用以實施發明之形態 本發明是關於一種著色光敏樹脂組成物，其包含鹼可溶性樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、著色劑(D)及溶劑(E)；前述著色劑(D)包含顏料(d1)及染料(d2)；前述鹼可溶性樹脂(A)包含化學式1所示之重複單位；前述樹脂之玻璃轉移溫度小於0℃；藉此可使組成物之顯影速度、感度及密著力顯著提升，同時將可能因著色劑而變大的圖型階差最小化，使穿透率顯著提升。 本發明之著色光敏樹脂組成物包含鹼可溶性樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、著色劑(D)及溶劑(E)。 ＜鹼可溶性樹脂(A)＞ 本發明所用之鹼可溶性樹脂(A)包含下述化學式1所示之重複單位，顯示小於0℃之玻璃轉移溫度。 [化學式1]式中，R1
及R2
分別獨自為氫原子或甲基，R3
是包含由酸酐衍生之羧酸的殘基。 本發明之鹼可溶性樹脂(A)包含前述重複單位，顯示小於0℃之玻璃轉移溫度，藉此可使組成物之顯影速度顯著提升，並且亦使感度及密著力提升，抑制因顯影速度增加所造成的圖型短路問題。 進而言之，利用含前述鹼可溶性樹脂(A)之組成物形成圖型時，能夠將可能因著色劑而變大的圖型階差最小化，使平滑性顯著提升，穿透率亦提升，可製造品質良好的彩色濾光片。 前述化學式1所示之重複單位等的含量並未特別限定，例如相對於鹼可溶性樹脂全體，可含50～90莫耳%，更宜含50～75莫耳%。符合前述範圍時，被聚合樹脂之玻璃轉移溫度更宜設為小於0℃。含前述重複單位等小於50莫耳%時，感度降低，會發生圖型短路，超過90莫耳%時，可能於聚合過程中凝膠化，即便聚合，樹脂的安全性也可能降低。 另，已聚合的鹼可溶性樹脂(A)之玻璃轉移溫度(Tg)為0℃以上時，因組成物內之著色劑含量而產生階差，難以確保平坦性。 本發明之鹼可溶性樹脂(A)除了用以實現化學式1之重複單位之單體(a1)以外，可進一步含有具有不飽和雙重結合之單體(a2)，予以共聚而製造。 前述可共聚之具有不飽和雙重結合之單體的種類並未特別限定，具體而言包含例如苯乙烯、乙烯基甲苯、a-甲基苯乙烯、對氯苯乙烯、鄰甲氧苯乙烯、間甲氧苯乙烯、對甲氧苯乙烯、鄰甲氧苯乙烯、鄰乙烯基苯甲醚、間乙烯基苯甲醚、對乙烯基苯甲醚、鄰乙烯基苯環氧丙基醚、間乙烯基苯環氧丙基醚、對乙烯基苯環氧丙基醚等芳族乙烯基化合物。 又，可舉出N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-鄰羥基苯基順丁烯二醯亞胺、N-間羥基苯基順丁烯二醯亞胺、N-對羥基苯基順丁烯二醯亞胺、N-鄰甲基苯基順丁烯二醯亞胺、N-間甲基苯基順丁烯二醯亞胺、N-對甲基苯基順丁烯二醯亞胺、N-鄰甲氧基苯基順丁烯二醯亞胺、N-間甲氧基苯基順丁烯二醯亞胺、N-對甲氧基苯基順丁烯二醯亞胺等N-取代順丁烯二醯亞胺系化合物。 又，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、正(甲基)丙烯酸丙酯、異(甲基)丙烯酸丙酯、正(甲基)丙烯酸丁酯、異(甲基)丙烯酸丁酯、二級(甲基)丙烯酸丁酯、三級(甲基)丙烯酸丁酯等(甲基)丙烯酸烷酯類。 又，可舉出環(甲基)丙烯酸苄酯、環(甲基)丙烯酸己酯、2-甲基(甲基)丙烯酸己酯、2-甲基環(甲基)丙烯酸己酯、三環[5.2.1.02,6]癸烷-8-基(甲基)丙烯酸酯、2-二環吩坦尼氧(甲基)丙烯酸乙酯、(甲基)丙烯酸異冰片酯等脂環族(甲基)丙烯酸酯類。 進而言之，2-羥基(甲基)丙烯酸乙酯、2-羥基(甲基)丙烯酸丙酯、4-羥基(甲基)丙烯酸丁酯、2-羥基-3-苯氧基(甲基)丙烯酸丙酯、N-羥基乙基丙烯醯胺等羥基(甲基)丙烯酸乙酯類。 進而言之，亦可舉出(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸芳酯類。 又，3-(甲基丙烯醯氧甲基)氧雜環丁烷、3-(甲基丙烯醯氧乙基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧乙基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧乙基)-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧乙基)氧雜環丁烷、2-(甲基丙烯醯氧乙基)-4-三氟甲基氧雜環丁烷等不飽和氧雜環丁烷化合物等。前述單體可分別單獨使用，或組合2種以上使用。 前述可共聚之具有不飽和雙重結合之化合物的含量並未特別限定，例如相對於用以聚合鹼可溶性樹脂之單體全體含量，可含10～50莫耳%，更宜設為30～40莫耳%。符合前述範圍時，樹脂之玻璃轉移溫度顯示小於0℃，可將階差最小化。 以下更詳細說明有關本發明之鹼可溶性樹脂(A)的製造方法。 以往，著色光敏樹脂組成物之鹼可溶性樹脂(A)，係為了對於形成圖型時的顯影處理步驟所用之鹼顯影液具有可溶性，以具有羧基之乙烯性不飽和單體作為必須成分而製造。然而，以這類製造方法形成的鹼可溶性樹脂，具有主鏈含有羧基，難以製造玻璃轉移溫度小於0℃之樹脂的問題。 然而，本發明之鹼可溶性樹脂(A)是以使得不是發生聚合反應之主鏈的側鏈，含有羧基的方式而製造，藉此賦予適當的顯影性，並且玻璃轉移溫度顯示小於0℃。 另，本發明之製造方法之一實現例包含如下階段：(S1)將(甲基)丙烯酸縮水甘油酯與具有不飽和雙重結合之單體(a2)的階段；(S2)使前述製造的共聚物，與具有羧基之乙烯性不飽和單體反應的階段；及(S3)使經過前述反應之共聚物，與酸酐反應的階段。 前述(S2)階段是用以對本發明之鹼可溶性樹脂(A)，賦予光硬化性的階段；於前述(S2)階段，具有羧基之乙烯性不飽和單體的種類若在進行其功能的範圍內均可，並未特別限定，可舉出例如(甲基)丙烯酸、乙基丙烯酸、丁基丙烯酸等，較宜為甲基丙烯酸。 前述(S3)階段是用以對本發明之鹼可溶性樹脂(A)，賦予適當之酸價的階段，更具體說明是使來自鹼可溶性樹脂之縮水甘油基之羥基，與酸酐反應，於鹼可溶性樹脂之側鏈導入羧基的階段。 前述(S3)階段所用之酸酐種類若在進行其功能的範圍內均可，並未特別限定，可舉出例如鄰苯二甲酸酐(Phthalic anhydride)、(2-十二烯-1-基)丁二酸酐((2-Dodecen-1-yl)succinic anhydride)、順丁烯二酸酐(Maleic anhydride)、丁二酸酐(Succinic anhydride)、檸康酸酐(Citraconic anhydride)、戊二酸酐(Glutaric anhydride)、甲基丁二酸酐(Methylsuccinic anhydride)、3,3-二甲基戊二酸酐(3,3-Dimethylglutaric anhydride)、苯基丁二酸酐(Phenylsuccinic anhydride)、衣康酸酐(Itaconic anhydride)、3,4,5,6-四氫鄰苯二甲酸酐(3,4,5,6-Tetrahydrophthalic anhydride)、偏苯三甲酸酐(Trimellitic anhydride)、六氫鄰苯二甲酸酐(Hexahydrophthalic anhydride)及卡比酸酐(Carbic anhydride)等。從成本及反應容易度方面來看，較宜為順丁烯二酸酐(Maleic anhydride)、鄰苯二甲酸酐(Phthalic anhydride)、偏苯三甲酸酐(Trimellitic anhydride)、丁二酸酐(Succinic anhydride)、六氫鄰苯二甲酸酐(Hexahydrophthalic anhydride)、卡比酸酐(Carbic anhydride)，更宜為偏苯三甲酸酐(Trimellitic anhydride)、丁二酸酐(Succinic anhydride)、六氫鄰苯二甲酸酐(Hexahydrophthalic anhydride)。 藉由前述製造方法製造的本發明之鹼可溶性樹脂(A)的酸價，為了確保與組成物所含染料之相溶性及組成物之保存安全性，可設為30～150mgKOH/g。前述鹼可溶性樹脂(A)的酸價小於30mgKOH/g時，著色光敏樹脂組成物可能難以確保充分的顯影速度。又，該酸價超過150mgKOH/g時，可能發生與基板的密著性減少，容易發生圖型短路，與染料的相溶性發生問題，著色光敏樹脂組成物內的染料析出，亦或著色光敏樹脂組成物之保存安全性降低，黏度上升的問題。 本發明之鹼可溶性樹脂(A)的含量並未特別限定，例如相對於組成物中之固體粉全體重量，可設為10～80重量%，更宜設為10～70重量%。符合前述範圍時，對顯影液的溶解性充足，容易形成圖型，防止顯影會減少曝光部之像素部的膜減少，非圖像部之脫離度變得良好，較為適宜。 ＜光聚合性化合物(B)＞ 本發明之光聚合性化合物(B)是能以下述光聚合起始劑(C)的作用聚合之化合物，採用單官能單體、2官能單體或多官能單體，較宜採用2官能以上之多官能單體。 前述單官能單體之具體例包括壬基苯基丙烯酸卡必酯、2-羥基-3-苯氧丙烯酸丙酯、2-乙基己基丙烯酸卡必酯、2-羥基丙烯酸乙酯或N-乙烯基砒喀烷酮等，但不限定於此。 前述2官能單體或多官能單體之具體例包括1,6–己二醯二(甲基)丙烯酸酯、二乙二醇二(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(丙烯醯氧乙基)醚或3-甲基戊烷二醇(甲基)丙烯酸酯等，但不限定於此。 前述多官能單體之具體例包括三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(乙氧化)三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化(丙氧化)三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙氧基化(乙氧化)二季戊四醇六(甲基)丙烯酸酯、丙氧基化(丙氧化)二季戊四醇六(甲基)丙烯酸酯或二季戊四醇六(甲基)丙烯酸酯等，但不限定於此。 前述光聚合性化合物(B)的含量並未特別限定，例如相對於組成物中之固體粉全體重量，可含5～45重量%，更宜設為7～45重量%。符合前述範圍時，像素部的強度或平滑性良好，故較適宜。 ＜光聚合起始劑(C)＞ 前述光聚合起始劑(C)若可使光聚合性化合物(B)聚合均可，不特別限制其種類而使用。特言之，前述光聚合起始劑(C)從聚合特性、起始效率、吸收波長、取得性、成本等觀點來看，宜使用從苯乙酮系化合物、二苯甲酮系化合物、三嗪系化合物、聯咪唑系化合物、肟系化合物及噻噸酮系化合物所組成的群組中選擇之1種以上的化合物。 前述苯乙酮系化合物之具體例可舉出二乙氧基苯乙酮、2-羥基-2-甲基-1–苯基丙烷-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧)苯基]-2-甲基丙烷-1-酮、1–羥基環己基苯酮、2–甲基-1-(4-甲基硫苯基)-2-嗎啉丙烷–1–酮、2-苄基-2-二甲胺-1-(4–嗎啉苯基)丁烷–1–酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮、2-(4-甲基苄基)-2-(二甲胺)-1-(4–嗎啉苯基)丁烷–1–酮等。 前述二苯甲酮系化合物包括例如二苯甲酮、鄰苯甲醯基苯酸甲基、4–苯基二苯甲酮、4–苯醯–4’–甲基二苯基硫化物、3,3’,4,4’–四(三級丁基過氧羧基)二苯甲酮、2,4,6–三甲基二苯甲酮等。 前述三嗪系化合物之具體例包括2,4–雙(三氯甲基)–6–(4-甲氧苯基)-1,3,5-三嗪、2,4–雙(三氯甲基)–6–(4-甲氧萘基)-1,3,5-三嗪、2,4–雙(三氯甲基)–6–胡椒基-1,3,5-三嗪、2,4–雙(三氯甲基)–6–(4-甲氧苯乙烯基)-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-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4–雙(三氯甲基)–6–[2-(3,4-二甲氧苯基)乙烯基]-1,3,5-三嗪等。 前述聯咪唑系化合物之具體例可舉出2,2’-雙(2-氯苯)-4,4’,5,5’-四苯聯咪唑、2,2’-雙(2,3-二氯苯)-4,4’,5,5’-四苯聯咪唑、2,2’-雙(2-氯苯)-4,4’,5,5’-四(烷氧苯)聯咪唑、2,2’-雙(2-氯苯)-4,4’,5,5’-四(三烷氧苯)聯咪唑、2,2’-雙(2,6-二氯苯)-4,4’,5,5’-四苯-1,2’-聯咪唑，或4,4’,5,5’位置之苯基由羧氧基取代的聯咪唑化合物等。其中，較宜使用2,2’-雙(2-氯苯)-4,4’,5,5’-四苯聯咪唑、2,2’-雙(2,3-二氯苯)-4,4’,5,5’-四苯聯咪唑、2,2’-雙(2,6-二氯苯)-4,4’,5,5’-四苯-1,2’-聯咪唑。 前述肟系化合物之具體例可舉出鄰乙氧羧基-a-羥亞胺基-1-苯丙烷-1-酮等，市售品以BASF公司OXE01、OXE02為代表。 前述噻噸酮系化合物包括例如2-異丙基噻噸酮、2,4–二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧噻噸酮等。 又，前述光聚合起始劑(C)為了使本發明之著色光敏樹脂組成物的感度提升，可進一步包含光聚合起始助劑(c1)。本發明之著色光敏樹脂組成物藉由含光聚合起始助劑(c1)，感度變得最高，可使生產性提升。 前述(c1)宜使用從例如胺化合物、羧基酸化合物、具有硫醇基之有機硫化合物所組成的群組中選擇之1種以上的化合物。 前述胺化合物宜使用芳族胺化合物，具體而言可使用三乙基醇胺、甲基二乙醇胺、三異丙醇胺等脂肪族胺化合物、4-二甲基胺基安息香酸甲基、4-二甲基胺基安息香酸乙基、4-二甲基胺基安息香酸異戊基、4-二甲基胺基安息香酸2-乙基己基、安息香酸2-二甲基胺基乙基、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮(通稱：米其勒酮)、4,4’-雙(二乙基胺基)二苯甲酮等。 前述羧基酸化合物宜為芳族雜醋酸類，具體而言可舉出苯硫醋酸、甲基苯硫醋酸、乙基苯硫醋酸、甲基乙基苯硫醋酸、二甲基苯硫醋酸、甲氧苯硫醋酸、二甲氧苯硫醋酸、氯苯硫醋酸、二氯苯硫醋酸、N-苯甘胺酸、苯氧醋酸、萘硫醋酸、N-萘甘胺酸、萘氧醋酸等。 前述具有硫醇基之有機硫化合物之具體例可舉出2-巰基苯并噻唑、1,4-雙(3-巰基丁酸乙酯)丁烷、1,3,5-三(3-巰基丁酸乙酯)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3–巰基丙酯)、新戊四醇肆(3–巰基丁酯)、新戊四醇肆(3–巰基丙酯)、二新戊四醇肆(3–巰基丙酯)、四乙二醇雙(3–巰基丙酯)等。 前述光聚合起始劑(C)的含量並未特別限定，例如相對於組成物中之固體粉全體重量，對於鹼可溶性樹脂(A)與光聚合性化合物(B)的含量，可含0.1～40重量%，更宜設為0.1～30重量%。符合前述範圍時，由於著色光敏樹脂組成物被高感度化，曝光時間縮短，因此生產性提升，可維持高解像度，故較適宜。 又，進一步使用前述光聚合起始助劑(c1)時，前述光聚合起始助劑(c1)的含量並未特別限定，例如針對組成物中之固體粉全體重量，對於鹼可溶性樹脂(A)與光聚合性化合物(B)的含量，可設為0.1～40重量%，更宜設為0.1～30重量%。符合前述範圍時，由於著色光敏樹脂組成物的感度最高，會提供使用前述組成物形成的彩色濾光片之生產性提升的效果。 ＜著色劑(D)＞ 本發明所用之著色劑(D)包含1種以上的顏料(d1)及1種以上的染料(d2)。 本發明之光敏樹脂組成物係藉由含有前述鹼可溶性樹脂(A)，即使著色劑(D)同時使用顏料(d1)及染料(d2)，仍可顯示良好的顯影性及密著力。顏料 (d1)
