TW201207559A

TW201207559A - Colored resin composition

Info

Publication number: TW201207559A
Application number: TW100119457A
Authority: TW
Inventors: Satoru Kobayashi; Hidehiro Arai; Yutaka Ishii; Takaaki Kurata; Makoto Teranishi; Hirokazu Nagahara
Original assignee: Nippon Kayaku Kk
Priority date: 2010-06-03
Filing date: 2011-06-02
Publication date: 2012-02-16
Also published as: KR20130048126A; CN102472850A; SG178850A1; JPWO2011152379A1; WO2011152379A1

Abstract

Disclosed is a crisp, bright and reliable blue pixel color filter with excellent color characteristics and resistance. The disclosed blue colored resin composition for the manufacture of a blue pixel color filter is obtained by means of using a specific blue dye colorant compound and also by admixture of a binder resin, a solvent, and a curing agent. The manufactured blue pixel color filter has excellent reliability and resistances, such as heat resistance, while having while having excellent dye color properties.

Description

201207559 六、發明說明：【發明所屬之技術領域】本發明係關於一種形成藍色像素之著色樹脂組合物，使用該著色樹脂組合物所形成之彩色濾光片，及使用該彩色 • 濾光片所形成之液晶顯示裝置、攝像元件（CCD(Charge-201207559 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a colored resin composition for forming a blue pixel, a color filter formed using the colored resin composition, and the use of the color filter. The liquid crystal display device and the imaging element (CCD (Charge-)

Coupled Device，電荷耦合元件）、CMOS(Complementary Metal-Oxide-Semiconductor，互補式金屬氧化物半導體））、有機EL(Electroluminescence，電致發光）顯示器等電子顯示裝置。【先别技術】對於筆記型電腦或液晶電視、行動電話等所代表之液晶顯不器（LCD ’ Liquid Crystal Display)等之液晶顯示元件或作為數位相機或彩色影印機等之輸入器件而使用的攝像元件（CCD、CMOS)之彩色化而言，需要彩色濾光片。作為製造該等液晶顯示裝置或固體攝像元件所使用之彩色濾光片之方法，有染色法、電鍍法、印刷法、顏料分散法等，近年來顏料分散法逐漸成為主流。作為圖案化之方法，具代表性的是光微影法，使用感光性樹脂組合物與顏料分散 . 體之混合物而形成彩色濾光片。最近亦實行以下方法：藉由喷墨印表機不介隔光罩而將著色油墨直接塗佈於基板 . 上’形成彩色濾光片。土作為彩色濾光片所要求之特性之色純度、彩度、亮卢及對比度的提高特別重要。藉由亮度提高，可：光量’亦可減少消耗電力，故就環境方面而言亦為必2 155795.doc 201207559 技術。為提高彩色濾光片之色純度，必須增加著色顏料之含量、或選擇分光波形更佳之顏料。另一方面，為提高亮度必須提高透射率，故必須反之而降低顏料濃度、或使膜厚變薄。為使該專相反之特性並存而實行顏料之微粒子化之方法。現狀為，若微粒子化亦不斷發展則於耐性或分散穩定性方面存在極限，即便亮度提高亦無法實現耐性之並存。為解決該等問題，作為其他途徑正在推進使用染料之彩色濾光片之研究。若使用染料，則有使用顏料時無法達成之色純度與亮度之並存、或由於並非粒子故可抑制光散射因此對比度亦可提咼之優點》然而，面向電視等需要長期可靠性之顯示體時，尤其需要耐光性或耐熱性，但特別是藍色染料中耐性明顯劣於顏料者較多。例如下述專利文獻 1及2中有與使用二苯基甲燒系化合物之彩色滤光片有關之報告，但三苯基甲烷系化合物之耐熱性明顯較差，並非實用水準。Μ线料之耐性優異為公知（專利文㈣，但由於其色特性並非藍色而通常為帶紅色之f色調，故無法形成鮮明之藍色像素。於彩色據光片中需要包含形成鮮明之藍色像素且可靠性優異之耐性較高之有色㈣的著色樹脂組合物，但現狀為幾乎未實用化。因&，作為下一代而謀求亮康優異且耐性優異之高品質之彩色濾光片。 ’、 [先前技術文獻] [專利文獻] 專利文獻！：日本專利特開平Μ·號公報 155795.doc 201207559 專利文獻2:日未專利特開2002·14222號公報專利文獻3:曰本專利特開昭60-249102號公報【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供一種具有染料之優異之色特性並且耐熱性優異的彩色濾光片之藍色像素。 [解決問題之技術手段] 發明者為解決上迷問題而進行了努力研究，結果發現’藉由將含有特定之藍色有色材料化合物之著色樹脂組合物用於彩色濾光片之藍色像素，可解決上述問題，從而完成了本發明。即’本發明係關於： (1)一種彩色濾光片用著色樹脂組合 _ σ物’其含有下述式（1) 所示之有色材料化合物、黏合樹I旨 9 冷劑、及硬化劑， [化1]An electronic display device such as a Coupled Device (charge coupled device), a CMOS (Complementary Metal-Oxide-Semiconductor), or an organic EL (Electroluminescence) display. [Technology] For liquid crystal display elements such as LCD computers, LCD TVs, mobile phones, etc., or as input devices such as digital cameras or color photocopiers. For colorization of an imaging element (CCD, CMOS), a color filter is required. As a method of producing the color filter used in the liquid crystal display device or the solid-state image sensor, there are a dyeing method, a plating method, a printing method, a pigment dispersion method, and the like, and in recent years, the pigment dispersion method has gradually become mainstream. As a method of patterning, a photolithography method is generally used, and a color filter is formed by using a mixture of a photosensitive resin composition and a pigment dispersion. Recently, the following method has also been carried out: a coloring ink is directly applied to a substrate by an ink jet printer without interposing a photomask. The color filter is formed on the upper side. Soil Color purity, chroma, brightness and contrast are particularly important as the characteristics required for color filters. By increasing the brightness, the amount of light can also reduce the power consumption, so it is also environmentally necessary. 2 155795.doc 201207559 Technology. In order to improve the color purity of the color filter, it is necessary to increase the content of the coloring pigment or to select a pigment having a better spectral shape. On the other hand, in order to increase the brightness, it is necessary to increase the transmittance, so it is necessary to reduce the pigment concentration or to thin the film thickness. A method of granulating pigments in order to coexist this specific characteristic. The current situation is that if the micronization is continuously developed, there is a limit in the resistance or dispersion stability, and even if the brightness is increased, the compatibility cannot be achieved. In order to solve these problems, research on color filters using dyes is being promoted as another means. When a dye is used, there is a difference in color purity and brightness which cannot be achieved when a pigment is used, or a contrast can be improved because it is not a particle, so that the contrast can be improved. However, for a display body requiring long-term reliability such as a television In particular, light resistance or heat resistance is required, but in particular, the resistance of the blue dye is significantly inferior to that of the pigment. For example, in the following Patent Documents 1 and 2, there are reports on color filters using a diphenylmethane-based compound, but the heat resistance of the triphenylmethane-based compound is remarkably poor, and it is not practical. It is known that the resistance of the twisted material is excellent (patent text (4), but since the color characteristic is not blue, it is usually a reddish h-tone, so that a clear blue pixel cannot be formed. In the color light film, it needs to be formed into a distinct color. A colored resin composition having a high color and a high reliability and having high color resistance (4), but the current state of the art is almost unutilized. As a result of the next generation, it