本發明在下文中更詳細地描述。 本發明之一個實施例係關於一種著色感光性樹脂組合物，其包含熱酸產生劑(A)、著色劑(B)、鹼溶性樹脂(C)、光聚合引發劑(D)、光可聚合化合物(E)及溶劑(F)，其中熱酸產生劑(A)包含式(I)化合物。熱酸產生 劑 ( A )
本發明之著色感光性樹脂組合物包含式(I)之非離子型熱酸產生劑，其使得可藉由在低於200℃之低溫下煅燒充分硬化，從而在藉由使用該組合物形成之顏色層中提供良好黏著性及對化學品之耐受性。熱酸產生劑(A)為藉由熱之作用產生酸之化合物，其中， R1
為C1
-C30
烷基、C2
-C30
烯基、C3
-C20
環烷基、C3
-C20
雜環烷基、C6
-C20
芳基或C6
-C20
雜芳基； R2
為C1
-C30
烷基、C2
-C30
烯基、C3
-C20
環烷基、C3
-C20
雜環烷基、C6
-C20
芳基或C6
-C20
雜芳基；且 R1
及R2
各自獨立地未經取代或經以下取代：鹵素、氰基、硝基、羰基、磺酸、羥基、甲醯基、胺基或C1
-C20
烷基。 在本發明之一個實施例中，R1
可為C5
-C7
環烷基，其未經取代或經羥基或C7
-C8
橋連環烷基取代。 此外，R2
可為C1
-C6
烷基或式(II)基團：其中， R3
至R7
各自獨立地為氫或C1
-C6
烷基，且 *表示欲鍵結之部分。 在本發明之一個實施例中，熱酸產生劑(A)可包含選自式(III)至(V)之化合物及其組合： 。 在本發明之一個實施例中，熱酸產生劑(A)之分解起始溫度可高於或等於140℃且低於200℃。因此，使用本發明中之此類熱酸產生劑(A)使得可藉由在低於200℃之相對低溫下煅燒充分硬化，由此可形成具有良好黏著性及對化學品之耐受性的彩色濾光片。 以鹼溶性樹脂(C)及光可聚合化合物(E)之總固體含量計，熱酸產生劑(A)可以80至90 wt%之量存在。當滿足此範圍時，在溶劑中確保溶液均勻性而改良溶解性，且著色感光性樹脂組合物具有高敏感性，從而在自其形成之像素中提供足夠強度及良好表面光滑度且改良黏著性。 著色劑(B) 在本發明之一個實施例中，著色劑(B)可包含一或多種顏料(b1)、一或多種染料(b3)或其混合物，尤其一或多種顏料(b1)。顏料 ( b1 )
顏料(b1)可為此項技術中通常使用之任何有機顏料或無機顏料。顏料必要時可進行樹脂處理、使用具有酸性基團或鹼性基團之顏料衍生物進行表面處理、用聚合物化合物在顏料表面上進行接枝處理、藉由硫酸微米化或其類似方法進行微米化處理、用有機溶劑或水進行清潔處理以移除雜質或藉由離子交換或其類似方法進行處理以移除離子雜質。 有機顏料可包括印刷油墨、噴墨油墨及其類似物中所用之各種顏料，例如水溶性偶氮基顏料、不溶性偶氮基顏料、酞菁顏料、喹吖啶酮顏料、異吲哚啉酮顏料、異吲哚啉顏料、苝顏料、哌瑞酮顏料、二噁嗪顏料、蒽醌顏料、二蒽醌基顏料、蒽嘧啶顏料、蒽嵌蒽醌顏料、陰丹士林顏料、黃士酮顏料、皮蒽酮顏料及二酮基吡咯并吡咯顏料。 無機顏料亦可包括金屬化合物，諸如金屬氧化物及金屬複合物，例如諸如Fe、Co、Al、Cd、Pb、Cu、Mg、Cr、Zn、Sb及Ti之金屬的氧化物、複合金屬氧化物及碳黑。 詳言之，有機顏料及無機顏料可包括Color Index (The Society of Dyers and Colourists)中歸類於顏料的化合物。舉例而言，顏料可為(但不限於)具有以下比色指數(C.I.)值之化合物。 C.I.顏料黃13、20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、153、154、166、173、180及185； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65及71； C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、208、215、216、224、242、254、255及264； C.I.顏料紫14、19、23、29、32、33、36、37及38； C.I.顏料藍15 (15:3、15:4、15:6及其類似物)、21、28、60、64及76； C.I.顏料綠7、10、15、25、36、47及58； C.I顏料棕28； C.I顏料黑1及7及其類似物。 以上顏料可單獨使用或以兩者或多於兩者之組合形式使用。 以上顏料中，較佳使用至少一種選自由以下組成之群的顏料：C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃185、C.I.顏料橙38、C.I.顏料紅122、C.I.顏料紅166、C.I.顏料紅177、C.I.顏料紅208、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料紫23、C.I.顏料藍15:3、C.I.顏料藍15:6、C.I.顏料綠7、C.I.顏料綠36及C.I.顏料綠58。 顏料較佳以顏料粒子均勻分散之分散溶液形式使用。為均勻分散顏料粒子，可包括顏料分散劑(b2)用於分散液，從而獲得顏料均勻分散之分散溶液。顏料分散劑 ( b2 )
使用顏料分散劑(b2)防止顏料凝集且維持顏料之穩定性。顏料分散劑之特定實例可包括陽離子型、陰離子型、非離子型、兩性、基於聚酯及基於聚胺之界面活性劑，其可單獨使用或以兩者或多於兩者之組合形式使用。 陽離子型界面活性劑之實例可包括胺及四級銨鹽，諸如硬脂胺鹽酸鹽及氯化月桂基三甲基銨。 陰離子型界面活性劑之實例可包括高級醇硫酸鹽，諸如月桂醇硫酸鈉及油醇硫酸鈉；烷基硫酸鹽，諸如月桂基硫酸鈉及月桂基硫酸銨；及烷基芳基磺酸鹽，諸如十二烷基苯磺酸鈉及十二烷基萘磺酸鈉。 非離子型界面活性劑之實例可包括聚氧伸乙基烷基醚、聚氧伸乙基芳基醚、聚氧伸乙基烷基芳基醚及其他聚氧伸乙基衍生物、氧化乙烯/氧化丙烯嵌段共聚物、脫水山梨糖醇脂肪酸酯、聚氧伸乙基脫水山梨糖醇脂肪酸酯、聚氧伸乙基山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧伸乙基脂肪酸酯及聚氧伸乙基烷基胺。 以顏料(b1)之總固體含量計，顏料分散劑(b2)可以5至60 wt%、較佳15至50 wt%之量存在。當顏料分散劑之量低於5 wt%時，可能難以進行顏料之微米化或可能在分散後誘導膠凝。當顏料分散劑之量超過60 wt%時，黏度可能升高。染料 ( b3 )
染料(b3)可為(但不限於)可溶於有機溶劑之任何染料。較佳地，染料在有機溶劑中具有溶解性且亦在鹼性顯影溶液中具有溶解性，且具有可靠性，諸如耐熱性及溶劑耐受性。 染料可選自具有酸性基團(諸如磺酸及羧酸)之酸性染料、酸性染料與含氮化合物之鹽、酸性染料之磺醯胺及其衍生物。亦可使用基於偶氮基、基於二苯并哌喃及基於酞菁之酸性染料及其衍生物。 詳言之，染料可包括Color Index (The Society of Dyers and Colourists)中歸類於染料的化合物或著色註解(Coloring)中所列之染料。 舉例而言，染料可包括C.I.溶劑染料，例如 C.I.溶劑紅8、45、49、89、111、122、125、130、132、146及179； C.I.溶劑藍5、35、36、37、44、59、67及70； C.I.溶劑紫8、9、13、14、36、37、47及49； C.I.溶劑黃4、14、15、23、24、38、62、63、68、82、94、98、99及162； C.I.溶劑橙2、7、11、15、26及56； C.I.溶劑綠1、3、4、5、7、28、29、32、33、34及35等。 在以上C.I.溶劑染料中，在有機溶劑中具有良好溶解性之C.I.溶劑黃14、16、21、56、79、93、151；C.I.溶劑紅8、49、89、111、122、132、146、179；C.I.溶劑橙41、45、62；C.I.溶劑藍35、36、44、45、70；C.I.溶劑紫13為較佳，且C.I.溶劑黃21、79；C.I.溶劑紅8、122、132；C.I.溶劑橙45、62為更佳。 C.I.酸染料亦可包括以下染料： C.I.酸紅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、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422及426； C.I.酸黃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.酸紫6B、7、9、17、19及66； C.I.酸綠1、3、5、9、16、25、27、50、58、63、65、80、104、105、106及109。 在以上C.I.酸染料中，在有機溶劑中具有良好溶解性之C.I.酸黃42；C.I.酸紅92；C.I.酸藍80、90；C.I.酸紫66；及C.I.酸綠27為較佳。 另外，C.I.直接染料可包括以下染料： 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。 此外，C.I.媒染染料可包括以下染料： C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62及65； C.I.媒染紅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.媒染橙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.媒染藍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.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53及58； C.I.媒染綠1、3、4、5、10、15、19、26、29、33、34、35、41、43及53。 以上染料可單獨使用或以兩者或多於兩者之組合形式使用。 以本發明之著色感光性樹脂組合物之總固體含量計，著色劑(B)可以10至70 wt%之量存在。當著色劑(B)之量滿足此範圍時，使得可在欲形成之彩色濾光片中獲得足夠色密度，而且可形成具有足夠機械強度之圖案。 如本文所用，術語著色感光性樹脂組合物之『固體含量』係指著色感光性樹脂組合物中除溶劑外的其他組分的總含量。鹼溶性 樹脂 ( C )
在本發明之一個實施例中，鹼溶性樹脂(C)通常藉由光或熱之作用及鹼溶解性而具有反應性，且其充當著色劑之分散劑。 鹼溶性樹脂(C)不受限制，只要其充當著色劑之黏合劑樹脂，且在顯影以製備彩色濾光片之步驟中其可溶於鹼性顯影溶液。 舉例而言，鹼溶性樹脂(C)可為含羧基單體與可與該單體共聚之其他單體之共聚物。 含羧基單體可包括分子中具有一或多個羧基之不飽和羧酸，諸如不飽和單羧酸、不飽和二羧酸及不飽和三羧酸。 不飽和單羧酸之實例可包括丙烯酸、甲基丙烯酸、丁烯酸、α-氯丙烯酸及肉桂酸。不飽和二羧酸之實例可包括順丁烯二酸、反丁烯二酸、衣康酸、甲基順丁烯二酸及甲基反丁烯二酸。不飽和二羧酸可為酸酐，例如順丁烯二酸酐、衣康酸酐及甲基順丁烯二酸酐。不飽和二羧酸亦可為其單(2-(甲基)丙烯醯氧基烷基)酯，例如丁二酸單(2-丙烯醯氧基乙基)酯、丁二酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯及鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯。另外，不飽和二羧酸可為二羧基聚合物在其兩個末端之單(甲基)丙烯酸酯，例如ω-羧基聚己內酯單丙烯酸酯及ω-羧基聚己內酯單甲基丙烯酸酯。此等含羧基單體可單獨使用或以兩者或多於兩者之組合形式使用。 可與含羧基單體共聚之其他單體可包括例如芳族乙烯基化合物，諸如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基苯甲基甲醚、間乙烯基苯甲基甲醚、對乙烯基苯甲基甲醚、鄰乙烯基苯甲基縮水甘油醚、間乙烯基苯甲基縮水甘油醚、對乙烯基苯甲基縮水甘油醚、茚等；不飽和羧酸酯，諸如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸第二丁酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、丙烯酸3-羥基丙酯、甲基丙烯酸3-羥基丙酯、丙烯酸2-羥基丁酯、甲基丙烯酸2-羥基丁酯、丙烯酸3-羥基丁酯、甲基丙烯酸3-羥基丁酯、丙烯酸4-羥基丁酯、甲基丙烯酸4 -羥基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、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、甲氧基二乙二醇丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、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、丙烯酸異冰片烷酯、甲基丙烯酸異冰片烷酯、丙烯酸二環戊二烯酯、甲基丙烯酸二環戊二烯酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸降冰片烷酯、丙烯酸2-羥基-3-苯氧基丙酯、甲基丙烯酸2-羥基-3-苯氧基丙酯、甘油單丙烯酸甘油單甲基丙烯酸酯等；不飽和羧酸之胺基烷基酯，諸如丙烯酸2-胺基乙酯、甲基丙烯酸2-胺基乙酯、丙烯酸2-二甲基胺基乙酯、甲基丙烯酸2-二甲基胺基乙酯、丙烯酸2-胺基丙酯、甲基丙烯酸2-胺基丙酯、丙烯酸2-二甲基胺基丙酯、甲基丙烯酸2-二甲基胺基丙酯、丙烯酸3-胺基丙酯、甲基丙烯酸3-胺基丙酯、丙烯酸3-二甲基胺基丙酯、甲基丙烯酸3-二甲基胺基丙酯等；不飽和羧酸之縮水甘油酯，諸如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等；羧酸之乙烯酯，諸如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等；不飽和醚，諸如乙烯基甲醚、乙烯基乙醚、烯丙基縮水甘油醚等；氰化之乙烯基化合物，諸如丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化之亞乙烯基等；不飽和醯胺，諸如丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等；不飽和醯亞胺，諸如順丁烯二醯亞胺、苯甲基順丁烯二醯亞胺、N -苯基順丁烯二醯亞胺、N -環己基順丁烯二醯亞胺等；脂族共軛二烯，諸如1,3-丁二烯、異戊二烯、氯丁二烯等；及在聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯或聚矽氧烷之聚合物鏈的末端具有單丙烯醯基或單甲基丙烯醯基的大分子單體。以上單體可單獨使用或以兩者或多於兩者之組合形式使用。 較佳地，鹼溶性樹脂之酸值在20至200 (KOH mg/g)範圍內。當酸值滿足此範圍時，改良在鹼性顯影溶液中之溶解性以誘導未曝露區之容易溶解且提高敏感性，從而在顯影期間保持曝露區之圖案以改良膜剩餘比。 如本文中所使用，術語『酸值』係指以中和1 g聚合物所要的氫氧化鉀之量(mg)形式量測的值，且一般藉由使用氫氧化鉀水溶液滴定來獲得。 此外，鹼溶性樹脂較佳具有3,000至200,000、更佳5,000至100,000之聚苯乙烯轉化之重量平均分子量(Mw