前述顏料是採用該領域一般使用的有機顏料或無機顏料。前述顏料可採用印刷墨水、噴墨墨水等所使用的各種顏料，具體而言可舉出水溶性偶氮顏料、不溶性偶氮顏料、酞菁顏料、喹吖酮顏料、異吲哚酮顏料、異吲哚啉顏料、芘顏料、苝顏料、二噁嗪顏料、蒽醌顏料、二蒽醌基顏料、蒽嘧啶顏料、蒽嵌蒽醌(anthanthrone)顏料、陰丹士林(indanthrone)顏料、黃士酮顏料、皮蒽酮(pyranthrone)顏料、二酮基吡咯并吡咯顏料等。前述無機顏料可舉出金屬氧化物或金屬錯鹽等金屬化合物，具體而言可舉出鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻、碳黑等金屬的氧化物或複合金屬氧化物等。特言之，前述有機顏料及無機顏料具體可舉出，作為顏料分類為色指數(The society of Dyers and Colourists出版)之化合物，更詳言之，可舉出如下色指數(C.I.)號碼的顏料，但為必要限定於該類顏料。 可舉出例如C.I.顏料(Pigment)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.顏料橘13、31、36、38、40、42、43、51、55、59、61、64、65及71。 又，可舉出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。 又，可舉出C.I.顏料紫14、19、23、29、32、33、36、37及38。 進而言之，可舉出C.I.顏料藍15(15:3、15:4、15:6等)、21、28、60、64及76。 進而言之，還可舉出C.I.顏料綠7、10、15、25、36、47及58。 又，可舉出C.I.顏料棕28。 又，可舉出C.I.顏料黑1及7等。 前述顏料(d1)可分別單獨使用，或組合2種以上使用。 前述例示的C.I.Pigment顏料中，尤宜使用從C.I.顏料橘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.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃185、C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58、C.I.顏料紫23、C.I.顏料藍15:3、顏料藍15:6選擇的顏料。 前述顏料宜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的一例，可舉出含有顏料分散劑(d3)而分散處理的方法等，若依據該方法，可獲得顏料均勻分散於溶液中的狀態的顏料分散液。 前述顏料分散劑之具體例可舉出陽離子系、陰離子系、非離子系、雙性、聚酯系、聚胺系等之界面活性劑等，該等可分別單獨使用，或組合2種以上使用。 前述顏料(d1)的含量係相對於顏料分散組成物中之全體固體粉，以質量分率而言為20～90質量%，更宜為30～70質量%的範圍。前述顏料的含量根據前述若為20～90質量%的範圍，黏度低、保存安全性良好，分散效率高，對亮暗比上升有效，故較適宜。 前述分散劑(d3)除了採用如前述之丙烯酸分散劑以外，還可採用其他類型的顏料分散劑。前述其他樹脂類型的顏料分散劑為習知之樹脂類型的顏料分散劑，尤其可舉出：聚氨酯、作為聚丙烯酸酯代表之聚羧基酸酯、不飽和聚醯胺、聚羧基酸、聚羧基酸之部分(胺鹽)、聚羧基酸之銨鹽、聚羧基酸之烷胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含烴基之聚羧酸酯或此等之改質物、或藉由具有游離(free)羧基之聚酯與聚(低級烷亞胺)反應所形成之醯胺或其鹽等類之乳質分散劑；(甲基)丙烯酸–苯乙烯共聚物、(甲基)丙烯酸–(甲基)丙烯酸酯共聚物、苯乙烯–順丁烯二酸共聚物、聚乙烯醇或聚乙烯吡咯醇等類之水溶性樹脂或水溶性聚合物化合物；聚酯；改質聚丙烯酸酯；乙烯氧化物/丙烯氧化物之附加生成物及燐酸酯等。作為前述樹脂型分散劑之市售品，陽離子系樹脂分散劑可舉出：BYK-Chemie之商品名：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184；BASF之商品名：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800；Lubirzol之商品名：SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；Kawaken Fine Chemicals之商品名：HINOACT T-6000、HINOACT T-7000、HINOACT T-8000；Ajinomoto之商品名：AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823；共榮社化學之商品名：FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33、FLORENE DOPA-44等。除了前述丙烯酸分散劑以外，其他樹脂類型之顏料分散劑可分別單獨使用，或組合2種以上使用，亦可與丙烯酸分散劑併用。 前述分散劑(d3)之使用量，係相對於所使用顏料(d1)之固體粉100質量部為5～60質量部，更宜為15～50質量部範圍。根據前述，分散劑(d3)的含量若超過60質量部，黏度會變高，小於5質量部時，會引起顏料微粒化變難，亦或分散後凝膠化等問題。染料 (d2)
前述染料若對於有機溶劑具有溶解性均可，可無限制地使用。宜使用對於有機溶劑具有溶解性，同時可確保對於鹼顯影液之溶解性及耐熱性、耐溶解性等可靠性之染料。 前述染料可從具有磺酸或羧基酸等酸性基之酸性染料、酸性染料與含氮化合物之鹽、酸性染料之磺醯胺等、及該等之衍生物選擇使用。此外，亦可選擇偶氮系、呫噸系、酞菁系之酸性染料及該等之衍生物。前述染料宜舉出色指數(The Society of Dyersand Colourists出版)內分類作為染料之化合物、記載於DYEING NOTE(色染社)之習知染料。 作為前述染料之具體例，C.I.溶劑染料可舉出下述染料。 可舉出例如C.I.溶劑紅8、45、49、89、111、122、125、130、132、146、179等紅色染料。 又，可舉出C.I.溶劑藍5、35、36、37、44、59、67、70等藍色染料。 又，可舉出C.I.溶劑紫8、9、13、14、36、37、47、49等紫色染料。 進而言之，可舉出C.I.溶劑黃4、14、15、23、24、38、62、63、68、82、94、98、99、162等黃色染料。 進而言之，還可舉出C.I.溶劑橘2、7、11、15、26、56等橘色染料。 又，可舉出C.I.溶劑綠1、3、4、5、7、28、29、32、33、34、35等綠色染料。 C.I.溶劑染料中，對於有機溶劑之溶解性良好之C.I.溶劑紅8、49、89、111、122、132、146、179；C.I.溶劑藍35、36、44、45、70；C.I.溶劑紫13較適宜，其中C.I.溶劑紅8、122、132尤宜。 進而言之，C.I.酸性染料可舉出下述染料。 可舉出例如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、426等紅色染料。 又，可舉出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、251等黃色染料。 又，可舉出C.I.酸性橘6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173等橘色染料。 進而言之，可舉出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、340等藍色染料。 進而言之，可舉出C.I.酸性紫6B、7、9、17、19、66等紫色染料。 又，可舉出C.I.酸性綠1、3、5、9、16、25、27、50、58、63、65、80、104、105、106、109等綠色染料等。 酸性染料中，對於有機溶劑之溶解度良好的C.I.酸性紅92；C.I.酸性藍80、90；C.I.酸性紫66尤宜。 進而言之，C.I.直接(Direct)染料可舉出下述染料。 可舉出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、250等紅色染料。 又，可舉出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、141等黃色染料。 又，可舉出C.I.直接橘34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等橘色染料。 進而言之，可舉出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、293等藍色染料。 進而言之，還可舉出C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等紫色染料。 又，可舉出C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等綠色染料等。 又，可舉出C.I.直接黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65等黃色染料。 又，可舉出C.I.媒染(Mordant)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、95等紅色染料。 又，可舉出C.I.媒染橘3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48等橘色染料。 進而言之，可舉出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、84等藍色染料。 進而言之，還可舉出C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等紫色染料。 又，可舉出C.I.媒染綠1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等綠色染料等。 該等染料可分別單獨使用，或組合2種以上使用。 前述著色劑(D)中之染料含量係相對於著色劑(D)中之固體粉，以重量分率而言宜含有0.5～80重量%，更宜為0.5～60重量%，尤宜為1～50重量%。前述著色劑(D)中之染料含量若在前述範圍，可防止圖型形成後，染料因有機溶劑而溶出之可靠性降低問題，感度良好，較為適宜。 本發明之含有顏料及染料之著色劑(D)的含量並未特別限定，例如相對於組成物中之固體粉全體重量，可含有5～60重量%，更宜設為10～45重量%。符合前述範圍時，即使形成薄膜，像素之色濃度充分，於顯影時，非圖像部之脫離度不會降低，不易產生殘渣，故較適宜。 ＜溶劑(E)＞ 本發明所用之溶劑(E)若對於使著色光敏樹脂組成物所含其他成分溶解有效均可，可無特別限制地使用，尤宜為醚類、芳族碳化氫類、酮類、醇類、酯類或醯胺類等。 前述溶劑(E)具體可舉出乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚等乙二醇單烷醚類。 又，可舉出二乙二醇二甲醚、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醚類。 又，可舉出甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯等二乙二醇烷醚乙酸酯類。 又，可舉出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、甲氧丁基乙酸酯、甲氧苄基乙酸酯等亞烷基二醇烷醚乙酸酯類。 進而言之，苯、甲苯、二甲苯、三甲苯等芳族碳化氫類。 進而言之，還可舉出甲基乙酮、丙酮、甲基胺酮、甲基異丁酮、環己酮等酮類。 又，可舉出乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油、4-羥-4-甲基-2-戊酮等醇類。 又，3-乙氧丙酸乙基、3-甲氧丙酸甲基等酯類、g-丁內酯等環狀酯類等。 從塗佈性及乾燥性方面來看，前述溶劑(E)宜為沸點100～200℃之有機溶劑，更宜使用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-乙氧丙酸乙基、3-甲氧丙酸甲基等。宜與可抑制染料析出、改善保存安全性之4-羥-4-甲基-2-戊酮等醇性溶劑混用。 前述例示的溶劑(E)可分別單獨使用，或組合2種以上使用，根據本發明之著色光敏樹脂組成物的全體重量，可含60～90重量%，更宜含70～85重量%。符合前述範圍時，以輥塗佈機、旋轉塗佈機、狹縫與旋轉塗佈機、狹縫塗佈機(有時亦稱為模塗佈機)、噴墨等塗佈裝置塗佈時，提供塗佈性變佳的效果。 本發明之著色光敏樹脂組成物可因應需要，進一步選擇性地含添加劑，可舉出高分子化合物、硬化劑、界面活性劑、密著促進劑、抗氧化劑、紫外線吸收劑、凝集防止劑等，但不限定於此。 前述其他高分子化合物之具體例可舉出環氧樹脂、順丁烯二醯亞胺樹脂等硬化性樹脂、聚乙烯醇、聚丙烯酸、聚乙二醇單烷醚、聚氟丙烯酸烷酯、聚酯、聚氨酯等熱塑性樹脂等。 前述硬化劑是為了提高深部硬化及機械性強度而使用，硬化劑之具體例可舉出環氧化合物、多官能異氰酸酯化合物、三聚氰胺化合物、氧雜環丁烷化合物等。 作為前述硬化劑，環氧化合物之具體例可舉出雙酚A系環氧樹脂、溴化雙酚A系環氧樹脂、雙酚F系環氧樹脂、溴化雙酚F系環氧樹脂、酚醛型環氧樹脂，此外可舉出芳族系環氧樹脂、脂環族系環氧樹脂、縮水甘油酯系樹脂，還可舉出該類環氧樹脂之溴化衍生物、環氧樹脂及其溴化衍生物以外之脂肪族、脂環族或芳族環氧化合物、丁二烯(共)聚合物環氧化物、異戊二烯(共)聚合物環氧化物、縮水甘油基(甲基)丙烯酸酯(共)聚合物、三縮水甘油基異氰脲酸酯等。 作為前述硬化劑，氧雜環丁烷化合物之具體例可舉出碳酸酯雙氧雜環丁烷、二甲苯雙氧雜環丁烷、己二酸雙氧雜環丁烷、對苯二甲酸酯雙氧雜環丁烷、環己烷二羧酸雙氧雜環丁烷等。 前述硬化劑可將硬化劑與硬化輔助化合物併用，以使環氧化合物之環氧基、氧雜環丁烷化合物之氧雜環丁烷骨架進行開環聚合。前述硬化輔助化合物包括例如多價羧酸類，多價羧酸酐類、酸產生劑等。前述多價羧酸酐類係使用作為環氧樹脂硬化劑市售之物。前述環氧樹脂硬化劑之具體例可舉出商品名(ADEKA HARDENER EH-700)(ADEKA工業股份有限公司製造)、商品名(RIKACID HH)(新日本理化股份有限公司製造)、商品名(MH-700)(新日本理化股份有限公司製造)等。前述例示之硬化劑可分別單獨使用，或組合2種以上使用。 前述界面活性劑可用以使光敏樹脂組成物之被膜形成性更提升而使用，宜使用氟素系界面活性劑或矽基系界面活性劑等。 前述矽基系界面活性劑例如作為市售品包括Dow Corning Toray Silicone之DC3PA、DC7PA、SH11PA、SH21PA、SH8400等、GE Toshiba Silicones之TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452。前述氟素系界面活性劑例如作為市售品包括DAINIPPON INK AND CHEMICALS之Megafac F-470、F-471、F-475、F-482、F-489等。前述例示之界面活性劑可分別單獨使用，或組合2種以上使用。 前述密著促進劑之具體例可舉出乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯三(2–甲氧基乙氧基)矽烷、N–(2–胺乙基)–3–胺丙基甲基二甲氧基矽烷、N–(2–胺乙基)–3–胺丙基三甲氧基矽烷、3–胺丙基三乙氧基矽烷、3–環氧丙氧基丙基三甲氧基矽烷、3–環氧丙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–氯丙基甲基三甲氧基矽烷、3–氯丙基三甲氧基矽烷、3–甲基丙烯酸酯丙基三甲氧基矽烷、3–巰基丙基三甲氧基矽烷、3-異氰酸酯三甲氧基矽烷等。前述例示之密著促進劑可分別單獨使用，或組合2種以上使用。前述密著促進劑係相對於著色光敏樹脂組成物中之固體粉，以重量分率而言宜含有0.01～10重量%，更宜含有0.05～2重量%。 前述抗氧化劑之具體例可舉出2,2’–硫雙(4–甲基–6–三級丁苯酚)、2,6–二-三級丁基-4-甲苯酚等。 前述紫外線吸收劑之具體例可舉出2–(3–三級丁基–2–羥基-5-甲基苯基)–5–氯苯并三唑、烷氧苯并苯酚等。 前述凝集防止劑之具體例可舉出聚丙烯酸鈉等。合成例 1 ：著色劑組成物合成 (1) 著色劑組成物 (M1)
顏料為C.I.顏料紅177、12.0質量部，顏料分散劑為DISPERBYK-2001(BYK製造)、4.0質量部，染料為Acid Red52、1.2質量部，溶劑為丙二醇甲醚乙酸酯、44質量部及4-羥-4-甲基-2-戊酮、20質量部，於12小時期間，以珠研磨機混合/分散，製造著色劑組成物(M1)。(2) 著色劑組成物 (M2)
顏料為C.I.顏料紅177、13.2質量部，顏料分散劑為DISPERBYK-2001(BYK製造)、4.0質量部，溶劑為丙二醇甲醚乙酸酯、44質量部及4-羥-4-甲基-2-戊酮、20質量部，於12小時期間，以珠研磨機混合/分散，製造著色劑組成物(M2)。合成例 2 ：鹼可溶性樹脂合成 (1) 鹼可溶性樹脂 (A - 1) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯100部、丙二醇單甲醚100部、AIBN5部、2-乙基丙烯酸烷酯23.0部、4-甲基苯乙烯1.6部、甲基丙烯酸縮水甘油酯46.0部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應4小時。接下來，將反應液的溫度降低至常溫，將燒瓶氣氛從氮置換為空氣後，放入三乙胺0.2部、4-甲氧苯酚0.1部、丙烯酸23.3部，從100℃反應6小時。其後，將反應液的溫度降低至常溫，放入丁二酸酐6.0部，從80℃反應6小時。 如此合成之鹼可溶性樹脂之固體粉酸價為32.8mgKOH/g，以GPC測定之重量平均分子量Mw約為6350，化學式1所示之重複單位為70莫耳%。 以示差掃描熱量計測定玻璃轉移溫度，結果為-12℃。(2) 鹼可溶性樹脂 (A - 2) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯100部、丙二醇單甲醚100部、AIBN5部、2-乙基丙烯酸烷酯21.4部、4-甲基苯乙烯1.5部、甲基丙烯酸縮水甘油酯42.8部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應4小時。接下來，將反應液的溫度降低至常溫，將燒瓶氣氛從氮置換為空氣後，放入三乙胺0.2部、4-甲氧苯酚0.1部、丙烯酸21.7部，從100℃反應6小時。其後，將反應液的溫度降低至常溫，放入丁二酸酐12.5部，從80℃反應6小時。 如此合成之鹼可溶性樹脂之固體粉酸價為68.6mgKOH/g，以GPC測定之重量平均分子量Mw約為5570，化學式1所示之重複單位為70莫耳%。 以示差掃描熱量計測定玻璃轉移溫度，結果為-8.3℃。(3) 鹼可溶性樹脂 (A - 3) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯100部、丙二醇單甲醚100部、AIBN5部、2-乙基丙烯酸烷酯17.3部、4-甲基苯乙烯1.2部、甲基丙烯酸縮水甘油酯59.4部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應4小時。接下來，將反應液的溫度降低至常溫，將燒瓶氣氛從氮置換為空氣後，放入三乙胺0.2部、4-甲氧苯酚0.1部、丙烯酸17.6部，從100℃反應6小時。其後，將反應液的溫度降低至常溫，放入丁二酸酐4.5部，從80℃反應6小時。 如此合成之鹼可溶性樹脂之固體粉酸價為24.98mgKOH/g，以GPC測定之重量平均分子量Mw約為5950，化學式1所示之重複單位為80莫耳%。以示差掃描熱量計測定玻璃轉移溫度，結果為-20.4℃。(4) 鹼可溶性樹脂 (A - 4) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯100部、丙二醇單甲醚100部、AIBN5部、2-乙基丙烯酸烷酯10.2部、4-甲基苯乙烯0.7部、甲基丙烯酸縮水甘油酯76.0部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應4小時。接下來，將反應液的溫度降低至常溫，將燒瓶氣氛從氮置換為空氣後，放入三乙胺0.2部、4-甲氧苯酚0.1部、丙烯酸10.4部，從100℃反應6小時。其後，將反應液的溫度降低至常溫，放入丁二酸酐2.7部，從80℃反應6小時。 如此合成之鹼可溶性樹脂之固體粉酸價為16.45mgKOH/g，以GPC測定之重量平均分子量Mw約為5450，化學式1所示之重複單位為90莫耳%。以示差掃描熱量計測定玻璃轉移溫度，結果為-28.4℃。(5) 鹼可溶性樹脂 (A - 5) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯120部、丙二醇單甲醚80部、AIBN2部、前述丙烯酸13.0部、甲基丙烯酸苄酯10部、4-甲基苯乙烯57.0部、甲基丙烯酸甲酯20部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應8小時。如此合成之鹼可溶性樹脂之固體粉酸價為98.2mgKOH/g，以GPC測定之重量平均分子量Mw約為14950。 以示差掃描熱量計測定玻璃轉移溫度，結果為95℃。(6) 鹼可溶性樹脂 (A - 6) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯120部、丙二醇單甲醚80部、AIBN2部、前述丙烯酸13.0部、甲基丙烯酸苄酯10部、4-甲基苯乙烯67.0部、甲基丙烯酸甲酯10部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應8小時。如此合成之鹼可溶性樹脂之固體粉酸價為81.6mgKOH/g，以GPC測定之重量平均分子量Mw約為16110。 以示差掃描熱量計測定玻璃轉移溫度，結果為85℃。(7) 鹼可溶性樹脂 (A - 7) 合成
