phthalocyanine pigment is 20 to 100% by weight based on the total weight of the pigment component, the copper phthalocyanine pigment is 〇80% by weight, and the yellow pigment is 〇~50% by weight. The more preferable pigment ratio is based on the pigment component, the zinc halide phthalocyanine pigment is 50 to 90% by weight, the copper halide phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. The chromaticity region can be enlarged by the composition ratio of such a pigment. In the photosensitive coloring composition of the present embodiment, the photosensitive coloring composition of the present embodiment is applied to a glass substrate or the like in the same color as the photosensitive coloring composition using a copper halide phthalocyanine pigment, and the coating film is measured. The transmittance is higher in the vicinity of 45 Onm to 53 Otim, and the transmittance is higher than that of the colored composition using the copper phthalocyanine pigment. Especially at the peak of the transmission -10- 201111910 rate, the transmittance is about 5% higher, which means about 90% of the enthalpy. Therefore, by combining the backlights which are usually used in a color liquid crystal display device, it is possible to obtain high luminance which cannot be obtained by using a photosensitive coloring composition of a halogenated copper phthalocyanine pigment such as C.I. Pigment Green 36 or C.I. Pigment Green 7. The pigment used in the photosensitive coloring composition of the present embodiment is preferably a material obtained by subjecting it to a salt milling treatment. The salt milling treatment uses a kneader of a kneader, a two-roll mill, a three-roll mill, a ball mill, a vertical ball mill, a sand mill, etc., while heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent. After mechanical kneading, the treatment of removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water is carried out. The water-soluble inorganic salt acts as a pulverization aid, and it is considered that the salt is pulverized by the high hardness of the inorganic salt during salt milling, whereby an active surface is formed to cause crystal growth. Therefore, the pulverization and crystal growth of the pigment are simultaneously generated at the time of kneading, and the primary particle diameter of the obtained pigment differs depending on the kneading conditions. The crystal growth is promoted by heating, and the heating temperature is preferably 40 to 150 °C. When the heating temperature is less than 40 ° C, the crystal growth is insufficient, and the shape of the pigment particles is close to amorphous, which is not preferable. On the other hand, when the heating temperature is higher than 150 °C, the crystal growth progresses excessively, and the primary particle diameter of the pigment becomes large, which is unsuitable as a coloring material for a coloring composition for a color filter. The kneading time of the salt milling treatment is preferably from 2 to 24 hours from the balance of the particle size distribution of the primary particles of the salt-milled pigment and the cost of the salt-grinding treatment. By optimizing the conditions for salt-milling the pigment, the primary particle size is very fine, and a pigment having a narrow distribution and a sharp particle size distribution can be obtained. -11-201111910 The primary particle diameter obtained by TEM (transmission electron microscope) of the green pigment contained in the photosensitive coloring composition of the present embodiment is preferably in the range of 20 to 100 nm. When the primary particle diameter is less than 20 nm, it is difficult to disperse in an organic solvent, and when it is larger than 100 nm, it is difficult to obtain a sufficient contrast. The range of 25 to 85 nm is particularly preferable. As the water-soluble inorganic salt used in the salt milling treatment, sodium chloride, cesium chloride, potassium chloride, sodium sulfate or the like can be used, and sodium chloride (salt) is preferably used in terms of price. The water-soluble inorganic salt is preferably 50 to 2000% by weight, and preferably 300 to 1000% by weight, based on the total weight of the pigment component, in terms of both the treatment efficiency and the production efficiency. The water-soluble organic solvent used in the salt milling treatment is not particularly limited as long as it is a pigment and a water-soluble inorganic salt, and is a water-soluble inorganic salt which can be dissolved (mixed) in water and substantially insoluble. However, in the salt-grinding treatment, the temperature is increased to cause the solvent to evaporate. From the viewpoint of safety, a boiling point of 12 (high-boiling solvent of TC or higher is preferable. Specific examples of the water-soluble organic solvent can be used. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or liquid polypropylene glycol, etc. The water-soluble organic solvent is based on the total weight of the pigment component, in the range of 5 to 1 000% by weight. It is preferably used in an amount of 50 to 500% by weight. In the case of salt-grinding, a resin may be added as needed. The type of the resin to be used is not particularly limited, and a natural resin or a modified natural resin can be used. -12- 201111910 Synthetic resin or synthetic resin modified with natural resin. The fat is preferably solid at room temperature and is insoluble in water, and is partially soluble in the above water-soluble organic solvent. The resin is used in an amount of 5 to 200% by weight based on the total weight of the pigment component. The range is good. <Pigment Derivative> In the coloring composition for a color filter of the present embodiment, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. The pigment derivative may be a compound obtained by introducing an iminoimine methyl group having a basic substituent 'acid substituent or a substituent to the organic pigment, anthracene, acridone or a triple well. Among these compounds, an organic pigment derivative represented by the formula P-Lm is preferred. In the general formula P-Lm, P is an organic pigment residue, and L is an integer having a basic substituent, an acidic substituent or a substituent which may be an imine methyl group, and a 111 system i to 4. The organic pigment derivative can be described, for example, in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, JP-A-5-9469, and the like. The above can be used alone or in combination of two or more types. The compounding amount of the organic pigment derivative is preferably from 1 to 50 parts by weight based on 1 part by weight of the pigment, more preferably from 3 to 3 parts by weight, more preferably from 5 to 25 parts by weight. When the pigment derivative is less than 1 part by weight based on 1 part by weight of the pigment, the dispersibility may be deteriorated, and when it is more than 5 parts by weight, heat resistance and light resistance may be deteriorated. -Lm, an organic pigment constituting an organic pigment residue of P, -13-201111910, for example, an azo pigment such as a diketopyrrolopyrrole pigment azo, a disazo, or a polyazo : phthalocyanine pigments such as copper phthalocyanine, copper phthalocyanine and metal-free phthalocyanine; amine guanidine, diamine bismuth, lysin, ketone, ketone, ketone, ketone Anthraquinone pigments such as anthrone and purpurin; quinophthalone pigments; diterpenoid pigments; perinone pigments; anthraquinone pigments; thioindigo pigments: isoindoles : isoindolinone pigment; quinoline yellow pigment: threne pigment: and metal complex pigment. In the photosensitive coloring composition for a color filter of the present invention, a dye derivative is preferably used for the purpose of improving the dispersibility of the pigment. <Photopolymerizable monomer> The photopolymerizable monomer is a monomer which induces polymerization by a radical. In particular, it means that a compound having an ethylenically unsaturated double bond is formed by irradiating ultraviolet rays to a colored composition to form a transparent resin, and the photopolymerizable monomer also contains an average molecular weight of about 1,000, which is usually called an oligomer. Oligomers and those having ethylenically unsaturated double bonds. When the photopolymerizable monomer is used, the amount of the green colorant is preferably from 10 to 300% by weight based on the total amount of the green colorant, and from 10 to 200 weights from the viewpoint of photocurability and developability. % is better. Specific examples of the photopolymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Monofunctional (meth) acrylates such as cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tricyclodecyl (meth) acrylate; polyethylene glycol di(methyl) Difunctional (such as acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acryl-14-201111910 acid ester Acrylates; trimethylolpropane tri(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra(meth) acrylate, dipentaerythritol hexa a trifunctional or higher polyfunctional (meth) acrylate such as methyl acrylate or dipentaerythritol penta (meth) acrylate: 1,6-hexanediol diepoxypropyl ether, and bisphenol A Epoxy compounds such as diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, and phenol novolak resin The reaction of acrylic acid, that is, epoxy (meth) acrylate; various polyester (meth) modified with polyester 'polyurethane, iso-cyanurate, methylolated melamine, etc. Acrylates; and (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, a monomer other than a (meth) acrylate such as N-methylol (meth) acrylamide, N-vinylformamide or acrylonitrile, and these may be used alone or in combination of two or more kinds, but are not necessarily limited. In these. The other photopolymerizable monomer which can be used as the photosensitive composition of the present embodiment includes a (meth) acrylonitrile group obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group. A functional urethane acrylate or an acrylate containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Further, the combination of the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate is optional and is not particularly limited. In addition, the acrylate containing one type of polyfunctional urethane or dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate may be used singly or in combination of two or more. Here, examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and trimethylolpropane-15-201111910. Acrylate, neopentyl alcohol tri(meth) acrylate, ditrimethylolpropane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ring Oxygen ethane modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerin Acrylate methacrylate, glycerin dimethacrylate, 2-hydroxy-3. propylene propyl methacrylate, reaction of epoxy group-containing compound with carboxy (meth) acrylate, hydroxyl group Polyol polyacrylate, etc. The polyfunctional isocyanate may, for example, be tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate or polyisocyanate. The photopolymerizable monomer which can be used in the photosensitive composition of the present embodiment contains the above-mentioned polyfunctional urethane acrylate, or dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. The ester acrylate may have a component having a double bond group as a further monomer having a double bond group having a (meth) propylene when reacting the polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group. The thiol-based polyfunctional urethane acrylate is not available. Further, the above-mentioned polyfunctional urethane acrylate has a base group of 0.7 χ 10 3 mol/g or more and a double bond group of 4.5 x 1 (T3 m 〇 l / g or more is preferred. Polyfunctional urethane) When the ethyl acrylate base number of the ethyl ester acrylate is less than 0.7 x 10 _3 mo Ι / g, the photosensitive composition after hardening is easily swollen by a drug or a solvent, and a transparent electrode (ITO) formed on the photosensitive composition layer ) cracks may occur, or the liquid crystal phase layered in the photosensitive composition layer may be easily extracted. Therefore, the voltage retention rate is lowered to -16119110, and display unevenness occurs, resulting in poor alignment, etc., resulting in liquid crystal The performance of the display element is low, and the display quality is greatly lowered. Further, the double bond base is less than 4.5x1 (at T3mol/g, since the exposure sensitivity is low and the resolution is deteriorated, neither case is preferable. <Polymerization Initiator> In the coloring composition for a color filter of the present embodiment, photopolymerization is added in order to cure the composition by ultraviolet irradiation or to form a filter segment by using a lithography method. Starting agent. The amount of the photopolymerization initiator is preferably from 5 to 200% by weight based on the total amount of the pigment, and more preferably from 1 to 150% by weight from the viewpoint of photocurability and developability. As the photopolymerization initiator, nonylphenidinium dichloride, 4-tris-butyl-dichloroacetonitrile, diethoxyethylbenzene, 1-(4-isopropylphenyl) can be used. )-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butane An acetophenone photopolymerization initiator such as 1-ketone or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one; benzoin, Benzoin photopolymerization initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; diphenyl ketone, benzamidine Benzoic acid, methyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl ketone, benzoated diphenyl ketone, and 4-benzylidene-4,-methyldiphenyl Diphenyl ketone photopolymerization initiator such as thioether; 9-oxosulfonate, comet, 2-chloro-9-oxosulfonate, 2-methyl-9-oxosulfonate, 9-oxosulfide D hawthorn photopolymerization initiator of isopropyl-9-oxosulfonate and 2,4-diisopropyl 9-oxosulfonium [1] comet; etc.; 2,4,6 -Trichloro-s-three tillage, 2-phenyl- 4,6-bis(trichloromethyl)-s-triterpenoid 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tripper, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Tri-trap, 2-piperonyl-17- 201111910 -4,6-bis(trichloromethyl)-s-tripper, 2,4-bis(trichloromethyl)-6-styryl-S·II Bismuth, 2-(naphthoquinone-1-yl)-4,6-bis(trichloromethyl)-S-triterpene, 2-(4-methoxy-naphthoquinone-1-yl)-4 ,6-bis(trichloromethyl)_5_three tillage, 2,4-trichloromethyl-(piperidinyl)-6-trimole, and 2,4-trichloromethyl (4,-methoxyl) Three-well photopolymerization initiators such as styryl)-6-tritrap, etc.: boron photopolymerization initiator; oxazole photopolymerization initiator; imidazole photopolymerization initiator; and oxime ester light A polymerization initiator or the like. The above photopolymerization initiators may be used singly or in combination of two or more. A-decyloxyester, decylphosphine oxide, methylphenyl glyoxylate, diphenylethylenedione, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4,-di can also be used in combination. Ethyl isodecyl benzophenone, 3,3', 4,4'-tetrakis(tertiary butylperoxycarbonyl)diphenyl ketone, and 4,4'-diethylaminodiphenyl ketone The compound acts as a sensitizer. When the sensitizer is used, the amount of the sensitizer is preferably from 3 to 60% by weight based on the photopolymerization initiator, and from 5 to 50% by weight from the viewpoint of photocurability and developability. good. <Solvent> The coloring composition for a color filter of the present embodiment contains a solvent for sufficiently dispersing the pigment on the pigment carrier and having a dry film thickness of 0.2 to 5 μm on a transparent substrate such as a glass substrate. It is easy to apply the coating to form the filter segments. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, and 1 , 3-butanediol diacetate, 1,4-dioxane, 2-heptanone '2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexanone -1-1-ketone, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3 -Methyl-1-201111910 Butanol, 3-methoxy-3-acetic acid methyl butyl ester, 3-methoxybutanol, 3-acetoxybutyl methacrylate, 4-heptanone, m-xylene, m-Diethylbenzene, m-dichlorobenzene 'N,N-dimethylacetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrole Pyridone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, dibutylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl Alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, Ethylene glycol monoterpene butyl ether, ethylene glycol monobutyl ether, ethylene Monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl _, ethylene glycol monomethyl hydrazine acetate, diisobutyl ketone, diethyl Glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Alcohol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, two Propylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl acid , propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, steam glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl acid, propylene glycol monomethyl ether, propylene glycol monomethyl Ethyl acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, B Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters and the like may be used alone or as a mixture of these two or more kinds thereof. <Epoxy compound> In the coloring composition for a color filter of the present embodiment, an epoxy compound of -19-201111910 may be mixed. The term "epoxy compound" refers to a compound having an epoxy group. When calcined in a color filter process, the epoxy group generates a thermosetting reaction to crosslink the surface and the interior of the coating film, and has the effect of inhibiting the zinc phthalocyanine pigment from the zinc halide or The impurity of the zinc halide phthalocyanine pigment dissolves into the liquid crystal phase. The epoxy compound may be a low molecular compound or a polymer compound, and representative examples thereof include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a hydrogenated bisphenol F system. Epoxy resin, epoxy resin, novolak type epoxy resin, cycloaliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, epoxypropylamine resin, epoxidized oil, etc. a brominated derivative of the above epoxy resin, or ginseng (epoxypropylphenyl)methane, trisepoxypropyl isomeric cyanurate or the like. Among them, a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a novolac epoxy resin, and a ring are used because the film has a high hardening density and has little adverse effect on the developability of the coloring composition. The aliphatic epoxy resin, the glycidyl ester resin 'epoxypropylamine resin, and the stilbene (glycidylphenyl) methane are preferred. Examples of the preferred commercially available epoxy compound which can be used in the present embodiment include EX1U and EX2 manufactured by NAGASECHEMTEX Co., Ltd. (U, EX411, EX901', EPPN501H manufactured by Sakamoto Chemical Co., Ltd., JER1 52 manufactured by JAPAN EPOXYRESIN Co., Ltd., etc. The compound is added in an amount of 10 to 3 parts by weight when the zinc halide phthalocyanine pigment in the photosensitive coloring composition is set to 1 part by weight. When the amount is less than 10 parts by weight, the hardening density of the film is lowered and the voltage is The effect of improving the retention rate is small. When the amount is more than 300 parts by weight, the amount of addition of the photopolymerizable monomer or the photopolymerization initiator is limited. In addition to the inability to ensure sufficient developability, -20-201111910, the stability over time is also Further, the term "epoxy equivalent" means the enthalpy defined by the "molecular weight + number of epoxy groups: unit g / eq" obtained from the chemical formula calculation of the epoxy compound, that is, the molecular weight per one epoxy group. In the present invention, the range of 100 to 500 is preferable, and the range of 100 to 250 is more preferable. When the epoxy equivalent is less than 1 Å, the hardenability is high and the crosslinking density of the film is too high, resulting in shrinkage upon hardening. Big without The film has flatness. When the epoxy equivalent is more than 500, the curability is insufficient and the