下面進一步詳細說明本發明。 本發明中，當記載為某一部件位於其他部件之“上”時，此不僅包括某一部件與其他部件接觸之情況，亦包括兩個部件之間設置有另一部件的情況。 本發明中，當記載某一部分“包括”某一構成要素時，在沒有明確相反之記載的情況下，表示並不排除其他構成要素，且可以進一步包括其他構成要素。 本發明提供著色感光性樹脂組合物及由其製造的彩色濾光片。著色感光性樹脂組合物
本發明之著色感光性樹脂組合物包含著色劑，該著色劑包含C.I.顏料綠59及C.I.顏料藍16。本發明之著色感光性樹脂組合物包含黏合劑樹脂、光聚合化合物、光聚合引發劑及溶劑，此外，亦可進一步包括此項技術常用之輔助成分，例如添加劑。著色劑
本發明之著色劑為了提供高色彩再現性的著色層而包含C.I.顏料綠59及C.I.顏料藍16。此外，本發明之著色劑包含C.I.顏料綠59及C.I.顏料藍16之外，亦可包含C.I.顏料綠58。 該著色劑藉由使用包含綠色顏料及藍色顏料之二元系混合顏料，不僅能夠實現綠色及藍色的寬色彩範圍，亦可呈現高亮度及高對比度或優異的著色力。此外，亦可呈現優異圖案形成性之優點。 在本發明中，該C.I.顏料綠59或C.I.顏料綠58主要起到使組合物呈現綠色之功能，C.I.顏料藍16起到使組合物呈現藍色之功能。 此時，C.I.顏料綠59相對於C.I.顏料藍16之重量比可配置為3:97至50:50，具體為5:95至15:75。 相對於該著色感光性樹脂組合物總固體成分，該著色劑組合物之含量可為10至60重量份，具體為20至60重量份；更具體為30至60重量份。該著色劑含量滿足上述範圍時，具有如下優點：即使形成薄膜，像素的色彩濃度亦充分，且能夠防止在顯影過程中非像素部的遺漏性降低的現象，因此有不易產生殘渣等優點。 在本發明中，該著色感光性樹脂組合物總固體成分或著色感光性樹脂組合物中的固體成分可以表示移除溶劑之成分的合計。 在上述著色劑包含顏料時，可藉由使著色劑含有顏料分散劑而進行分散處理，從而能夠獲得顏料在溶液中均勻分散狀態的顏料分散液。 該顏料分散劑可為例如陽離子類、陰離子類、非離子類、陽性、聚酯類、聚胺類及聚丙烯酸類等界面活性劑等，可以單獨使用或以兩種以上之組合使用。使用顏料分散劑時，相對於著色材料1重量份，其使用量較佳為低於1重量份，更佳為0.05至0.5重量份。顏料分散劑的使用量在上述範圍時，由於能夠獲得均勻分散狀態的顏料，因此較佳。 根據本發明之著色劑除了上述的顏料之外，在不超出本發明目的之範圍內，亦可包含此項技術使用的顏料及染料。 例如，該著色劑亦可包含C.I.顏料黃系列。該著色劑進一步包含C.I.顏料黃系列時，具有能夠實現更寬色彩範圍的優點。 本發明中可以進一步包含的顏料包括有機顏料及無機顏料。 該有機顏料可以使用用於印刷墨水、噴墨墨水等之各種顏料，具體地可以舉例為鐵酞菁(Phthalocyan)(水溶性偶氮顏料、不溶性偶氮顏料)、酞菁顏料、喹吖啶酮顏料、異吲哚啉酮顏料、異吲哚啉顏料、二萘嵌苯顏料、茈酮(perynone)顏料、二噁嗪顏料、蒽醌顏料、二蒽醌顏料、蒽并嘧啶(anthrapyrimidine)顏料、蒽嵌蒽醌(anthanthrone)顏料、陰丹酮(indanthrone)顏料、黃烷士酮(flavanthrone)顏料、皮蒽酮(pyranthrone)顏料或吡咯并吡咯二酮顏料等。 該無機顏料可為金屬氧化物或金屬錯合物等金屬化合物，具體可以舉例為鐵、鈷、鋁、鎘、錫、銅、鈦、鎂、鉻、鋅、銻等金屬的氧化物或複合金屬氧化物等。 具體而言，該有機顏料及無機顏料具體地可為在染料索引(英國染色工作者協會出版)中分類為顏料的化合物，更具體地，可為下列染料索引(C.I.)號的顏料，但不限於此。 根據本發明之顏料分散組合物中使用的顏料可為此項技術通常使用之有機顏料或無機顏料，其可單獨使用或兩種以上之組合使用。 該顏料根據需要進行如下處理：樹脂處理；利用導入酸性基團或鹼性基團之衍生物等的表面處理；利用高分子化合物等之顏料表面接枝處理；利用硫酸微粒化法等之微粒化處理或用於除去雜質之利用有機溶劑或水等的洗滌處理；藉由離子交換法等的離子型雜質的移除處理等。 該顏料的具體例有： C.I.顏料黃20、24、31、53、83、86、93、94、109、110、117、125、129、137、138、147、148、153、154、166、173、180及185； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65及71； C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、215、216、224、242、254、255及264； C.I.顏料紫14、19、23、32、33、36及38； C.I.顏料藍15(15:3、15:4、15:6等)、21、28、64及76； C.I.顏料綠10、15、25、36、47、62及63； C.I.顏料棕28。 該顏料較佳使用其粒徑均勻分散的顏料分散液。作為使顏料粒徑均勻分散的方法，可舉例藉由包含顏料分散劑而進行分散處理之方法等，藉由該方法能夠獲得顏料在溶液中均勻分散之狀態的顏料分散液。 對於本發明之著色感光性樹脂組合物，可採用顏料分散組合物之形態包含該顏料。 該顏料分散組合物包含顏料、分散劑、分散輔助劑，且為了儲藏穩定性及容易分散，可以進一步包含分散樹脂。 此外，相對於顏料分散組合物中固體成分總重量，該顏料之含量可在20至90重量份的範圍內，較佳在30至70重量份的範圍內。該顏料之含量不在上述範圍內時，黏度高、儲藏穩定性不佳、分散效率低，從而亦對對比度產生不良影響。 該染料只要對有機溶劑具有溶解性的染料即可不受限制地使用，較佳使用對有機溶劑具有溶解性的同時，能夠確保對鹼性顯影液具有溶解性、耐熱性及耐溶劑性等可靠性之染料。 該染料可以使用選自磺酸或羧酸等具有酸性基團之酸性染料、酸性染料及含氮化合物之鹽、酸性染料的磺胺類等及其衍生物中的染料，除此之外，亦可選擇偶氮類、氧雜蒽類、鈦箐類的酸性染料及其衍生物。 較佳地，該染料為在染料索引(英國染色工作者協會出版)中分類為顏料之化合物，或染色手冊(染色公司)中記載的習知染料。 該染料的具體例有： 作為C.I.溶劑染料有： C.I.溶劑黃4、14、15、21、23、24、38、62、63、68、82、94、98、99及162； C.I.溶劑紅8、45、49、122、125及130； C.I.溶劑橙2、7、11、15、26及56； C.I.溶劑藍35、37、59及67； C.I.溶劑綠1、3、4、5、7、28、29、32、33、34及35等綠色染料等。 此外，作為C.I.酸性染料有： C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243及251； C.I.酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422及426； C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169及173； C.I.酸性藍1、7、9、15、18、23、25、27、29、40、42、45、51、62、70、74、80、83、86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、267、278、280、285、290、296、315、324:1、335及340； C.I.酸性紫6B、7、9、17及19； C.I.酸性綠1、3、5、9、16、25、27、50、58、63、65、80、104、105、106及109等染料。 此外，作為C.I.直接顏料有： C.I.直接黃2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138及141； C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246及250； C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106及107； C.I.直接藍38、44、57、70、77、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275及293； C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103及104； C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79及82等染料。 此外，作為C.I.媒介染料有： C.I.媒介黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62及65； C.I.媒介紅1、2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94及95； C.I.媒介橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47及48； C.I.媒介藍1、2、3、7、8、9、12、13、15、16、19、20、21、22、23、24、26、30、31、32、39、40、41、43、44、48、49、53、61、74、77、83及84； C.I.媒介紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53及58； C.I.媒介綠1、3、4、5、10、15、19、26、29、33、34、35、41、43及53等染料。 以該著色劑中的固體成分計，該染料之含量可為0.5至80重量份，較佳為0.5至60重量份，更佳為1至50重量份。染料之含量以上述基準在上述範圍內時，能夠防止在形成圖案後有機溶劑使染料溶出之問題，而且由於其敏感度優異而較佳。 包含在該著色劑中的成分可以預先分散/溶解於後述的組合物溶劑中的一部分，以添加於該著色感光性樹脂組合物中，但不限於此。黏合劑樹脂
該黏合劑樹脂通常具有在光或熱的作用下的反應性及鹼性溶解性，可以作用為著色劑之分散劑。具體地，該黏合劑樹脂可以對著色劑起黏合劑樹脂之作用。例如，該黏合劑樹脂可為能夠溶解於用於製造彩色濾光片之顯影步驟中使用的鹼性顯影液中的黏合劑樹脂。 例如，該黏合劑樹脂可為含羧基單體、與該單體能夠共聚之其他單體的共聚物等。例如，含羧基單體可為不飽和單羧酸或不飽和多元羧酸等不飽和羧酸，其中，多元羧酸在分子中具有一個以上之羧基，且諸如為不飽和二羧酸、不飽和三羧酸等。 例如，該不飽和單羧酸可為丙烯酸、甲基丙烯酸、丁烯酸、α-氯丙烯酸、肉桂酸等。 例如，該不飽和二羧酸可為馬來酸、富馬酸、衣康酸、檸康酸、中康酸等。 該不飽和多元羧酸可為酸酐，具體可為馬來酸酐、衣康酸酐、檸康酸酐等。此外，不飽和多元羧酸可為多元羧酸之單(2-甲基丙烯醯氧基烷基)酯，例如可為單(2-丙烯醯氧基乙基)琥珀酸酯、單(2-甲基丙烯醯氧基乙基)琥珀酸酯、單(2-丙烯醯氧基乙基)鄰苯二甲酸酯、單(2-甲基丙烯醯氧基乙基)鄰苯二甲酸酯等。不飽和多元羧酸可為其兩個末端為二羧基之聚合物的單(甲基)丙烯酸，例如，可為ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。此等含羧基單體可以單獨使用或以兩種以上混合使用。該與含羧基單體能夠共聚之其他單體例如可為苯乙烯、α-甲基苯乙烯、o-乙烯基甲苯、m-乙烯基甲苯、p-乙烯基甲苯、p-氯苯乙烯、o-甲氧基苯乙烯、m-甲氧基苯乙烯、p-甲氧基苯乙烯、o-乙烯基苄基甲醚、m-乙烯基苄基甲醚、p-乙烯基苄基甲醚、o-乙烯基苄基縮水甘油醚、m-乙烯基苄基縮水甘油醚、p-乙烯基苄基縮水甘油醚、茚等芳族乙烯基化合物；丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、n-丙烯酸丙酯、n-甲基丙烯酸丙酯、i-丙烯酸丙酯、i-甲基丙烯酸丙酯、n-丙烯酸丁酯、n-甲基丙烯酸丁酯、i-丙烯酸丁酯、i-甲基丙烯酸丁酯、sec-丙烯酸丁酯、sec-甲基丙烯酸丁酯、t-丙烯酸丁酯、t-甲基丙烯酸丁酯、丙烯酸-2-羥乙酯、甲基丙烯酸-2-羥乙酯、丙烯酸-2-羥丙酯、甲基丙烯酸-2-羥丙酯、丙烯酸-3-羥丙酯、甲基丙烯酸-3-羥丙酯、丙烯酸-2-羥丁酯、甲基丙烯酸-2-羥丁酯、丙烯酸-3-羥丁酯、甲基丙烯酸-3-羥丁酯、丙烯酸-4-羥丁酯、甲基丙烯酸-4-羥丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸-2-甲氧基乙酯、甲基丙烯酸-2-甲氧基乙酯、丙烯酸-2-苯氧基乙酯、甲基丙烯酸-2-苯氧基乙酯、甲氧基二甘醇丙烯酸酯、甲氧基二甘醇甲基丙烯酸酯、甲氧基三甘醇丙烯酸酯、甲氧基三甘醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、雙環戊二烯丙烯酸酯、雙環戊二烯甲基丙烯酸酯、甲基丙烯酸金剛烷酯、甲基丙烯酸降冰片酯、2-羥基-3-苯氧基丙烯酸丙酯、2-羥基-3-苯氧基甲基丙烯酸丙酯、甘油單丙烯酸酯、甘油單甲基丙烯酸酯等不飽和羧酸酯類；2-胺基丙烯酸乙酯、2-胺基甲基丙烯酸乙酯、2-二甲基胺基丙烯酸乙酯、2-二甲基胺基甲基丙烯酸乙酯、2-胺基丙烯酸丙酯、2-胺基甲基丙烯酸丙酯、2-二甲基胺基丙烯酸丙酯、2-二甲基胺基甲基丙烯酸丙酯、3-胺基丙烯酸丙酯、3-胺基甲基丙烯酸丙酯、3-二甲基胺基丙烯酸丙酯、3-二甲基胺基甲基丙烯酸丙酯等不飽和羧酸胺基烷基酯類；丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯等不飽和羧酸縮水甘油酯類；乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯類；乙烯基甲醚、乙烯基乙醚、烯丙基縮水甘油醚等不飽和醚類；丙烯腈、甲基丙烯腈、α-氯丙烯腈、亞乙烯基二氰等丙烯腈化合物；丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等不飽和胺類；馬來醯亞胺、苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等不飽和亞胺類；1、3-丁二烯、異戊二烯、氯丁二烯等脂肪族共軛二烯類；及聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚-n-丙烯酸丁酯、聚-n-甲基丙烯酸丁酯、聚矽氧烷的聚合物分子鏈末端具有單丙烯醯基或單甲基丙烯醯基的巨大單體類等。 該單體可分別單獨使用或以兩種以上混合使用。尤其是，作為能夠與該含羧酸單體共聚之其他單體，較佳具有降冰片基骨架之單體、具有金剛烷骨架之單體、具有松香骨架之單體等，因為此等膨脹(bulky)單體具有降低介電常數之傾向。 該黏合劑樹脂之酸值可為20至200(KOHmg/g)。該黏合劑樹脂的酸值滿足上述範圍時，提高在顯影液中的溶解性以使非裸露部容易溶解，從而具有敏感度增加之優點。由此，最終裸露部之圖案在顯影時遺留下來，從而具有改善留膜率(film remainig ratio)之優點。 本發明中酸值係指測定用於中和1g聚合物所需之氫氧化鉀的量(g)的值，通常可藉由使用氫氧化鉀水溶液進行滴定而求得。 此外，該黏合劑樹脂之重量平均分子量具體可為3000至200000，具體可為5000至100000，但不限於此。該重量平均分子量可為藉由凝膠滲透色譜(GPC：四氫呋喃作為溶出溶劑)測定之聚苯乙烯換算重量平均分子量。該黏合劑樹脂之分子量滿足上述範圍時，提高塗覆膜之硬度以使留膜率提高，且具有使顯影液中之非裸露部的溶解性變得優異且提高清晰度的優點。 該黏合劑樹脂的分子量分佈(重量平均分子量(Mv)/數目平均分子量(Mn))為1.5至6.0，具體可為1.8至4.0，但不限於此。但該黏合劑樹脂的分子量分佈滿足上述範圍的時候，顯影性優異，因此上述範圍較佳。 相對於該著色感光性樹脂組合物總固體成分，該黏合劑樹脂之含量可為5至85重量份，具體可為10至70重量份。該黏合劑樹脂相對於該著色感光性樹脂組合物總固體成分的含量在上述範圍內時，由於對顯影液之溶解性充分而能夠防止在非像素部分的基板上產生顯影殘渣的現象，且防止在顯影時漏光部之像素部分的膜減少的現象，從而具有趨於使得非像素部分的遺漏性良好的優點。光聚合化合物