is a high-quality color filter that is excellent in brightness and excellent in resistance. '. [Previous Technical Literature] [Patent Literature] Patent Literature!: Japanese Patent Laid-Open Publication No. 155795.doc 201207559 Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-14222 Patent Document 3: Japanese Patent [Problem to be Solved by the Invention] An object of the present invention is to provide a blue pixel of a color filter having excellent color characteristics of a dye and excellent heat resistance. Technical means of the problem] The inventors made an effort to solve the above problem and found that 'by combining a colored resin containing a specific blue colored material compound The present invention has been accomplished by using a blue pixel for a color filter to solve the above problems. That is, the present invention relates to: (1) A coloring resin combination for a color filter _ σ object which contains the following formula (1) The colored material compound, the adhesive tree I, the 9 refrigerant, and the hardener, [Chemical Formula 1]

155795.doc 201207559 (式（）中R, R6为別獨立表示氫原子、碳數卜6之烧基苯基或苄基’至少-個為分支烷基、或環狀烷基； R7★分別獨立表示氫原子、碳數卜6之烧基、或齒素原子；陰離子部X-表示卷_三氣甲基續酿基〒基化物或雙-三氟甲基磺醯亞胺）； (2) 如（1)之著色樹脂組合物，其含有銅酞菁顏料； (3) —種彩色濾光片用著色硬化膜，其係使用如或（幻之著色樹脂組合物進行圖案化而成者； (4) 一種彩色濾光片，其包含如（3)之彩色濾光片用著色硬化膜； (5) —種液晶顯示裝置及有機el顯示器，其係安裝如（4)之彩色濾光片而成者；以及 (6) —種固體攝像元件，其係安裝如（句之彩色濾光片而成者。 [發明之效果] 本發明之藍色著色樹脂組合物藉由含有特定之藍色有色材料化合物，可提供一種耐熱性優異之彩色濾光片用之高品質之藍色像素。【實施方式】本發明之藍色著色樹脂組合物含有黏合樹脂、溶劑、硬化劑、及特定之藍色有色材料化合物，視需要可含有其他顏料或染料等有色材料化合物、界面活性劑、光聚合起始劑、熱聚合起始劑、聚合抑制劑及紫外線吸收劑等各種添加物，並不限定於該等，特定之有色材料化合物以外之成 155795.doc -6 - 201207559 分可無特別限制地使用。作為使用本發明之著色樹脂組合物之像素製造方法，主要可列舉光微影法與喷墨法，前者中使用利用光聚合起始劑之顯影性優異之感光性樹脂組合物，後者中未必需要光聚合起始劑而使用熱硬化性樹脂組合物。本發明所使用之特定之有色材料化合物係以上述式（i) 所不。於通式（1)之R!〜R6中，碳數卜6之烷基亦可具有取代基。作為碳數1〜6之烷基，例如可列舉：甲基、乙基' 丙基、異丙基、丁基、卜曱基丙基（第二丁基）、異丁基、戊基、1-乙基丙基、1·曱基丁基、環戊基、己基、丨曱基戊基、1-乙基丁基、環己基、羥基丙基、2_磺基乙基、羧基乙基、氰基乙基、甲氧基乙基、乙氧基乙基、丁氧基乙基、三氟甲基、五氟乙基等。於通式（1)之R〗〜R6中，苯基或苄基亦可具有取代基，作為取代基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基等（C1〜C5)烷基，氟原子、氯原子、溴原子、碘原子等齒素原子，磺酸基，甲氧基、乙氧基、丙氧基、丁氧基、第三丁氧基、己氧基等 (C1〜C6)烷氧基，羥基乙基、羥基丙基等羥基（C1〜C5)烷基，甲氧基乙基、乙氧基乙基、乙氧基丙基、丁氧基乙基等（C1〜C5)烷氧基（C1〜C5)烷基，2_羥基乙氧基等羥基 (C1〜C5)烷氧基，2_甲氧基乙氧基、2乙氧基乙氡基等烷氧基（C1〜C5)烷氧基，2_磺基乙基，羧基乙基，氰基乙基等。 155795.doc 201207559 於通式（1)之R,〜R6中，作為至少一個以上之分支烷基、環狀烷基，可列舉：異丙基、丨_甲基丙基（第二丁基）、卜乙基丙基、1-曱基丁基、丨-甲基戊基、i•乙基丁基、環丙基、環丁基、環戊基、環己基等。作為通式（1)之R广R0，較佳為氫原子或碳數丨〜6之未經取代之烷基、分支烷基、環狀烷基。於通式（1)之R7〜R2〇中’碳數1〜6之烷基亦可具有取代基。作為較佳之碳數1〜6之烷基，例如可列舉：甲基、乙基'丙基'異丙基、丁基、異丁基、戊基、環戊基、己基、環己基、羥基丙基、2-磺基乙基、羧基乙基、氰基乙基甲氧基乙基、乙氧基乙基、丁氧基乙基、三氟甲基、五氣i乙基等。於通式（1)之R7〜，作為齒素原子，可列舉：氟原子、氣原子、溴原子、破原子。作為通式（1)之R7〜’較佳為氫原子、氣原子、或碳數 1〜6之未經取代之烷基。於通式（1)中，陰離子部χ-表示叁_三氟曱基磺醯基曱基化物或雙-三氟曱基磺醯亞胺。本發明之式（1)所表示之有色材料化合物例如可藉由以下方式獲得：將藉由專利文獻（W〇 2009/107734之合成例 19)或非專利文獻（J· Am· Chem. Soc. 1996，118, 7215)所記載之合成法而獲得之前驅物之氣化合物（例如χ-為氣陰離子）’谷解於反應溶劑（例如可列舉水或甲醇、乙醇、異丙醇、丙醇、Ν，Ν-二甲基甲醯胺（以下簡稱為DMF)、Ν_曱基- 155795.doc 201207559 2-°比洛㈣等水溶性極性_，該等㈣可單獨使用或亦可混口使用)中’添加0.5〜3當量左右之對應之鹽或酸，於特定溫度（例如〇〜1 00°C )下措拙_ ;卜撹拌，可容易地合成，並濾取所析出之結晶。本’X明之藍色著色樹脂組合物之總固體成分(係指包含 :色材料化。物、黏合樹脂、硬化劑等之固體成分之總 1以下亦以相同含意使用）中所含之上述式⑴所示之有色材料化合物之含量較佳為質量份，更佳為5〜3〇質量份。於含量多於該範圍之情形時，會發生析出或凝聚之問題，或由於硬化不充分而引起與基板之密接性之下降。於含量較少之情料雖無較大問題，但有無法獲得作為色特性之充分之色純度的傾向。於上述式⑴所示之有色材料化合物於著色樹脂組合物中之溶解性較低之情料’亦可與後述作為任意成分之顏料同樣地使用分散劑進行分散。上述式〇)所示之有色材料化合物可混合使用兩種以上亦可單獨使用，亦可混合其他染料或顏料。由於本發明係關於藍色像素者，故較理想的疋與么知之藍色染料或紫色染料、或者藍色顏料或紫色碩料等混合。 / 本發明中所使用之黏合樹脂於光微影法之設計方面而言，較理想的是可溶於製造彩色濾光片時之顯影處理步驟中所使用之驗性顯影液，進而為形成良好之微細圖案，較理想的是具有與光聚合起始劑、光聚合性單體等之充分之硬化特性者。又’顏料分散樹脂組合物亦必須與光聚合起 155795.doc 201207559 始劑、光聚合性單體、顏料分散液等構成材料之相溶性較佳、’穩定以不發生析出或凝聚等。於喷墨法之情形時，由 :並不特別需要鹼可溶性，故只要選擇與其他有色材料化合物或添加劑之相溶性較佳之樹脂即可。作為點合樹脂，亦可使用公知之樹脂，更佳為以下將列舉之具有-個以上之艘基或經基之乙烯性不飽和單體、或其他可共聚合之具有芳香族烴基或脂肪族烴基之乙稀性不飽和單體等之共聚物較為理想。x，亦可使詩該等之側鍵或末％等具有環氧基者、進而加成有丙烯酸g旨之環氧丙烯酸酯樹脂。該等單體等可為單獨一種亦可組合兩種以上0 作為本發明中可使用之上述含有羧基之不飽和單體之具體例’可列舉：丙婦酸、甲基丙浠酸、丁烯酸、α·氣丙婦乙基丙烯g文、肉桂酸等不飽和單缓酸類；順丁烯二酸、順丁烯二酸酐'反丁烯二酸、衣康酸、衣康酸酐、曱基順丁烯二酸、甲基順丁烯二酸酐、甲基反丁烯二酸等不飽矛一缓酉文（針）類，3元以上之不飽和多元缓酸（肝）類、2_ (甲基）丙烯醯氧基乙基六氫鄰苯二甲酸、2-曱基丙烯醯氧基乙基-2-羥基丙基鄰苯二甲酸酯、2·丙烯醯氧基乙基_2_ 經基乙基鄰苯二曱酸等。該等含有羧基之乙烯性不飽和單體可單獨使用亦可混合使用兩種以上。作為本發明中可使用之上述含有羥基之不飽和單體之具體例，可列舉：（甲基）丙烯酸_2_羥基乙酯、（甲基）丙烯酸· 2-經基丙酯、（甲基）丙烯酸_3_羥基丙酯、（甲基）丙烯酸_4_ 155795.doc 201207559 羥基丁酯、（甲基）丙烯酸-3-羥基丁酯、（甲基）丙烯酸-5-羥基戊酯、（甲基）丙烯酸-4-羥基戊酯、（甲基）丙烯酸-3-羥基戊酯、（甲基）丙烯酸-6-羥基己酯、（曱基）丙烯酸-5-羥基己酯、（曱基）丙烯酸-4-羥基己酯、（曱基）丙烯酸羥基-3-曱基-戊酯、環己烷-1,4-二甲醇-單（甲基）丙烯酸酯、（曱基）丙稀酸-2-(2-經基乙氧基）乙酯、甘油單甲基丙稀酸酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、聚 (乙二醇-丙二醇）單甲基丙烯酸酯等羥基末端聚烷二醇單 (曱基）丙稀酸酯等。該等含有經基之乙婦性不飽和單體可單獨使用，亦可混合使用兩種以上。又，作為上述其他不飽和單體，例如可列舉：苯乙稀、 α-曱基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基曱苯、鄰氣苯乙烯、間氣苯乙浠、對氯苯乙烯、對甲氧基苯乙烯等芳香族乙烯基化合物；（甲基）丙烯酸曱酯、（曱基）丙烯酸乙酯、（甲基）丙烯酸正丙酯甲基）丙烯酸異丙酉曰、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（曱基）丙烯酸第二丁酯、（甲基）丙烯酸第三丁酯、（曱基）丙烯酸_2_ 羥基乙酯、（甲基）丙烯酸苄酯、對異丙苯基苯氧基乙二醇 (甲基）丙烯酸酯、（曱基）丙烯酸_2_羥基_3_笨氧基丙酯、鄰苯基苯酚縮水甘油醚（曱基）丙烯酸酯、鄰苯基苯酚（甲基）丙烯酸酯羥乙基化物、（曱基）丙烯酸苯氧基乙酯等不飽和羧酸酯類；（曱基）丙烯酸環戊酯、（曱基）丙烯酸環己酯、 (曱基）丙烯酸二甲基環己酯、（曱基）丙烯酸降捐基酯、（甲基）丙烯酸降葙基甲酯、（曱基）丙烯酸苯基降葙基酯、（甲 155795.doc -11· 201207559 基）丙稀酸氰基降箱基醋、（甲基）丙稀酸異捐基醋、（甲基）丙稀酸^白基醋、（曱基）丙稀酸堇基醋、（曱基）丙稀酸持基酯、（甲基）丙烯酸金剛烷基酯、（甲基）丙烯酸二甲基金剛烷基酯、曱基丙烯酸三環[5.2.1.02,6]癸-8-基酯、（曱基）丙稀酸二環[5.2.1.02,6]癸-4-曱g旨、（甲基）丙稀酸環癸醋、2_ (甲基）丙烯酿氧基乙基六氫鄰苯二曱酸、（甲基）丙稀酸第三丁基環己醋等脂環骨架類；聚乙二醇單（曱基）丙烯酸醋、聚丙二醇單（曱基）丙浠酸醋、聚（乙二醇-丙二醇）單曱基丙烯酸酯等羥基末端聚烷二醇單（曱基）丙烯酸酯類；曱氧基聚乙二醇單甲基丙稀酸酯、月桂氧基聚乙二醇單（甲基）丙烯酸酯、辛氧基聚乙二醇聚丙二醇單（曱基）丙烯酸 Sa、壬基本氧基聚乙二醇单丙稀酸醋、壬基苯氧基聚丙二醇單丙烯酸酯、烯丙氧基聚乙二醇-聚丙二醇單（曱基）丙稀酸酯專烧基末端聚烧二醇單（曱基）丙烯酸酯類；丙烯酸_2_ 胺基乙酯、甲基丙烯酸-2-胺基乙酯、丙烯酸_2-胺基丙酯、甲基丙烯酸-2-胺基丙酯、丙稀酸_3-胺基丙酯、曱基丙烯酸-3-胺基丙酯等不飽和羧酸胺基烷基酯類；丙烯酸縮水甘油酯、曱基丙烯酸縮水甘油酯、（甲基）丙烯酸_3,4_環氧丁醋、（甲基）丙烯酸（3,4_環氧環己基）甲酯、（曱基）丙烯酸-4-羥基丁酯縮水甘油醚等不飽和羧酸縮水甘油酯類；乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯類；乙烯基甲醚、乙浠基乙醚、烯丙基縮水甘油醚、f基烯丙基縮水甘油醚等不飽和醚類；丙烯腈、曱基丙烯腈、α-氣丙烯腈、二氰乙烯等氰乙烯化合物；丙烯醯 I55795.doc 12 201207559 胺、甲基丙烯醯胺、α-氣丙烯醯胺、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N_(甲基）丙烯酿基鄰苯二甲酿亞胺、N_(2_羥基乙基）丙烯醯胺、N-(2-羥基乙基）甲基丙稀酿胺、順丁烯二醯亞胺等不飽和醯胺或不飽和醯亞胺類；1，3-丁二烯、異戊二烯、氣丁二烯等脂肪族共軛二稀類；聚苯乙烯、聚丙烯酸曱酯、聚曱基丙烯酸曱酯、聚. 丙稀酸正丁酯、聚甲基丙烯酸正丁酯、聚矽酮等在共聚物分子鏈之末端具有單丙烯醯基或單曱基丙烯醯基之巨單體類等。該等其他不飽和單體可單獨使用或混合使用兩種以上。又’於共聚物之側鏈上進而導入有不飽和雙鍵之共聚物亦有用。例如可列舉：對於順丁烯二酸酐與可共聚合之苯乙婦、乙烯基笨酚、丙烯酸、丙烯酸酯、丙烯醯胺等的共聚物之順丁烯二酸酐部，使丙烯酸羥基乙酯等具有醇性羥基的丙烯酸酯或甲基丙烯酸縮水甘油酯等具有環氧基的丙嫦酸醋進行反應而半酯化的化合物；及對於丙烯酸、丙烯酸醋與丙烯酸羥基乙酯等具有醇性羥基之丙烯酸酯的共聚物之經基’使丙烯酸進行反應而成之化合物等。又，亦可使用胺基甲酸酯樹脂或聚醯胺、聚醯亞胺樹脂、聚酯樹脂、市售之 ACA-200M(DAICEL 製造）、〇RGA-3060(大阪有機化學製造）、AX3-BNX02(日本觸媒製造）、UXE-3024 (曰本化藥製造）、UXE-3000(曰本化藥製造）、ZGA-287H (曰本化藥製造）、TCR-1338H(日本化藥製造）、ZXR-1722H(日本化藥製造）、ZFR-1401 H(日本化藥製造）、ZCR- 155795.doc 13 201207559 1642(日本化藥製造）β 於製造本發明中所使用之黏合樹脂（共聚物）之情形時，使用聚合起始劑。