於具備攪拌機、溫度計回流冷卻管、裝填區及氮導入管之燒瓶，放入丙二醇單甲醚乙酸酯120部、丙二醇單甲醚80部、AIBN2部、前述丙烯酸5.0部、甲基丙烯酸苄酯20部、4-甲基苯乙烯55.0部、甲基丙烯酸甲酯20部、正十二巰3部，進行氮置換。其後，攪拌並使反應溫度上升至80℃，反應8小時。如此合成之鹼可溶性樹脂之固體粉酸價為17.4mgKOH/g，以GPC測定之重量平均分子量Mw約為17370。 以示差掃描熱量計測定玻璃轉移溫度，結果為82℃。實施例及比較例
採用下述表1的成分及含量來製造光敏樹脂組成物。 試驗方法 (1) 顯影速度及密著性評估
使用前述實施例及比較例製造的著色光敏樹脂組成物，製造彩色濾光片。 具體而言，以旋轉塗佈法，將前述各著色光敏樹脂組成物塗佈於2英吋見方的玻璃基板(Corning製造，「EAGLE XG」)上之後，於加熱板上，以100℃的溫度維持3分鐘，以使其形成薄膜。接下來，於前述薄膜上，載置具有穿透率在1～100%的範圍內階段性變化之圖型與1～100mm之線/間距圖型之試驗光罩，設定與試驗光罩的間隔為300mm，照射紫外線。此時，紫外線光源係使用包含g、h、i射線全部之1KW高壓水銀燈，以照度60mJ/cm2
照射，不使用特別的光學濾光片。將前述紫外線照射過之薄膜，浸漬於pH10.5之KOH水溶液顯影溶液2分鐘而顯影。使用蒸餾水，洗淨塗佈有前述薄膜之玻璃板後，噴霧氮氣予以乾燥，以200℃的加熱烤箱加熱25分鐘，製造彩色濾光片。 前述所製造的彩色濾光片之薄膜厚度為2.4mm。 測定前述步驟中，於顯影時非曝光部完全溶解於顯影液所花費的時間(顯影速度)，記載於下述表2。 又，藉由光學顯微鏡評估所生成的圖型時，以圖型的剝離現象層級來評估密著性，表示於下述表2。 ＜評估基準＞ ○：無圖型剝離 △：圖型剝離1～3個 ×：圖型剝離4個以上(2) 穿透率測定 (%)
除了不使用試驗光罩以外，其他均與試驗方法(1)採同一方法製造彩色濾光片。 使用色度計(Olympus製造，OSP-200)測定所形成的圖型中100mm之線圖型部分的穿透率，表示於下述表2。(3) 階差測定 ( Å )
以旋轉塗佈法，將前述實施例及比較例之著色光敏樹脂組成物，塗佈於被圖型化而成為黑矩陣為1.5mm厚度之線/間距之2英吋見方基板後，以真空乾燥裝備減壓至65Pa，予以真空乾燥。然後在加熱板基板上，以100℃的溫度維持3分鐘，以使其形成薄膜。其後，於加熱板上，無光罩而照射紫外線。此時，紫外線光源係使用包含g、h、i射線全部之1KW高壓水銀燈，以照度40mJ/cm2
照射，不使用特別的光學濾光片。將前述紫外線照射過之薄膜，浸漬於pH10.5之KOH水溶液顯影溶液2分鐘而顯影。使用蒸餾水，洗淨塗佈有前述薄膜之玻璃板後，吹送氮氣予以乾燥，以230℃的加熱烤箱加熱25分鐘，製造彩色濾光片。使用Surface Profiler(表面輪廓儀)(Veeco Dektak 6M)，測定形成於BM圖型上之彩色光阻與形成於Glass(玻璃)上之彩色光阻間之階差，於下述表2表示其結果。
參考表2，本發明之著色光敏樹脂組成物(實施例1-4)的情況，可確認即使顯影速度非常快，仍顯示出良好的黏附力，又，適合製造階差值非常小、穿透率高、品質良好的彩色濾光片。 其中，可確認鹼可溶性樹脂稍微過量含有化學式1之重複單位之實施例4的情況，顯影速度及密著力較其他實施例稍微降低。 可確認雖使用了本發明之鹼可溶性樹脂，但著色劑只使用顏料之比較例2的情況，顯影速度及密著力顯示出與實施例同一水準，但穿透率的減少及階差值顯著增加。 可確認未使用本發明之鹼可溶性樹脂之比較例1、3及4的情況，顯影速度及密著力顯著降低，階差值亦增加。尤其可確認比較例3及比較例4，著色劑只使用顏料，穿透率值顯著減少。The present invention relates to a colored photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent. (E); the colorant (D) comprises a pigment (d1) and a dye (d2); the alkali-soluble resin (A) comprises a repeating unit represented by Chemical Formula 1; the glass transition temperature of the resin is less than 0 ° C; The development speed, sensitivity, and adhesion of the composition are remarkably improved, and the pattern step which may become large due to the colorant is minimized, so that the transmittance is remarkably improved. The colored photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), and a solvent (E). <Alkali-Soluble Resin (A)> The alkali-soluble resin (A) used in the present invention contains a repeating unit represented by the following Chemical Formula 1, and exhibits a glass transition temperature of less than 0 °C. [Chemical Formula 1]Where, R1
And R2
Alone as a hydrogen atom or a methyl group, R3
It is a residue comprising a carboxylic acid derived from an acid anhydride. The alkali-soluble resin (A) of the present invention contains the above-mentioned repeating unit and exhibits a glass transition temperature of less than 0 ° C, whereby the development speed of the composition can be remarkably improved, and the sensitivity and adhesion are also improved, and the increase in development speed is suppressed. The resulting pattern short circuit problem. Further, when the pattern is formed by using the composition containing the alkali-soluble resin (A), the pattern step which may become large due to the coloring agent can be minimized, the smoothness is remarkably improved, and the transmittance is also improved. Good quality color filters can be manufactured. The content of the repeating unit or the like represented by the above Chemical Formula 1 is not particularly limited, and may be, for example, 50 to 90 mol%, more preferably 50 to 75 mol%, based on the entire alkali-soluble resin. When the above range is satisfied, the glass transition temperature of the polymerized resin is more preferably set to less than 0 °C. When the repeating unit or the like is less than 50 mol%, the sensitivity is lowered, and pattern short-circuiting occurs. When it exceeds 90 mol%, gelation may occur during the polymerization, and even if it is polymerized, the safety of the resin may be lowered. When the glass transition temperature (Tg) of the polymerized alkali-soluble resin (A) is 0° C. or more, a step difference occurs due to the colorant content in the composition, and it is difficult to ensure flatness. The alkali-soluble resin (A) of the present invention may further contain a monomer (a2) having an unsaturated double bond in addition to the monomer (a1) for repeating the chemical formula 1, and may be produced by copolymerization. The type of the copolymerizable unsaturated double-bonded monomer is not particularly limited, and specifically includes, for example, styrene, vinyl toluene, a-methylstyrene, p-chlorostyrene, o-methoxystyrene, and Methoxystyrene, p-methoxystyrene, o-methoxystyrene, o-vinyl anisole, m-vinyl anisole, p-vinyl anisole, o-vinyl phenyl epoxy propyl ether, methylene An aromatic vinyl compound such as phenyl epoxypropyl ether or p-vinylbenzene epoxy propyl ether. Further, examples thereof include N-cyclohexylmethyleneimine, N-benzyl maleimide, N-phenyl maleimide, and N-o-hydroxyphenyl-butene. Diimine, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl maleimide, N- M-methylphenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxy An N-substituted maleimide compound such as phenyl maleimide or N-p-methoxyphenyl maleimide. Further, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, propyl iso(meth)acrylate, butyl (meth)acrylate, iso(methyl) A (meth)acrylic acid alkyl ester such as butyl acrylate, butyl (meth) acrylate or butyl (meth) acrylate. Further, examples thereof include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methyl (meth) hexyl acrylate, 2-methylcyclo (meth) hexyl acrylate, and tricyclic ring. [5.2.1.02,6] Cyclohexane-8-yl (meth) acrylate, ethyl 2-bicyclophenetanyl (meth) acrylate, isobornyl (meth) acrylate, etc. Base) acrylates. Further, ethyl 2-hydroxy(meth)acrylate, propyl 2-hydroxy(meth)acrylate, butyl 4-hydroxy(meth)acrylate, 2-hydroxy-3-phenoxy (methyl) Hydroxy (meth) acrylate such as propyl acrylate or N-hydroxyethyl acrylamide. Further, examples thereof include aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate. Further, 3-(methacrylomethoxymethyl)oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane, 3-(methacrylofluoreneoxy) 2-trifluoromethyloxetane, 3-(methacrylomethoxyethyl)-2-phenyloxetane, 2-(methacrylomethoxyethyl)oxa An unsaturated oxetane compound such as cyclobutane or 2-(methacrylomethoxyethyl)-4-trifluoromethyloxetane. These monomers may be used alone or in combination of two or more. The content of the copolymerizable compound having an unsaturated double bond is not particularly limited, and may be, for example, 10 to 50 mol%, more preferably 30 to 40 mol, based on the total amount of the monomer used for polymerizing the alkali-soluble resin. ear%. When the above range is satisfied, the glass transition temperature of the resin shows less than 0 ° C, and the step difference can be minimized. Hereinafter, the method for producing the alkali-soluble resin (A) of the present invention will be described in more detail. Conventionally, the alkali-soluble