)，其藉由凝膠滲透層析法(GPC)使用四氫呋喃作為溶離溶劑來量測。 當該分子量滿足此範圍時，塗佈膜具有改良硬度以提供高膜剩餘比，未曝露區在顯影溶液中之溶解性優良且解析度改良。 此外，鹼溶性樹脂之分子量分佈[重量平均分子量(Mw
) /數目平均分子量(Mn
)]可謂1.5至6.0，較佳1.8至4.0。當鹼溶性樹脂之分子量分佈滿足此範圍時，顯影性可改良。 在本發明中，以著色感光性樹脂組合物之總固體含量計，鹼溶性樹脂(C)可以5至85 wt%之量存在。當鹼溶性樹脂(C)之量滿足此範圍時，在顯影溶液中之溶解性可為足夠的，從而使其難以在非像素化部分之基板上產生顯影殘餘物，且可防止顯影期間曝露區中像素化部分之膜減少，從而使得非像素化部分可充分洩漏。光聚合引發劑 ( D )
在本發明之一個實施例中，光聚合引發劑(D)不受限制，只要其可用於聚合光可聚合化合物(E)。 詳言之，就聚合特性、引發效率、吸收波長、獲取條件、成本等而言，光聚合引發劑可為至少一種選自由以下組成之群的化合物：基於苯乙酮、二苯甲酮、三嗪、聯咪唑、噻噸酮之化合物基肟化合物。 基於苯乙酮之化合物之實例可包括二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苯甲基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙-1-酮及2-(4-甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)丁-1-酮。 基於二苯甲酮之化合物之實例可包括二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧羰基)二苯甲酮及2,4,6-三甲基二苯甲酮。 基於三嗪之化合物之實例可包括2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪。 基於聯咪唑之化合物之實例可包括2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑、2,2-雙(2,6-二氯苯基)-4,4'5,5'-四苯基-1,2'-聯咪唑及如下咪唑，其中4,4',5,5'位之苯基經烷氧羰基取代。其中，2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑及2,2-雙(2,6-二氯苯基)-4,4'5,5'-四苯基-1,2'-聯咪唑為較佳。 肟化合物之實例可包括鄰乙氧基羰基-α-氧亞胺-1-苯基丙-1-酮，且其市售化合物可代表性地包括OXE-01及OXE-02 (BASF)。 基於噻噸酮之化合物之實例可包括2-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮。 另外，此項技術中已知之其他光聚合引發劑可一起使用，除非其破壞本發明之效果。 其他光聚合引發劑可為例如基於安息香及蒽之化合物、2,4,6-三甲基苯甲醯基二苯基膦氧化物、10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌、苯基乙醛酸甲酯及二茂鈦化合物。 基於安息香之化合物之實例可包括安息香、安息香甲醚、安息香乙醚、安息香異丙醚及安息香異丁醚。 基於蒽之化合物的實例可包括9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽及2-乙基-9,10-二乙氧基蒽。 此外，光聚合引發劑(D)可與光引發佐劑(D-1)一起使用。當光聚合引發劑(D)與光引發佐劑(D-1)一起使用時，著色感光性樹脂組合物可具有提高之敏感性以使得生產力改良。 詳言之，光引發佐劑可選自由以下組成之群：胺、羧酸、具有硫醇基之有機含硫化合物及其混合物。 胺之實例可包括脂族胺，諸如三乙醇胺、甲基二乙醇胺及三異丙醇胺；及芳族胺，諸如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、4-二甲基胺基苯甲酸2-乙基己酯、苯甲酸2-二甲基胺基乙酯、N,N-二甲基-對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(米氏酮(Michler's ketone))及4,4'-雙(二乙基胺基)二苯甲酮。芳族胺為較佳。 羧酸可包括芳族雜乙酸，例如苯基硫乙酸、甲基苯基硫乙酸、乙基苯基硫乙酸、甲基乙基苯基硫乙酸、二甲基苯基硫乙酸、甲氧基苯基硫乙酸、二甲氧基苯基硫乙酸、氯苯基硫乙酸、二氯苯基硫乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸及萘氧基乙酸。 具有硫醇基之有機含硫化合物之實例可包括2-巰基苯并噻唑、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-參(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷參(3-巰基丙酸酯)、異戊四醇肆(3-巰基丁酸酯)、異戊四醇肆(3-巰基丙酸酯)、二異戊四醇六(3-巰基丙酸酯)及四乙二醇雙(3-巰基丙酸酯)。 以著色感光性樹脂組合物之總固體含量計，光聚合引發劑(D)可以0.1至30 wt%之量存在。當光聚合引發劑(D)之量滿足此範圍時，本發明之著色感光性樹脂組合物可具有高敏感性而縮短曝露時間，從而改良生產力，且維持高解析度。此類著色感光性樹脂組合物亦可提供足夠像素強度且在像素表面上具有良好光滑度。 此外，當進一步使用光引發佐劑(D-1)時，其可以每1 mol光聚合引發劑10 mol或小於10 mol、較佳0.01至5 mol之量包含在內。當光引發佐劑之量滿足此範圍時，本發明之著色感光性樹脂組合物可具有得到更大改良之敏感性且提高包含該組合物之彩色濾光片的生產力。光可聚合化合物 ( E )
在本發明之一個實施例中，光可聚合化合物(E)為可藉由光聚合引發劑(D)之作用聚合的化合物。光可聚合化合物可為(但不限於)單官能、雙官能及三官能光可聚合化合物。 單官能光可聚合化合物之實例可包括壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯及N-乙烯基吡咯啶酮。此外，作為市售化合物，可提及Aronix M-101 (Toagosei)、KAYARAD TC-110S (Nippon Kayaku)或Viscoat 158 (Osaka Organic Chemical Industry)。 雙官能光可聚合化合物之實例可包括1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚及3-甲基戊二醇二(甲基)丙烯酸酯。此外，作為市售化合物，可提及Aronix M-210、M-1100、1200 (Toagosei)、KAYARAD HDDA (Nippon Kayaku)、Viscoat 260 (Osaka Organic Chemical Industry)、AH-600、AT-600或UA-306H (Kyoeisha Chemical)。 具有3個或多於3個官能基之多官能光可聚合化合物之實例可包括三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、二異戊四醇五(甲基)丙烯酸酯、乙氧基化二異戊四醇六(甲基)丙烯酸酯、丙氧基化二異戊四醇六(甲基)丙烯酸酯及二異戊四醇六(甲基)丙烯酸酯。此外，作為市售化合物，可提及Aronix M-309、TO-1382 (Toagosei)、KAYARAD TMPTA、KAYARAD DPHA或KAYARAD DPHA-40H (Nippon Kayaku)。 在此等光可聚合化合物中，具有3個或多於3個官能基之(甲基)丙烯酸酯具有良好聚合以改良強度。 以著色感光性樹脂組合物之總固體含量計，光可聚合化合物(E)可以5至50 wt%之量存在。當光可聚合化合物(E)之量滿足此範圍時，像素之強度及光滑度可改良。(F) 溶 劑
在本發明之一個實施例中，溶劑(F)可為可溶解本發明之著色感光性樹脂組合物中所含有之其他組分的任何溶劑。詳言之，醚、乙酸酯、芳族烴、酮、醇及酯為較佳。 醚之實例可包括乙二醇單烷基醚，諸如乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚及乙二醇單丁醚；二乙二醇二烷基醚，諸如二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚及二乙二醇二丁醚。 乙酸酯之實例可包括甲基乙二醇乙酸乙醚、乙基乙二醇乙酸乙醚、乙酸乙酯、乙酸丁酯、乙酸戊酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基-1-丁酯、乙酸甲氧基戊酯、乙二醇單乙酸酯、乙二醇二乙酸酯、3-甲氧基丙酸甲酯、丙二醇甲醚乙酸酯、1,2-丙二醇二乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、二丙二醇甲醚乙酸酯、1,3-丁二醇二乙酸酯、二乙二醇單丁醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙酸酯、二乙二醇二乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、碳酸伸乙酯及碳酸伸丙酯。 芳族烴之實例可包括苯、甲苯、二甲苯及均三甲苯。 酮之實例可包括甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮及環己酮。 醇之實例可包括乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙三醇及4-羥基-4-甲基-2-戊酮。 酯之實例可包括3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯及γ-丁內酯。 此等溶劑可單獨使用或以兩者或多於兩者之組合形式使用。 就塗覆及乾燥而言，溶劑較佳可為沸點為100至200℃之有機溶劑，例如烷二醇烷基醚乙酸酯、酮、酯(諸如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯)，更佳丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己酮、乳酸乙酯、乳酸丁酯、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。 以著色感光性樹脂組合物之總重量計，溶劑(F)可以60至90 wt%之量存在。當溶劑之量滿足此範圍時，可使用塗覆機(諸如滾塗機、旋塗器、狹縫及旋轉式塗佈機、狹縫塗佈機(亦稱為『模塗機』)及噴墨)獲得良好塗覆。 必要時，本發明之著色感光性樹脂組合物可進一步包含添加劑(G)，諸如填充劑、其他聚合物、增黏劑、抗氧化劑、UV吸收劑、防凝劑等。 填充劑之實例可包括玻璃、矽膠及氧化鋁。 其他聚合物之實例可包括可固化樹脂，諸如環氧及順丁烯二醯亞胺樹脂；及熱塑性樹脂，諸如聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯、聚酯及聚胺基甲酸酯。 增黏劑之實例可包括乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(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-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、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及3-巰基丙基三甲氧基矽烷。 抗氧化劑之實例可包括2,2'-硫雙(4-甲基-6-第三丁基酚)及2,6-二-第三丁基-4-甲基酚。 UV吸收劑之實例可包括2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并三唑及烷氧基二苯甲酮。 防凝劑之實例可包括聚丙烯酸鈉。 本發明之一個實施例的著色感光性樹脂組合物可藉由以下方法製備。 舉例而言，將著色劑(B)中之顏料(b1)與溶劑(F)混合，且使用珠磨機分散混合物直至顏料之平均直徑達到約0.2 μm或小於0.2 μm為止。必要時，將顏料分散劑、一部分或所有鹼溶性樹脂(C)或染料(b3)與溶劑(F)混合以用於溶解或分散。向混合分散液中添加染料(b3)、剩餘鹼溶性樹脂(C)、光聚合引發劑(D)、光可聚合化合物(E)及添加劑，且必要時，可進一步添加溶劑(F)以獲得所要濃度，從而製備本發明之著色感光性樹脂組合物。 本發明之一個實施例係關於一種藉由使用上述著色感光性樹脂組合物形成的彩色濾光片。本發明之一個實施例的彩色濾光片包含著色層，其藉由在基板上塗佈著色感光性樹脂組合物繼而曝光且顯影以形成圖案來形成。 在下文中，將詳細描述使用本發明之著色感光性樹脂組合物形成圖案之方法。 首先，將本發明之著色感光性樹脂組合物塗覆在基板(通常為玻璃)上或著色感光性樹脂組合物中預形成之固體層上，繼而加熱且乾燥以移除揮發性組分(諸如溶劑)，得到光滑塗佈膜。 塗覆製程可藉由各種方法進行，諸如旋塗、澆鑄、滾塗、狹縫及旋轉式塗佈及狹縫塗佈。塗覆後，藉由加熱及乾燥(預烘烤)或藉由在減壓下乾燥隨後加熱使諸如溶劑之揮發性組分揮發。加熱通常在70至200℃、較佳80至130℃下進行。加熱且乾燥後，塗佈膜通常具有1至8 μm之厚度。 用UV射線穿過遮罩照射因此獲得之塗佈膜以形成所要圖案。為用平行射線均勻照射整個曝露區且將遮罩與基板恰當對準，較佳使用遮罩對準器或步進器。UV照射使得經照射部分固化。作為UV射線，可使用g射線(436 nm)、h射線、i射線(365 nm)。UV射線之輻照度可視需要適當選擇，且本發明不限於此。 使經固化塗佈膜與顯影溶液接觸以溶解非曝露區而進行顯影，從而獲得所要圖案。顯影製程可藉由(但不限於)溶液添加、浸漬或噴灑方法進行。此外，在顯影期間，基板可以視情況選用之角度傾斜。顯影溶液通常為含有鹼性化合物及界面活性劑之水溶液。 鹼性化合物可為無機或有機鹼性化合物。無機鹼性化合物之實例可包括氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀及氨。 此外，有機鹼性化合物之實例可包括氫氧化四甲銨、氫氧化2-羥基乙基三甲銨、單甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺及乙醇胺。 此等無機及有機鹼性化合物可單獨使用或以兩者或多於兩者之組合形式使用。以顯影溶液之總重量計，鹼性化合物可以0.01至10 wt%、較佳0.03至5 wt%之量包含在內。 顯影溶液中之界面活性劑可為至少一種選自由非離子型、陰離子型及陽離子型界面活性劑組成之群的界面活性劑。以顯影溶液之總重量計，界面活性劑可以0.01至10 wt%、較佳0.05至8 wt%、更佳0.1至5 wt%之量包含在內。 顯影後，可洗滌膜，且必要時在140至200℃下進行後烘烤10至60分鐘。 如上文所提及，將著色感光性樹脂組合物進行塗覆、乾燥、曝光以進行圖案化，且顯影，得到像素或黑色矩陣，其對應於感光性樹脂組合物中著色材料之各顏色，且根據彩色濾光片必需之顏色數重複此類程序，從而獲得彩色濾光片。彩色濾光片之構造及製備為此項技術中已知，因此本文省略其詳細描述。 本發明之一個實施例係關於一種具有上述彩色濾光片之液晶顯示裝置。 本發明之液晶顯示裝置具有上述彩色濾光片且包含此項技術中已知之其他組件。亦即，本發明中包括可使用本發明之彩色濾光片的任何液晶顯示裝置。舉例而言，存在一種透射液晶顯示裝置，其中具有薄膜電晶體(TFT)、像素電極及配向層之相對電極基板以預定間隔彼此面對，且將液晶材料引入間隔中，形成液晶層。此外，可提及反射液晶顯示裝置，其在基板與彩色濾光片之著色層之間具有反射層。另外，可提及如下液晶顯示裝置，其包含組合在彩色濾光片之透明電極上的薄膜電晶體(TFT)基板及固定在TFT基板之一位置處與彩色濾光片重疊的背光。 本發明藉由以下實例、比較實例及實驗實例進一步說明，該等實例不應理解為限制本發明之範疇。製備實例 1 ： 製備鹼溶性 樹脂