作為合成共聚物時所使用之聚合起始劑之具體例，可列舉：α，α，_偶氮雙（異丁腈）、2,2，_偶氮雙（2_ 曱基丁腈）、過氧化辛酸第三丁酯、過氧化二第三丁基、過氧化苯甲醯、過氧化曱基乙基酮等。相對於共聚物之合成所使用之所有單體之合計量’聚合起始劑之使用比例為 0.01〜25質量份，又，於合成共聚物之情形時，較佳為使用下述將說明之有機溶劑，但要使用對於所使用之單官能之單體或聚合起始劑等具有充分之溶解力者。合成共聚物時之反應溫度較佳為50〜120«>c，尤佳為8〇〜1〇〇<>c。又反應時間較佳為1〜60小時，更佳為3〜20小時。共聚物之較佳酸值為10〜300(mgKOH/g)，較佳羥值為 10〜200(mgK〇H/g)。於酸值或羥值為1〇以下之情形時顯影性下降。共聚物之重量平均分子量（Mw)較佳為 2000〜400000，更佳為3000〜100000。於該重量平均分子量為2000以下、或4〇〇〇〇〇以上之情形時，感度及顯影性等下降。於本發明中，上述黏合樹脂可單獨使用或混合使用兩種以上。相對於著色樹脂組合物之總固體成分1 00質量份，本發明令之黏合樹脂之含量通常為0.5〜99質量份，較佳為 5〜50質量份。於該情形時’若黏合樹脂之含量未達〇 5質量份，則有可能鹼顯影性下降、或產生於形成有像素之部分以外之區域中的版汙或殘膜等問題。 I55795.doc 201207559 於自由基聚合之情形時155795.doc 201207559 (R, R6 in the formula () is independently a hydrogen atom, a phenyl group or a benzyl group of at least 6 is a branched alkyl group, or a cyclic alkyl group; R7★ is independently Represents a hydrogen atom, a carbon number of a carbon atom, or a dentate atom; an anion moiety X- represents a volume of a trimethylmethyl thioglycolate or a bis-trifluoromethylsulfonimide; (2) The colored resin composition according to (1), which comprises a copper phthalocyanine pigment; (3) a coloring cured film for a color filter, which is obtained by patterning or using a magical resin composition; (4) A color filter comprising a colored hardening film for a color filter as (3); (5) a liquid crystal display device and an organic EL display, which are mounted with a color filter such as (4) And (6) a solid-state imaging device which is mounted as a color filter of a sentence. [Effects of the Invention] The blue colored resin composition of the present invention contains a specific blue color A compound of a colored material provides a high-quality blue pixel for a color filter excellent in heat resistance. The blue colored resin composition of the present invention contains a binder resin, a solvent, a curing agent, and a specific blue colored material compound, and may optionally contain a coloring material compound such as a pigment or a dye, a surfactant, and a photopolymerization initiator. The various additives such as the thermal polymerization initiator, the polymerization inhibitor, and the ultraviolet absorber are not limited thereto, and the 155795.doc -6 - 201207559 other than the specific colored material compound can be used without particular limitation. In the method of producing a pixel of the colored resin composition of the present invention, a photolithography method and an inkjet method are mainly used, and a photosensitive resin composition excellent in developability by a photopolymerization initiator is used in the former, and light is not necessarily required in the latter. The thermosetting resin composition is used as a polymerization initiator. The specific color material compound used in the present invention is not represented by the above formula (i). In the R! to R6 of the formula (1), the carbon number is 6 The alkyl group may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl 'propyl group, an isopropyl group, a butyl group, and a decyl propyl group (second butyl group). ), isobutyl, pentyl, 1-ethylpropyl, 1 decyl butyl, cyclopentyl, hexyl, decylpentyl, 1-ethylbutyl, cyclohexyl, hydroxypropyl, 2 _ sulfoethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl, etc. in the general formula (1) In the case of R to R6, the phenyl group or the benzyl group may have a substituent. Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group. a pentyl group (C1 to C5) alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., a sulfonic acid group, a sulfonic acid group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a third Butyloxy, hexyloxy, etc. (C1~C6) alkoxy, hydroxyethyl, hydroxypropyl and the like hydroxy (C1~C5) alkyl, methoxyethyl, ethoxyethyl, ethoxypropyl a (C1 to C5) alkoxy (C1 to C5) alkyl group such as a butoxyethyl group, a hydroxyl group (C1 to C5) alkoxy group such as a 2-hydroxyethoxy group, a 2-methoxyethoxy group, 2 alkoxy group (C1~C5) alkoxy group, 2-sulfoethyl group, carboxy group B , Cyanoethyl and the like. 155795.doc 201207559 In the R, R6 to R6 of the formula (1), as at least one of the branched alkyl groups and the cyclic alkyl group, an isopropyl group, a 丨-methyl propyl group (second butyl group) may be mentioned. , ethyl propyl, 1-mercaptobutyl, hydrazine-methylpentyl, i. butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. R broadly R0 of the formula (1) is preferably an unsubstituted alkyl group, a branched alkyl group or a cyclic alkyl group having a hydrogen atom or a carbon number of 丨~6. The alkyl group having 1 to 6 carbon atoms in R7 to R2 of the formula (1) may have a substituent. Preferred examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl 'propyl 'isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a hydroxy group. Base, 2-sulfoethyl, carboxyethyl, cyanoethylmethoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, penta-ethyl iethyl, and the like. R7~ in the general formula (1), examples of the dentate atom include a fluorine atom, a gas atom, a bromine atom, and a broken atom. R7 to '' of the formula (1) is preferably a hydrogen atom, a gas atom, or an unsubstituted alkyl group having 1 to 6 carbon atoms. In the formula (1), the anion moiety χ- represents 叁_trifluorodecylsulfonyl sulfhydryl or bis-trifluorodecylsulfonimide. The colored material compound represented by the formula (1) of the present invention can be obtained, for example, by the following patent document (Synthesis Example 19 of W〇2009/107734) or non-patent literature (J. Am. Chem. Soc. In the synthesis method described in 1996, 118, 7215), a gas compound (for example, ruthenium-gas anion) of the precursor is obtained, and the solution is dissolved in a reaction solvent (for example, water or methanol, ethanol, isopropanol, propanol, Ν, Ν-dimethylformamide (hereinafter abbreviated as DMF), Ν_曱基- 155795.doc 201207559 2-°Bilo (four) and other water-soluble polar _, these (d) can be used alone or in combination In the middle of adding '0.5 to 3 equivalents