effect of improving the voltage holding ratio is small. Further, in order to promote the curing of the epoxy compound, an epoxy curing agent may be used in combination. The curing agent is exemplified by two types of an acid-based curing agent and an amine-based curing agent, which are characterized in that the amine-based curing agent has a high reaction rate, and has a single component, which is difficult to stabilize, and is maintained by a liquid crystal phase extraction voltage. In the case where the rate is deteriorated, and the compatibility with the zinc phthalocyanine pigment is poor, and it is difficult to ensure the dispersion stability, the acid-based curing agent is preferably used in the present invention. Aenedioic acid, citric acid, tetrahydrofurfuric acid, hexahydrononanoic acid, pyrogal acid 'diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid 'diphenyl fluorene tetra An acid anhydride of a carboxylic acid, etc., in which it is preferable to have two or more anhydride groups in one molecule from the viewpoint of being able to construct a dense crosslinked structure, and optical properties such as good transmission at a short wavelength or The liquid crystal voltage retention rate remains high Cyclohexanone hospital tetracarboxylic dianhydride such as saturated hydrocarbon-based polyfunctional acid anhydride is preferred. <Resin> The colored composition of the present embodiment contains a resin. When the photosensitive coloring composition of the present invention contains a resin, the dispersion stability is improved. When the colored material layer 21 - 201111910 in which the colored filter is formed using the colored composition, a small amount of pigment aggregates can be obtained. A layer of colored material having good developability and pattern shape. The resin is preferably an alkali-soluble vinyl resin obtained by copolymerizing a thermoplastic resin, a thermosetting resin, or an acidic group-containing ethylenically unsaturated monomer, and an energy ray-curable resin having an ethylenically unsaturated active double bond. The spectral transmittance in the full-wavelength region of 400 to 7 〇 Onm in the visible light region is preferably 80% or more, more preferably 95% or more. The thermoplastic resin may, for example, be a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, or the like. Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin. Further, examples of the thermosetting resin include benzoquinone-well resin, rosin-modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, and phenol resin. When the photosensitive coloring composition of the color filter of the present embodiment is used in the form of an alkali-developing colored resist, copolymerization using an acidic group-containing ethylenically unsaturated monomer such as (meth)acrylic acid is used. Alkaloid-soluble ethylene-based resin is preferred as the binder resin. Further, as the binder resin, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. In the method for producing the resin, for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group is prepared as a precursor of the resin, and a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group is provided ( (meth)acrylic acid compound or cinnamic acid reaction, -22-201111910, a method of introducing a resin obtained by introducing a photocrosslinkable group such as a (meth)acryl fluorenyl group or a styryl group into the linear polymer; or A linear polymer having an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer or the like is a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate. The method of semi-esterification and the like. Among the binder resins, those having both alkali-soluble energy and energy ray-curing properties can be used as both of an alkali-soluble vinyl-based resin and an energy-line-curable resin having an ethylenically unsaturated active double bond. . In order to disperse the pigment well, the weight average molecular weight (Mw) of the resin is preferably in the range of 5,000 to 100,000, preferably in the range of 5,000 to 80,000, more preferably in the range of 5,000 to 30,000. Further, the number average molecular weight (?n) is preferably in the range of 5,000 to 50,000, and the Mw/Mn is preferably 10 or less. When the weight average molecular weight (Mw) of the resin is more than 100,000 or more, the interaction between the resins becomes strong, and the viscosity of the photosensitive coloring composition becomes high, which makes handling difficult. When the weight average molecular weight (Mw) is less than 5,000, the problem of developability or adhesion to a substrate such as glass may cause problems. The resin can be used in an amount of 0 to 500 parts by weight based on the total weight of the green colorant. When the amount is 30 to 500 parts by weight, and the amount is less than 30 parts by weight, the developability, film formability, and various resistances are likely to be insufficient. When the amount is more than 500 parts by weight, the pigment concentration is lowered to exhibit color characteristics. Further, from the viewpoints of pigment dispersibility, developability, and heat resistance, it is used as a carboxyl group of an alkali-soluble group at the time of pigment adsorption and development, an aliphatic group used as a pigment carrier, and an affinity group for a solvent of -23-201111910 and The balance of the aromatic group is important for pigment dispersibility, developability, and durability. Therefore, the acid value of the resin is preferably in the range of 20 to 300 mgKOH/g. The acid value is preferably in the range of 50 to 150 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, and it is difficult to form a fine pattern. When it is more than 300 mgKOH/g, there is a case where the fine pattern is not retained. Further, when the acid value is in the range of 50 to 150 mgKOH/g, the dispersion stability of the photosensitive colored composition is improved and the suppression of crystal foreign matter is further improved. <Leveling agent> In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition of the present embodiment. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by TORAY-DOWCORNING Co., Ltd., BYK-3 3 3 manufactured by BYK-Chemie Co., Ltd., and the like. Specific examples of the dimethyl siloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Further, dimethyl siloxane having a polyether structure in the main chain and dimethyl methoxy alkane having a polyester structure in the main chain may be used in combination. The content of the leveling agent is generally 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight). Preferred examples of the leveling agent include a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Although the leveling agent has a hydrophilic group, it has a small solubility in water. Therefore, when it is added to a colored composition, it has a feature that its surface tension reducing performance is low. Moreover, 'in this leveling agent' -24-201111910 is useful for the wettability of the glass sheet despite the low surface tension reduction performance, and is used in the amount of coating film defects caused by no occurrence of foaming. Among them, it is preferable that the chargeability can be sufficiently suppressed. The leveling agent is preferably a dimethylpolysiloxane having a polyalkylene oxide unit. The polyalkylene oxide unit has a polyethylene oxide unit and a polypropylene oxide unit, and the dimethyl polyoxyalkylene may have both a polyethylene oxide unit and a polypropylene oxide unit. Further, the bonding form of the polyalkylene oxide unit to the dimethyl polyoxyalkylene may be any one of the following, including: a repeating unit in which the polyalkylene oxide unit is bonded to the dimethyl polyoxyalkylene. a side-by-side type; a terminally modified type bonded to the end of a dimethyl polyoxane; and a linear block copolymer which is alternately and repeatedly bonded with dimethyl polyoxyl Type. A dimethylpolysiloxane having a polyalkylene oxide unit, which is commercially available from TORAY-DOWCORNING Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166' FZ-219 FZ-2203 'FZ-2207, but not limited by this" In the leveling agent, an anionic, cationic, nonionic or amphoteric surfactant may also be added in an auxiliary manner. It is also possible to use a surfactant in a mixture of two or more types. The anionic surfactant which is auxiliaryly added to the leveling agent may, for example, be an alkali metal salt of a polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate or a styrene-acrylic acid copolymer. Sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate 'Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate , monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkane-25-201111910-based ether phosphate, etc. The cationic surfactant which is auxiliaryly added to the leveling agent may be an alkyl 4-grade ammonium salt or the like. Ethylene oxide adducts. The nonionic surfactant to be auxiliaryly added to the leveling agent may, for example, be a polyoxyethylene oil methyl ether, a polyoxyethylene lauryl ether, a polyoxyethylene nonylphenyl ether or a polyoxyethylene alkyl ether phosphate. , polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; may also be an alkyl dimethylamino acetic acid betaine, alkyl imidazoline and other amphoteric surfactants, and Fluorine-based or polyoxo-based surfactant. <Other components> In order to stabilize the viscosity of the composition over time, the colored composition of the present embodiment can contain a storage stabilizer. Further, in order to improve the adhesion to the transparent substrate, it is also possible to contain an adhesion promoter such as a decane coupling agent. Examples of the storage stabilizer include a grade 4 ammonium chloride such as benzyltrimethyl chloride or diethylhydroxylamine: an organic acid such as lactic acid or oxalic acid, and a methyl ether thereof; a tertiary butyl catechol; An organophosphine such as ethylphosphine or tetraphenylphosphine; a phosphite. The