該光聚合化合物只要能夠基於光或後述光聚合引發劑的作用而聚合的化合物即不受限制，例如，可為單官能單體、雙官能單體、其他多官能單體。 單官能單體具體可為壬基苯基丙烯酸卡必酯(nonylphenyl carbitol acrylate)、2-羥基-3-苯氧基丙基丙烯酸酯(2-hydroxy-3-phenoxypropyl acrylate)、2-乙基己基丙烯酸卡必酯、丙烯酸-2-羥乙酯、N-乙烯基吡咯啶酮等。 雙官能單體具體例可為二甲基丙烯酸1,6-己二醇酯(1,6-hexanediol dimethacrylate)、二甲基丙烯酸乙二醇酯、二甲基丙烯酸新戊二醇酯、三乙二醇二甲基丙烯酸酯、雙酚A的雙丙烯醯氧基乙基醚(bis[2-(acryloyloxy)ethyl]ether)、二甲基丙烯酸3-甲基戊二醇酯(3-methylpentandiol dimethacrylate)等。 其他多官能團單體的具體例可為三羥甲基丙烷三甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯(pentaerythritol trimethacrylate)、季戊四醇四甲基丙烯酸酯(pentaerythritol tetramethacrylate)、聚二季戊四醇五甲基丙烯酸酯(dipentaerythritol pentamethacrylate)、聚二季戊四醇六甲基丙烯酸酯(dipentaerythritol hexamethacrylate)等。較佳使用其中雙官能以上之多官能單體。 相對於自發光感光樹脂中的固體成分，該光聚合化合物之含量通常可在5至50重量份的範圍內，較佳在7至45重量份的範圍內，但不限於此。當光聚合化合物之含量在上述範圍內時，能夠使得像素部之強度或平滑性趨於良好。光聚合引發劑
該光聚合引發劑只要是此項技術常用之光聚合引發劑即不受限制，具體地可含有苯乙酮類化合物。 苯乙酮類化合物例如可為二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮(Benzil Dimethyl Ketal)、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙烷-1-酮、1-羥基環己烷苯酮、2-甲基-1-(4-甲基硫代苯基)-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、2-羥基-2-甲基 [4-(1-甲基乙烯基)苯基]丙烷-1-酮的低聚體等。較佳2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮。 此外，亦可組合使用上述苯乙酮類之外的光聚合引發劑。該除了苯乙酮類之外的光聚合引發劑可為藉由照射光而產生活性自由基之活性自由基發生劑、增敏劑、酸發生劑等。該活性自由基發生劑例如可為安息香類化合物、二苯甲酮類化合物、噻噸酮類化合物、三嗪類化合物等。該安息香類化合物例如可為安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等。該二苯甲酮化合物例如可為二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯偶氮基苯酮(4-phenylazo phenone)、4-苯甲醯-4'-甲基二苯硫醚、3,3',4,4'-四(第三丁基過氧羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等。該噻噸酮類化合物例如可為2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 該三嗪類化合物例如可為2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。該活性自由基發生劑例如可為2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2-雙(o-氯苯)-4,4',5,5'-四苯基-1,2'-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、苄基、9,10-菲醌、樟腦醌、苯甲醯甲酸甲酯(Methyl phenylglyoxylate)、二茂鈦化合物等。該酸發生劑例如可為4-羥苯基二甲基鋶對甲苯磺酸鹽、4-羥苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基碘鎓對甲苯磺酸鹽、二苯基碘鎓六氟銻酸等鎓鹽類或硝基苄基甲苯磺酸鹽類、安息香甲苯磺酸鹽類等。此外，作為活性自由基發生劑的上述化合物中亦同時產生活性自由基及酸之化合物，例如，三嗪類光聚合化合物亦用作酸發生劑。 進而，本發明中亦可使用光聚合引發輔助劑。該光聚合引發輔助劑可與上述光聚合引發劑組合使用，其為用於促進由上述光聚合引發劑引發的該光聚合化合物的聚合的化合物。該光聚合引發輔助劑可為胺類化合物、烷氧基蒽類化合物、噻噸酮類化合物等。 該胺類化合物例如可為三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(統稱：米希勒酮)、4,4'-雙(二乙胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等。其中較佳使用4,4'-雙(二乙胺基)二苯甲酮，但不限於此。 該烷氧基蒽類化合物例如可為9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽等。該噻噸酮類化合物例如可為2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 該光聚合引發劑或該光聚合引發輔助劑可以單獨使用或以多個組合使用亦無妨。此外，該光聚合引發輔助劑可以使用市售的，市售光聚合引發輔助劑例如可為商品名為EAB-F(製造商：保土谷化學工業株式會社(Hodogaya Chemical Co,. LTD))等。 以總固體成分計，相對於該黏合劑樹脂及該光聚合化合物總量，本發明之自發光感光樹脂組合物中光聚合引發劑之含量為0.1至40重量份，較佳為1至30重量份。當該光聚合引發劑滿足上述範圍時，該著色感光性樹脂組合物具有高敏感度，以使得使用該組合物形成之像素部具有良好強度，且使得該像素部之表面具有良好的平滑性，因此較佳。 當使用該光聚合引發輔助劑時，相對於光聚合引發劑1莫耳，其使用量通常低於10莫耳，較佳為0.01~5莫耳。當該光聚合引發輔助劑滿足上述範圍時，該著色感光性樹脂組合物的敏感度變得更高，以使得使用該組合物形成之彩色濾光片的生產性趨於提高，因此較佳。溶劑
本發明之著色感光性樹脂中含有的溶劑不受特別限制，可為著色感光性樹脂組合物領域中通常使用之有機溶劑。 具體可為乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚等乙二醇單烷基醚類；二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚、二乙二醇二丁醚等二乙二醇二烷基醚類；醋酸甲氧乙酯、醋酸乙氧乙酯等乙二醇烷基醚醋酸酯類；丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙酸甲氧基丁酯、乙酸甲氧基戊酯等亞烷基乙二醇烷基醚乙酸酯類；苯、甲苯、二甲苯、均三甲苯等芳香烴類；甲基乙基酮、丙酮、甲基戊酮、甲基異丁酮、環己酮等酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等醇類；乙烷基3-乙氧丙酸酯、甲烷基3-甲氧丙酸酯等酯類；γ-丁內酯等環狀酯類等。鑒於塗覆性、乾燥性方面，在上述溶劑中較佳沸點為100℃至200℃的有機溶劑，更佳為亞烷基乙二醇烷基醚乙酸酯類、酮類、乙烷基3-乙氧丙酸酯或甲烷基3-甲氧丙酸酯等酯類，最佳丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己醇、乙烷基3-乙氧丙酸酯、甲烷基3-甲氧丙酸酯等。此等溶劑可以分別單獨使用或以兩種以上混合使用。 相對於該著色感光性樹脂組合物總體，該溶劑之含量可為60至90重量份，具體可為70至85重量份。相對於該著色感光性樹脂組合物總體，當該溶劑之含量在上述範圍內時，若使用輥塗機、旋塗機、狹縫式及旋轉式塗佈機、夾縫式塗佈機或模具式塗佈機、噴墨機等塗覆裝置進行塗覆，塗覆性趨於良好，因此較佳。添加劑
本發明之著色感光性樹脂組合物根據需要亦可包含填充劑、其他高分子化合物、顏料分散劑、密著促進劑、防氧化劑、紫外線吸收劑、抗凝劑等添加劑，但不限於此。 該填充劑之具體例有玻璃、二氧化矽、氧化鋁等。 該其他高分子化合物具體可為環氧樹脂、馬來醯亞胺樹脂等固化樹脂；聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、丙烯酸多氟烷基酯、聚酯、聚亞胺酯等熱固性樹脂等。 該顏料分散劑可以利用市售界面活性劑，例如矽樹脂類、氟類、酯類、陽離子類、陰離子類、非離子類、陽性等界面活性劑等。其可分別單獨使用或以兩種以上之組合使用。 該界面活性劑例如可為聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、失水山梨醇脂肪酸酯類、脂肪酸改質聚酯類、三元胺改質聚亞胺酯類、聚乙烯亞胺類等，除此之外可以舉例商品名為KP(由信越化學工業株式會社(SHIN-ETSU CHEMICAL CO., LTD)製造)、POLYFLOW(由共榮社化學株式會社(KYOEISHA CHEMICAL CO., LTD)製造)、EFTOP(由TOHKEM PRODUCTS CORPORATION製造)、MEGAFAC(由大日本墨水化學工業株式會社(DIC CORPORATION)製造)、Flourad(由住友3M株式會社(SUMITOMO 3M LTD)製造)、Asahi guard、Surflon(以上由旭硝子株式會社(ASAHI GLASS CO., LTD)製造)、SOLSPERSE(由ZENECA CO., LTD製造)、EFKA(由伊夫卡化學品公司(EFKA CHEMICALS B.V.)製造)、PB 821(由味之素株式會社(AJNOMOTO CO., INC)製造)等。 該密著促進劑例如可為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油醚氧丙基三甲氧基矽烷、3-縮水甘油醚氧丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。 該防氧化劑具體可為2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基-4-甲基苯酚等。 該紫外線吸收劑具體可為2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并噻唑、烷氧基苯甲酮等。 該抗凝劑具體可為聚丙烯酸鈉等。 相對於該著色感光組合物總體而言，該添加劑之含量可為0.1至10重量份，具體地可為0.1至5重量份，更具體地可為0.1至1重量份，但不限於此。當上述添加劑的含量在上述範圍內時，能夠在不降低由該著色感光性樹脂組合物製造的彩色濾光片的性能的同時，賦予各個添加劑所預期達到的性能。 本發明之著色劑感光樹脂組合物例如可以藉由以下方法製造。預先將著色劑與溶劑混合，使用砂磨機等使著色劑分散至平均粒徑低於0.2μm的程度。此時，根據需要可以使用顏料分散劑，有時亦可配伍黏合劑樹脂的一部分或全部。獲得之分散液(以下亦可稱為粉碎物料)中進一步添加黏合劑樹脂之剩餘部分、光聚合化合物及光聚合引發劑、根據需要而使用之其他成分、根據需要而使用之額外溶劑，使其濃度達到預定濃度，從而獲得所需著色感光性樹脂組合物。濾光片及圖像顯示裝置
本發明提供由該著色感光性樹脂組合物製造之彩色濾光片及包含該彩色濾光片的圖像顯示裝置。 本發明中，該著色感光性樹脂組合物可用於綠色像素，但不限於此。 可以配置此彩色濾光片之圖像顯示裝置有液晶顯示裝置、OLED、柔性顯示器等，但不限於此，此項技術已知可使用之所有圖像顯示裝置均可。 可以藉由將前述本發明之著色感光性樹脂組合物塗覆於基材之上且進行光固化及顯影而形成圖案，從而製造彩色濾光片。 首先，將著色感光性樹脂組合物塗覆於基材上後，藉由加熱乾燥而移除溶劑等揮發成分，從而獲得平滑塗覆膜。 塗覆方法例如可以藉由使用旋塗、柔韌塗覆法、輥塗、狹縫式及旋轉式塗覆或狹縫式塗覆等來實施。藉由在塗覆後進行加熱乾燥(預烘)，或在減壓乾燥後進行加熱而將溶劑等揮發成分揮發。此時，加熱溫度通常為70至200℃，較佳80至130℃。加熱乾燥後之塗覆膜的厚度通常為1至8μm程度。藉由用於形成所需圖案之掩膜，向由此獲得之塗覆膜照射紫外線。此時，可向漏光部整體均勻照射平行光線，且較佳使用掩膜對準器或步進機等裝置以使掩膜及基板精確對準位置。照射紫外線時，紫外線照射到的部位發生固化。 該紫外線可以使用g線(波長：436nm)、h線、i線(波長：365nm)等。紫外線照射量可以根據需要適當選擇，本發明中對此並不限定。若使完成固化之塗覆膜接觸顯影液以使非曝光部位溶解顯影，則可以形成所需的圖案形狀。 上述顯影方法使用添液法、浸漬法、噴霧法等中的任一者亦無妨。此外，顯影時可以將基板以任意角度傾斜。該顯影液為含有通常鹼性化合物及界面活性劑之水溶液。該鹼性化合物可為無機鹼性化合物及有機鹼性化合物中的任一者。無機鹼性化合物之具體例子可為氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、氨等。此外，有機鹼性化合物的具體例可為羥化四甲銨、2-羥基乙基三甲基氫氧化銨、一甲胺、二甲胺、三甲胺、一乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺、乙醇胺等。 此等無機鹼性化合物及有機鹼性化合物可單獨使用或以兩種以上之組合使用。鹼性顯影液中之鹼性化合物的濃度較佳為0.01至10重量份，更佳為0.03至5重量份。 該鹼性顯影液中的界面活性劑可以使用選自由非離子型界面活性劑、陰離子型界面活性劑或陽離子型界面活性劑組成的組中的至少一者。 該非離子型界面活性劑的具體例有聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚及其他聚氧乙烯衍生物；氧乙烯/氧丙烯嵌段共聚物；山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚氧乙烯脂肪酸山梨醇酯；脂肪酸甘油酯；聚氧乙烯脂肪酸酯；聚氧乙烯烷基胺等。 該陰離子型界面活性劑的具體例可為月桂醇硫酸酯鈉或油醇硫酸酯鈉等高級醇硫酸酯鹽類；十二烷基硫酸鈉或十二烷基硫酸銨等烷基硫酸鹽類；十二烷基苯磺酸鈉或十二烷基萘磺酸銨等烷基芳基磺酸鹽類等。 該陽離子型界面活性劑的具體例可為硬脂醯胺鹽酸鹽或十二烷基三甲基氯化銨等銨鹽或4元銨鹽等。此等界面活性劑可以單獨使用或以兩種以上之組合使用。 該顯影液中的界面活性劑的濃度通常可為0.01至10重量份，較佳為0.05至8重量份，更佳為0.1至5重量份。在顯影後，進行水洗，且根據需要可在150至230℃實施10至60分鐘的後烘焙。 以下結合實施例進一步詳細說明本發明。下面揭示之本發明的實施形態僅為示例性的，本發明之範圍並不由此等實施形態限定。本發明的範圍由隨附申請專利範圍限定，尤其包括與申請專利範圍中記載均等之含義及範圍內的所有的變更。此外，以下實施例、比較例中表示含量的“%”及“份”在沒有特別說明的情況下均表示質量基準。黏合劑樹脂的合成例 黏合劑樹脂 (B)