向配備有攪拌器、溫度計、回流冷凝器、滴加分配器及用於引入氮氣之管的燒瓶中添加200重量份丙二醇單甲醚乙酸酯、45重量份丙二醇單甲醚、2重量份偶氮雙異丁腈(AIBN)、15重量份丙烯酸、70重量份甲基丙烯酸苯甲酯、15重量份苯乙烯及3重量份正十二烷基硫醇，繼而進行氮氣替換。隨後，在攪拌下使反應溶液之溫度升至110℃且使反應持續8小時，得到鹼溶性樹脂。經證實，如藉由GPC所量測，所得鹼溶性樹脂的重量平均分子量(Mw)為約16,000，且酸值為100.4 mg KOH/g。實例 1 至 6 及比較實例 1 至 6 ： 製備著色感光性樹脂組合物
藉由以下表1中所列之比率(單位：重量份)混合該等組分製備著色感光性樹脂組合物。 [表1]
1) LTN-207 (Loum Hitech)2) LTN-201 (Loum Hitech)3) LTN-107 (Loum Hitech)4)對甲苯磺酸吡啶鎓(Sigma-Aldrich)5) C.I顏料藍15:6 6)製備實例1中所獲得之樹脂 7)二異戊四醇六丙烯酸酯(Nippon Kayaku) 8)2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮(Ciba Specialty Chemicals) 9)丙二醇單甲醚乙酸酯實驗實例 1 ： 評估對溶劑之耐受性及黏著性
使用實例及比較實例中所製備之著色感光性樹脂組合物製備彩色濾光片。 特定言之，借助於旋塗將各著色感光性樹脂組合物塗覆在玻璃基板上，且將玻璃基板置放在熱板上，其中維持100℃之溫度3分鐘，在玻璃基板上形成薄膜。隨後，將圖案展示在1至100%範圍內之逐步透射率且具有1至50 μm線/間隙圖案的測試光罩置放在薄膜上，以100 μm薄膜與測試光罩之間的間隔使用1 KW高壓汞燈在100 mJ/cm2
下在無任何特定光學濾波器下進行UV照射，其中汞燈含有g、h及i射線中之全部。將經UV照射之薄膜浸在用作顯影溶液之KOH水溶液(pH 10.5)中2分鐘。顯影後，用蒸餾水洗滌薄膜且用氮氣乾燥，繼而在設定為150℃之烘箱中加熱20分鐘，得到彩色濾光片。經證實彩色濾光片之所得薄膜之厚度為2.0 μm。 藉由以下方法評估各樣品對溶劑之耐受性及黏著性。結果展示於表2中。 (1)對溶劑之耐受性 將所製備之彩色濾光片浸在作為溶劑之N-甲基吡咯啶酮中30分鐘，隨後比較其在浸漬之前及之後的顏色變化。藉由以下方程式1計算顏色變化，其將3維色度計中之顏色變化描述為L*、a*、b*。顏色變化之值愈低，可製備之彩色濾光片之可靠性愈高。 [方程式1] ΔEab*
= [(ΔL*
)2
+(Δa*
)2
+(Δb*
)2
](1/2)
(2)黏著性 經由光學顯微鏡觀測所形成之圖案，隨後證實圖案上剝離之程度以評估黏著性。 ○：圖案上無剝離 Δ：圖案上1至3處剝離 X：圖案上4處或多於4處剝離 [表2]
如表2中所示，相較於比較實例1至6之組合物，含有指定量之非離子型熱酸產生劑的本發明之實例1至6之著色感光性樹脂組合物提供在對溶劑之耐受性及黏著性方面具有優良特性的彩色濾光片。 儘管已展示及描述本發明之特定實施例，但熟習此項技術者應瞭解其不欲將本發明限制於較佳實施例，且熟習此項技術者將顯而易見可在不背離本發明之精神及範疇下進行各種改變及修改。 因此，本發明之範疇將由隨附申請專利範圍及其等效物界定。The invention is described in more detail below. An embodiment of the present invention relates to a colored photosensitive resin composition including a thermal acid generator (A), a colorant (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a photopolymerizable polymer. Compound (E) and solvent (F), wherein the thermal acid generator (A) comprises a compound of formula (I).Thermal acid production Agent ( A )
The colored photosensitive resin composition of the present invention contains a non-ionic thermal acid generator of the formula (I), which makes it possible to sufficiently harden by calcination at a low temperature of less than 200 ° C, thereby forming a composition formed by using the composition. Provides good adhesion and chemical resistance in the color layer. The thermal acid generator (A) is a compound that generates an acid by the action of heat,Where R1
For C1
-C30
Alkyl, C2
-C30
Alkenyl, C3
-C20
Cycloalkyl, C3
-C20
Heterocycloalkyl, C6
-C20
Aryl or C6
-C20
Heteroaryl; R2
For C1
-C30
Alkyl, C2
-C30
Alkenyl, C3
-C20
Cycloalkyl, C3
-C20
Heterocycloalkyl, C6
-C20
Aryl or C6
-C20
Heteroaryl; and R1
And R2
Each independently unsubstituted or substituted by: halogen, cyano, nitro, carbonyl, sulfonic acid, hydroxyl, formamyl, amine or C1
-C20
alkyl. In one embodiment of the invention, R1
Can be C5
-C7
Cycloalkyl, which is unsubstituted or hydroxyl or C7
-C8
Bridged cycloalkyl substitution. In addition, R2
Can be C1
-C6
Alkyl or group of formula (II):Where R3
To R7
Each independently hydrogen or C1
-C6
Alkyl, and * indicates the portion to be bonded. In one embodiment of the present invention, the thermal acid generator (A) may include a compound selected from the formulae (III) to (V) and a combination thereof: . In one embodiment of the present invention, the decomposition start temperature of the thermal acid generator (A) may be higher than or equal to 140 ° C and lower than 200 ° C. Therefore, the use of such a thermal acid generator (A) in the present invention makes it possible to sufficiently harden by calcination at a relatively low temperature of less than 200 ° C, thereby forming a chemical compound having good adhesion and resistance to chemicals Color filters. The thermal acid generator (A) may be present in an amount of 80 to 90 wt% based on the total solid content of the alkali-soluble resin (C) and the photopolymerizable compound (E). When the range is satisfied, the uniformity of the solution in the solvent is improved to improve the solubility, and the coloring photosensitive resin composition has high sensitivity, thereby providing sufficient strength and good surface smoothness in the pixels formed therefrom and improving adhesion. . Colorant (B) In one embodiment of the present invention, the colorant (B) may include one or more pigments (b1), one or more dyes (b3), or a mixture thereof, especially one or more pigments (b1).pigment ( b1 )
The pigment (b1) may be any organic pigment or inorganic pigment generally used in this technology. The pigment may be subjected to resin treatment if necessary, surface treatment using a pigment derivative having an acidic group or a basic group, graft treatment with a polymer compound on the surface of the pigment, micronization by sulfuric acid micronization or the like Chemical treatment, cleaning treatment with an organic solvent or water to remove impurities or treatment by ion exchange or the like to remove ionic impurities. Organic pigments may include various pigments used in printing inks, inkjet inks, and the like, such as water-soluble azo-based pigments, insoluble azo-based pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments. , Isoindoline pigment, perylene pigment, piperidone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinone-based pigment, anthracene pyrimidine pigment, anthracene anthraquinone pigment, indanthrene pigment, flavone pigment Dermatanone pigment and diketopyrrolopyrrole pigment. Inorganic pigments may also include metal compounds such as metal oxides and metal composites, such as oxides of metal such as Fe, Co, Al, Cd, Pb, Cu, Mg, Cr, Zn, Sb, and Ti, and composite metal oxides. And carbon black. In detail, organic pigments and inorganic pigments may include compounds classified as pigments in the Color Index (The Society of Dyers and Colourists). For example, the pigment may be, but is not limited to, a compound having the following color index (C.I.) value. CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149 , 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 and the like), 21, 28, 60, 64, and 76; CI Pigment Green 7, 10, 15, 25, 36, 47, and 58; CI Pigment Brown 28; CI Pigment Black 1 and 7 and the like. The above pigments may be used alone or in a combination of two or more. Among the above pigments, at least one pigment selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 122, and CI Pigment is preferably used. Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15: 3, CI Pigment Blue 15: 6, CI Pigment Green 7. CI Pigment Green 36 and CI Pigment Green 58. The pigment is preferably used in the form of a dispersion solution in which pigment particles are uniformly dispersed. In order to uniformly disperse the pigment particles, a pigment dispersant (b2) may be included in the dispersion liquid to obtain a dispersion solution in which the pigment is uniformly dispersed.Pigment dispersant ( b2 )
The pigment dispersant (b2) is used to prevent pigment aggregation and maintain pigment stability. Specific examples of the pigment dispersant may include cationic, anionic, nonionic, amphoteric, polyester-based, and polyamine-based surfactants, which may be used alone or in a combination of two or more. Examples of cationic surfactants may include amines and quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride. Examples of the anionic surfactant may include higher alcohol sulfates such as sodium lauryl sulfate and sodium oleyl alcohol; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; and alkylaryl sulfonates, Such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Examples of non-ionic surfactants may include polyoxyethylene alkyl ether, polyoxyethyl aryl ether, polyoxyethyl aryl ether and other polyoxyethyl derivatives, ethylene oxide / Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glyceryl fatty acid ester, polyoxyethylene Fatty acid esters and polyoxyethylene alkylamines. The pigment dispersant (b2) may be present in an amount of 5 to 60 wt%, preferably 15 to 50 wt%, based on the total solids content of the pigment (b1). When the amount of the pigment dispersant is less than 5 wt%, micronization of the pigment may be difficult or gelation may be induced after dispersion. When the amount of the pigment dispersant exceeds 60 wt%, the viscosity may increase.dye ( b3 )
The dye (b3) may be, but is not limited to, any dye that is soluble in an organic solvent. Preferably, the dye is soluble in an organic solvent and also soluble in an alkaline developing solution, and has reliability such as heat resistance and solvent resistance. The dye may be selected from acid dyes having acidic groups such as sulfonic acids and carboxylic acids, salts of acid dyes and nitrogen-containing compounds, sulfonamide of acid dyes, and derivatives thereof. It is also possible to use azo-based, dibenzopiperan-based and phthalocyanine-based acid dyes and their derivatives. In detail, dyes may include compounds classified in the Color Index (The Society of Dyers and Colourists) or dyes listed in Coloring. For example, the dyes may include CI solvent dyes, such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179; CI solvent blue 5, 35, 36, 37, 44, 59, 67, and 70; CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, and 49; CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162; CI solvent orange 2, 7, 11, 15, 26, and 56; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. Among the above CI solvent dyes, CI solvent yellow 14, 16, 21, 56, 79, 93, 151, which has good solubility in organic solvents; CI solvent red 8, 49, 89, 111, 122, 132, 146, 179; CI solvent orange 41, 45, 62; CI solvent blue 35, 36, 44, 45, 70; CI solvent violet 13 is better, and CI solvent yellow 21, 79; CI solvent red 8, 122, 132; CI Solvent oranges 45 and 62 are more preferred. CI acid dyes can also include the following dyes: 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, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426; 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 lime 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 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, 19, and 66; CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109. Among the above C.I. acid dyes, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; and C.I. Acid Green 27, which have good solubility in organic solvents, are preferred. In addition, CI direct dyes can include the following dyes: 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 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 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 Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104 ; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82. In addition, CI mordant dyes can include the following dyes: CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; CI mordant 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 mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24 , 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48; CI mordant 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 mordant purple 1, 2, 4 , 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58; CI mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53. The above dyes can be used alone or in a combination of two or more. The colorant (B) may be present in an amount of 10 to 70% by weight based on the total solids content of the colored photosensitive resin composition of the present invention. When the amount of the colorant (B) satisfies this range, a sufficient color density can be obtained in a color filter to be formed, and a pattern having sufficient mechanical strength can be formed. As used herein, the term "solid content" of the colored photosensitive resin composition refers to the total content of other components in the colored photosensitive resin composition other than the solvent.Alkali-soluble Resin ( C )