resin (A) of the colored photosensitive resin composition is produced in order to be soluble in the alkali developing solution used in the development processing step in forming the pattern, and an ethylenically unsaturated monomer having a carboxyl group as an essential component. However, the alkali-soluble resin formed by such a production method has a problem that the main chain contains a carboxyl group, and it is difficult to produce a resin having a glass transition temperature of less than 0 °C. However, the alkali-soluble resin (A) of the present invention is produced in such a manner that a side chain of a main chain which does not undergo polymerization reaction contains a carboxyl group, whereby appropriate developability is imparted, and the glass transition temperature shows less than 0 °C. Further, an embodiment of the production method of the present invention comprises the following steps: (S1) a stage in which glycidyl (meth)acrylate is combined with a monomer (a2) having an unsaturated double bond; (S2) copolymerization of the aforementioned production a stage of reacting with an ethylenically unsaturated monomer having a carboxyl group; and (S3) a stage of reacting the copolymer having undergone the foregoing reaction with an acid anhydride. The (S2) stage is a stage for imparting photocurability to the alkali-soluble resin (A) of the present invention; and in the above (S2) stage, the type of the ethylenically unsaturated monomer having a carboxyl group is in the range in which the function is performed. The content is not particularly limited, and examples thereof include (meth)acrylic acid, ethacrylic acid, and butylacrylic acid, and methacrylic acid is preferred. The above (S3) stage is a stage for imparting an appropriate acid value to the alkali-soluble resin (A) of the present invention, and more specifically, the hydroxyl group of the glycidyl group derived from the alkali-soluble resin is reacted with an acid anhydride in the alkali-soluble resin. The side chain is introduced into the carboxyl group. The type of the acid anhydride used in the above (S3) stage is not particularly limited as long as it functions within the range of its function, and examples thereof include Phthalic anhydride and (2-dodecen-1-yl). (2-Dodecen-1-yl) succinic anhydride, Maleic anhydride, Succinic anhydride, Citracononic anhydride, Glutaric anhydride , Methylsuccinic anhydride, 3,3-Dimethylglutaric anhydride, Phenylsuccinic anhydride, Itaconic anhydride, 3, 4,5,6-Tetrahydrophthalic anhydride, Trimellitic anhydride, Hexahydrophthalic anhydride, and Carbic Anhydride (Carbic anhydride) and so on. From the viewpoint of cost and ease of reaction, it is preferably maleic anhydride, Phthalic anhydride, Trimellitic anhydride, Succinic anhydride, Hexahydrophthalic anhydride, Carbic anhydride, more preferably Trimellitic anhydride, Succinic anhydride, Hexahydrophthalic anhydride ). The acid value of the alkali-soluble resin (A) of the present invention produced by the above-described production method can be 30 to 150 mgKOH/g in order to ensure compatibility with the dye contained in the composition and storage safety of the composition. When the acid value of the alkali-soluble resin (A) is less than 30 mgKOH/g, it may be difficult to ensure a sufficient development speed of the colored photosensitive resin composition. Further, when the acid value is more than 150 mgKOH/g, the adhesion to the substrate may be reduced, pattern pattern short-circuiting may occur, and compatibility with the dye may occur, and the dye in the colored photosensitive resin composition may be precipitated or colored photosensitive resin. The storage safety of the composition is lowered and the viscosity is increased. The content of the alkali-soluble resin (A) of the present invention is not particularly limited, and may be, for example, 10 to 80% by weight, and more preferably 10 to 70% by weight based on the total weight of the solid powder in the composition. When the above range is satisfied, the solubility in the developer is sufficient, the pattern is easily formed, and the development of the film portion of the exposed portion is reduced, and the degree of detachment of the non-image portion is preferably improved. <Photopolymerizable Compound (B)> The photopolymerizable compound (B) of the present invention is a compound which can be polymerized by the action of the photopolymerization initiator (C) described below, using a monofunctional monomer, a bifunctional monomer or a polyfunctional compound. As the monomer, a polyfunctional monomer having two or more functional groups is preferably used. Specific examples of the aforementioned monofunctional monomer include carbyl phenyl acrylate, propyl 2-hydroxy-3-phenoxy acrylate, carbitol 2-ethylhexyl acrylate, ethyl 2-hydroxy acrylate or N-ethylene Base carbitol or the like, but is not limited thereto. Specific examples of the aforementioned bifunctional monomer or polyfunctional monomer include 1,6-hexanedi(di)di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(methyl) But not limited to acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(propylene oxime) ether or 3-methylpentane diol (meth) acrylate . Specific examples of the aforementioned polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated (ethoxylated) trimethylolpropane tri(meth)acrylate, propoxylation (propoxylation) Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated (ethoxylated) Dipentaerythritol hexa(meth) acrylate, propoxylated (propoxylated) dipentaerythritol hexa(meth) acrylate or dipentaerythritol hexa (meth) acrylate, etc., but is not limited thereto. The content of the photopolymerizable compound (B) is not particularly limited, and may be, for example, 5 to 45% by weight, and more preferably 7 to 45% by weight based on the total weight of the solid powder in the composition. When the above range is satisfied, the strength or smoothness of the pixel portion is good, which is preferable. <Photopolymerization Initiator (C)> When the photopolymerizable compound (B) is polymerizable, the photopolymerizable compound (C) can be used without particular limitation. In particular, the photopolymerization initiator (C) is preferably an acetophenone-based compound, a benzophenone-based compound, or the like from the viewpoints of polymerization characteristics, initial efficiency, absorption wavelength, availability, cost, and the like. One or more compounds selected from the group consisting of a azine compound, a biimidazole compound, an anthraquinone compound, and a thioxanthone compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxyl group. 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-methyl-1-(4-methylthiophenyl) )-2-morpholinepropane-1-ketone, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenyl)butane-1-one, 2-hydroxy-2-methyl-1 -[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamine)-1-(4-morpholinylphenyl) Butane-1 1-ketone, etc. The aforementioned benzophenone-based compound includes, for example, benzophenone, o-benzylidene benzoic acid methyl, 4-phenylbenzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3 , 3', 4, 4' - tetra (tertiary butyl peroxycarboxy) benzophenone, 2, 4, 6 - trimethyl benzophenone and the like. Specific examples of the aforementioned triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane). (6)(6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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-diethylamine-2-methylphenyl)vinyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like. Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis (2,3- Dichlorobenzene)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2'-bis(2,6-dichlorobenzene) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, or a biimidazole compound in which a phenyl group at the 4,4', 5,5' position is substituted by a carboxyoxy group. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2,3-dichlorobenzene)-4 is preferably used. , 4',5,5'-tetrabenzimidazole, 2,2'-bis(2,6-dichlorobenzene)-4,4',5,5'-tetraphenyl-1,2'-biimidazole . Specific examples of the lanthanoid compound include o-ethoxycarboxy-a-hydroxyimino-1-phenylpropan-1-one, and commercial products are represented by BASF Corporation OXE01 and OXE02. The aforementioned thioxanthone-based compound includes, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. . Further, the photopolymerization initiator (C) may further contain a photopolymerization initiation aid (c1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition of the present invention has the highest sensitivity by the photopolymerization-containing starting assistant (c1), and the productivity can be improved. As the above (c1), one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group are preferably used. The above amine compound is preferably an aromatic amine compound, and specifically, an aliphatic amine compound such as triethylolamine, methyldiethanolamine or triisopropanolamine, or 4-dimethylaminobenzoic acid methyl group, 4 may be used. - dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl , N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name: Michlerone), 4,4'-bis(diethylamino) ) benzophenone and the like. The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenyl thioacetic acid, methyl phenyl thioacetic acid, ethyl phenyl thioacetic acid, methyl ethyl phenyl thioacetic acid, dimethyl phenyl thioacetic acid, and A. Oxybenzene thioacetate, dimethoxybenzene thioacetate, chlorophenyl sulphuric acid, dichlorobenzene sulphuric acid, N-phenylglycine, phenoxyacetic acid, naphthalene sulphuric acid, N-naphthylglycine, naphthyloxyacetic acid, and the like. Specific examples of the above-mentioned organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyrate)butane, and 1,3,5-tris(3-indenyl). Ethyl butyrate)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-nonylpropyl), neopentyl pentoxide (3 - mercaptobutyl ester), neopentyl alcohol oxime (3 - mercaptopropyl ester), dipentaerythritol bismuth (3 - mercaptopropyl ester), tetraethylene glycol bis (3- propyl propyl ester) and the like. The content of the photopolymerization initiator (C) is not particularly limited. For example, the content of the alkali-soluble resin (A) and the photopolymerizable compound (B) may be 0.1 to 0.1% by weight based on the total weight of the solid powder in the composition. 40% by weight, more preferably 0.1 to 30% by weight. When the above range is satisfied, since the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, productivity is improved and high resolution can be maintained, which is preferable. Further, when the photopolymerization initiation aid (c1) is further used, the content of the photopolymerization initiation aid (c1) is not particularly limited, and for example, the total weight of the solid powder in the composition, and the alkali-soluble resin (A) The content of the photopolymerizable compound (B) can be 0.1 to 40% by weight, more preferably 0.1 to 30% by weight. When the above range is satisfied, since the coloring photosensitive resin composition has the highest sensitivity, the effect of improving the productivity of the color filter formed using the above composition can be provided. <Colorant (D)> The coloring agent (D) used in the present invention contains one or more kinds of pigments (d1) and one or more kinds of dyes (d2). The photosensitive resin composition of the present invention contains the alkali-soluble resin (A), and even when the coloring agent (D) is used together with the pigment (d1) and the dye (d2), good developability and adhesion can be exhibited.pigment (d1)
The aforementioned pigments are organic pigments or inorganic pigments which are generally used in the field. The pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinophthalone pigments, isodecyl ketone pigments, and the like. Porphyrin pigments, anthraquinone pigments, anthraquinone pigments, dioxazine pigments, anthraquinone pigments, diterpene based pigments, pyrimidine pigments, anthanthrone pigments, indanthrone pigments, yellow sage Ketone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal-stack salts, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Oxide or composite metal oxide, etc. In particular, the above-mentioned organic pigments and inorganic pigments are specifically exemplified as a pigment which is classified as a color index (published by The Society of Dyers and Colourists), and more specifically, a pigment having the following color index (CI) number is exemplified. However, it is necessary to be limited to such pigments. For example, 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, 13, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71. Further, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264 are exemplified. Further, C.I. Pigment Violet 14, 14, 23, 29, 32, 33, 36, 37 and 38 can be mentioned. Further, C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76 can be cited. Further, C.I. Pigment Greens 7, 10, 15, 25, 36, 47 and 58 can also be mentioned. Further, C.I. Pigment Brown 28 can be mentioned. Further, C.I. Pigment Black 1 and 7, etc. may be mentioned. These pigments (d1) may be used alone or in combination of two or more. Among the above-exemplified CIPigment pigments, it is particularly preferable to use from CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red. 255, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Violet 23, CI Pigment Blue 15:3, Pigment Blue 15:6 selected pigment. As the pigment, it is preferred to use a pigment dispersion liquid whose particle diameter is uniformly dispersed. An example of a method of uniformly dispersing a pigment particle size is a method of dispersing a pigment dispersant (d3), and a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained according to the method. Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. These may be used alone or in combination of two or more. . The content of the pigment (d1) is in the range of 20 to 90% by mass, and more preferably 30 to 70% by mass, based on the total solid powder in the pigment dispersion composition. The content of the pigment is preferably in the range of 20 to 90% by mass as described above, and has a low viscosity, good storage safety, high dispersion efficiency, and is effective for increasing the ratio of light to dark. The foregoing dispersant (d3) may employ other types of pigment dispersants in addition to the acrylic dispersant as described above. The pigment dispersant of the other resin type is a pigment dispersant of a conventional resin type, and particularly, a polyurethane, a polycarboxylate represented by a polyacrylate, an unsaturated polyamine, a polycarboxy acid, a polycarboxy acid a part (amine salt), an ammonium salt of a polycarboxylate, an alkylamine salt of a polycarboxy acid, a polyoxyalkylene oxide, a long-chain polyamine guanamine phosphate, a hydrocarbon-containing polycarboxylate or a modified substance thereof, Or an emulsion dispersant such as a guanamine or a salt thereof formed by reacting a polyester having a free carboxyl group with a poly(lower alkylenimine); (meth)acrylic acid-styrene copolymer, (methyl a water-soluble resin or a water-soluble polymer compound such as an acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol or a polyvinylpyrrolidone; a polyester; a modified poly Acrylate; an additional product of ethylene oxide/propylene oxide, phthalic acid ester, and the like. As a commercial product of the above-mentioned resin type dispersant, the cationic resin dispersant may be exemplified by BYK-Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050 , EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemicals trade name: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto trade name: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB- 823; trade name of Kyoeisha Chemical: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. Other than the acrylic dispersing agent, other resin type pigment dispersing agents may be used alone or in combination of two or more kinds, or may be used in combination with an acrylic dispersing agent. The amount of the dispersant (d3) to be used is 5 to 60 parts by mass, more preferably 15 to 50 parts by mass, per 100 parts by mass of the solid powder of the pigment (d1) to be used. As described above, when the content of the dispersant (d3) exceeds 60 parts by mass, the viscosity becomes high, and when it is less than 5 parts by mass, the pigment fine particles are difficult to be formed, or the gelation after dispersion is caused.dye (d2)