在具有攪拌器、溫度計、回流冷凝管、滴定物料及氮氣導入管的燒瓶中加入丙二醇單甲醚醋酸酯182g，使燒瓶的氛圍從空氣置換為氮氣後，升溫至100℃，隨後將含有甲基丙烯酸苄酯70.5g(0.40莫耳)、甲基丙烯酸45.0g(0.50莫耳)、碳環骨架的單甲基丙烯酸44.5g(0.10莫耳)及丙二醇單甲醚醋酸酯136g的混合物中添加偶氮二異丁腈3.6g的溶液，藉由滴定物料導入口向燒瓶中滴落2小時，繼續在100℃攪拌5小時。接著，將燒瓶中的氛圍從氮氣替換為空氣後，將甲基丙烯酸縮水甘油酯30g(0.2莫耳，相對於本發明中使用的甲基丙烯酸的羧基而言為40莫耳%)、三二甲基胺基甲基苯酚0.9g及對苯二酚0.145g投入到燒瓶中，在110℃繼續反應6小時，獲得了固體成分的酸值為99mgKOH/g的樹脂B。藉由GPC測定之聚苯乙烯換算的重量平均分子量為28000，分子量分佈(Mw/Mn)為2.2。 對於該黏合劑樹脂的重量平均分子量(Mw)及數目平均分子量(Mn)，利用GPC法按照下列條件進行測定。 裝置：HLC-8120GPC(由東曹株式會社(TOSOH CORPORATION)製造) 色譜柱：TSK-GELG4000HXL + TSK-GELG2000HXL(串聯連接) 柱溫：40℃ 流動相溶劑：四氫呋喃 流速：1.0㎖/分鐘 注入量：50㎕ 偵測器：RI 測定試樣濃度：0.6質量%(溶劑=四氫呋喃) 校正用標準物質：TSK STANDARD POLYSTYRENE F-40、F-4、F-1、A-2500、A-500(由東曹株式會社製造) 將上述獲得之重量平均分子量及數目平均分子量的比作為分子量分佈(Mw/Mn)。實施例
按照下列表1之成分及含量製備著色感光性樹脂組合物。 [表1]
1)光聚合化合物(C)：雙季戊四醇六丙烯酸酯(KAYARAD DPHA；由日本化藥株式會社(NIPPON KAYAKU CO., LTD)製造) 2)引發劑(D1)：2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-醇(Irgacure 369；由汽巴精化(Ciba Specialty Chemical)公司製造) 引發劑(D2)：4,4'-二(N,N'-二甲基胺基)-苯甲酮(EAB-F；由保土谷化學工業株式會社製造) 3)溶劑(E)：丙二醇甲醚醋酸酯 4)添加劑(F)：丙烯酸類顏料分散劑(Disper byk-2001，畢克化學(BYK)公司製造)亮度、色座標及對比度測定 測定試片製備
利用上述實施例1至4及比較例1至4製備之著色感光性樹脂組合物製造著色層。即，將上述著色感光性樹脂組合物利用旋塗法塗覆於玻璃基板上，隨後放置於加熱板上且在100℃溫度下維持3分鐘形成薄膜。接著，使用同時含有g、h、i線的1kW高壓水銀燈以100mJ/cm2
的照射量照射。此時，未使用特殊的光學過濾片。將上述照射紫外線之薄膜在pH 10.5的KOH水溶液顯影液中浸漬2分鐘進行顯影。將上述塗覆薄膜的玻璃基板用蒸餾水洗滌後，吹氮氣進行乾燥，在200℃加熱箱中加熱30分鐘。由此獲得之著色層的厚度為1~5μm，更佳2~4μm左右。亮度測定方法
利用顯微光譜儀OSP-SP2000測定。亮度在下表2中示出。 亮度(Y)的評價標準如下。 ○：Y≥40，△：38≤Y＜40，X：Y＜38對比度測定方法
利用拓普康(TOPCON)公司的對比度測定儀BM-5A進行了測定，且測定標準為玻璃基板(著色層形成前)的對比度的1/30000。其結果在下表2中示出。 對比度的評級標準如下。 ◎：CR≥15000，○：12000≤CR＜15000，△：10000≤CR＜12000，X：CR＜10000著色力區分及彩色濾光片的圖案形成 著色力
著色力以製造成目標塗覆膜厚度所需的著色感光性樹脂組合物內的顏料含量比為基準。其結果在下表2中示出。 ○：著色力＜0.45，△：0.45≤著色力＜0.5，X：著色力＞0.5彩色濾光片的圖案形成
將製造的著色感光性樹脂組合物用旋塗法塗覆於玻璃基板(#1737，康寧(CORNING)公司製造)後，放置於加熱板上且在100℃溫度下維持3分鐘形成薄膜。接著，在上述薄膜上放置具有在透過率1至100%的範圍內以階梯狀變化之圖案的試驗光掩膜，與試驗光掩膜的距離設置為1000μm，利用超高壓水銀燈(USH-250D，由牛尾電機株式會社(USHIO INC.)製造)，在大氣氛圍下，以40mJ/cm2
的曝光量(365nm)進行光照射。利用pH為12.5的KOH水溶液顯影液的噴霧顯影儀，對上述照射紫外線的薄膜進行80秒顯影。使用蒸餾水將該包覆有薄膜的玻璃板洗滌後，吹入氮氣進行乾燥，在220℃的加熱箱中加熱20分鐘，由此製造彩色濾光片圖案。上述製造之彩色濾光片的圖案形狀(薄膜)厚度為2.5至2.9μm。 [表2]
如上表2所示，該實施例1至4及比較例1及4的比較結果為，與比較例1至4相比，使用C.I.顏料綠59及C.I.顏料藍16或者同時使用C.I.顏料綠58、C.I.顏料藍16及C.I.顏料綠59的實施例1至4的亮度、對比度及/或著色力特性更優異。 自上表2中可以確認，對於同一色座標的觀點而言時，與比較例相比，實施例之亮度、對比度更優異，且高色彩再現中的著色力優異，從而有利於液晶顯示裝置中的圖案形成，因此顯示不良發生之可能性低。The invention is described in further detail below. In the present invention, when a component is referred to as being "on" another component, this includes not only the case where one component is in contact with other components, but also the case where another component is provided between the two components. In the present invention, when a part is referred to as "comprising" a certain constituent element, the other constituent elements are not excluded, and other constituent elements may be further included. The present invention provides a colored photosensitive resin composition and a color filter produced therefrom.Colored photosensitive resin composition
The colored photosensitive resin composition of the present invention contains a colorant comprising C.I. Pigment Green 59 and C.I. Pigment Blue 16. The colored photosensitive resin composition of the present invention contains a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and may further include an auxiliary component commonly used in the art, such as an additive.Colorant
The coloring agent of the present invention comprises C.I. Pigment Green 59 and C.I. Pigment Blue 16 in order to provide a coloring layer with high color reproducibility. Further, the coloring agent of the present invention may contain C.I. Pigment Green 58 in addition to C.I. Pigment Green 59 and C.I. Pigment Blue 16. By using a binary mixed pigment containing a green pigment and a blue pigment, the coloring agent can realize not only a wide color range of green and blue, but also high brightness and high contrast or excellent coloring power. In addition, the advantages of excellent pattern formability can also be exhibited. In the present invention, the C.I. Pigment Green 59 or C.I. Pigment Green 58 functions primarily to render the composition green, and C.I. Pigment Blue 16 functions to render the composition blue. At this time, the weight ratio of C.I. Pigment Green 59 to C.I. Pigment Blue 16 can be configured to be 3:97 to 50:50, specifically 5:95 to 15:75. The colorant composition may be contained in an amount of 10 to 60 parts by weight, particularly 20 to 60 parts by weight; more specifically 30 to 60 parts by weight, based on the total solid content of the colored photosensitive resin composition. When the content of the coloring agent satisfies the above range, there is an advantage that even if a film is formed, the color density of the pixel is sufficient, and the phenomenon that the leakage of the non-pixel portion is reduced during development can be prevented, so that there is an advantage that residue is less likely to occur. In the present invention, the total solid content of the colored photosensitive resin composition or the solid content in the colored photosensitive resin composition may represent the total of the components of the solvent to be removed. When the colorant contains a pigment, the coloring agent may be subjected to a dispersion treatment by containing a pigment dispersant, whereby a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained. The pigment dispersant may be, for example, a surfactant such as a cationic, an anionic, a nonionic, a positive, a polyester, a polyamine or a polyacrylic acid, and may be used singly or in combination of two or more. When the pigment dispersant is used, it is preferably used in an amount of less than 1 part by weight, more preferably 0.05 to 0.5 part by weight, per part by weight of the coloring material. When the amount of the pigment dispersant used is in the above range, a pigment in a uniformly dispersed state can be obtained, which is preferable. The coloring agent according to the present invention may contain, in addition to the above-mentioned pigments, pigments and dyes used in the art without departing from the object of the present invention. For example, the colorant may also comprise a C.I. Pigment Yellow series. When the colorant further contains a C.I. Pigment Yellow series, it has the advantage of being able to achieve a wider color range. Pigments which may be further included in the present invention include organic pigments and inorganic pigments. As the organic pigment, various pigments for printing inks, inkjet inks and the like can be used, and specific examples thereof include Phthalocyan (water-soluble azo pigment, insoluble azo pigment), phthalocyanine pigment, and quinacridone. Pigments, isoindolinone pigments, isoporphyrin pigments, perylene pigments, perynone pigments, dioxazine pigments, anthraquinone pigments, diterpene pigments, anthrapyrimidine pigments, An anthanthrone pigment, an indanthrone pigment, a flavanthrone pigment, a pyranthrone pigment or a pyrrolopyrroledione pigment. The inorganic pigment may be a metal compound such as a metal oxide or a metal complex, and specifically may be an oxide or a composite metal of a metal such as iron, cobalt, aluminum, cadmium, tin, copper, titanium, magnesium, chromium, zinc or bismuth. Oxide, etc. Specifically, the organic