of the corresponding salt or acid, at a specific temperature (for example, 〇~1 00 ° C), the mixture can be easily synthesized, and the precipitated crystals are collected by filtration. The total solid content of the blue colored resin composition of the present invention is the above-mentioned formula contained in the total content of the solid components of the material, the binder resin, the hardener, and the like, which are also used in the same meaning. The content of the compound of the colored material shown in (1) is preferably a part by mass, more preferably 5 to 3 parts by mass. When the content is more than the above range, precipitation or aggregation may occur, or adhesion to the substrate may be lowered due to insufficient hardening. Although there is no major problem in the case of a small amount of content, there is a tendency to obtain sufficient color purity as a color characteristic. In the case where the solubility of the colored material compound represented by the above formula (1) in the colored resin composition is low, the dispersion can be carried out using a dispersant in the same manner as the pigment as an optional component described later. The colored material compound represented by the above formula (〇) may be used singly or in combination of two or more kinds, or may be mixed with other dyes or pigments. Since the present invention relates to a blue pixel, it is preferable to mix it with a blue dye or a violet dye, or a blue pigment or a purple powder. / In the design of the photolithography method, the adhesive resin used in the present invention is preferably an insoluble developer which is soluble in the development processing step in the production of the color filter, and is formed well. The fine pattern preferably has sufficient curing properties such as a photopolymerization initiator and a photopolymerizable monomer. Further, the pigment-dispersed resin composition must have good compatibility with a constituent material such as photopolymerization, a photopolymerizable monomer, and a pigment dispersion liquid, and is stable so as not to precipitate or aggregate. In the case of the ink jet method, since alkali solubility is not particularly required, it is only necessary to select a resin which is more compatible with other colored material compounds or additives. As the point-and-match resin, a known resin may be used, and more preferably an ethylenically unsaturated monomer having more than one or a base group or a base group as exemplified below, or another copolymerizable aromatic hydrocarbon group or aliphatic group A copolymer of a hydrocarbon group such as an ethylenically unsaturated monomer is preferred. Further, it is also possible to add an epoxy acrylate resin having an epoxy group to a side bond or a terminal group having an epoxy group. These monomers and the like may be used singly or in combination of two or more. Specific examples of the above-mentioned carboxyl group-containing unsaturated monomer which can be used in the present invention include: propylene glycol, methyl propyl phthalate, butylene Acid, α·g-propyl ethyl propylene g-type, cinnamic acid and other unsaturated mono-acids; maleic acid, maleic anhydride 'fumaric acid, itaconic acid, itaconic anhydride, sulfhydryl Maleic acid, methyl maleic anhydride, methyl fumaric acid, etc., non-sufficient spears (needle), more than 3 yuan of unsaturated polybasic acid (liver), 2_ ( Methyl)propenyloxyethylhexahydrophthalic acid, 2-mercaptopropenyloxyethyl-2-hydroxypropyl phthalate, 2·propenyloxyethyl 2_2 Base ethyl phthalic acid and the like. These carboxyl group-containing ethylenically unsaturated monomers may be used singly or in combination of two or more. Specific examples of the above-mentioned hydroxyl group-containing unsaturated monomer which can be used in the present invention include 2-hydroxyethyl (meth)acrylate, 2-methylpropyl methacrylate, and (methyl) Acrylic acid_3_hydroxypropyl ester, (meth)acrylic acid_4_ 155795.doc 201207559 hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, (A) 4-hydroxypentyl acrylate, 3-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 5-hydroxyhexyl (decyl) acrylate, (fluorenyl) 4-hydroxyhexyl acrylate, hydroxy-3-indolyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate, (mercapto) acrylic acid - 2-(2-P-ethoxyethyl)ethyl ester, glycerol monomethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol) - propylene glycol) a hydroxyl terminated polyalkylene glycol mono(indenyl) acrylate such as monomethacrylate. These ethylenically unsaturated monomers containing a trans-group may be used singly or in combination of two or more. Further, examples of the other unsaturated monomer include styrene, α-mercaptostyrene, o-vinyltoluene, m-vinyltoluene, p-vinylfluorene, styrene, and m-phenylene. An aromatic vinyl compound such as fluorene, p-chlorostyrene or p-methoxystyrene; decyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate methyl acrylate酉曰, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylate 2 _ hydroxy Ester, benzyl (meth) acrylate, p-cumyl phenoxy ethylene glycol (meth) acrylate, (mercapto) acrylate 2 - hydroxy - 3 - oxypropyl propyl ester, o-phenyl phenol Non-saturated carboxylic acid esters such as glycidyl ether (mercapto) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate, phenoxyethyl acrylate; (fluorenyl) acrylate Ester, cyclohexyl (meth) acrylate, dimethylcyclohexyl (mercapto) acrylate, Hydrazinyl methacrylate, methyl (meth) acrylate methyl thiol, (mercapto) phenyl decyl acrylate, (A 155795.doc -11· 201207559 base) acrylic acid cyano lowering box Base vinegar, (meth)acrylic acid isobutyl vinegar, (meth) acrylic acid white vinegar, (mercapto) acrylic acid sulfonic acid, (mercapto) acrylic acid group, ( Adamantyl methyl methacrylate, dimethyl hydroxyalkyl (meth) acrylate, tricyclo [5.0.1.02,6] fluoren-8-yl acrylate, (fluorenyl) acrylic acid bicyclic [5.2.1.02,6]癸-4-曱g, (meth)acrylic acid cyclic vinegar, 2_(meth)acrylic oxyethylhexahydrophthalic acid, (methyl) propyl An alicyclic skeleton such as dibutylcyclohexanacetic acid; polyethylene