The dye may be used in an organic solvent, and may be used without limitation. It is preferable to use a dye which has solubility in an organic solvent and ensures reliability such as solubility in an alkali developing solution, heat resistance, and solubility resistance. 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 the like. Further, an azo type, a xanthene type, a phthalocyanine type acid dye, and the like may be selected. The aforementioned dyes are preferably classified as a dye compound in the excellent index (published by The Society of Dyers and Colourists), and a conventional dye described in DYEING NOTE. As a specific example of the above dye, the C.I. solvent dye may be exemplified by the following dyes. For example, a red dye such as C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179 may be mentioned. Further, a blue dye such as C.I. Solvent Blue 5, 35, 36, 37, 44, 59, 67, 70 may be mentioned. Further, a violet dye such as C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49 may be mentioned. Further, a yellow dye such as C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 may be mentioned. Further, an orange dye such as C.I. solvent orange 2, 7, 11, 15, 26, 56 may be mentioned. Further, a green dye such as C.I. solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 may be mentioned. Among CI solvent dyes, CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179 with good solubility in organic solvents; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13 Suitably, CI solvent red 8, 122, 132 is particularly suitable. Further, the C.I. acid dye may be exemplified by the following dyes. For example, 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 Red dyes such as 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426. Further, 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, 251 and other yellow dyes. Further, CI acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc. Orange dye. Further, 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, 340 and other blue dyes. Further, a violet dye such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 may be mentioned. Further, a green dye such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, or the like can be given. Among the acid dyes, C.I. Acid Red 92 having a good solubility in an organic solvent; C.I. Acid Blue 80, 90; C.I. Acid Violet 66 is particularly preferred. Further, the C.I. Direct dye may be exemplified by 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, Red dyes such as 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250. Further, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, Yellow dyes such as 108, 109, 129, 136, 138, and 141. Further, an orange dye such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 may be mentioned. In other words, 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, Blue dyes such as 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293. In other words, CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc. dye. Further, a green dye such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, or the like can be given. Further, a yellow dye such as C.I. Direct Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 may be mentioned. Further, CI mordant red, 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36 may be mentioned. Red dyes such as 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95. Further, CI mordant oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 orange dyes. In other words, CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, Blue dyes such as 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84. In other words, CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 Wait for purple dyes. Further, a green dye such as C.I. mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53 may be mentioned. These dyes may be used alone or in combination of two or more. The dye content in the coloring agent (D) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 by weight, based on the solid powder in the coloring agent (D). ～50% by weight. When the content of the dye in the coloring agent (D) is in the above range, it is possible to prevent the problem that the dye is eluted by the organic solvent after the pattern formation is formed, and the sensitivity is good, which is preferable. The content of the coloring agent (D) containing the pigment and the dye of the present invention is not particularly limited, and may be, for example, 5 to 60% by weight, and more preferably 10 to 45% by weight based on the total weight of the solid powder in the composition. When the film is formed in the above range, even if a film is formed, the color density of the pixel is sufficient, and the degree of separation of the non-image portion during development is not lowered, and residue is less likely to occur, which is preferable. <Solvent (E)> The solvent (E) used in the present invention can be effectively used for dissolving other components contained in the colored photosensitive resin composition, and can be used without particular limitation, and is particularly preferably an ether or an aromatic hydrocarbon. Ketones, alcohols, esters or guanamines. Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Further, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether may be mentioned. Further, diethylene glycol alkyl ether acetates such as methyl sarprosone acetate and ethyl sirolimus acetate may be mentioned. Further, an alkylene glycol alkane such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate or methoxybenzyl acetate may be mentioned. Ether acetates. In other words, aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene. Further, ketones such as methyl ethyl ketone, acetone, methyl ketone, methyl isobutyl ketone, and cyclohexanone may also be mentioned. Further, examples thereof include alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone. Further, an ester such as 3-ethoxypropionic acid ethyl or 3-methoxypropionic acid methyl or a cyclic ester such as g-butyrolactone. The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200 ° C from the viewpoint of coatability and drying property, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, or lactic acid. Ethyl ester, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. It is preferably mixed with an alcohol solvent such as 4-hydroxy-4-methyl-2-pentanone which can inhibit dye precipitation and improve storage safety. The solvent (E) exemplified above may be used alone or in combination of two or more. The total weight of the colored photosensitive resin composition according to the present invention may be 60 to 90% by weight, more preferably 70 to 85% by weight. When the above range is satisfied, it is applied by a coating device