In one embodiment of the present invention, the alkali-soluble resin (C) is generally reactive by the action of light or heat and alkali solubility, and it acts as a dispersant for the colorant. The alkali-soluble resin (C) is not limited as long as it serves as a binder resin for a colorant, and it is soluble in an alkaline developing solution in the step of developing to prepare a color filter. For example, the alkali-soluble resin (C) may be a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer. The carboxyl group-containing monomer may include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, methyl maleic acid, and methyl fumaric acid. Unsaturated dicarboxylic acids may be anhydrides, such as maleic anhydride, itaconic anhydride, and methyl maleic anhydride. Unsaturated dicarboxylic acids can also be their mono (2- (meth) acryloxyalkyl) esters, such as succinic acid mono (2-acryloxyethyl) ester, succinic acid mono (2- Methacryloxyethyl), mono (2-acryloxyethyl) phthalate, and mono (2-methacryloxyethyl) phthalate. In addition, the unsaturated dicarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, such as ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylic acid. ester. These carboxyl group-containing monomers may be used alone or in a combination of two or more. Other monomers copolymerizable with carboxyl-containing monomers may include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene , O-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene, etc .; unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, acrylic acid Ethyl ester, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-methacrylate Hydroxybutyl, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, methyl formate Cyclohexyl acrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-methacrylate Phenoxyethyl ester, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid dimethacrylate Cyclopentadienyl, dicyclopentadienyl methacrylate, ( Base) adamantyl acrylate, norbornane (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monoacrylate Methacrylates, etc .; amino alkyl esters of unsaturated carboxylic acids, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, methacrylic acid 2-dimethylaminoethyl acrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate Esters, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc .; of unsaturated carboxylic acids Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc .; vinyl esters of carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; unsaturated ethers, such as Vinyl methyl ether, vinyl ether, allyl glycidyl ether, etc .; cyanated vinyl compounds such as acrylonitrile, methyl propyl Nitriles, α-chloroacrylonitrile, cyanidized vinylidene, etc .; unsaturated fluorenes, such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethyl methacrylamide and the like; unsaturated amines, such as cis butene diimide, benzyl cis butylene diimide, N-phenyl cis butylene diimide Amines, N-cyclohexyl cis butene difluorene imine, etc .; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, etc .; and in polystyrene, polyacrylic acid Polymeric chains of methyl, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, or polysiloxane having a monoacryl group or a monomethacryl group at the end of a polymer chain body. The above monomers can be used alone or in a combination of two or more. Preferably, the acid value of the alkali-soluble resin is in the range of 20 to 200 (KOH mg / g). When the acid value satisfies this range, the solubility in the alkaline developing solution is improved to induce easy dissolution of the unexposed areas and increase sensitivity, thereby maintaining the pattern of the exposed areas during development to improve the film remaining ratio. As used herein, the term "acid value" refers to a value measured in the form of the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and is generally obtained by titration with an aqueous potassium hydroxide solution. In addition, the alkali-soluble resin preferably has a weight average molecular weight (M) of polystyrene conversion of 3,000 to 200,000, more preferably 5,000 to 100,000.w
), Which was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a dissolution solvent. When the molecular weight satisfies this range, the coating film has improved hardness to provide a high film residual ratio, excellent solubility of the unexposed area in the developing solution, and improved resolution. In addition, the molecular weight distribution of the alkali-soluble resin [weight average molecular weight (Mw
) / Number average molecular weight (Mn
)] Can be described as 1.5 to 6.0, preferably 1.8 to 4.0. When the molecular weight distribution of the alkali-soluble resin satisfies this range, developability can be improved. In the present invention, the alkali-soluble resin (C) may be present in an amount of 5 to 85% by weight based on the total solids content of the colored photosensitive resin composition. When the amount of the alkali-soluble resin (C) satisfies this range, the solubility in the developing solution may be sufficient, making it difficult to generate development residues on the substrate of the non-pixelated portion, and preventing the exposed area during development The film of the middle pixelated portion is reduced, so that the non-pixelated portion can be fully leaked.Photopolymerization initiator ( D )
In one embodiment of the present invention, the photopolymerization initiator (D) is not limited as long as it can be used for polymerizing the photopolymerizable compound (E). In detail, in terms of polymerization characteristics, initiation efficiency, absorption wavelength, acquisition conditions, cost, etc., the photopolymerization initiator may be at least one compound selected from the group consisting of acetophenone, benzophenone, Compounds of hydrazine, biimidazole, and thioxanthone. Examples of acetophenone-based compounds may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthienyl) ) -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butan-1-one, 2-hydroxy-2- Methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinylphenyl) butan-1-one. Examples of the benzophenone-based compound may include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl Thioether, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone. Examples of triazine-based compounds may include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-triazine , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl]- 1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine . Examples of biimidazole-based compounds may include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkoxy) Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2,2-bis (2 , 6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole and the following imidazoles, of which the phenyl group at the 4,4 ', 5,5' position is alkoxylated Carbonyl substitution. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biphenyl Imidazole is preferred. Examples of the oxime compound may include o-ethoxycarbonyl-α-oxyimine-1-phenylpropan-1-one, and commercially available compounds thereof may typically include OXE-01 and OXE-02 (BASF). Examples of thioxanthone-based compounds may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxan Tons of ketones. In addition, other photopolymerization initiators known in the art can be used together unless they destroy the effect of the present invention. Other photopolymerization initiators may be, for example, benzoin and anthracene-based compounds, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. Examples of benzoin-based compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of anthracene-based compounds may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene. Further, the photopolymerization initiator (D) can be used together with the photoinitiator adjuvant (D-1). When the photopolymerization initiator (D) is used together with the photoinitiator adjuvant (D-1), the colored photosensitive resin composition may have improved sensitivity to improve productivity. In detail, the photo-initiated adjuvant may be selected from the group consisting of amines, carboxylic acids, organic sulfur-containing compounds having a thiol group, and mixtures thereof. Examples of the amine may include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amines such as methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Ethyl formate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-di Methyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone) and 4,4'-bis (diethylamino) benzophenone ketone. Aromatic amines are preferred. The carboxylic acid may include aromatic heteroacetic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene Thioglycolic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine Acid and naphthyloxyacetic acid. Examples of the organic sulfur-containing compound having a thiol group may include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-ginseno (3-mercaptobutoxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane (3-mercaptopropionate), isopentaerythritol (3-mercaptobutyrate), isopentaerythritol (3-mercaptopropionate), diisopentaerythritol hexa (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) ). The photopolymerization initiator (D) may be present in an amount of 0.1 to 30 wt% based on the total solids content of the colored photosensitive resin composition. When the amount of the photopolymerization initiator (D) satisfies this range, the colored photosensitive resin composition of the present invention can have high sensitivity and shorten exposure time, thereby improving productivity and maintaining high resolution. Such a colored photosensitive resin composition can also provide sufficient pixel strength and have good smoothness on the pixel surface. In addition, when the photoinitiator adjuvant (D-1) is further used, it may be included in an amount of 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photopolymerization initiator. When the amount of the photo-initiated adjuvant satisfies this range, the colored photosensitive resin composition of the present invention can have greater improved sensitivity and increase the productivity of a color filter including the composition.Photopolymerizable compound ( E )
In one embodiment of the present invention, the photopolymerizable compound (E) is a compound that can be polymerized by the action of a photopolymerization initiator (D). Photopolymerizable compounds can be, but are not limited to, monofunctional, difunctional, and trifunctional photopolymerizable compounds. Examples of the monofunctional photopolymerizable compound may include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate And N-vinyl pyrrolidone. In addition, as commercially available compounds, Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscoat 158 (Osaka Organic Chemical Industry) can be mentioned. Examples of the difunctional photopolymerizable compound may include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethyl Glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate. In addition, as commercially available compounds, Aronix M-210, M-1100, 1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Organic Chemical Industry), AH-600, AT-600, or UA- 306H (Kyoeisha Chemical). Examples of the polyfunctional photopolymerizable compound having 3 or more functional groups may include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate , Propoxylated trimethylolpropane tri (meth) acrylate, isopentaerythritol tri (meth) acrylate, isopentaerythritol tetra (meth) acrylate, diisopentaerythritol penta (methyl) Acrylate), ethoxylated diisopentaerythritol hexa (meth) acrylate, propoxylated diisopentaerythritol hexa (meth) acrylate, and diisopentaerythritol hexa (meth) acrylic acid ester. In addition, as commercially available compounds, Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD DPHA-40H (Nippon Kayaku) can be mentioned. Among these photopolymerizable compounds, (meth) acrylates having 3 or more functional groups have good polymerization to improve strength. The photopolymerizable compound (E) may be present in an amount of 5 to 50 wt% based on the total solids content of the colored photosensitive resin composition. When the amount of the photopolymerizable compound (E) satisfies this range, the intensity and smoothness of the pixel can be improved.(F) Dissolve Agent