storage stabilizer is used in an amount of 0.1 part by weight to 1 part by weight based on 100 parts by weight of the pigment in the coloring composition. Examples of the adhesion-improving agent include vinyl decanes such as vinyl ginseng (β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane; γ-methyl propylene methoxy propylene (Meth)propenyl decanes such as trimethoxy decane; β-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)methyl Trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltriethoxy decane, β-(3,4-epoxycyclohexyl)methyltriethoxy fluorene-26-201111910环-glycidoxypropyltrimethoxy sands, γ-glycidoxypropyl diethoxy sands, etc.; Ν-β(aminoethyl)γ-amine Propyltrimethoxydecane, Ν-β (aminoethyl) γ-aminopropyltriethoxydecane, Ν_ρ (amine ethyl) γ-aminopropylmethyldiethoxylate, γ-amine C Triethoxy silane, γ-aminopropyl trimethoxy decane, Ν-phenyl-γ-aminopropyltrimethoxy decane, fluorenyl-phenyl-γ-aminopropyltriethoxy decane, etc. Amino decanes; 丫_hydrothiopropyltrimethoxy sands, γ-hydrothiopropyl three Sulfur oxanes such as ethoxylate sands. The decane coupling agent is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, per part by weight of the pigment in the coloring composition. The photosensitive coloring composition of the present embodiment can use a green coloring agent containing at least a zinc halide phthalocyanine pigment, preferably in a coloring agent carrier such as a resin or an organic solvent together with a dye derivative and/or a dispersing aid. It is manufactured by finely dispersing various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and a vertical ball mill. Further, the photosensitive colored composition of the present embodiment may be produced by mixing a plurality of types of coloring agents in a colorant carrier. <Dispersion aid> When the colorant is dispersed in the colorant carrier, a dispersion aid such as a resin type dispersant or a surfactant can be suitably used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, the photosensitive coloring composition to be used is formed by dispersing a coloring agent in a colorant carrier using a dispersing aid. A color filter having a high spectral transmittance can be obtained. -27- 201111910 Resin-type dispersant has: a coloring agent affinity site, which has a property of adsorbing to a coloring agent; and a site compatible with the coloring agent carrier; the action is to adsorb the coloring agent and stabilize the coloring agent to coloring Dispersion of the carrier. As the resin type dispersant, specifically, a polycarboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, or a polycarboxylic acid can be used. Ammonium salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, hydroxyl group-containing polycarboxylate or the like, poly(lower alkylene imine) and An oily dispersant such as guanamine or a salt thereof formed by reacting a polyester having a free carboxyl group, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene - a water-soluble resin such as a maleic acid copolymer, a polyvinyl alcohol or a polyvinylpyrrolidone or a water-soluble polymer compound, a polyester type, a modified polyacrylate type, or an ethylene oxide / propylene oxide An addition compound, a phosphate ester type, etc. can be used individually or in mixture of 2 or more types. The surfactant may, for example, be sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali metal salt of a styrene-acrylic acid copolymer, sodium stearate or an alkane. Sodium naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, An anionic surfactant such as polyoxyethylene alkyl ether phosphate; polyoxyethylene oil decyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, poly a nonionic surfactant such as oxyethylene sorbitan monostearate or polyethylene glycol monolaurate; a cationic interface such as an alkyl 4-grade ammonium salt or such an ethylene oxide adduct An active agent; an alkyl beet such as alkyl dimethylaminoacetic acid betaine, etc. - 201111910 base; an amphoteric surfactant such as an alkyl imidazoline. These may be used alone or in combination of two or more. (Removal of coarse particles) The coloring composition containing the above-described respective components can be in the form of a printing ink for gravure offset printing, a waterless offset printing ink, an ink for silk screen printing, a solvent developing type or an alkali developing type colored photoresist. To modulate. Further, the colored photoresist is obtained by dispersing a colorant in a composition containing a transparent resin, a monomer, a photopolymerization initiator, and an organic solvent. The coloring composition of the embodiment of the present invention is preferably a coarse particle of 5 μm or more, more preferably a coarse particle of Ιμη or more, and more preferably 0.5 μm or more, by means of a centrifugal separation, a sintered filter, a membrane filter or the like. Removal of coarse particles and mixed dust is desirable. As described above, the colored composition of the present embodiment preferably contains no particles of 0.5 μm or more. It is more preferable that the particle diameter is 0.3 μm or less (according to the particle diameter of S EM ). Next, a color filter according to a second embodiment of the present invention will be described. The color filter of the second embodiment of the present invention can be produced by the printing method or the lithography method using the coloring composition of the first embodiment described above. The formation of the filter segment by the printing method is capable of patterning by repeating printing and drying of the colored composition prepared by printing ink, and is a method for producing a color filter, which is low-cost and mass-produced. excellent. Moreover, due to the development of printing technology, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. For printing, the composition of the colored composition is preferably such that the ink does not dry on the printing plate or on the tape, and -29-201111910 is cured. Further, it is also important to control the fluidity on the printing press, and it is also possible to use a dispersing agent or an extender pigment to adjust the viscosity of the ink. When the filter segment is formed by the lithography method, the colored composition prepared by the solvent development type or the alkali development type colored photoresist is used, and spray coating, spin coating, slit coating, roll coating, or the like is used. The coating method was applied to a transparent substrate so that the dried film thickness was 0.2 to 5 μm. Ultraviolet exposure is performed by a photomask provided in a state of being in contact with or not in contact with the film and having a predetermined pattern as needed. Subsequently, the desired layer is formed by immersing in a solvent or an alkaline developer or by spraying the developer with a spray or the like to remove the uncured portion, and the same operation is repeated for the other colors to produce a color filter. Further, in order to promote polymerization of the colored photoresist, heating may be performed as needed. When the lithography method is used, it is possible to manufacture a color filter having a higher precision than the above printing method. At the time of development, an aqueous solution of sodium carbonate or sodium hydroxide can be used as the alkaline developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer. Further, in order to enhance the ultraviolet exposure sensitivity, after applying the colored photoresist and drying, an aqueous solution or an alkali water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to prevent polymerization inhibition by oxygen. After the film, ultraviolet exposure was performed. The color filter of the present embodiment can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, and any of the above-described coloring compositions can be used. Further, the electrodeposition method produces a color filter by using a transparent conductive film formed on a substrate and electrode-forming a filter segment of each color by electrophoresis on the transparent conductive film by electrophoresis of the colloidal particles. Further, -30-201111910 The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer substrate, and the filter segment is transferred to a desired substrate. The color filter of the present embodiment includes at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one green filter segment uses the color of the first embodiment of the present invention described above. The filter is formed using a colored composition. The red filter segments can be formed using a typical red coloring composition. The red coloring composition can be used, for example, C. I. Pigment Red 7, 14, 4, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2 , red pigments of 81:3, 81:4, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202 '208, 210, 246 '254, 255, 264' 270, 272, 279, etc. . In the red coloring composition, an orange pigment such as CI Pigment Orange 43, 71, 73, and/or CI Pigment Yellow 1, 2, 3' 4, 5, 6, 10, 12, 13, 14, 15, 16 may be used in combination. , 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65 '73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 , 123, 126, 127, 128, 129, 138, 139, 147 '150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172 Yellow pigments of 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, and the like. Further, the blue filter segment can be formed using a general blue coloring composition. As the blue coloring composition, for example, a blue pigment such as C.I. Pigment Blue 15, 15:1, -31-201111910 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64 or the like can be used. Further, in the blue coloring composition, a violet pigment such as C.I. pigment purpura, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 may be used in combination. Before the filter segments are formed on the transparent substrate or the reflective substrate, if a black matrix is formed in advance, the contrast of the liquid crystal display panel can be further improved. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film obtained by dispersing a light-shielding agent can be used, but it is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the over-fired sheet section ' on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved. On the color filter, a protective film or a column spacer, a transparent conductive film, a liquid crystal alignment film, or the like can be formed as needed. The color filter is bonded to the opposite substrate by using a sealant, and after the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a phase difference is attached to the outside of the substrate as needed. A film can manufacture a liquid crystal display panel. Such a liquid crystal display panel can be used for TN (Twisted Nematic), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA) A liquid crystal display mode in which color filters are used to colorize, such as OCB (Optically Compensatory Bend). [Examples] Hereinafter, examples and comparisons of a synthetic example of a polyfunctional acrylate as a photopolymerizable monomer and a coloring sensitivity group of 32-201111910 containing various photopolymerizable monomers will be specifically described. The invention is not limited by the embodiments, and various modifications can be made without departing from the spirit and scope of the invention. In addition, the "parts" of the examples are "parts by weight". Further, Mw and Μη each mean a number average molecular weight and a weight average molecular weight. (Synthesis Example 1) 623 g of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) and 44 g of hexamethylene diisocyanate were added to a 5-port reaction vessel having a content of 1 L, and the mixture was made at 60 ° C. The reaction was carried out for 8 hours to obtain a product containing a polyfunctional acrylate (1) having a (meth) acrylonitrile group and a urethane base number of 1.64 x 1 (T3 mol/g, double The number of bond groups was 8.22×l (T3m〇l/g. In the product, the occupation ratio of the polyfunctional acrylate (1) was 45% by weight, and the remainder was occupied by other photopolymerizable monomers. Further, it was confirmed by IR analysis. The isocyanate group was not present in the reaction product. (Synthesis Example 2) In a 5-port reaction vessel having a content of 1 L, 142 g of glycidyl methacrylate, 77 g of acrylic acid, 0.2 g of methoxyphenol, and 3 g of triphenylphosphine were added. And reacting at 80 ° C for 12 hours to obtain 2-hydroxy-3-propenyl propyl methacrylate. Further, here, 490 g of trimethylolpropane hexamethylene diisocyanate was added. [CORONATE HL (曰本POLYURETHANE)) and make it reverse at 60 °C 8 hours, to obtain a product containing a polyfunctional acrylate (2) having a (meth) acrylonitrile group and a urethane base number of 4.82 x 1 (T3 mol/g, double bond group number) The ratio of the polyfunctional acrylate (2) to the product was found to be 100% by weight. Further, according to IR analysis, it was confirmed that the isocyanate group was not contained in the reaction product. (Synthesis of Acrylic Resin A and Preparation of Its Solution) Add 800 parts of cyclohexanone to the reaction vessel, and heat to 100 ° C while injecting nitrogen gas into the vessel, and add 80.0 parts of styrene, 40.0 at the same temperature for 1 hour. a polymerization reaction was carried out by mixing a mixture of methacrylic acid, 85.0 parts of N,N-methyl methacrylate, 95.0 parts of n-butyl methacrylate and 10.0 parts of azobisisobutyronitrile. After the dropwise addition, further at 100 ° C After reacting for 3 hours, 50 parts of cyclohexanone was added to dissolve 2.0 parts of azobisisobutyronitrile, and the reaction was further continued at 1 ° C for 1 hour to obtain a weight average molecular weight of about 3 0000, cyclohexanone of acrylic resin A having an acid value of 87 mg KOH/g After cooling to room temperature, the resin solution was sampled to about 2 g, and dried by heating at 180 ° C for 20 minutes, and the non-volatile component was measured, and the resin solution synthesized in the foregoing was made into a non-volatile component of 20% by weight. Ethylene glycol monomethyl ether acetate was added to prepare an acrylic resin A solution. (Synthesis of acrylic resin B to E and preparation of the solution) According to the monomer composition and initiator described in Table 1 below ( Azobisisobutyronitrile) and its amount (parts by weight) were synthesized in the same manner as in the above-described method of synthesizing the acrylic resin A to prepare the solutions. Further, the acid value and weight average molecular weight of the synthesized resin are shown in Table 1 below. [Table 1] Acrylic resin solution Styrene MA MMA nBMA A1BN Acid value"----- Molecular weight A 80.0 40.0 85.0 95.0 2.0 87 3000Π~~~ B 80.0 25.3 100.0 95.0 6.0 55 13⁄4 C 80.0 56.1 101.0 95.0 3.5 122 21900 D 80.0 9.7 115.0 95.0 1.5 21 3820 (Ρ~ E 80.0 75.0 106.0 95.0 1.7 1 163 35〇m' 201111910 However, the short codes and the like in Table 1 above are each as follows. MA: 甲基 methacrylate: methacrylic acid Ester ηΒΜΑ: n-butyl methacrylate ΑΙΒΝ : azobisisobutyronitrile (preparation of resin type dispersant solution 1) A commercially available resin type dispersant, SOLSPERSE 56000 and ethylene glycol monomethyl group manufactured by LUBRIZOL Co., Ltd., was used. The ether acetate was prepared into a solution having a nonvolatile component content of 40% by weight, and was used as a resin type dispersant solution 1. (Preparation of Resin Type Dispersant Solution 2) A commercially available resin type dispersant, that is, CIBA JAPAN was used. EFKA4 3 00 and ethylene glycol monomethyl ether acetate were prepared and prepared into a solution having a nonvolatile content of 40% by weight, and used as a resin type dispersant solution 2 ° [Example 1] 11.0 parts Zinc halide A mixture of a cyanine green pigment (CI Pigment Green 58), 2.5 parts of the above resin type dispersant solution, 40.0 parts of the above acrylic resin A solution, and 46.5 parts of ethylene glycol monomethyl ether acetate is uniformly stirred and mixed. The zirconia beads having a diameter of 55 mm were dispersed by an Eiger mill ("MINIMODEL M-250 MKII" manufactured by EIGER JAPAN Co., Ltd.) for 5 hours, and then filtered using a 5.00 μm filter. Green pigment dispersion. Subsequently, 40.0 parts of the above green pigment dispersion, 22.4 parts by weight of an acrylic resin hydrazine solution, and 2.9 parts by weight of a photopolymerizable monomer were synthesized in the synthesis of -35-201111910. 1), 0.2 parts of photopolymerization initiator ("IRGACURE OXE-02" manufactured by CIBA JAPAN Co., Ltd.), 34.5 parts of cyclohexanone, ethylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionic acid The mixture of the ester mixed solutions was uniformly stirred and mixed, and then filtered using a filter having a diameter of .μΐΏ to obtain an alkali-developing type green photoresist 1. [Example 2 ' 3] Polyfunctional acrylic acid was used in the same manner as in Example 1. Ester (1) as a photopolymerizable single The alkali-developing type green photoresists 2 and 3 having the compositions shown in Table 1 below were produced in the same manner as in Example 1 except that the amount of the addition was changed to the amount shown in the following Table 1. [Example 4] The green-developing type green photo-resist material 4 having the composition shown in the following Table 1 was produced in the same manner as in Example 2 except that the amount of the green pigment dispersion was reduced to 20.0 parts. [Example 5] The green-developing type green photo-resist material 5 having the composition shown in the following Table 1 was produced in the same manner as in Example 2 except that the green pigment dispersion was increased to 50% by weight. [Example 6] An alkali development of the composition shown in Table 1 below was carried out in the same manner as in Example 1 except that the photopolymerizable monomer was changed to the polyfunctional acrylate (2) synthesized in Synthesis Example 2. Type green photoresist 6. [Examples 7 to 8] The same procedure as in Example 6 was carried out in the same manner as in Example 6 except that the polyfunctional acrylate (2) was used as the photopolymerizable monomer, and the amount of addition was changed to the amount described in Table 1 below. The alkali-developing type green photoresists 7 to 8 having the compositions shown in Table 1 below were produced. [Example 9] An alkali-developing type green photoresist 9 having the composition shown in Table 1 below was produced in the same manner as in Example 7 except that the amount of the green pigment dispersion was reduced to 20.0 parts. [Example 10] An alkali-developing type green photoresist 10 having the composition shown in Table 2 below was produced in the same manner as in Example 7 except that the green pigment dispersion was increased to 50.0 parts. [Example 1 1] In addition to changing a photopolymerizable monomer to a monomer containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ARONIX M-402 manufactured by Toagosei Co., Ltd.) In the same manner as in Example 1, an alkali-developing type green photoresist 11 having the composition shown in Table 1 below was produced. [Examples 12 and 13] A monomer containing dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("ARONIX M-402" manufactured by Toagosei Co., Ltd.) was used as a photopolymerizable monomer, and The alkali-developing type green photoresist members 12 and 13 having the compositions shown in Table 1 below were produced in the same manner as in Example 11 except that the amount of the addition was changed to the amount shown in the following Table 1. [Example 14] An alkali-developing type green photoresist member 14 was obtained in the same manner as in Example 12 except that the amount of the green pigment dispersion was reduced to 20.0 parts. The detailed composition is as shown in Table 1 below. -37-201111910 [Example 15] An alkali-developing type green photoresist 1 having the composition shown in Table 2 below was obtained in the same manner as in Example 12 except that the green pigment dispersion was increased to 50.0 parts. 