such as a roll coater, a spin coater, a slit and a spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet. Provides an effect of improving coating properties. The colored photosensitive resin composition of the present invention may further optionally contain an additive as needed, and examples thereof include a polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and a coagulation preventing agent. However, it is not limited to this. Specific examples of the other polymer compound include a curable resin such as an epoxy resin or a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and poly A thermoplastic resin such as an ester or a polyurethane. The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound as the curing agent include a bisphenol A epoxy resin, a brominated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a brominated bisphenol F epoxy resin. Examples of the phenolic epoxy resin include an aromatic epoxy resin, an alicyclic epoxy resin, and a glycidyl ester resin, and examples thereof include a brominated derivative of the epoxy resin and an epoxy resin. An aliphatic, alicyclic or aromatic epoxy compound other than a brominated derivative thereof, a butadiene (co)polymer epoxide, an isoprene (co)polymer epoxide, a glycidyl group (A) Acrylate (co)polymer, triglycidyl isocyanurate, and the like. Specific examples of the oxetane compound as the curing agent include carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and terephthalic acid. Ester dioxetane, cyclohexane dicarboxylic acid dioxetane, and the like. The hardener may be used in combination with a hardening auxiliary compound to effect ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound. The hardening auxiliary compound includes, for example, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, an acid generator, and the like. The above polyvalent carboxylic anhydrides are commercially available as an epoxy resin hardener. Specific examples of the epoxy resin curing agent include ADEKA HARDENER EH-700 (manufactured by ADEKA Industries Co., Ltd.), trade name (RIKACID HH) (manufactured by Shin-Nippon Chemical Co., Ltd.), and trade name (MH). -700) (manufactured by New Japan Physical and Chemical Co., Ltd.), etc. The hardeners exemplified above may be used alone or in combination of two or more. The surfactant may be used to improve the film formability of the photosensitive resin composition, and a fluorine-based surfactant or a sulfhydryl surfactant is preferably used. The above-mentioned fluorenyl-based surfactants are commercially available, for example, as DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF of GE Toshiba Silicones. -4460, TSF-4452. The above-mentioned fluorine-based surfactant is, for example, commercially available as Megafac F-470, F-471, F-475, F-482, F-489, etc. of DAINIPPON INK AND CHEMICALS. The surfactants exemplified above may be used alone or in combination of two or more. Specific examples of the adhesion promoter include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3 Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropane Trimethoxy decane, 3-glycidoxypropylmethyldimethoxydecane, 2–(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyltrimethyl Oxaloxane, 3-chloropropyltrimethoxydecane, 3-methacrylate propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatetrimethoxydecane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter is preferably contained in an amount of from 0.01 to 10% by weight, more preferably from 0.05 to 2% by weight, based on the weight of the solid powder in the colored photosensitive resin composition. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tri-n-butylphenol) and 2,6-di-tertiarybutyl-4-methylphenol. Specific examples of the above ultraviolet absorber include 2 - (3 - tri-butyl - 2 - hydroxy-5-methylphenyl) - 5 - chlorobenzotriazole, alkoxybenzophenol and the like. Specific examples of the above-mentioned aggregation inhibitor include sodium polyacrylate and the like.Synthesis example 1 : colorant composition synthesis (1) Colorant composition (M1)
The pigment is CI Pigment Red 177, 12.0 parts by mass, the pigment dispersant is DISPERBYK-2001 (manufactured by BYK), 4.0 parts by mass, the dye is Acid Red 52, 1.2 parts by mass, the solvent is propylene glycol methyl ether acetate, 44 parts by mass and 4 -Hydroxy-4-methyl-2-pentanone, 20 parts by mass, mixed/dispersed in a bead mill during 12 hours to prepare a colorant composition (M1).(2) Colorant composition (M2)
The pigment was CI Pigment Red 177, 13.2 parts by mass, the pigment dispersant was DISPERBYK-2001 (manufactured by BYK), 4.0 parts by mass, the solvent was propylene glycol methyl ether acetate, 44 parts by mass, and 4-hydroxy-4-methyl-2. - Pentanone, 20 parts by mass, mixed/dispersed in a bead mill during 12 hours to produce a colorant composition (M2).Synthesis example 2 : Synthesis of alkali soluble resin (1) Alkali soluble resin (A - 1) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 2 parts of AIBN, and 23.0 parts of 2-ethyl acrylate were placed. 1.6 parts of 4-methylstyrene, 46.0 parts of glycidyl methacrylate, and 3 parts of n-xenon were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 4 hours. Next, the temperature of the reaction liquid was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen, and then 0.2 parts of triethylamine, 0.1 part of 4-methoxyphenol, and 23.3 parts of acrylic acid were placed, and the mixture was reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 6.0 parts of succinic anhydride was placed, and the reaction was carried out at 80 ° C for 6 hours. The solid powder acid price of the alkali-soluble resin thus synthesized was 32.8 mgKOH/g, the weight average molecular weight Mw measured by GPC was about 6,350, and the repeating unit shown by Chemical Formula 1 was 70 mol%. The glass transition temperature was measured by a differential scanning calorimeter and found to be -12 °C.(2) Alkali soluble resin (A - 2) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 2 parts of AIBN, and 21.4 parts of 2-ethyl acrylate were placed. 1.5 parts of 4-methylstyrene, 42.8 parts of glycidyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 4 hours. Next, the temperature of the reaction liquid was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen, and then 0.2 parts of triethylamine, 0.1 part of 4-methoxyphenol, and 21.7 parts of acrylic acid were placed, and the mixture was reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 12.5 parts of succinic anhydride was placed, and the reaction was carried out at 80 ° C for 6 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 68.6 mgKOH/g, the weight average molecular weight Mw measured by GPC was about 5,570, and the repeating unit shown by Chemical Formula 1 was 70 mol%. The glass transition temperature was measured by a differential scanning calorimeter and found to be -8.3 °C.(3) Alkali soluble resin (A - 3) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 17.3 parts of 2-ethyl acrylate were placed. 1.2 parts of 4-methylstyrene, 59.4 parts of glycidyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 4 hours. Next, the temperature of the reaction liquid was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen, and then 0.2 parts of triethylamine, 0.1 part of 4-methoxyphenol, and 17.6 parts of acrylic acid were placed, and the reaction was carried out at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 4.5 parts of succinic anhydride was placed, and the reaction was carried out at 80 ° C for 6 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 24.98 mgKOH/g, the weight average molecular weight Mw measured by GPC was about 5,950, and the repeating unit shown by Chemical Formula 1 was 80 mol%. The glass transition temperature was measured by a differential scanning calorimeter and found to be -20.4 °C.