In one embodiment of the present invention, the solvent (F) may be any solvent that can dissolve other components contained in the colored photosensitive resin composition of the present invention. Specifically, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters are preferred. Examples of the ether may include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ether, Such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether. Examples of the acetate may include methyl ethylene glycol ethyl acetate, ethyl ethylene glycol ethyl acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-acetate Methoxybutyl, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, 3-methoxy Methyl propionate, propylene glycol methyl ether acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate , 1,3-butanediol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetic acid Ester, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, carbonic acid Ethylene and propyl carbonate. Examples of the aromatic hydrocarbon may include benzene, toluene, xylene, and mesitylene. Examples of the ketone may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the alcohol may include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone. Examples of the ester may include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone. These solvents may be used alone or in a combination of two or more. For coating and drying, the solvent may preferably be an organic solvent having a boiling point of 100 to 200 ° C, such as alkanediol alkyl ether acetates, ketones, esters (such as ethyl 3-ethoxypropionate and 3 -Methyl methoxypropionate), more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and 3 -Methyl methoxypropionate. The solvent (F) may be present in an amount of 60 to 90 wt% based on the total weight of the colored photosensitive resin composition. When the amount of the solvent satisfies this range, a coater (such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also known as a "die coater"), and a spray coater can be used. Ink) to obtain a good coating. If necessary, the colored photosensitive resin composition of the present invention may further contain additives (G) such as fillers, other polymers, tackifiers, antioxidants, UV absorbers, anticoagulants, and the like. Examples of the filler may include glass, silicone, and alumina. Examples of other polymers may include curable resins such as epoxy and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylic acid. Esters, polyesters and polyurethanes. Examples of the tackifier may include vinyltrimethoxysilane, vinyltriethoxysilane, vinylgins (2-methoxyethoxy) silane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyl Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Examples of the antioxidant may include 2,2′-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol. Examples of the UV absorber may include 2- (3-thirdbutyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the anticoagulant may include sodium polyacrylate. The colored photosensitive resin composition according to an embodiment of the present invention can be prepared by the following method. For example, the pigment (b1) in the colorant (B) is mixed with the solvent (F), and the mixture is dispersed using a bead mill until the average diameter of the pigment reaches about 0.2 μm or less. If necessary, a pigment dispersant, a part or all of the alkali-soluble resin (C) or the dye (b3) is mixed with the solvent (F) for dissolution or dispersion. To the mixed dispersion, dye (b3), remaining alkali-soluble resin (C), photopolymerization initiator (D), photopolymerizable compound (E), and additives are added, and if necessary, a solvent (F) may be further added to obtain At the desired concentration, the colored photosensitive resin composition of the present invention is prepared. An embodiment of the present invention relates to a color filter formed by using the above-mentioned colored photosensitive resin composition. A color filter according to an embodiment of the present invention includes a colored layer, which is formed by applying a colored photosensitive resin composition on a substrate, and then exposing and developing to form a pattern. Hereinafter, a method for forming a pattern using the colored photosensitive resin composition of the present invention will be described in detail. First, the colored photosensitive resin composition of the present invention is coated on a substrate (usually glass) or a pre-formed solid layer in the colored photosensitive resin composition, and then heated and dried to remove volatile components such as Solvent) to obtain a smooth coating film. The coating process can be performed by various methods such as spin coating, casting, roll coating, slit and spin coating and slit coating. After coating, volatile components such as solvents are volatilized by heating and drying (pre-baking) or by drying under reduced pressure followed by heating. Heating is usually performed at 70 to 200 ° C, preferably 80 to 130 ° C. After heating and drying, the coating film usually has a thickness of 1 to 8 μm. The coating film thus obtained is irradiated with UV rays through the mask to form a desired pattern. In order to uniformly irradiate the entire exposed area with parallel rays and properly align the mask with the substrate, a mask aligner or a stepper is preferably used. UV irradiation causes the irradiated portion to cure. As UV rays, g-rays (436 nm), h-rays, and i-rays (365 nm) can be used. The irradiance of UV rays can be appropriately selected according to need, and the present invention is not limited thereto. The cured coating film is brought into contact with a developing solution to dissolve the non-exposed area and developed to obtain a desired pattern. The development process can be performed by, but not limited to, solution addition, dipping or spraying. In addition, during development, the substrate may be tilted at an optional angle. The developing solution is usually an aqueous solution containing a basic compound and a surfactant. The basic compound may be an inorganic or organic basic compound. Examples of the inorganic basic compound may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, carbonic acid Sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate and ammonia. In addition, examples of the organic basic compound may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoethylamine Isopropylamine, diisopropylamine and ethanolamine. These inorganic and organic basic compounds may be used alone or in a combination of two or more. The basic compound may be included in an amount of 0.01 to 10 wt%, preferably 0.03 to 5 wt% based on the total weight of the developing solution. The surfactant in the developing solution may be at least one surfactant selected from the group consisting of nonionic, anionic and cationic surfactants. The surfactant may be included in an amount of 0.01 to 10 wt%, preferably 0.05 to 8 wt%, and more preferably 0.1 to 5 wt% based on the total weight of the developing solution. After development, the film may be