glycol mono(indenyl)acrylic acid vinegar, polypropylene glycol mono(indenyl)propionic acid vinegar, poly(ethylene glycol-propylene glycol) monodecyl group Hydroxyl-terminated polyalkylene glycol mono(mercapto) acrylates such as acrylate; decyloxy polyethylene glycol monomethyl acrylate, lauryl oxy polyethylene glycol mono (meth) acrylate, octyloxy Polyethylene glycol polypropylene Mono (indenyl)acrylic acid Sa, hydrazine basic oxy polyethylene glycol monoacrylic acid vinegar, mercaptophenoxy polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol mono(decyl)propyl Dilute ester-specific polyalkylene diol mono(indenyl) acrylate; acrylic acid 2-_2 aminoethyl ester, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, methyl Aminoalkyl esters of unsaturated carboxylic acids such as 2-aminopropyl acrylate, -3-3-aminopropyl acrylate, 3-aminopropyl methacrylate, glycidyl acrylate, methacrylic acid Glycidyl ester, (meth)acrylic acid_3,4_epoxybutyl vinegar, (meth)acrylic acid (3,4-epoxycyclohexyl) methyl ester, (mercapto)acrylic acid-4-hydroxybutyl ester glycidol An unsaturated carboxylic acid glycidyl ester such as ether; a vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; vinyl methyl ether, ethyl ethyl ether, allyl shrinkage Unsaturated ethers such as glyceryl ether and f-allyl glycidyl ether; cyanoethylene such as acrylonitrile, mercapto acrylonitrile, α-gas acrylonitrile, and dicyanoethylene Acrylhydrazine 55I55795.doc 12 201207559 Amine, methacrylamide, α-aluminum acrylamide, N-phenyl maleimide, N-cyclohexyl maleimide, N_ (Methyl) propylene-based phthalic acid, N-(2-hydroxyethyl) acrylamide, N-(2-hydroxyethyl)methyl propylene amide, maleimide Isounsaturated decylamine or unsaturated quinone imines; aliphatic conjugated diasternesides such as 1,3-butadiene, isoprene, and gas butadiene; polystyrene, polydecyl acrylate, polyfluorene A macromonomer having a monoacrylonitrile group or a monomercaptopropenyl group at the end of the copolymer molecular chain, such as decyl acrylate, polybutyl acrylate, n-butyl methacrylate, polyfluorenone or the like Wait. These other unsaturated monomers may be used singly or in combination of two or more. Further, a copolymer in which an unsaturated double bond is further introduced into a side chain of the copolymer is also useful. For example, a maleic anhydride moiety of a copolymer of maleic anhydride and a copolymerizable styrene, vinyl phenol, acrylic acid, acrylate, acrylamide or the like may be used, and hydroxyethyl acrylate or the like may be used. a compound which is reacted and half-esterified by an acrylate having an alcoholic hydroxyl group or a glycidyl methacrylate such as glycidyl methacrylate; and an alcoholic hydroxyl group for acrylic acid, acrylic acid vinegar and hydroxyethyl acrylate A compound obtained by reacting acrylic acid with a base of an acrylate copolymer. Further, a urethane resin, a polyamide, a polyimide resin, a polyester resin, a commercially available ACA-200M (manufactured by DAICEL), a 〇RGA-3060 (manufactured by Osaka Organic Chemicals), or AX3- may also be used. BNX02 (manufactured by Nippon Shokubai), UXE-3024 (manufactured by Sakamoto Chemical Co., Ltd.), UXE-3000 (manufactured by Sakamoto Chemical Co., Ltd.), ZGA-287H (manufactured by Sakamoto Chemical Co., Ltd.), TCR-1338H (manufactured by Nippon Chemical Co., Ltd.) , ZXR-1722H (manufactured by Nippon Kayaku Co., Ltd.), ZFR-1401 H (manufactured by Nippon Kayaku Co., Ltd.), ZCR-155795.doc 13 201207559 1642 (manufactured by Nippon Kayaku Co., Ltd.) β Adhesive resin (copolymer) used in the production of the present invention In the case of a), a polymerization initiator is used. Specific examples of the polymerization initiator used in the synthesis of the copolymer include α,α,_azobis(isobutyronitrile), 2,2,-azobis(2-decylbutyronitrile), and Oxidation of butyl octanoate, dibutyl butyl peroxide, benzammonium peroxide, decyl ethyl ketone peroxide, and the like. The total amount of all the monomers used in the synthesis of the copolymer 'the polymerization initiator is 0.01 to 25 parts by mass. Further, in the case of synthesizing the copolymer, it is preferred to use the organic matter described below. A solvent, but a sufficient solvency for a monofunctional monomer or a polymerization initiator to be used. The reaction temperature at the time of synthesizing the copolymer is preferably from 50 to 120 «>c, particularly preferably from 8 Å to 1 Å <> Further, the reaction time is preferably from 1 to 60 hours, more preferably from 3 to 20 hours. The copolymer preferably has an acid value of 10 to 300 (mgKOH/g), preferably a hydroxyl value of 10 to 200 (mgK〇H/g). The developability is lowered when the acid value or the hydroxyl value is 1 Torr or less. The weight average molecular weight (Mw) of the copolymer is preferably from 2,000 to 400,000, more preferably from 3,000 to 100,000. When the weight average molecular weight is 2,000 or less or 4 Å or more, the sensitivity and developability are lowered. In the present invention, the above-mentioned binder resin may be used alone or in combination of two or more. The content of the binder resin in the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition. In this case, if the content of the binder resin is less than 5 parts by mass, there is a possibility that the alkali developability is lowered or a problem such as a segregation or a residual film in a region other than the portion in which the pixel is formed is caused. I55795.doc 201207559 In the case of free radical polymerization