pigment and the inorganic pigment may specifically be a compound classified as a pigment in the dye index (published by the British Dyeing Workers Association), and more specifically, may be a pigment of the following dye index (CI) number, but not Limited to this. The pigment used in the pigment dispersion composition according to the present invention may be an organic pigment or an inorganic pigment which is generally used in the art, and may be used singly or in combination of two or more. The pigment is subjected to a treatment as follows: a resin treatment; a surface treatment by introducing a derivative of an acidic group or a basic group; a surface grafting treatment using a polymer compound or the like; and a micronization using a sulfuric acid micronization method or the like. A washing treatment using an organic solvent or water or the like for treating or removing impurities; a treatment for removing ionic impurities by an ion exchange method or the like. Specific examples of the pigment are: CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 147, 148, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 32, 33, 36 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 64 and 76; CI Pigment Green 10, 15, 25, 36, 47, 62 and 63; CI Pigment Brown 28. The pigment is preferably a pigment dispersion liquid whose particle diameter is uniformly dispersed. As a method of uniformly dispersing the particle diameter of the pigment, for example, a method of dispersing a pigment by dispersing a pigment, and the like, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in a solution can be obtained. In the colored photosensitive resin composition of the present invention, the pigment may be contained in the form of a pigment dispersion composition. The pigment dispersion composition contains a pigment, a dispersant, and a dispersion aid, and may further contain a dispersion resin for storage stability and easy dispersion. Further, the content of the pigment may be in the range of 20 to 90 parts by weight, preferably 30 to 70 parts by weight, based on the total weight of the solid content in the pigment dispersion composition. When the content of the pigment is out of the above range, the viscosity is high, the storage stability is poor, and the dispersion efficiency is low, which also adversely affects the contrast. The dye can be used without limitation as long as it has a solubility in an organic solvent, and it is preferable to use a solubility in an organic solvent and ensure reliability such as solubility, heat resistance, and solvent resistance to an alkaline developer. Dye. The dye may be selected from an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a dye thereof. Acid dyes and derivatives thereof of azo, xanthene, and titanium are selected. Preferably, the dye is a compound classified as a pigment in the dye index (published by the British Dyers Association), or a conventional dye described in the dyeing manual (dyeing company). Specific examples of the dye are: CI solvent dyes are: CI Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162; CI Solvent Red 8 , 45, 49, 122, 125 and 130; CI Solvent Orange 2, 7, 11, 15, 26 and 56; CI Solvent Blue 35, 37, 59 and 67; CI Solvent Green 1, 3, 4, 5, 7, Green dyes such as 28, 29, 32, 33, 34 and 35. In addition, as the CI acid dyes are: CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79 , 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172 , 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242 , 243 and 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 6 2, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51 , 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243 , 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335 and 340; CI Acid Violet 6B, 7, 9, 17 and 19; CI Acid Green 1, 3, 5, 9 Dyes such as 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109. In addition, as CI direct pigments are: CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98 , 102, 108, 109, 129, 136, 138, and 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, and 250; CI Direct Orange 34, 39, 41, 46 , 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268 274, 275 and 293; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; CI Direct Green Dyes such as 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82. In addition, as the CI medium dyes are: CI medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65; CI medium red 1, 2 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95; CI medium oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28 , 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48; CI medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84; CI medium purple 1, 2, 4, 5 , 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; CI medium green 1, 3, 4, 5, 10, 15, 19, Dyes such as 26, 29, 33, 34, 35, 41, 43 and 53. The dye may be included in an amount of from 0.5 to 80 parts by weight, preferably from 0.5 to 60 parts by weight, more preferably from 1 to 50 parts by weight, based on the solid content of the coloring agent. When the content of the dye is within the above range based on the above criteria, it is possible to prevent the problem that the organic solvent dissolves the dye after the pattern is formed, and it is preferable because it is excellent in sensitivity. The component contained in the coloring agent may be previously dispersed/dissolved in a part of the composition solvent described later to be added to the colored photosensitive resin composition, but is not limited thereto.Adhesive resin
The binder resin generally has reactivity and alkali solubility under the action of light or heat, and acts as a dispersant for the colorant. Specifically, the binder resin can function as a binder resin for the colorant. For example, the binder resin may be a binder resin which can be dissolved in an alkaline developer used in a developing step for producing a color filter. For example, the binder resin may be a copolymer of a carboxyl group-containing monomer, another monomer copolymerizable with the monomer, or the like. For example, the carboxyl group-containing monomer may be an unsaturated carboxylic acid such as an unsaturated monocarboxylic acid or an unsaturated polycarboxylic acid, wherein the polycarboxylic acid has one or more carboxyl groups in the molecule, and is, for example, an unsaturated dicarboxylic acid, unsaturated. Tricarboxylic acid, etc. For example, the unsaturated monocarboxylic acid may be acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid or the like. For example, the unsaturated dicarboxylic acid may be maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid or the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specifically may be maleic anhydride, itaconic anhydride, citraconic anhydride or the like. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polycarboxylic acid, and may be, for example, mono(2-propenyloxyethyl) succinate, mono(2- Methyl propylene methoxyethyl) succinate, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Wait. The unsaturated polycarboxylic acid may be a mono(meth)acrylic acid having a dicarboxy group polymer at both ends thereof, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethyl group Acrylate and the like. These carboxyl group-containing monomers may be used singly or in combination of two or more. The other monomer copolymerizable with the carboxyl group-containing monomer may be, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o -methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, an aromatic vinyl compound such as hydrazine; methyl acrylate, methyl methacrylate, acrylic acid B Ester, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, I-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, Acrylic acid-2- Hydroxybutyrate , 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acryl allyl Ester, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate , 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diglycol acrylate, methoxy diglycol Methacrylate, methoxytriethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, A Oxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, adamantyl methacrylate, norbornyl methacrylate , 2-hydroxy-3-phenoxy propyl acrylate, 2-hydroxy-3-phenoxymethyl propylene Unsaturated carboxylic acid esters such as propyl ester, glycerin monoacrylate, glycerol monomethacrylate; 2-ethyl methacrylate, 2-aminoethyl methacrylate, ethyl 2-dimethylaminoacrylate , 2-dimethylaminoethyl methacrylate, 2-amino propyl acrylate, 2-aminopropyl methacrylate, 2-dimethylamino propyl acrylate, 2-dimethylamino Unsaturated, such as propyl methacrylate, propyl 3-aminoacrylate, propyl 3-aminopropyl methacrylate, propyl 3-dimethylaminoacrylate, propyl 3-dimethylaminopropyl methacrylate Aminoalkyl carboxylic acid esters; glycidyl acrylates, glycidyl methacrylates, and other unsaturated glycidyl carboxylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Ethylene carboxylate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; acrylonitrile such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene dicyandiamide Compound; acrylamide, methacrylamide, α-chloropropenylamine, N-2-hydroxyethyl decylamine, N-2-hydroxyethylmethacryl An unsaturated amine such as guanamine; an unsaturated imine such as maleic imine, benzyl maleimide, N-phenyl maleimide or N-cyclohexylmaleimide; An aliphatic conjugated diene such as 3-butadiene, isoprene or chloroprene; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly -n-butyl methacrylate or polyoxyalkylene has a macromonomer of a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end of the polymer molecular chain. The monomers may be used singly or in combination of two or more. In particular, as the other monomer copolymerizable with the carboxylic acid-containing monomer, a monomer having a norbornene-based skeleton, a monomer having an adamantane skeleton, a monomer having a rosin skeleton, or the like is preferable because of such expansion ( Bulky) monomers have a tendency to lower the dielectric constant. The binder resin may have an acid value of 20 to 200 (KOH mg/g). When the acid value of the binder resin satisfies the above range, the solubility in the developer is improved to make the non-naked portion easy to dissolve, and the sensitivity is increased. Thereby, the pattern of the final exposed portion is left behind at the time of development, thereby having the advantage of improving the film remainig ratio. The acid value in the present invention means a value for determining the amount (g) of potassium hydroxide required for neutralizing 1 g of the polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution. Further, the weight average molecular weight of the binder resin may specifically be from 3,000 to 200,000, specifically from 5,000 to 100,000, but is not limited thereto. The weight average molecular weight may be a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC: tetrahydrofuran as a dissolution solvent). When the molecular weight of the binder resin satisfies the above range, the hardness of the coating film is increased to increase the film retention ratio, and the solubility in the non-naked portion in the developer is excellent, and the definition is improved. The molecular weight distribution (weight average molecular weight (Mv) / number average molecular weight (Mn)) of the binder resin is from 1.5 to 6.0, specifically from 1.8 to 4.0, but is not limited thereto. However, when the molecular weight distribution of the binder resin satisfies the above range, the developability is excellent, so the above range is preferable. The binder resin may be included in an amount of 5 to 85 parts by weight, particularly 10 to 70 parts by weight, based on the total solid content of the colored photosensitive resin composition. When the content of the binder resin in the total solid content of the colored photosensitive resin composition is within the above range, the solubility in the developer is sufficient, and it is possible to prevent the occurrence of development residue on the substrate of the non-pixel portion and prevent it. The phenomenon that the film of the pixel portion of the light leakage portion is reduced at the time of development has an advantage that the leakage of the non-pixel portion tends to be good.Photopolymerizable compound
The photopolymerizable compound is not particularly limited as long as it can be polymerized by light or the action of a photopolymerization initiator described later, and may be, for example, a monofunctional monomer, a difunctional monomer, or another polyfunctional monomer. The monofunctional monomer may specifically be nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl Carbene acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. Specific examples of the bifunctional monomer may be 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and triethyl acrylate. Diol dimethacrylate, bis[2-(acryloyloxy)ethyl]ether, 3-methylpentandiol dimethacrylate )Wait. Specific examples of other polyfunctional monomers may be trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, polydipentaerythritol pentamethacrylate. Dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, and the like. It is preferred to use a polyfunctional monomer having a difunctional or higher functionality. The content of the photopolymerizable compound is usually in the range of 5 to 50 parts by weight, preferably 7 to 45 parts by weight, based on the solid content in the self-luminous photosensitive resin, but is not limited thereto. When the content of the photopolymerizable compound is within the above range, the strength or smoothness of the pixel portion can be made good.Photopolymerization initiator
The photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator commonly used in the art, and specifically may contain an acetophenone compound. The acetophenone compound can be, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Benzil Dimethyl Ketal, 2 -hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexane-benzophenone, 2-methyl-1-(4-methyl) Thiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2 An oligomer or the like of -hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one. Preferred is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one. Further, a photopolymerization initiator other than the above acetophenones may be used in combination. The photopolymerization initiator other than the acetophenone may be an active radical generator, a sensitizer, an acid generator or the like which generates an active radical by irradiation with light. The active radical generator may be, for example, a benzoin compound, a benzophenone compound, a thioxanthone compound, a triazine compound or the like. The benzoin compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether or the like. The benzophenone compound may be, for example, benzophenone, methyl phthalic acid benzoate, 4-phenylazo phenone, 4-benzylidene-4'-methyl bis Phenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like. The thioxanthone compound can be, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone and the like. The triazine compound can be, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane). 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1 ,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3 , 4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like. The active radical generator may be, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'- Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl benzhydrazide (Methyl phenylglyoxylate), titanocene compound, and the like. The acid generator may be, for example, 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethenyloxyphenyldimethylhydrazine Tosylate, 4-ethoxymethoxyphenylmethylbenzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium An anthracene salt such as tosylate or diphenyliodonium hexafluoroantimonate, a nitrobenzyl tosylate or a benzoin tosylate. Further, as the active compound generating agent, a compound of an active radical and an acid is simultaneously produced, and for example, a triazine-based photopolymerizable compound is also used as an acid generator. Further, a photopolymerization initiation aid can also be used in the present invention. The photopolymerization initiating auxiliary agent can be used in combination with the above photopolymerization initiator, which is a compound for promoting polymerization of the photopolymerizable compound initiated by the above photopolymerization initiator. The photopolymerization initiation auxiliary agent may be an amine compound, an alkoxy oxime compound, a thioxanthone compound or the like. The amine compound may be, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (collectively: Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (ethyl group) Amino group) benzophenone and the like. Among them, 4,4'-bis(diethylamino)benzophenone is preferably used, but is not limited thereto. The alkoxy quinone compound may be, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, and the like. The thioxanthone compound can be, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone and the like. The photopolymerization initiator or the photopolymerization initiation aid may be used singly or in combination of two or more. Further, as the photopolymerization initiating auxiliary agent, a commercially available photopolymerization initiating auxiliary agent such as EAB-F (manufacturer: Hodogaya Chemical Co., Ltd.) can be used. . The content of the photopolymerization initiator in the self-luminous photosensitive resin composition of the present invention is from 0.1 to 40 parts by weight, preferably from 1 to 30% by weight based on the total solid content of the total of the binder resin and the photopolymerizable compound. Share. When the photopolymerization initiator satisfies the above range, the colored photosensitive resin composition has high sensitivity so that the pixel portion formed using the composition has good strength, and the surface of the pixel portion has good smoothness. Therefore, it is preferred. When the photopolymerization initiating adjuvant is used, it is usually used in an amount of less than 10 mol, preferably 0.01 to 5 mol, based on 1 mol of the photopolymerization initiator. When the photopolymerization initiating auxiliary agent satisfies the above range, the sensitivity of the colored photosensitive resin composition becomes higher, so that the productivity of the color filter formed using the composition tends to be improved, and thus it is preferable.Solvent
The solvent contained in the colored photosensitive resin of the present invention is not particularly limited, and may be an organic solvent generally used in the field of colored photosensitive resin compositions. Specifically, it may be ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as alcohol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate such as methoxyethyl acetate or ethoxyethyl acetate Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate Classes; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol , alcohols such as hexanol, cyclohexanol, ethylene glycol, glycerin; esters such as ethane 3-ethoxypropionate, methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; Classes, etc. In view of coatability and drying property, an organic solvent having a boiling point of preferably from 100 ° C to 200 ° C in the above solvent is preferred, and an alkylene glycol alkyl ether acetate, a ketone or an ethane group is more preferred. Esters such as ethoxypropionate or methyl 3-methoxypropionate, preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanol, ethane 3-ethoxypropionate , methyl 3-methoxy propionate and the like. These solvents may be used alone or in combination of two or more. The solvent may be contained in an amount of 60 to 90 parts by weight, particularly 70 to 85 parts by weight, based on the total of the colored photosensitive resin composition. With respect to the entire coloring photosensitive resin composition, when the content of the solvent is within the above range, a roll coater, a spin coater, a slit type and a rotary coater, a slit coater or a mold type are used. Coating with a coating machine such as a coater or an ink jet machine is preferable because the coating property tends to be good.additive