washed, and if necessary, post-baked at 140 to 200 ° C for 10 to 60 minutes. As mentioned above, the colored photosensitive resin composition is coated, dried, exposed for patterning, and developed to obtain a pixel or a black matrix corresponding to each color of the coloring material in the photosensitive resin composition, and This procedure is repeated according to the number of colors necessary for the color filter to obtain a color filter. The structure and preparation of color filters are known in the art, so detailed descriptions thereof are omitted herein. An embodiment of the present invention relates to a liquid crystal display device having the above color filter. The liquid crystal display device of the present invention has the above-mentioned color filter and includes other components known in the art. That is, the present invention includes any liquid crystal display device that can use the color filter of the present invention. For example, there is a transmissive liquid crystal display device in which opposing electrode substrates having a thin film transistor (TFT), a pixel electrode, and an alignment layer face each other at a predetermined interval, and a liquid crystal material is introduced into the interval to form a liquid crystal layer. Furthermore, a reflective liquid crystal display device may be mentioned, which has a reflective layer between the substrate and the colored layer of the color filter. In addition, mention may be made of a liquid crystal display device including a thin film transistor (TFT) substrate combined on a transparent electrode of a color filter and a backlight fixed at one position of the TFT substrate and overlapping the color filter. The invention is further illustrated by the following examples, comparative examples, and experimental examples, which should not be construed as limiting the scope of the invention.Preparation example 1 : Preparation of alkali-soluble Resin
200 parts by weight of propylene glycol monomethyl ether acetate, 45 parts by weight of propylene glycol monomethyl ether, and 2 parts by weight of a flask equipped with a stirrer, a thermometer, a reflux condenser, a dripping dispenser, and a tube for introducing nitrogen were added. Nitrobisisobutyronitrile (AIBN), 15 parts by weight of acrylic acid, 70 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, and 3 parts by weight of n-dodecyl mercaptan, followed by nitrogen replacement. Subsequently, the temperature of the reaction solution was raised to 110 ° C. with stirring and the reaction was continued for 8 hours to obtain an alkali-soluble resin. It was confirmed that, as measured by GPC, the weight average molecular weight (Mw) of the obtained alkali-soluble resin was about 16,000, and the acid value was 100.4 mg KOH / g.Examples 1 to 6 And comparative examples 1 to 6 : Preparation of colored photosensitive resin composition
These components were mixed by the ratio (unit: weight part) listed in the following Table 1 to prepare a colored photosensitive resin composition. [Table 1]
1) LTN-207 (Loum Hitech)2) LTN-201 (Loum Hitech)3) LTN-107 (Loum Hitech)4) Pyridinium p-toluenesulfonate (Sigma-Aldrich)5) CI Pigment Blue 15: 6 6) Resin obtained in Preparation Example 7) Diisopentaerythritol hexaacrylate (Nippon Kayaku) 8) 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butan-1-one (Ciba Specialty Chemicals) 9) Propylene glycol monomethyl ether acetateExperimental example 1 : Assess solvent resistance and adhesion
A color filter was prepared using the colored photosensitive resin composition prepared in the examples and comparative examples. Specifically, each colored photosensitive resin composition was coated on a glass substrate by spin coating, and the glass substrate was placed on a hot plate, and the temperature was maintained at 100 ° C. for 3 minutes to form a thin film on the glass substrate. Subsequently, a test mask with a pattern showing progressive transmission in the range of 1 to 100% and a line / gap pattern of 1 to 50 μm was placed on the film, and the interval between the 100 μm film and the test mask was 1 KW high pressure mercury lamp at 100 mJ / cm2
UV irradiation is performed without any specific optical filter, in which a mercury lamp contains all of g, h, and i rays. The UV-irradiated film was immersed in an aqueous KOH solution (pH 10.5) used as a developing solution for 2 minutes. After development, the film was washed with distilled water and dried with nitrogen, and then heated in an oven set at 150 ° C for 20 minutes to obtain a color filter. The thickness of the obtained film of the color filter was confirmed to be 2.0 μm. The solvent resistance and adhesion of each sample were evaluated by the following methods. The results are shown in Table 2. (1) Resistance to solvent The prepared color filter was immersed in N-methylpyrrolidone as a solvent for 30 minutes, and then its color change before and after immersion was compared. The color change is calculated by the following Equation 1, which describes the color change in the 3-dimensional colorimeter as L *, a *, b *. The lower the color change value, the higher the reliability of the color filter that can be prepared. [Equation 1] ΔEab*
= [(ΔL*
)2
+ (Δa*
)2
+ (Δb*
)2
](1/2)
(2) Adhesiveness The pattern formed was observed through an optical microscope, and then the degree of peeling on the pattern was confirmed to evaluate the adhesiveness. ○: No peeling on the pattern Δ: 1 to 3 peelings on the pattern X: 4 or more peelings on the pattern [Table 2]
As shown in Table 2, compared with the compositions of Comparative Examples 1 to 6, the colored photosensitive resin compositions of Examples 1 to 6 of the present invention containing a specified amount of a nonionic thermal acid generator were provided in A color filter with excellent characteristics in terms of resistance and adhesion. Although specific embodiments of the present invention have been shown and described, those skilled in the art should understand that they do not wish to limit the invention to the preferred embodiments, and it will be apparent to those skilled in the art that the present invention can be made without departing from the spirit and Various changes and modifications are made under the category. Accordingly, the scope of the invention will be defined by the scope of the accompanying patent applications and their equivalents.