5. -38- 201111910 实施 Example 15 PG58 warp gg r癍M-402 OXE-02 cyclohexanone/PGMAc/ EEP ο 窆ο 00 rn cs d Ο cs (N 100.0 29.3% 1 series 2 shirt PG58 acrylic resin A M-402 OXE-02 cyclohexanone / PGMAc / EEP ο different ο ON CS oo; VO 100.0 29.3% Example 13 PG58 loaded with sg M-402 ΌΧΕ-02 cyclohexanone / PGMAc / EEP ο ο ο r^* 00 Cn rs op 100.0 29.3% Example 12 PG58 趦 < KM M-402 OXE-02 cyclohexanone / PGMAc / EEP ο ο ο 〇 \ o (N 〇 00 100.0 式 29.3% Example 11 PG58 via C Sg KM M-402 OXE-02 1 cyclohexanone / PGMAc/ EEP ο ο VO (S <N 〇00 100.0 〇29.3% Example _10 ; PG58 趦c ΐ 艇 boat multi-functional acrylate (2) OXE-02 | cyclohexanone / PGMAc / EEP ο 佘oo 00 v〇CN 〇cs inch 100.0 36.7% Example 9 PG58 Acrylic Resin A Polyfunctional Acrylate (2) OXE-02 | Cyclohexanone / PGMAc / EEP ο omo K (N d 00 100.0 14.7% Example 8 PG58 趑 < K癍 Multifunctional Acrylate (2) OXE-02 Cyclohexanone / PGMAc / EEP ρ ο od ό (N 〇σί 100.0 ! 29.3% Example 7 PG58 趦c 跋Sg 1E Boat Multifunctional Acrylate (2) Γ〇ΧΕ-02 | Cyclohexanone / PGMAc / EEP ο ο V〇〇s <N 〇 rn inch 100.0 29.3% Example 6 PG58 Zhao <1 KU Multifunctional Acrylate (2) OXE-02 Cyclohexanone / PGMAc / EEP ρ ο 00 oi (N rn fS d «η m 100.0 Ό 29.3% Example 5 PG58 Zhao C 跋S5 1E® Multifunctional Acrylic Ester (1) OXE-02 cyclohexanone / PGMAc / EEP ο 戋o 卜 vri CN d 100.0 36.8% Example 4 PG58 m < 跋鹊 polyfunctional acrylate (1) OXE-02 cyclohexanone / PGMAc / EEP ο iso q ΓΛ 卜 CN o 100.0 14.7% Example 3 PG58 < ί ^ gg KM polyfunctional acrylate (1) OXE-02 cyclohexanone / PGMAc / EEP ο 〇 00 n d 〇 \ 100.0 1 29.3% : 1 Example 2 PG58 <c 跋sg E靼 Multifunctional Acrylate (1) OXE-02 I Cyclohexanone /PGMAc/ EEP ο ο <s o σ> μ 100.0 29.3% Example 1 PG58 via c 缑Sg KM-polyfunctional acrylate (1) OXE-02 cyclohexanone /PGMAc/ EEP ο ο inch cs Os CS <N 〇yr) 100.0 -1 29.3% 1 Pigment type transparent resin m 4niS Photopolymerization initiator Organic solvent Pigment dispersion Transparent resin Photopolymerizable monomer Photopolymerization initiator Organic solvent total fr 颜料 Pigment amount in solid content painting
〇\ CO 201111910 [比較例1 ] 除了使用多官能丙烯酸酯（1)作爲光聚合性單體 添加量變更爲下述表2所記載的量以外，與實施例 地進行，來製造下述表2所表示組成之鹼顯影型綠. 材16。 [比較例2] 除了使用多官能丙烯酸酯（2)作爲光聚合性單體 添加量變更爲下述表2所記載的量以外，與實施例 地進行，來製造下述表2所表示組成之鹼顯影型綠 材17。 [比較例3 ] 除了使用含有二新戊四醇五丙烯酸酯及二新戊 丙烯酸酯之單體（東亞合成公司製「ARONIXM-402」 光聚合性單體，並將添加量變更爲下述表2所記載 外，與實施例1 1同樣地進行，來製造下述表2所表 之鹼顯影型綠色光阻材1 8。 [比較例4] 除了將光聚合性單體變更爲己內酯改質二新戊 丙烯酸酯（日本化藥公司製「DPCA-30」）以外，與實 同樣地進行，來製造下述表2所表示組成之鹼顯影 光阻材1 9。 [比較例5、6 ] 除了使用己內酯改質二新戊四醇六丙烯酸酯（ 藥公司製「DPCA-30」）作爲光聚合性單體，並將添 更爲下述表2所記載的量以外，與比較例4同樣地 ，並將 1同樣 色光阻 ，並將 6同樣 色光阻 四醇六 )作爲 的量以 示組成 四醇六 施例1 型綠色 曰本化 加量變 進行， -40- 201111910 來製造下述表2所表不組成之鹼顯影型綠色光阻材2〇、21。 [比較例7] 除了使用鹵化銅酞菁綠色顏料（C.I.顏料綠36)代替鹵 化辞駄菁綠色顏料（C·1·顔料綠58)以外，與實施例2同樣地 進行’來製造下述表2所表示組成之鹼顯影型光阻材22。 [比較例8 ] 除了使用鹵化銅酞菁綠色顏料（C.I·顏料綠36)代替鹵 化鋅駄菁綠色顏料（C.I.顏料綠58)以外’與實施例7同樣地 進行’來製造下述表2所表示組成之鹼顯影型光阻材23。 [比較例9 ] 除了使用鹵化銅酞菁綠色顏料（C·;[•顏料綠36)代替鹵 化鋅酞菁綠色顏料（C.I·顔料綠58)以外，與實施例12同樣 地進行，來製造下述表3所表示組成之鹼顯影型光阻材2心 -41- 201111910 【ε嗽】 比較例9 PG36 獎SS 贮蕕 M-402 OXE-02 環己酮/ PGMAc/EEP 00 (N m (N ο <N Ο 37.70 100.0 29.3% 比較例8 PG36 丙烯酸 樹脂A 多官能 丙烯酸酯 _0_; OXE-02 環己酮/ PGMAc/EEP 〇〇 ΓΛ 00 ρ 卜· CN Ο 41.50 100.0 容 29.3% 1 比較例7 PG36 ! 氍< 褰Sg Km 多官能 丙烯酸酯 OXE-02 環己酮/ PGMAc/EEP 00 cs η OS 00 uS <N 42.50 100.0 〇 m 29.3% 比較例ό PG58 經c 跋鋰 DPCA30 OXE-02 環己酮/ PGMAc/EEP ο ο <N o 00 CN 〇 52.80 100.0 29.3% 比較例5 PG58 丙烯酸 樹脂Λ DPCA30 OXE-02 環己酮/ PGMAc/EEP ο ο «η — (N 〇 00 100.0 29.3% 比較例4 PG58 丙烯酸 樹脂A DPCA30 OXE-02 環己酮/ PGMAc/EEP ο CS 兮 o cn cs CN 〇i (N d Ό 100.0 \n 29.3% 比較例3 PG58 丙烯酸 樹脂A M-402 OXE-02 環己酮/ PGMAc/EEP ο ο 卜 o <N d Ό 00 CN 100.0 式 V-) 29.3% 比較例2 PG58 m< 嫂鋰 1E^ 多官能 丙烯酸酯 J2) OXE-02 環己酮/ PGMAc/EEP ο ο o 佘 CN (N d v〇 00 (N 100.0 容 in 29.3% 比較例1 PG58 M< 裝sg E艇 多官能 丙烯酸酯 __(D___ OXE-02 環己酮/ PGMAc/EEP ο ο o 〇 (N o 00 00 (N 100.0 29.3% 顏料麵 透明樹脂 光聚合性單體 光聚合起始劑 有機溶劑 顏料分散體 透明樹脂 光聚合性 單體 光聚合起始劑 |有機溶劑1 合計 固體成分中單體量 固體成分中顔料量 璀链 .0?i 201111910 (評價方法） 使用在以上實施例及比較例中所得到的 材1〜24來進行確認電壓保持率、亮度、異 各試驗。該等程序係如以下所表示。 (電壓保持率測定法） 將鹼顯影型光阻材1〜24使用旋轉塗布 的厚度爲1.8 μιη的方式塗布在玻璃基板（10 cr 使用50m J/cm2的曝光量進行曝光。隨後，藉 0.2重量％的碳酸鈉水溶液噴霧顯影30秒， 230 °C燒製，來得到光阻材1〜24的塗布基板 藉由從所得到的塗布基板削取0.0 5 g光 漬於 1 .5g 液晶（Merck(股）製、MLC-204 1 )，Μ 熟化60分鐘，且以4000rpm離心分離15分 清液來製造光阻萃取液晶試樣液。 另一方面，將2片具有ITO透明電極（有 lOmmxlOmm)之玻璃基板，以ITO透明電極 方式對向配置，並以液晶胞間隙爲9μιη的方 來製造小型液晶胞。 在該小型液晶胞的液晶胞間隙之間液入 試樣液並在60°C以電壓5V施加壓電60μ秒 Technica製VHR-1S測定電壓釋放後經過16. 晶胞電壓 測定係重複進行5，次並將所測定的電 後，使用所得到的液晶胞電壓’依照下述式 持率（％)。 鹼顯影型光阻 物產生狀況之 器以乾燥皮膜 nxlOcm)上，並 由使用23°C之 並使用烘箱於 〇 阻塗膜後，浸 S在1 2 0 °C烘箱 鐘後，採取上 效電極尺寸爲 之間係相向的 式使用密封劑 光阻萃取液晶 ，且使用東陽 6 7 m秒後之液 壓平均化。然 來求取電壓保 -43- 201111910 電壓保持率（％) = ([νΠ/5)χ1〇〇 電壓保持率（％)的評價基準係.如以下》 ◎:電壓保持率爲95%以上 〇：電壓保持率爲90%以上、小於95% △:電壓保持率爲85%以上、小於90% X :電壓保持率爲小於8 5 % (亮度的測定法） 從所得到的鹼顯影型光阻材1〜24使用旋轉塗布器並 變更轉速而以乾燥膜厚度係在CIE表色系的色度 y爲 0.62、0.6' 0.58的方式製造3個塗布基板。 塗布後在23 0°C使用熱風烘箱乾燥40分鐘後，測定各 自的膜厚度及對比，並從3個的數據以一次關連法求取色 度y爲0.6時之亮度及對比。色度係使用顯微分光光度計 (Olympus光學公司製「OSP-SP100」）來測定。 該等的結果係如下述表4所表示。 -44- 201111910 [表4] 顏料 種類 單體種類 單體添b曈 (固體成分中 重量 電壓 保持率 ί%) 亮度 實施例1 光阻材1 PG58 多官能 丙烯酸酯⑴ 15% 〇 55.8 實施例2 光阻材2 T Τ 30% 〇 55.6 實施例3 光阻材3 T ΐ 45% ◎ 55.3 實施例4 光阻材4 T Τ 30% 〇 55.1 實施例5 光阻材5 T ί T 〇 55.9 實施例6 光阻材6 T 多官能 丙烯酸酯(2) 15% 〇 55.6 實施例7 光阻材7 T Τ 30% 〇 55.2 實施例8 光阻材8 T Τ 45% ◎ 55.5 實施例9 光阻材9 T Τ 30% 〇 55.2 實施例10 光阻材10 t Τ t 〇 55.8 實施例11 光阻材11 T Μ-402 10% 〇 55.3 實施例12 光阻材12 T Τ 20% 〇 55.3 實施例13 光阻材13 t Τ 25% ◎ 55.6 實施例14 光阻材14 τ Τ 20% 〇 55.1 實施例15 光阻材15 τ Τ t 〇 55.9 比較例1 光阻材16 τ 多官能 丙烯酸酯Π) 5% X 55.1 比較例2 光阻材17 τ #官能 丙烯酸酯(2) Τ X 55.3 比較例3 光 沮材18 τ Μ-402 τ X 55.3 hMM 4 光 沮材19 个 DPCA30 15% X 55.4 比較例5 光 沮材20 个 Τ 30% X 55.3 比較例6 光 沮材21 个 Τ 45% X 55.8 比較例7 光阻材22 PG36 多官能 丙烯酸酯(1) 30% ◎ 52.3 比較例8 光阻材23 Τ 多官能 丙烯酸酯(2) Τ ◎ 52.3 比較例9 光阳材24 τ Μ-402 t ◎ 52.1 從上述表4，得知相較於使用鹵化銅酞菁綠色顏料之 光阻材22〜24，使用鹵化鋅酞菁綠色顏料之光阻材1〜21 係亮度優良。另一方面’得知雖然使用鹵化鋅酿菁綠色顏 料時電壓保持率低落’但是藉由使用規定量的多官能丙稀 酸酯作爲光聚合性單體（實施例1〜15)，能夠改善電壓保持 率。又，藉由增加多官能丙烯酸酯的添加量’電壓保持率 的改善度增加且能夠達成高電壓保持率。 -45- 201111910 相對於此’使用己內酯改質二新戊四醇六丙烯酸酯作 爲光聚合性單體來調製鹼顯影型綠色光阻材而成之比較例 4〜6’未觀察到電壓保持率的改善。又，即便使用與實施 例相同的光聚合性單體時，當其添加量少時（比較例1〜 3)，亦無法觀察到電壓保持率的改善。 如以上’藉由使用規定量之規定的光聚合性單體作爲 光聚合性單體，亦即感光性組成物的含有成分，能夠製造 電壓保持率優良之含鹵化鋅酞菁綠色顔料的鹼顯影型光阻 材。 [實施例16〜27、比較例10〜21] (綠色顏料分散體1的製造） 將1 1 ·0份鹵化鋅酞菁系顔料（C.I.顏料綠58)、2.5份上 述樹脂型分散劑溶液2、40.0份上述丙烯酸樹脂a溶液及 46.5份乙二醇單甲基醚乙酸酯的混合物均勻地攪拌混合 後，使用直徑〇.5mm的氧化鉻珠粒並藉由艾格爾碾磨機 (Eiger mill)(EIGER JAPAN 公司製「MINIMODEL M-250 MKII」分散5小時後’使用5·0μιη的過濾機過濾來製造綠 色顔料分散體1。 (綠色顏料分散體2的製造） 除了使用鹵化銅酞菁綠色顏料（C.I.顏料綠36)代替鹵 化鋅酞菁綠色顏料（C.I.顔料綠58)以外，與綠色顏料分散體 1同樣地進行，來製造綠色顏料分散體2。 將下述表5所表示的各組成物及其量（重量份）以成爲 均勻的方式各自攪拌混合後，使用直徑1.0 μη的過濾機過 濾而得到鹼顯影型綠色光阻材25〜48。 -46- 201111910 顯影性 <1 < < <!<]〇〇 〇〇〇〇〇 〇〇〇〇〇χ〇〇χχχ〇 異物 〇〇〇 〇〇〇〇 〇〇〇〇〇 〇〇〇<!<!〇0〇〇X Χ〇 亮度 50.2 50.2 50.3 50.1 50.1 50.2 50.3 50.2 50.1 50.2 50.2 50.3 50.3 50.2 50.2 50.2 50.2 50.1 50.3 50.1 50.1 50.1 50.1 47.1 霣IB 保持率 (%) ◎〇◎ ◎◎◎〇 〇〇〇〇◎ X X X X χ〇χ X Χ<1<^® 環氧 化飾/ PG58 綱 重量％ 114% T T t ! r ! 68% 23% 23% T T T 227% 0% 0% 0% 0% ! 0% 1 318% 8% 114% 114% 114% 114% 合計 o o o o o o o o o o o o ooo oooo o o o o o Ψ-Λ F-^ ^ 〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇 MM w^t Ψ^* 有機 溶劑 Φ 51.3 51.3 51.3 51.3 51.3 43.3 35.3 35.3 35.3 35.3 35.3 51.3 31.3 31.3 31.3 31.3 31.3 59.3 33.3 151.3 51.3 51.3 51.3 31.3 敏化劑 Φ ooo oooo ooooo ι〇ι/Ί*〇ν^»ο»〇»Λΐη*π»τ>ίΛ»ο ΟΟΟΟΟΟΟΟΟΟΟΟ 18¾ Φ r4 fS (N <N fS <N PM is CnJ rvj «Μ *·· Γ^ΓΝΐ<ΝίΝΓνί(Ν(Ν<Ν<ΝίΝ<ΝίΝ Ψ^β Μ* ^-1 νΜ νΜ 光， (NtNiN (NtNfSfN (NiSrSP^ra <S<Nr4<NiNCS(N(N(Nr«i<N<N 樹脂溶液 〇〇〇 〇〇2® SSSSS 懸 < < P3 U Q ω < urn atn Din ΰΰί i]tn Dni ΰΐπ 111 j j t〇2 U1J lllj - 1: ujj 1 I I I I ® ® 蹈蹈蹈艇靼 111 11趣趣 趦趣趦趦趙 ^ !g SI >g >g >g !g Ur U?7 li?7 lIT 1171 llT Ur tti. nx. ni_ HL r〇- to. < CQ U Q ω < < < flm flm am flm fltn flm fltn am iii^ *->i y 0¾ ιπ2 Q33 π 11 mj ujj ®g 靼靼整 | | | 3g 趙趣趙趦趦氍趦1 1 1 1趣 发遐捱逻线发践 跋 EKKEKEE K 環氧化合物 »〇v~>r〇 一一 — — — ooooor*»^«o»o»Ai〇〇 11 »nt*-〇N Ot-»i〇v*> fsj (*«· wm 11111=Ssllll m S Ccqu ω tt. < < <<<·<< ^ ^ ® ^ ^ ^ ^ g g © <π <π <π <|π Φ <c in <a <n <n <n <〇 嫲祕祕祕嘁嫲嘁 祕祕祕祕嫲 醛酹酹酹醛醛酹 m«m^m iiiiii μ μ 1i iiiiil 顔雛散體 _______ _{ ooo oooo ooooo 甘々甘 甘甘甘々 节兮守，ΓΊ m ·Μ W-* W 幽觀酸觀製廳S觀 親猫溢 齡藏齡雜 溢溢締溢齡 Φ Φ ¢: Φ; Φ Φ Φ Φ φ Φ Φ: Φ 金实龚 ^¾¾¾ ^¾¾¾¾ 魅魅魅 魅魅魅魅 瞄越魅藤魅 «μ r—a 觀£觀觀鹏趣觀製觀製 游雜經趣齡插經溢龜趣經猫 途:遠:¾¾¾¾¾¾途遠:¾¾ ,rv *Πχ *ΓΝ ^Ρν ^Γν 魅瞄魅赌魅魅魅魅氍魅魅瞇 光阻材 駿 itmll B 光阻材25 光阻材26 光阻材27 光阻材28 光阻材29 光阻材30 光阻材31 光阻材32 光阻材33 光阻材34 光阻材35 光阻材36 光阻材37 光阻材38 光阻材39 光阻材40 光阻材41 光阻材42 光阻材43 光阻材44 光阻材45 光阻材46 光阻材47 光阻材48 όγ*-οο Os© — rs m 守 ι〇ν〇 卜 —一— r^r^<N(N(N 辑辑揖 握揭握握 握握揖揖握 ·«- · ><- · M—· «i_. Μ. . Μ_ · «1- . Μ —. Μ . »1 . ·1 . 挪侧ρ WWKK Κ俩MKW 比較例10 比較例Π 比較例12 比較例13 比較例14 比較例15 比較例16 比較例17 比較例18 比較例19 比較例20 比較例21 201111910 但是，上述表5中的簡碼係各自如以下。 光聚合性單體：二新戊四醇六丙烯酸酯 光聚合起始劑· 2 -甲基-1-[4-(甲硫基）苯基]-2_味琳丙院-1_ _(CIBA JAPAN 公司製「IRGACURE 907」） 敏化劑：4,4’-二乙胺基二苯基酮（HODOGAYA公司製 「EAB-F」） 有機溶劑：乙二醇單甲基醚乙酸酯 環氧化合物A〜G:各自爲下述表6所表示。 丙烯酸化合物A〜G:各自爲下述表6所表示。 -48- 201111910 [表6] 酸物 嫌合C 丙化〇 \ CO 201111910 [Comparative Example 1] The following Table 2 was produced except that the amount of the photopolymerizable monomer added was changed to the amount described in the following Table 2 using the polyfunctional acrylate (1). The alkali-developing green material 16 of the composition is represented. [Comparative Example 2] The composition shown in Table 2 below was produced by using the polyfunctional acrylate (2) as the amount of the photopolymerizable monomer added in the amounts shown in Table 2 below. Alkali-developed green material 17. [Comparative Example 3] In addition to the use of a monomer containing dipentaerythritol pentaacrylate and dipentyl acrylate (ARONIX M-402) photopolymerizable monomer manufactured by Toagosei Co., Ltd., the amount of addition was changed to the following table. In the same manner as in Example 1, the alkali-developing type green photoresist member 18 shown in Table 2 below was produced in the same manner as in Example 1. [Comparative Example 4] The photopolymerizable monomer was changed to caprolactone. The alkali-developed photo-resist material 1 of the composition shown in the following Table 2 was produced in the same manner as in the above, except that the modified dipentyl acrylate ("DPCA-30" manufactured by Nippon Kayaku Co., Ltd.) was used. [Comparative Example 5 6] In addition to the use of caprolactone-modified dipentaerythritol hexaacrylate ("DPCA-30" manufactured by Pharmaceutical Co., Ltd.) as a photopolymerizable monomer, and adding the amount described in Table 2 below, In the same manner as in Comparative Example 4, the same color resist was used, and the amount of the same color resisting tetraol (6) was used as the composition of the composition of the tetraol six-component type 1 green mash, and was produced by -40-201111910. The alkali-developable green light-blocking materials 2, 21 which are not composed of the following Table 2 are shown. [Comparative Example 7] The following table was produced in the same manner as in Example 2 except that a copper halide phthalocyanine green pigment (CI Pigment Green 36) was used instead of the halogenated phthalocyanine green pigment (C·1·Pigment Green 58). 