The colored photosensitive resin composition of the present invention may contain an additive such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anticoagulant, if necessary, but is not limited thereto. Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like. The other polymer compound may specifically be a cured resin such as an epoxy resin or a maleimide resin; polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, poly A thermosetting resin such as an amine ester. As the pigment dispersant, a commercially available surfactant such as an anthracene resin, a fluorine compound, an ester, a cation, an anion, a nonionic or a positive surfactant can be used. They may be used alone or in combination of two or more. The surfactant may be, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, ternary Amine-modified polyimine esters, polyethyleneimines, and the like can be exemplified by a trade name of KP (manufactured by Shin-Etsu Chemical Co., Ltd.) and POLYFLOW (by a total of Manufactured by KYOEISHA CHEMICAL CO., LTD., EFTOP (manufactured by TOHKEM PRODUCTS CORPORATION), MEGAFAC (manufactured by DIC CORPORATION), and Flourad (by Sumitomo 3M Co., Ltd.) Manufactured by SUMITOMO 3M LTD), Asahi guard, Surflon (above manufactured by ASAHI GLASS CO., LTD), SOLSPERS (manufactured by ZENECA CO., LTD), EFKA (by IFKA Chemicals (EFKA) Manufactured by CHEMICALS BV), PB 821 (manufactured by AJNOMOTO CO., INC), and the like. The adhesion promoter may be, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-shrinkage Glyceroloxypropyltrimethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropane Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. The antioxidant may specifically be 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol or the like. The ultraviolet absorber may specifically be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone or the like. The anticoagulant may specifically be sodium polyacrylate or the like. The additive may be contained in an amount of 0.1 to 10 parts by weight, specifically 0.1 to 5 parts by weight, more specifically 0.1 to 1 part by weight, based on the total of the coloring photosensitive composition, but is not limited thereto. When the content of the above additives is within the above range, the properties expected of the respective additives can be imparted without lowering the performance of the color filter produced by the colored photosensitive resin composition. The coloring agent photosensitive resin composition of the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent in advance, and the colorant is dispersed using a sand mill or the like to an extent that the average particle diameter is less than 0.2 μm. At this time, a pigment dispersant may be used as needed, and some or all of the binder resin may be blended. Further, the obtained dispersion liquid (hereinafter also referred to as pulverized material) is further added with a remainder of the binder resin, a photopolymerizable compound, a photopolymerization initiator, other components used as needed, and an additional solvent used as needed. The concentration reaches a predetermined concentration to obtain a desired coloring photosensitive resin composition.Filter and image display device
The present invention provides a color filter produced from the colored photosensitive resin composition and an image display device including the color filter. In the present invention, the colored photosensitive resin composition can be used for a green pixel, but is not limited thereto. The image display device in which the color filter can be disposed has a liquid crystal display device, an OLED, a flexible display, etc., but is not limited thereto, and all image display devices that can be used in the art are known. The color filter can be produced by applying the above-described colored photosensitive resin composition of the present invention onto a substrate and performing photocuring and development to form a pattern. First, after the colored photosensitive resin composition is applied onto a substrate, volatile components such as a solvent are removed by heat drying to obtain a smooth coating film. The coating method can be carried out, for example, by using spin coating, flexible coating, roll coating, slit type, and rotary coating or slit coating. Volatile components such as a solvent are volatilized by heating drying (pre-baking) after coating or heating after drying under reduced pressure. At this time, the heating temperature is usually from 70 to 200 ° C, preferably from 80 to 130 ° C. The thickness of the coated film after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays by a mask for forming a desired pattern. At this time, parallel light can be uniformly irradiated to the entire light leakage portion, and a device such as a mask aligner or a stepper is preferably used to precisely align the mask and the substrate. When ultraviolet rays are irradiated, the portion irradiated with ultraviolet rays is solidified. As the ultraviolet light, a g-line (wavelength: 436 nm), an h-line, an i-line (wavelength: 365 nm), or the like can be used. The amount of ultraviolet irradiation can be appropriately selected as needed, and is not limited in the present invention. If the cured coating film is brought into contact with the developing solution to dissolve and develop the non-exposed portion, a desired pattern shape can be formed. The development method may be any one of a liquid addition method, a dipping method, a spray method, and the like. Further, the substrate can be tilted at an arbitrary angle during development. The developer is an aqueous solution containing a usual basic compound and a surfactant. The basic compound may be any of an inorganic basic compound and an organic basic compound. Specific examples of the inorganic basic compound may be sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, Sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Further, specific examples of the organic basic compound may be tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine. Amine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic basic compounds and organic basic compounds may be used singly or in combination of two or more. The concentration of the basic compound in the alkaline developing solution is preferably from 0.01 to 10 parts by weight, more preferably from 0.03 to 5 parts by weight. The surfactant in the alkaline developing solution may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant. Specific examples of the nonionic surfactant are polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether and other polyoxyethylene derivatives; oxyethylene/oxypropylene block copolymer; Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid sorbitol ester; fatty acid glyceride; polyoxyethylene fatty acid ester; polyoxyethylene alkylamine. Specific examples of the anionic surfactant may be higher alcohol sulfate salts such as sodium lauryl sulfate or sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; An alkylarylsulfonate such as sodium dodecylbenzenesulfonate or ammonium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant may be an ammonium salt such as stearylamine hydrochloride or lauryltrimethylammonium chloride or a 4-membered ammonium salt. These surfactants may be used singly or in combination of two or more. The concentration of the surfactant in the developer may be usually 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight. After development, water washing is performed, and post-baking may be carried out at 150 to 230 ° C for 10 to 60 minutes as needed. The invention will now be described in further detail in connection with the examples. The embodiments of the present invention disclosed below are merely exemplary, and the scope of the present invention is not limited by the embodiments. The scope of the present invention is defined by the scope of the appended claims. In addition, in the following Examples and Comparative Examples, "%" and "parts" indicating the content indicate the mass basis unless otherwise specified.Synthesis example of binder resin Adhesive resin (B)