(4) Alkali soluble resin (A - 4) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 10.2 parts of 2-ethyl acrylate were placed. 0.7 parts of 4-methylstyrene, 76.0 parts of glycidyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 4 hours. Next, the temperature of the reaction liquid was lowered to normal temperature, and the atmosphere of the flask was replaced with air from nitrogen, and then 0.2 parts of triethylamine, 0.1 part of 4-methoxyphenol, and 10.4 parts of acrylic acid were placed, and the mixture was reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 2.7 parts of succinic anhydride was placed, and the reaction was carried out at 80 ° C for 6 hours. The solid powder acid price of the alkali-soluble resin thus synthesized was 16.45 mgKOH/g, the weight average molecular weight Mw measured by GPC was about 5,450, and the repeating unit shown by Chemical Formula 1 was 90 mol%. The glass transition temperature was measured by a differential scanning calorimeter and found to be -28.4 °C.(5) Alkali soluble resin (A - 5) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone and a nitrogen introduction tube, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN 2 part, 13.0 parts of the above-mentioned acrylic acid, and benzyl methacrylate were placed. 10 parts, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 8 hours. The solid powder acid price of the alkali-soluble resin thus synthesized was 98.2 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 14,950. The glass transition temperature was measured by a differential scanning calorimeter and found to be 95 °C.(6) Alkali soluble resin (A - 6) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone and a nitrogen introduction tube, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN 2 part, 13.0 parts of the above-mentioned acrylic acid, and benzyl methacrylate were placed. 10 parts, 67.0 parts of 4-methylstyrene, 10 parts of methyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 8 hours. The solid powder acid value of the alkali-soluble resin thus synthesized was 81.6 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 16,110. The glass transition temperature was measured by a differential scanning calorimeter and found to be 85 °C.(7) Alkali soluble resin (A - 7) synthesis
In a flask equipped with a stirrer, a thermometer reflux cooling tube, a filling zone and a nitrogen introduction tube, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, AIBN 2 part, 5.0 parts of the above-mentioned acrylic acid, and benzyl methacrylate were placed. 20 parts, 55.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecyl were replaced by nitrogen. Thereafter, the mixture was stirred and the reaction temperature was raised to 80 ° C, and the reaction was carried out for 8 hours. The alkali powder-soluble resin thus synthesized had a solid powder acid value of 17.4 mgKOH/g, and the weight average molecular weight Mw measured by GPC was about 17,370. The glass transition temperature was measured by a differential scanning calorimeter and found to be 82 °C.Examples and comparative examples
The photosensitive resin composition was produced using the components and contents of the following Table 1. experiment method (1) Development speed and adhesion evaluation
A color filter was produced using the colored photosensitive resin composition produced in the foregoing Examples and Comparative Examples. Specifically, each of the colored photosensitive resin compositions described above was applied onto a 2 inch square glass substrate (manufactured by Corning, "EAGLE XG") by a spin coating method, and then heated at a temperature of 100 ° C on a hot plate. Hold for 3 minutes to form a film. Next, a test mask having a pattern having a transmittance of 1 to 100% in a range of 1 to 100% and a line/pitch pattern of 1 to 100 mm is placed on the film to set an interval from the test mask. It is 300mm and is exposed to ultraviolet rays. At this time, the ultraviolet light source uses a 1KW high-pressure mercury lamp including g, h, and i rays, and the illumination is 60 mJ/cm.2
Irradiation, no special optical filters are used. The ultraviolet ray-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to develop. The glass plate coated with the above film was washed with distilled water, dried with nitrogen, and heated in a heating oven at 200 ° C for 25 minutes to produce a color filter. The film thickness of the above-described color filter was 2.4 mm. In the above-described step, the time (developing speed) taken for the non-exposed portion to completely dissolve in the developing solution at the time of development was measured and described in Table 2 below. Further, when the pattern formed by the optical microscope was evaluated, the adhesion was evaluated in the pattern peeling level, and it is shown in Table 2 below. <Evaluation Criteria> ○: No pattern peeling △: Pattern peeling is 1 to 3 ×: Pattern peeling is 4 or more(2) Penetration rate measurement (%)
A color filter was produced in the same manner as in Test Method (1) except that the test mask was not used. The transmittance of the line pattern portion of 100 mm in the formed pattern was measured using a colorimeter (manufactured by Olympus, OSP-200), and is shown in Table 2 below.(3) Step difference measurement ( Å )
The colored photosensitive resin composition of the above-mentioned Examples and Comparative Examples was applied by a spin coating method to a 2-inch square substrate which was patterned to have a black matrix of 1.5 mm thick line/pitch, and then vacuum dried. The equipment was depressurized to 65 Pa and vacuum dried. Then, it was maintained at a temperature of 100 ° C for 3 minutes on a hot plate substrate to form a film. Thereafter, ultraviolet rays were irradiated on the hot plate without a mask. At this time, the ultraviolet light source uses a 1KW high-pressure mercury lamp including g, h, and i rays, and the illuminance is 40 mJ/cm.2
Irradiation, no special optical filters are used. The ultraviolet ray-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to develop. The glass plate coated with the above film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 25 minutes to produce a color filter. The surface difference between the color resist formed on the BM pattern and the color resist formed on the glass was measured using a Surface Profiler (Veeco Dektak 6M), and the results are shown in Table 2 below. .
Referring to Table 2, in the case of the colored photosensitive resin composition of the present invention (Examples 1-4), it was confirmed that even if the development speed was very fast, a good adhesion force was exhibited, and it was suitable for manufacturing a step difference which was very small and penetrated. High-quality, high-quality color filters. In the case of Example 4 in which the alkali-soluble resin contained a repeating unit of Chemical Formula 1 in a slight excess, the development speed and the adhesion were slightly lower than those in the other examples. It was confirmed that the alkali-soluble resin of the present invention was used, but in the case of Comparative Example 2 in which the coloring agent was only a pigment, the development speed and the adhesion were the same as those of the examples, but the decrease in the transmittance and the step difference were remarkably increased. . In the case of Comparative Examples 1, 3 and 4 in which the alkali-soluble resin of the present invention was not used, the development speed and the adhesion were remarkably lowered, and the step value was also increased. In particular, in Comparative Example 3 and Comparative Example 4, only the pigment was used as the colorant, and the transmittance value was remarkably reduced.