2 shows an alkali-developing type resist member 22 having a composition. [Comparative Example 8] The following Table 2 was produced except that a copper halide phthalocyanine green pigment (CI·Pigment Green 36) was used instead of the zinc halide phthalocyanine green pigment (CI Pigment Green 58) in the same manner as in Example 7. The alkali developing type resist member 23 of the composition is shown. [Comparative Example 9] The same procedure as in Example 12 was carried out except that a copper halide phthalocyanine green pigment (C·; [• Pigment Green 36) was used instead of the zinc halide phthalocyanine green pigment (CI·Pigment Green 58). Alkali development type resistive material 2 represented by Table 3 -41-201111910 [ε嗽] Comparative Example 9 PG36 Award SS Storage M-402 OXE-02 Cyclohexanone / PGMAc/EEP 00 (N m (N ο <N Ο 37.70 100.0 29.3% Comparative Example 8 PG36 Acrylic Resin A Multifunctional Acrylate_0_; OXE-02 Cyclohexanone / PGMAc/EEP 〇〇ΓΛ 00 ρ Bu · CN Ο 41.50 100.0 Capacity 29.3% 1 Comparative Example 7 PG36 ! 氍< 褰Sg Km Multifunctional acrylate OXE-02 Cyclohexanone / PGMAc/EEP 00 cs η OS 00 uS <N 42.50 100.0 〇m 29.3% Comparative Example PG58 via c 跋 Lithium DPCA30 OXE-02 Cyclohexanone / PGMAc / EEP ο ο <N o 00 CN 〇 52.80 100.0 29.3% Comparative Example 5 PG58 Acrylic Resin Λ DPCA30 OXE-02 Cyclohexanone / PGMAc/EEP ο ο «η — (N 〇00 100.0 29.3% Comparative Example 4 PG58 Acrylic Resin A DPCA30 OXE-02 Cyclohexanone / PGMAc/EEP ο CS 兮o cn cs CN 〇i (N d Ό 100.0 \n 29.3% Comparative Example 3 PG58 Acrylic resin A M-402 OXE-02 cyclohexanone / PGMAc / EEP ο ο 卜 o < N d Ό 00 CN 100.0 Formula V-) 29.3% Comparative Example 2 PG58 m< Lithium 1E^ Polyfunctional acrylate J2) OXE-02 cyclohexanone / PGMAc / EEP ο ο o 佘CN (N dv〇00 (N 100.0 in 293% Comparative Example 1 PG58 M< loaded sg E boat multi-functional acrylate __(D___ OXE-02 ring Ketone / PGMAc / EEP ο ο o 〇 (N o 00 00 (N 100.0 29.3% pigment surface transparent resin photopolymerizable monomer photopolymerization initiator organic solvent pigment dispersion transparent resin photopolymerizable monomer photopolymerization initiator In the total amount of the solid content, the amount of the pigment in the solid content is 璀 chain. 0?i 201111910 (Evaluation method) The materials 1 to 24 obtained in the above examples and comparative examples were used to confirm the voltage holding ratio, Brightness, different test. These procedures are as follows. (Measurement of Voltage Retention Rate) The alkali-developing type resist members 1 to 24 were applied to a glass substrate by spin coating at a thickness of 1.8 μm (10 cr was exposed using an exposure amount of 50 m J/cm 2 . A sodium carbonate aqueous solution was spray-developed for 30 seconds, and fired at 230 ° C to obtain a coated substrate of the photoresists 1 to 24 by removing 0.05 g of the light-sensitive coating from the obtained coated substrate to 1.5 g of liquid crystal (Merck ( )), MLC-204 1 ), Μ aging for 60 minutes, and centrifuging 15 minutes at 4000 rpm to produce a photoresist extraction liquid crystal sample solution. On the other hand, two sheets of ITO transparent electrode (with 10 mm x 10 mm) The substrate is disposed opposite to the ITO transparent electrode, and a small liquid crystal cell is fabricated with a liquid crystal cell gap of 9 μm. The sample liquid is introduced between the liquid crystal cell gaps of the small liquid crystal cell and applied at a voltage of 5 V at 60 ° C. Piezoelectric 60 μsec Technica VHR-1S measurement voltage was released after 16. The cell voltage measurement system was repeated 5 times, and the measured liquid crystal voltage was used, and the obtained liquid crystal cell voltage was used according to the following formula (%). Alkali-developed photoresist The condition of the device is dried on the film nxlOcm), and after using the oven at 23 ° C and using the oven to coat the film, the S is immersed in the oven clock at 120 ° C, and the size of the upper electrode is taken as the phase contrast. The formula uses a sealant photoresist to extract the liquid crystal, and uses the hydraulic averaging after Dongyang 6 7 m seconds. Then, the voltage is maintained at -43-201111910. Voltage holding ratio (%) = ([νΠ/5) χ1〇〇 Voltage holding ratio (%) is evaluated as follows. ◎: Voltage holding ratio is 95% or more〇 : The voltage holding ratio is 90% or more and less than 95% Δ: The voltage holding ratio is 85% or more and less than 90% X: The voltage holding ratio is less than 85% (measurement method of brightness) From the obtained alkali developing type resist The materials 1 to 24 were manufactured by using a spin coater and changing the number of revolutions to produce a three-coated substrate so that the chromaticity y of the CIE color system was 0.62 and 0.6' 0.58 in a dry film thickness. After coating, after drying at 230 ° C for 40 minutes in a hot air oven, the respective film thicknesses and contrasts were measured, and the brightness and contrast of the color y of 0.6 were obtained from the three data in a single correlation method. The chromaticity was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). The results are shown in Table 4 below. -44-201111910 [Table 4] Pigment type monomer type monomer addition b曈 (weight-voltage retention rate in solid content ί%) Brightness Example 1 Photoresist material 1 PG58 Multifunctional acrylate (1) 15% 〇55.8 Example 2 Photoresist 2 T Τ 30% 〇 55.6 Example 3 Photoresist 3 T ΐ 45% ◎ 55.3 Example 4 Photoresist 4 T Τ 30% 〇 55.1 Example 5 Photoresist 5 T ί T 〇 55.9 Example 6 Photoresist 6 T Multifunctional acrylate (2) 15% 〇 55.6 Example 7 Photoresist 7 T Τ 30% 〇 55.2 Example 8 Photoresist 8 T Τ 45% ◎ 55.5 Example 9 Photoresist 9 T Τ 30% 〇 55.2 Example 10 Photoresist 10 t Τ t 〇 55.8 Example 11 Photoresist 11 T Μ-402 10% 〇 55.3 Example 12 Photoresist 12 T Τ 20% 〇 55.3 Example 13 Light Resistive material 13 t Τ 25% ◎ 55.6 Example 14 Photoresist 14 τ Τ 20% 〇 55.1 Example 15 Photoresist 15 τ Τ t 〇 55.9 Comparative Example 1 Photoresist 16 τ Multifunctional acrylate Π) 5% X 55.1 Comparative Example 2 Photoresist 17 τ #functional acrylate (2) Τ X 55.3 Comparative Example 3 Photoaccuracy 18 τ Μ-402 τ X 55.3 hMM 4 Photoaccuracy 19 DPCA30 15% X 55 .4 Comparative Example 5 Photoaccuracy 20 Τ 30% X 55.3 Comparative Example 6 Photoaccuracy 21 Τ 45% X 55.8 Comparative Example 7 Photoresist 22 PG36 Polyfunctional acrylate (1) 30% ◎ 52.3 Comparative Example 8 Photoresist 23 Τ Polyfunctional acrylate (2) Τ ◎ 52.3 Comparative Example 9 Photoreceptor 24 τ Μ-402 t ◎ 52.1 From the above Table 4, it was found that the photoresist was compared with the use of a copper halide phthalocyanine green pigment. 22 to 24, the use of a zinc halide phthalocyanine green pigment photoresist material 1 to 21 is excellent in brightness. On the other hand, 'the voltage retention rate is low when using a zinc halide green pigment,' but the voltage can be improved by using a predetermined amount of a polyfunctional acrylate as a photopolymerizable monomer (Examples 1 to 15). Retention rate. Further, by increasing the amount of addition of the polyfunctional acrylate, the degree of improvement in the voltage holding ratio is increased and a high voltage holding ratio can be achieved. -45-201111910 No comparison was made between Comparative Examples 4 to 6' in which an alkali-developed green photoresist was prepared by using caprolactone-modified dipentaerythritol hexaacrylate as a photopolymerizable monomer. Improvement in retention rate. Further, even when the same photopolymerizable monomer as in the examples was used, when the amount of addition was small (Comparative Examples 1 to 3), improvement in voltage holding ratio was not observed. As described above, by using a predetermined amount of a photopolymerizable monomer as a photopolymerizable monomer, that is, a component containing a photosensitive composition, alkali development of a zinc halide-containing phthalocyanine green pigment excellent in voltage retention can be produced. Type of photoresist. [Examples 16 to 27, Comparative Examples 10 to 21] (Production of Green Pigment Dispersion 1) 1 1 · 0 parts of a zinc halide phthalocyanine pigment (CI Pigment Green 58), and 2.5 parts of the above resin type dispersant solution 2 40.0 parts of the above mixture of the acrylic resin a solution and 46.5 parts of ethylene glycol monomethyl ether acetate were uniformly stirred and mixed, and then chrome oxide beads having a diameter of 〇5 mm were used and passed through an Eiger mill (Eiger mill). (The MINIMODEL M-250 MKII manufactured by EIGER JAPAN Co., Ltd. was dispersed for 5 hours and then filtered using a 5.00 μm filter to produce green pigment dispersion 1. (Production of Green Pigment Dispersion 2) In addition to the use of copper halide phthalocyanine green The green pigment dispersion 2 was produced in the same manner as the green pigment dispersion 1 except that the pigment (CI pigment green 36) was used instead of the zinc halide phthalocyanine green pigment (CI pigment green 58). The compositions shown in Table 5 below were prepared. The materials and their amounts (parts by weight) were stirred and mixed in a uniform manner, and then filtered using a filter having a diameter of 1.0 μη to obtain alkali-developing type green photoresist members 25 to 48. -46 - 201111910 Developing property <1 <<<!