182 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a thermometer, a reflux condenser, a titration material, and a nitrogen introduction tube, and the atmosphere of the flask was replaced with nitrogen by air, and then the temperature was raised to 100 ° C, followed by the methyl group. Adding a mixture of 70.5 g (0.40 mol) of benzyl acrylate, 45.0 g (0.50 mol) of methacrylic acid, 44.5 g (0.10 mol) of monocyclic methacrylic acid of the carbocyclic skeleton, and 136 g of propylene glycol monomethyl ether acetate A solution of 3.6 g of nitrogen diisobutyronitrile was dropped into the flask by titration of the material introduction port for 2 hours, and stirring was continued at 100 ° C for 5 hours. Next, after replacing the atmosphere in the flask with nitrogen from air, 30 g of glycidyl methacrylate (0.2 mol, 40 mol% relative to the carboxyl group of methacrylic acid used in the present invention), three two 0.9 g of methylaminomethylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a resin B having a solid content of 99 mg KOH/g. The polystyrene-equivalent weight average molecular weight measured by GPC was 28,000, and the molecular weight distribution (Mw/Mn) was 2.2. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured by the GPC method under the following conditions. Device: HLC-8120GPC (manufactured by TOSOH CORPORATION) Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection) Column temperature: 40 ° C Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50μl detector: RI determination sample concentration: 0.6% by mass (solvent = tetrahydrofuran) Standards for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (by East Cao Co., Ltd.) The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as a molecular weight distribution (Mw/Mn).Example
The colored photosensitive resin composition was prepared in accordance with the components and contents of the following Table 1. [Table 1]
1) Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 2) Initiator (D1): 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)butan-1-ol (Irgacure 369; manufactured by Ciba Specialty Chemical Co., Ltd.) Initiator (D2): 4,4'- (N,N'-dimethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 3) Solvent (E): propylene glycol methyl ether acetate 4) Additive (F): Acrylic acid Pigment-like dispersant (Disper byk-2001, manufactured by BYK)Brightness, color coordinates and contrast measurement Test strip preparation
A colored layer was produced by using the colored photosensitive resin compositions prepared in the above Examples 1 to 4 and Comparative Examples 1 to 4. Namely, the above colored photosensitive resin composition was applied onto a glass substrate by spin coating, and then placed on a hot plate and maintained at a temperature of 100 ° C for 3 minutes to form a film. Next, use a 1kW high-pressure mercury lamp containing g, h, and i lines at 100mJ/cm.2
Irradiation of the amount of exposure. At this time, no special optical filter was used. The above-mentioned ultraviolet-irradiated film was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes for development. The glass substrate coated with the above film was washed with distilled water, dried with nitrogen, and heated in a heating cabinet at 200 ° C for 30 minutes. The thickness of the colored layer thus obtained is from 1 to 5 μm, more preferably from about 2 to 4 μm.Brightness measurement method
It was measured using a microspectrometer OSP-SP2000. The brightness is shown in Table 2 below. The evaluation criteria of the brightness (Y) are as follows. ○: Y≥40, △: 38≤Y<40, X:Y<38Contrast determination method
The measurement was performed using a contrast meter BM-5A of TOPCON, and the measurement standard was 1/30000 of the contrast of the glass substrate (before the formation of the colored layer). The results are shown in Table 2 below. The rating criteria for contrast are as follows. ◎: CR ≥ 15000, ○: 12000 ≤ CR < 15000, △: 10000 ≤ CR < 12000, X: CR < 10000Coloring force distinction and patterning of color filters Tint strength
The coloring power is based on the ratio of the pigment content in the colored photosensitive resin composition required to produce the target coating film thickness. The results are shown in Table 2 below. ○: tinting strength <0.45, Δ: 0.45 ≤ tinting strength < 0.5, X: tinting strength > 0.5Patterning of color filters
The produced colored photosensitive resin composition was applied to a glass substrate (#1737, manufactured by CORNING Co., Ltd.) by spin coating, placed on a hot plate, and maintained at a temperature of 100 ° C for 3 minutes to form a film. Next, a test photomask having a pattern which changes stepwise in a range of transmittance of 1 to 100% was placed on the film, and the distance from the test photomask was set to 1000 μm, and an ultrahigh pressure mercury lamp (USH-250D, Made by Okinawa Electric Co., Ltd. (USHIO INC.), at 40 mJ/cm in an atmospheric atmosphere2
The exposure amount (365 nm) was irradiated with light. The above-mentioned ultraviolet-irradiated film was developed by a spray developing device of a KOH aqueous solution developing solution having a pH of 12.5 for 80 seconds. The film-coated glass plate was washed with distilled water, dried with nitrogen gas, and heated in a heating cabinet at 220 ° C for 20 minutes to produce a color filter pattern. The color filter of the above-described color filter has a pattern shape (film) thickness of 2.5 to 2.9 μm. [Table 2]
As shown in Table 2 above, the comparison results of Examples 1 to 4 and Comparative Examples 1 and 4 were such that CI Pigment Green 59 and CI Pigment Blue 16 were used or CI Pigment Green 58 was used at the same time as Comparative Examples 1 to 4. Examples 1 to 4 of CI Pigment Blue 16 and CI Pigment Green 59 were more excellent in brightness, contrast, and/or coloring power characteristics. As can be seen from the above Table 2, the brightness and contrast of the examples are superior to those of the comparative examples, and the coloring power in high color reproduction is excellent, which is advantageous in the liquid crystal display device. The pattern is formed, so the possibility of display failure is low.