基丙酿、酿、（曱基）丙烯酸-2-乙基己酯、作為本發明中所使用之硬化劑，可列舉光聚合單體，於離子硬化脂’於其他情形時可列舉三聚氰磨、（甲基）丙稀酸-2-經乙二醇二（甲基）丙烯酸醋、二乙二醇二（甲基）丙稀酸醋、三乙二醇（曱基）丙稀酸酯、四乙二醇（甲基）丙烯酸醋、三羥甲基丙烷三（曱基）丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季戊四醇三（曱基）丙烯酸酯、季戊四醇四（曱基）丙烯酸酯、二季戊四醇六 (甲基）丙烯酸酯、甘油（曱基）丙烯酸酯、雙酚A型環氧二 (曱基）丙烯酸酯、雙酚F型環氧二（曱基）丙烯酸酯、雙酚苐型％氧一（曱基）丙稀酸酯、乙氧化三經曱基丙院三（甲基）丙烯酸酯、丙氧化三羥曱基丙烷三（甲基）丙烯酸酯、乙氧化甘油二（甲基）丙稀酸酯、乙氧化異三聚氰酸三（甲基）丙烯酸酯、二（三羥甲基丙烷）四（甲基）丙烯酸酯、乙氧化季戊四醇四（甲基）丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基）苯基]苐、Kayarad RP-1040(日本化藥製造）、Kayarad DPCA-30(曰本化藥製造）、UA-33H(新中村化學製造）、 UA-53H(新中村化學製造）、M-8060(東亞合成製造）；作為硫醇系聚合單體之TEMPIC(堺化學製造）、ΤΜΜΡ(堺化學製造）、ΡΕΜΡ(堺化學製造）、DPMP(堺化學製造）；作為環氧樹脂之曰本化藥產品之NC-6000、NC-3000、EOCN-1020、XD-1000、ΕΡΡΝ-501Η、BREN-S、NC-7300L， DAICEL 化學產品之 Celloxide 2021P、EHPE3150、 155795.doc •15· 201207559Examples of the curing agent used in the present invention include a photopolymerizable monomer, and in other cases, melamine is exemplified. Grinding, (meth)acrylic acid-2-ethyl glycol di(meth)acrylate vinegar, diethylene glycol di(meth)acrylic acid vinegar, triethylene glycol (mercapto) acrylate , tetraethylene glycol (meth) acrylate, trimethylolpropane tri(decyl) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tris(decyl) acrylate, pentaerythritol tetrakis(mercapto) acrylate Ester, dipentaerythritol hexa(meth) acrylate, glycerol (mercapto) acrylate, bisphenol A epoxy bis(indenyl) acrylate, bisphenol F epoxy bis(indenyl) acrylate, bisphenol苐-type % oxo-(mercapto) acrylate, ethoxylated tri- sulfhydryl-propyl tris(meth) acrylate, propoxylated trihydrocarbyl propane tri(meth) acrylate, ethoxylated glycerol Methyl) acrylate, ethoxylated isocyanuric acid tris (meth) acrylate, two ( Hydroxymethylpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, Kayarad RP -1040 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-30 (manufactured by Sakamoto Chemical Co., Ltd.), UA-33H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-53H (manufactured by Shin-Nakamura Chemical Co., Ltd.), M-8060 (manufactured by Toyo Chemical Co., Ltd.); TEMPIC (manufactured by Sigma Chemical Co., Ltd.), ΤΜΜΡ (堺堺堺堺 ΡΕΜΡ 、、、 DP DP DP DP DP DP DP DP ; ; ; ; ; ; ; ; NC NC NC NC NC NC NC NC NC NC NC NC NC NC , NC-3000, EOCN-1020, XD-1000, ΕΡΡΝ-501Η, BREN-S, NC-7300L, DAICEL Chemical Products Celloxide 2021P, EHPE3150, 155795.doc •15· 201207559

Cyclomer M100、Epolead PB3600 ’日本環氧樹脂產品之Cyclomer M100, Epolead PB3600 'Japan Epoxy Resin Products

Epikote 828、Epikote YX8000、Epikote γχ4〇〇〇，Sila-Ace S510(ChiSS〇)，TEPIC(日產化學工業）等；作為三聚氰胺硬化劑之羥曱基化三聚氰胺或Mw-30(三和化學）等。該等可單獨使用或混合使用兩種以上。相對於著色樹脂組合物之總固體成分100質量份，該等之含量為i〜8〇質量份，較佳為5〜30質量份。本發明之樹脂著色組合物中可併用之色素較佳為具有適合於彩色滤光片之分光特性者，可自染料、有機顏料、益機顏料之中適當選擇，視需要可單獨使用，或亦可^使用兩種以上。相對於著色樹脂組合物之總固體成分刚質量份，該等之含量為0〜6〇質量份，較佳為5〜30質量份。以下示出該等各種顏料及染料。 ^本發明中可併用之有機_，並無_ 可列舉：葱酿系、酞菁系、三苯 ”如系、心丫㈣系、偶氣整合物系、偶Μ系異本弁/米錢異t朵琳酮系、皮葱酮系、陰丹士 ^琳系、蒽缔⑽、…系，、_系::：:：靛藍系、々并系、喹,η酮系二苯并：利用各沈澱劑使酸性染料、驗南系專顏料；成之色澱顏料、染附色澱顏料等更具體二料等不溶而引例如可列舉：顏料藍丨、1:2、9、Μ、言，以染料索旧、15:4、15:6、16、17:19:二:二，、 35、36、56、56:1、60、6l、6l. 28、29、33、 1 62 ' 63 '66 >67， I55795.doc 201207559 68、71、72、73、74、7 2^2:2.3.3-1.33 , 78、79，顏料紫 ii:!、夂1、3:3、5、5:1、14 25、27、29、31、32 5、16、19、23、 32、37、39、42、44、4 料紫 3、4、27、39等 47、49、50，顏寺。尤其是顏料齄於色相、耐性等良好故更佳。 5.6、顏料紫23由作為本發明中可併用之無機顏料可列舉：複合金屬氧化物顏料—…、特別限制，例如主馮乳化物顏科、碳黑、里氧化鈦、硫酸鋇、#ώ ^ , …色低彳貝氧化鈦、藍、氧化絡、録白、m丹n载丹群青、鐵敍、铉呰. I化辞、錄黃、鎘紅、化物# ' ^、硫酸鋇、碳酸料金屬氧化物、金屬β 化物、硫酸鹽、金屬氫氧化物、金屬碳酸越等。金屬‘ 酸性染萘酚染本發明中可併用之染料並無特別限制，可列舉料 '鹼性染料、言搵迅姐 _ 卞η直接杂枓、硫化染料、甕染料、料、反應染料、分散染料等。並為可溶於有機溶劑 11 ’旦即便為不溶於有機溶劑之染料，亦可藉由製分散罈而適當地使用。關於上述中不溶於有機溶劑之染料，作為廣為人知之配方，例如於酸性染料或鹼性染料之情形時已知有：使有機胺化合物(例如正丙胺、乙基己基丙酸胺等)反應而改質成胺鹽染料；或使該有機胺化合物與其祕基反應而改質成具有磺酿胺基之染料等。該等經胺改質之染料亦可於本發明之著色樹脂組合物令使用。作為其具體之染料，以染料索引例如可列舉··溶劑藍2、3、4、5、6、23、35、％、 37 、 38 、 43 、 48 、 58 、 59 、 67 、 70 、 78 、 98 ' 1〇2 、 1〇4 ， 155795.doc •17- 201207559 鹼性藍7，酸性藍8〇、83、9〇 ,作為紫色染料之溶劑紫8、 9，紫4、5、14，鹼性紫1〇等。作為光微影法所使用之本發明之著色樹脂組合物中所添加的光聚合起始劑，較佳為對自通常用作曝光光源之超高壓水銀燈所射出之紫外線具有充分感度者，可列舉自由基聚合性之光自由基起始劑、離子硬化性之光酸產生劑或光鹼產生劑等。於光聚合之情形時，可組合使用以更少之曝光旎量使硬化進行之被稱為增感劑的聚合促進劑之成分。可使用之光聚合起始劑並無特別限制’作為具體例可列舉：二苯基乙二酮、安息香醚、安息香丁醚、安息香丙醚、一苯甲酮、3，3’-二甲基-4-曱氧基二苯甲酮、苯曱醯基笨曱酸、笨甲醯基苯甲酸之酯化物、4_苯甲醯基_4,_曱基二苯硫醚、苯偶醯二甲基縮酮、2_ 丁氧基乙基_4_甲基胺基苯甲酸酯、氣-9-氧硫咄p星、甲基_9-氧硫咄p星、乙基_9_氧硫咄嗤、異丙基-9-氧硫咄唑、二甲基_9_氧硫星、二乙基-9-氧硫p山p星、二異丙基氧硫p山p星、苯曱酸二曱基胺基曱酯、1-(4-十二烷基苯基）_2_羥基>2-甲基丙烷酮、^ 經基環己基笨基酮、2-經基-2-曱基_丨_苯基丙烧_丨_酮、卜 (4-異丙基苯基）-2-羥基-2-甲基丙烷_丨_酮、苯甲醯曱酸甲酯、2-甲基-1-(4-甲硫基苯基）_2_味啉基丙烷_丨_酮、2苄基-2_二曱基胺基咪琳基苯基）-丁酿I -1、2,4-雙（三氯甲基）-6-(4-甲氧基本基）-1，3,5-均三π井、2,4,6 -三（三氣甲基）-1，3,5-均三畊、2,4-雙（三溴甲基）·6_(4·曱氧基苯基）_ 1，3,5-均三畊、2,4,6-二（三溴曱基）_13 5均三畊、2 4雙 155795.doc 201207559 (三氣甲基）-6-(l，3-苯并二氧戊環-5-基）-1,3,5-均三畊、二苯甲酮、苯甲醯基苯曱酸、1-(4-苯基硫基苯基）丁烷-1，2-二酮-2-肟-Ο-苯甲酸酯、1-(4-曱基硫基苯基）丁烷-1，2-二酮-2-肟-0-乙酸酯、1-(4-甲基硫基苯基）丁烷-1-酮肟-Ο乙酸酯、4,4’-雙（二乙基胺基）二苯甲酮、對二甲胺基苯曱酸異戊酯、對二曱胺基苯甲酸乙酯、2,2’-雙（鄰氯苯基）-4,4'，5,5'-四苯基-1，2'-聯咪唑、重氮萘醌系起始劑，以及市售之 Kayacure DMBI、Kayacure BDMK、Kayacure BP-100 ' Kayacure BMBI ' Kayacure DETX-S ' Kayacure EPA(均為日本化藥製造)，Darocure 1173 ' Darocure 1116(均為 Merck Japan製造），Irgacure 907、Irgacure 369 (BASF JAPAN製造），Irgacure 379EG(BASF JAPAN製造）、 Irgacure OXE-01(BASF JAPAN製造）、Irgacure OXE-02 (BASF JAPAN 製造）、Irgacure PAG103(BASF JAPAN 製造），TME-Triazine(三和化學製造），聯咪唑（黑金化成製造），STR-110、STR-1(均為 Respe Chemical 製造）等。於噴墨法等中所使用之熱硬化性樹脂組合物之情形時，通常使用熱聚合起始劑，但視需要亦可併用光聚合起始劑。作為熱聚合起始劑，有偶氮系化合物或有機過氧化物系者，例如可列舉：2,2’-偶氮雙異丁腈、2,2·-偶氮雙（2,4-二甲基戊腈）、2,2'-偶氮雙（2-甲基丁腈）、過氧化二第三丁基、過氧化二苯甲醯、過氧化新癸酸異丙苯酯等。該等聚合起始劑視需要可單獨使用，或亦可組合使用兩種以上。於將著色樹脂組合物之總固體成分設為100質量 155795.doc -19- 201207559 份時，該等之含量為0.5〜50質量份，較佳為卜乃質量份。本發明t所用之有機溶劑可使用對於作為著色樹脂組合物之構成成分之黏合樹脂、光聚合性單體、光聚合起始劑等具有充分之溶解力，且對於黏合樹脂之合成十所使用之單官能之單體或聚合起始劑等亦具有充分之溶解力者。又，於製作顏料分散體時，亦可使用能確保分散穩定性者。關於本發明中所用之有機溶劑，只要可使用則並無特別限制，作為具體例可列舉：苯、曱苯、二甲苯等苯類；甲基溶纖劑、乙基溶纖劑、丁基溶纖劑等溶纖劑類；甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯等溶纖劑乙酸酯類；丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丁醚乙酸酯等丙二醇單烷基醚乙酸酯類，·甲氧基丙酸曱酯、曱氧基丙酸乙酯、乙氧基丙酸甲酯 '乙氧基丙酸乙酯等丙酸酯類；乳酸曱酯、乳酸乙酯、乳酸丁酯等乳酸酯類；二乙二醇單曱醚、二乙二醇單乙喊等二乙二醇類；乙酸曱酯、乙酸乙酯、乙酸丁酯等乙酸酯類；二曱醚'二乙醚、四氫呋喃、二嘮烷等醚類；丙醇、甲基乙基酮、曱基丁基酮、環己酮等酮類；曱醇、乙醇、丁醇、異丙醇、苄醇等醇類。該等有機溶劑可單獨使用或組合使用兩種以上。又，相對於著色樹脂組合物之總固體成分100質量份，有機溶劑之使用量較佳為40〜10000質量份，更佳為1〇〇〜1〇〇〇質量份。 155795.doc -20· 201207559 本發明之著色樹脂組合物係藉由分散攪拌機或均質攪拌機等將上述黏合樹脂、硬化劑、光聚合起始劑、特定之有色材料化合物、有機溶劑等混合攪拌而製造。X，視需要亦可添加其他顏料或染料，但於顏料或溶解性較低之染料之it形時’使用適當之分散劑藉由塗料振盪器等分散機獲得分散體，並添加至著色樹脂組合物中進行混合。本發明之著色樹脂組合物中視需要可進—步添加各種添加劑’例如填充劑、界面活性劑、熱聚合防止劑、密接促進劑、抗氧化劑、紫外線吸收劑、抗凝聚劑等。又，本發明之著色樹脂組合物亦可於其製備後利用過濾器等進㈣濾以去除異物等。其次’對由本發明之著色樹脂組合物製備其硬化物之方法進行說明。首先’藉由旋轉塗佈法、輕塗佈法、狹縫式旋轉塗佈法，佈法、棒塗佈法等，以膜厚成為約 0.1〜20 _、更佳為0.5〜5㈣之方式將本發明之著色樹脂組合物塗佈於玻璃基板1基板等基板上，視需要在減壓腔室内以乾燥條件為溫度23〜15〇。匸下且時間1〜分鐘 '更佳為溫度6〇〜12(rc下且時fsn〜10分鐘而進行㈣乾燥，進而利用加熱板或潔淨烘箱等進行預烘烤處理而製膜。其次’藉由通常之光微影法通過特定之光㈣案照射放射線 (例如電子束、紫外線，較佳為紫外線），㈣界面活性劑水溶液、純水溶液、或界面活性劑與㈣之混合水溶液進行顯影。顯影方式有浸潰法、喷霧法、喷淋法、搜摔法、超音波顯影法等，亦可將該等任意組合。藉由顯影而 155795.doc 21 201207559 示未…、射。p分，以水沖洗後，進行後烘烤處理，處理例如係以溫度130〜30吖下且時間卜⑵分鐘、更佳為溫度 150 250 C下且時間卜3()分鐘之條件進行獲得包含本發明之著色硬化膜之像素。上述中’作為界面活性劑可使用聚氧乙烯烷基醚、聚氧伸烧基貌基ϋ等。又’作為驗劑，可使用碳酸納、碳酸鉀、虱氧化鈉、氫氧化鉀、二乙醇胺、氫氧化四甲基銨等於本發明中，車交佳為使用包含驗劑與界面活性劑兩者之水溶液。顯影係於通常10〜50。。