<]〇〇〇〇 〇〇〇〇〇〇〇χ〇〇χχχ〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 <!<!〇0〇〇X Χ〇 brightness 50.2 50.2 50.3 50.1 50.1 50.2 50.3 50.2 50.1 50.2 50.2 50.3 50.3 50.2 50.2 50.2 50.2 50.1 50.3 50.1 50.1 50.1 50.1 47.1 霣 IB retention ratio (%) ◎〇◎ ◎◎◎〇〇〇〇〇◎ XXXX χ〇χ X Χ<1<^® Epoxy decoration/ PG58 重量重量% 114% TT t ! r ! 68% 23% 23% TTT 227% 0% 0% 0% 0% ! 0% 1 318% 8% 114% 114% 114% 114% Total oooooooooooo ooo oooo ooooo Ψ -Λ F-^ ^ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇MM w^t Ψ^* Organic solvent Φ 51.3 51.3 51.3 51.3 51.3 43.3 35.3 35.3 35.3 35.3 35.3 51.3 31.3 31.3 31.3 31.3 31.3 59.3 33.3 151.3 51.3 51.3 51.3 31.3 Sensitizer Φ ooo oooo ooooo ι〇ι/Ί*〇ν^»ο»〇»Λΐη*π»τ>ίΛ»ο ΟΟΟΟΟΟΟΟΟΟΟΟ 183⁄4 Φ r4 fS ( N <N fS <N PM is CnJ rvj «Μ *·· Γ^ΓΝΐ<ΝίΝΓνί(Ν(Ν<Ν<ΝίΝ<ΝίΝ Ψ^β Μ* ^-1 νΜ Μ光, (NtNiN (NtNfSfN (NiSrSP^ra <S<Nr4<NiNCS(N(N(Nr«i<N<N resin solution〇〇〇〇〇2® SSSSS suspension<< P3 UQ ω < Urn atn Din ΰΰί i]tn Dni ΰΐπ 111 jjt〇2 U1J lllj - 1: ujj 1 IIII ® ® 靼 靼 111 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 SI SI SI SI SI SI SI GE GE GE GE g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g g !g Ur U?7 li?7 lIT 1171 llT Ur tti. nx. ni_ HL r〇- to. < CQ UQ ω <<< flm flm am flm fltn flm fltn am iii^ *->iy 03⁄4 ιπ2 Q33 π 11 mj ujj ®g |整| | | 3g 赵趣赵趦趦氍趦1 1 1 1趣发遐挨 线线发跋 EKKEKEE K epoxy compound»〇v~>r〇 one- — ooooor*»^«o»o»Ai〇〇11 »nt*-〇N Ot-»i〇v*> fsj (*«· wm 11111=Ssllll m S Ccqu ω tt. <<<<<·<< ^ ^ ® ^ ^ ^ ^ gg © <π <π <π <|π Φ <c in <a <n <n <n < 〇嫲秘秘秘嘁嫲嘁秘秘秘秘嫲醛酹酹酹醛醛酹m«m^m iiiiii μ μ 1i iiiiil 颜雏散体_______ _{ ooo oooo ooooo Ganzi Gan Gan Gan Gan兮守,ΓΊ m ·Μ W-* W 幽 酸 观 厅 S 观 亲 溢 溢 藏 藏 藏 藏 Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ 3⁄43⁄43⁄4 ^3⁄43⁄43⁄43⁄4 Charm Enchantment Charm Charm Sight Charm μ « « « « « « « « « « « « « « « 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 《 3⁄43⁄4 , rv *Πχ *ΓΝ ^Ρν ^Γν Charm enchantment enchantment charm enchantment 眯 眯 it it itmll B photoresist material 25 photoresist material 26 photoresist material 27 photoresist material 28 photoresist material 29 light Resistor 30 Photoresist 31 Photoresist 32 Photoresist 33 Photoresist 34 Photoresist 35 Photoresist 36 Photoresist 37 Photoresist 38 Photoresist 39 Photoresist 40 Photoresist 41 Photoresist 42 Photoresist 43 Photoresist 44 Photoresist 45 Photoresist 46 Photoresist 47 Photoresist 48 όγ*-οο Os© — rs m 守ι〇ν〇卜—一—r^r^<N (N(N 辑 揖 揭 揭 揭 握 « « « « « « « « « « « « « « i i i i i i i i · i i · · · · · · · · · · · · · · · · · · · · · · · · 1. No. ρ WWKK Trick MKW Comparative Example 10 Comparative Example Π Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparison Comparative Example 18 Comparative Example 19 Comparative Example 20 21 201 111 910 However, the short code system in Table 5 are each as follows. Photopolymerizable monomer: dipentaerythritol hexaacrylate photopolymerization initiator · 2-methyl-1-[4-(methylthio)phenyl]-2_味琳丙院-1_ _(CIBA "IRGACURE 907" manufactured by JAPAN Co., Ltd.) Sensitizer: 4,4'-diethylaminodiphenyl ketone ("EAB-F" manufactured by HODOGAYA Co., Ltd.) Organic solvent: ethylene glycol monomethyl ether acetate epoxy Compounds A to G: each are represented by the following Table 6. The acrylic compounds A to G: each represented by the following Table 6. -48- 201111910 [Table 6] Acids
Ν,Ν-二甲基胺基乙基甲基丙烯酸酯 -49- 201111910 (評價方法） 使用以上實施例及比較例所得到的鹼顯影型光阻材25 〜48來進行確認電壓保持率、亮度、異物產生狀況及顯影 性之各試驗。又，電壓保持率的評價係如上述，亮度評價 的程序、結晶異物的觀察法及顯影性評價係如以下所表示。 (亮度的測定法） 將各鹼顯影型綠色光阻材使用旋轉塗布器並變更轉速 而以乾燥膜厚度係在CIE表色系之使用C光源的色度y爲 0.62、0.60、0.58的方式各自製造3個塗布基板。塗布後 在80 °C使用熱風烘箱乾燥30分鐘，並從3個的數據以一次 關連法求取色度y爲0.6時之亮度。色度係使用顯微分光 光度計（Olympus光學公司製「OSP-SP100」）來測定。 (結晶異物的觀察法） 將各鹼顯影型綠色光阻材30ml在40 °C的環境下靜置7 天，.並使用安裝在注射器之5 μιη孔徑的過濾器過濾後，使 用2 0ml乙二醇單甲基醚乙酸酯洗淨過濾器，並將過濾部取 下且使用顯微鏡觀察、評價在過濾器上殘留的異物。評價 基準係如以下。 〇：未觀察到異物 △:觀察到的異物爲5個以下 X:觀察到的異物爲大於5個之多數 (顯影性評價） 將各鹼顯影型綠色光阻材旋轉塗布在10x10cm的透明 玻璃基板上，並在70 °C進行預烘烤20分鐘來形成乾燥膜厚 度爲約2.0 μιη的塗膜，隨後以曝光量50m J/cm2進行紫外線 -50- 201111910 曝光’並算出以0.15重量％碳酸鈉、0.05重量％碳酸氫鈉、 0.1重量％陰離子系界面活性劑（花王公司製「PELEXNBLJ) 及99.7重量％水之鹼性顯影液溶解未曝光部的圖案全部之 時間（T 1 )，並將延長顯影時間至τ 1的1 . 5倍時間設作顯影 終點。在顯影終點，將曝光部無圖案缺損者評價爲〇’有 圖案缺損者爲X。 該等結果係如上述表5所表示。 實施例16〜27係含有含鹵化辞酞菁顏料的綠色著色 劑，且使用環氧當量爲100至500的環氧化合物’因爲環 氧化合物的添加量係相對於100重量份之鹵化鋅酞菁顏料 爲以1 0〜3 00重量份爲最佳添加量，所以顯示高亮度，而 且在電壓保持率（％)評價、異物評價' 所以顯影性評價之任 —者均顯示優良的結果。特別是實施例16〜18、19、20, 因爲充分地添加環氧當量爲在100〜250的範圍內之環氧 化合物，所以顯示良好的電壓保持率（％)之結果。 又，而且實施例21〜27係不僅是電壓保持率（％)，顯 影性亦顯示良好的結果，而且藉由使用樹脂酸價爲50〜 150mgKOH/g、重量平均分子量爲5,000〜1 00,000的樹脂， 能夠製造顯影性以及進一步結晶異物均優良的感光性著色 組成物。 相對於此，不添加環氧化合物之比較例1 0〜1 4，或環 氧化合物的添加量少之比較例1 6，使用環氧當量高的環氧 化合物之比較例1 7之任一者，均未觀察到電壓保持率（％) 的改善。又，因爲比較例1 5添加過量的環氧化合物，顯影 性產生問題。 -51 - 201111910 比較例1 8〜2 0係使用與環氧化合物同樣地 化性之丙烯酸化合物，但是未觀察到環氧化合物 電壓保持率改善效果，而且在結晶異物、顯影性 觀察到問題。 因爲比較例21係未使用鹵化鋅酞菁顏料，雖 持率（％)、結晶異物的產生係無問題，但是結果赛 從以上，得知藉由滿足使用環氧當量爲1〇〇~ 圍內之環氧化合物及環氧化合物的添加量係相對 量份鹵化鋅酞菁顏料爲10〜300重量份之條件， 顯像性良好，且抑制結晶異物之產生，且電壓保 之含有鹵化鋅酞菁顏料的彩色濾光片用感光性 物。 【圖式簡單說明】 姐。 【主要元件符號說明】 〇 具有熱硬 的程度之 的任一者 然電壓保 ;度變低。 / 5 0 0的範 於1〇〇重 能夠製造 持率優良 著色組成 -52-Ν, Ν-dimethylaminoethyl methacrylate-49-201111910 (Evaluation method) The alkali-developing type resist members 25 to 48 obtained in the above Examples and Comparative Examples were used to confirm the voltage holding ratio and brightness. , tests for the occurrence of foreign matter and developability. In addition, as for the evaluation of the voltage holding ratio, the procedure of the brightness evaluation, the observation method of the crystal foreign matter, and the developability evaluation are as follows. (Measurement method of brightness) Each of the alkali-developing type green photoresist materials was changed to have a rotation speed by using a spin coater, and the chromaticity y of the C light source system used in the CIE color system was 0.62, 0.60, and 0.58. Three coated substrates were produced. After coating, it was dried at 80 ° C for 30 minutes in a hot air oven, and the luminance was obtained from the three data in a single correlation method with a color y of 0.6. The chromaticity was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). (Observation method of crystal foreign matter) 30 ml of each alkali-developing type green photoresist was allowed to stand in an environment of 40 ° C for 7 days, and filtered using a filter installed in a syringe of 5 μm pore size, and then 20 ml of ethylene was used. The filter was washed with alcohol monomethyl ether acetate, and the filter portion was taken out and the foreign matter remaining on the filter was observed using a microscope. The evaluation criteria are as follows. 〇: No foreign matter was observed Δ: 5 or less foreign substances were observed. X: Most of the observed foreign matter was more than 5 (developability evaluation) Each alkali-developing type green photoresist was spin-coated on a transparent glass substrate of 10×10 cm. And pre-baking at 70 ° C for 20 minutes to form a coating film having a dry film thickness of about 2.0 μm, followed by exposure to UV-50-201111910 at an exposure amount of 50 m J/cm 2 and calculating 0.15% by weight of sodium carbonate. 0.05 wt% sodium hydrogencarbonate, 0.1 wt% anionic surfactant (PELEXNBLJ manufactured by Kao Corporation) and an alkaline developer of 99.7 wt% water dissolve the pattern of the unexposed portion for the entire time (T 1 ) and will be prolonged The developing time was set to 1.5 times of τ 1 as the development end point. At the development end point, those who had no pattern defect in the exposed portion were evaluated as 〇 'The pattern defect was X. The results are shown in Table 5 above. Examples 16 to 27 are green colorants containing a halogenated phthalocyanine pigment, and an epoxy compound having an epoxy equivalent of 100 to 500 is used because the epoxy compound is added in an amount relative to 100 parts by weight of the zinc halide phthalocyanine pigment.Since the amount of 10 to 300 parts by weight is the optimum addition amount, high brightness is exhibited, and in the evaluation of the voltage holding ratio (%) and the evaluation of the foreign matter, the evaluation of the developability is excellent, and in particular, the examples are shown. 16 to 18, 19, and 20, since the epoxy compound having an epoxy equivalent in the range of 100 to 250 is sufficiently added, it exhibits a good voltage holding ratio (%). Further, Examples 21 to 27 are also used. Not only the voltage retention ratio (%), but also the developability shows good results, and it is possible to produce developability and further crystallize foreign matter by using a resin having a resin acid value of 50 to 150 mgKOH/g and a weight average molecular weight of 5,000 to 10,000,000. In contrast, in Comparative Example 10 to 1 4 in which no epoxy compound was added, or Comparative Example 1 in which the amount of epoxy compound added was small, an epoxy compound having a high epoxy equivalent was used. No improvement in the voltage holding ratio (%) was observed in any of Comparative Example 1 7. Further, since the excess epoxy compound was added in Comparative Example 15, the developability was problematic. -51 - 201111910 Comparative Example 1 In the case of using an acrylic compound having the same chemical properties as the epoxy compound, the effect of improving the voltage retention of the epoxy compound was not observed, and a problem was observed in the crystal foreign matter and developability. Since Comparative Example 21 was not used for halogenation. Zinc phthalocyanine pigments have no problem in the yield (%) and crystal foreign matter generation, but the results are as follows. By satisfying the use of epoxy compounds and epoxy compounds having an epoxy equivalent of 1 Å. The addition amount is a condition that the relative amount of the zinc halide phthalocyanine pigment is 10 to 300 parts by weight, the development property is good, and the generation of the crystal foreign matter is suppressed, and the color filter for the color filter containing the zinc halide phthalocyanine pigment is protected by the voltage. Sex. [Simple description of the schema] Sister. [Explanation of main component symbols] 任一 Any one of the degree of thermosetting has a low voltage. / 500 results in a weight of 1 able to manufacture excellent holding ratio coloring composition -52-