、較佳為20〜4(rc之處理溫度下’以通常30〜6〇〇秒、較佳為3〇〜12〇秒之處理行。本發明之著色樹脂組合物之硬化物作為適合於液晶顯示裝置、有機EL顯示器、或數位相機等所使用之固體攝像元件等的彩色遽光片而有帛，該彩色濾光片具有包含如上述般所製備之本發明之著色樹脂組合物之硬化物的經圖案化的藍色像素。本發明之液晶顯示裝置例如係以依序積層㈣光源、偏光膜、顯示電極、液晶、配向膜、共通電極、本發明之彩色濾、光片、偏光膜等之構造而製作。又，有機職示器係於多層之有機發光元件之上面或下據光片而製作。關於固體攝像元件面之任一面上形成彩色 ’例如係藉由在設有轉明之彩色濾光片移電極、光二極體之矽晶圓上設置本發層’繼而積層微透鏡而製作。 [實施例] 155795.doc •22- 201207559 以下藉由實施例更詳細地說明本發明，但本發明並不限定於該等實施例。再者，實施例中，Γ %」只要無特別指定則係指「質量％」。又，對於分光特性，藉由分光光度計「島津製作所UV-3 1 50」測定分光透射率，計算出χγζ 表色系統中之色度，評價著色體之耐性。合成例1 (關於化合物2-Α之合成） [化2]Epikote 828, Epikote YX8000, Epikote γχ4〇〇〇, Sila-Ace S510 (ChiSS〇), TEPIC (Nissan Chemical Industry), etc.; hydroxylated melamine or Mw-30 (Sanwa Chemical) as a melamine hardener. These may be used alone or in combination of two or more. The content is from i to 8 parts by mass, preferably from 5 to 30 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition. The pigment which can be used in combination in the resin coloring composition of the present invention preferably has a spectroscopic property suitable for a color filter, and can be appropriately selected from dyes, organic pigments, and Yiji pigments, and can be used alone or as needed. You can use two or more types. The content is from 0 to 6 parts by mass, preferably from 5 to 30 parts by mass, based on the total solid content of the colored resin composition. These various pigments and dyes are shown below. ^ Organics in the present invention can be used together, and there is no _ can be enumerated: onion brewing system, phthalocyanine system, triphenyl" such as system, heart 丫 (four) system, even gas integrated system, even 异异弁米 / 米钱异tDolinone, lycopene, yin yin ^ lin, 蒽 ( (10), ..., _ series::::: indigo, 々系, quinine, η ketone dibenzo: use Each precipitating agent makes an acid dye, a virgin pigment, a lake pigment, a dyed lake pigment, and the like, and is insoluble, and the like, for example, a pigment blue enamel, 1:2, 9, Μ, 言, with dyes old, 15:4, 15:6, 16, 17:19: two: two, 35, 36, 56, 56:1, 60, 6l, 6l. 28, 29, 33, 1 62 ' 63 '66 >67, I55795.doc 201207559 68,71,72,73,74,7 2^2:2.3.3-1.33, 78,79, Pigment Violet ii:!, 夂1, 3:3, 5 , 5:1, 14 25, 27, 29, 31, 32 5, 16, 19, 23, 32, 37, 39, 42, 44, 4, material purple 3, 4, 27, 39, etc. 47, 49, 50, Yan Temple, especially the pigment is better in hue, tolerance, etc. 5.6. Pigment Violet 23 is exemplified by inorganic pigments which can be used in combination in the present invention: Metal oxide pigments - ..., particularly limited, for example, main von emulsion Yanke, carbon black, titanium oxide, barium sulfate, #ώ ^, ... color low mussel titanium oxide, blue, oxide, white, m Dan n contains Dan Qunqing, Tiexu, 铉呰. I Hua Ci, recorded yellow, cadmium red, compound # ' ^, barium sulfate, carbonic acid metal oxides, metal β compounds, sulfates, metal hydroxides, metal carbonates The more the metal' acid dyed naphthol dyes can be used in the present invention, and the dyes are not particularly limited, and the materials can be cited as 'basic dyes, 搵搵姐 _ 卞直接直接 direct 枓, sulphur dyes, oxime dyes, materials, reactions A dye, a disperse dye, etc., which is a dye which is soluble in an organic solvent, and which is insoluble in an organic solvent, can be suitably used by dispersing an altar. The above-mentioned dye which is insoluble in an organic solvent is widely known. Formulations, for example, in the case of acid dyes or basic dyes, are known to react an organic amine compound (for example, n-propylamine, ethylhexylpropionate, etc.) to form an amine salt dye; or to make the organic amine compound Secret reaction It is modified into a dye having a sulfonamide group, etc. These amine-modified dyes can also be used in the colored resin composition of the present invention. As a specific dye thereof, for example, a dye index can be cited. , 3, 4, 5, 6, 23, 35, %, 37, 38, 43, 48, 58, 59, 67, 70, 78, 98 '1〇2, 1〇4, 155795.doc •17- 201207559 Basic blue 7, acid blue 8 〇, 83, 9 〇, as a purple dye solvent purple 8, 9, purple 4, 5, 14, alkaline purple 1 〇 and so on. The photopolymerization initiator added to the colored resin composition of the present invention used in the photolithography method is preferably one which is sufficiently sensitive to ultraviolet rays emitted from an ultrahigh pressure mercury lamp which is generally used as an exposure light source. A radically polymerizable photoradical initiator, an ionic hardening photoacid generator or a photobase generator. In the case of photopolymerization, a component of a polymerization accelerator called a sensitizer which is hardened by less exposure to light can be used in combination. The photopolymerization initiator which can be used is not particularly limited. Specific examples thereof include diphenylethylenedione, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, and 3,3'-dimethyl group. -4-decyloxybenzophenone, benzoyl alumic acid, esterified product of benzoyl benzoic acid, 4-benzylidene sulfonyl-4, fluorenyl diphenyl sulfide, benzoin Methyl ketal, 2-butoxyethyl 4-methylamino benzoate, gas-9-oxopurine p-star, methyl-9-oxathiop-pin, ethyl_9_oxygen Thiopurine, isopropyl-9-oxothioxazole, dimethyl-9-oxythione, diethyl-9-oxosulfonate p-star, diisopropyloxysulf-pyrene p-star, benzene Didecylamino decyl phthalate, 1-(4-dodecylphenyl)_2-hydroxy> 2-methylpropanone, Cyclohexyl phenyl ketone, 2-yl-2-yl曱基_丨_Phenylpropanone _丨-ketone, Bu (4-isopropylphenyl)-2-hydroxy-2-methylpropane 丨 ketone, methyl benzoate, 2-A -1 -4-methylthiophenyl) 2 - benzoylpropane oxime ketone, 2 benzyl-2 -didecylamine imilinyl phenyl) - butyl I - 1, 2, 4-bis(trichloromethyl)-6-(4-methoxybenyl)-1,3,5 -All three π wells, 2,4,6-tris(tri-gas methyl)-1,3,5-all three tillage, 2,4-bis(tribromomethyl)·6_(4·decyloxybenzene Base)_1,3,5-all three tillage, 2,4,6-di(tribromoindolyl)_13 5 three tillage, 2 4 double 155795.doc 201207559 (three gas methyl)-6-(l , 3-benzodioxolan-5-yl)-1,3,5-all three tillage, benzophenone, benzhydryl benzoic acid, 1-(4-phenylthiophenyl) Butane-1,2-dione-2-indole-indole-benzoate, 1-(4-mercaptothiophenyl)butane-1,2-dione-2-indole-0-B Acid ester, 1-(4-methylthiophenyl)butan-1-one oxime-indole acetate, 4,4'-bis(diethylamino)benzophenone, p-dimethylamine Isoamyl phenyl phthalate, ethyl p-nonylaminobenzoate, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, diazonaphthoquinone initiator, and commercially available Kayacure DMBI, Kayacure BDMK, Kayacure BP-100 'Kayacure BMBI 'Kayacure DETX-S 'Kayacure EPA (all manufactured by Nippon Kayaku), Darocure 1173 ' Darocure 1116 (all manufactured by Merck Japan), Irgacure 907, Irgacure 369 (manufactured by BASF JAPAN), Irgacure 379EG (BAS F JAPAN manufacturing), Irgacure OXE-01 (manufactured by BASF JAPAN), Irgacure OXE-02 (manufactured by BASF JAPAN), Irgacure PAG103 (manufactured by BASF JAPAN), TME-Triazine (manufactured by Sanwa Chemical Co., Ltd.), biimidazole (manufactured by Heijin Chemical Co., Ltd.) , STR-110, STR-1 (all manufactured by Respe Chemical), and the like. In the case of a thermosetting resin composition used in an inkjet method or the like, a thermal polymerization initiator is usually used, but a photopolymerization initiator may be used in combination as needed. Examples of the thermal polymerization initiator include an azo compound or an organic peroxide. Examples thereof include 2,2'-azobisisobutyronitrile and 2,2·-azobis (2,4-di). Methyl valeronitrile), 2,2'-azobis(2-methylbutyronitrile), ditributyl peroxide, dibenzoyl peroxide, cumene peroxynonanoate, and the like. These polymerization initiators may be used singly or in combination of two or more kinds as needed. When the total solid content of the colored resin composition is 100 mass 155795.doc -19 - 201207559 parts, the content is 0.5 to 50 parts by mass, preferably iv. The organic solvent used in the present invention can have sufficient dissolving power for a binder resin, a photopolymerizable monomer, a photopolymerization initiator or the like which is a constituent component of the colored resin composition, and is used for the synthesis of the binder resin. A monofunctional monomer or a polymerization initiator or the like also has sufficient solvency. Further, in the case of producing a pigment dispersion, those which ensure dispersion stability can also be used. The organic solvent used in the present invention is not particularly limited as long as it can be used, and specific examples thereof include benzenes such as benzene, toluene, and xylene; methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Such cellosolve; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, etc. cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acid esters, propylene glycol monobutyl ether acetate, methoxy methoxypropionate, ethyl methoxy propionate, methyl ethoxy propionate ethoxypropionic acid Propionates such as ethyl ester; lactic acid esters such as lactic acid lactide, ethyl lactate, and butyl lactate; diethylene glycol such as diethylene glycol monoterpene ether and diethylene glycol monoethyl phthalate; An acetate such as ethyl acetate or butyl acetate; an ether such as dioxyl ether, diethyl ether, tetrahydrofuran or dioxane; a ketone such as propanol, methyl ethyl ketone, mercaptobutyl ketone or cyclohexanone; An alcohol such as decyl alcohol, ethanol, butanol, isopropanol or benzyl alcohol. These organic solvents may be used alone or in combination of two or more. Further, the organic solvent is preferably used in an amount of 40 to 10,000 parts by mass, more preferably 1 to 1 part by mass, per 100 parts by mass of the total solid content of the colored resin composition. 155795.doc -20·201207559 The colored resin composition of the present invention is produced by mixing and stirring the above-mentioned binder resin, curing agent, photopolymerization initiator, specific colored material compound, organic solvent, or the like by a dispersing mixer or a homomixer. . X, other pigments or dyes may be added as needed, but in the case of pigments or dyes having a lower solubility, 'dispersions are obtained by a disperser such as a paint shaker using a suitable dispersant, and added to the colored resin combination. Mix in the mixture. In the colored resin composition of the present invention, various additives such as a filler, a surfactant, a thermal polymerization inhibitor, a adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent and the like can be further added as needed. Further, the colored resin composition of the present invention may be filtered by a filter or the like after the preparation thereof to remove foreign matter or the like. Next, a method of preparing a cured product from the colored resin composition of the present invention will be described. First, by the spin coating method, the light coating method, the slit spin coating method, the cloth method, the bar coating method, or the like, the film thickness is about 0.1 to 20 Å, more preferably 0.5 to 5 (four). The colored resin composition of the present invention is applied onto a substrate such as a glass substrate 1 substrate, and if necessary, is dried at a temperature of 23 to 15 Torr in a decompression chamber. It is more preferably a temperature of 6 〇 to 12 (the temperature is 6 〇 to 12 (r) and fsn to 10 minutes (4), and then pre-baked by a hot plate or a clean oven to form a film. The normal light lithography method is used to irradiate radiation (for example, electron beam, ultraviolet ray, preferably ultraviolet ray) through a specific light (4) case, (4) aqueous solution of a surfactant, a pure aqueous solution, or a mixed aqueous solution of the surfactant and (4) for development. The method includes an immersion method, a spray method, a spray method, a search method, an ultrasonic wave method, etc., and any combination thereof may be used. By development, 155795.doc 21 201207559 shows no, shot, p, After rinsing with water, a post-baking treatment is carried out, for example, at a temperature of 130 to 30 Torr for a period of time (2) minutes, more preferably at a temperature of 150 250 C and for a time of 3 () minutes. The pixel of the colored cured film. In the above, as the surfactant, polyoxyethylene alkyl ether, polyoxyalkylene base, and the like can be used. As an assay, sodium carbonate, potassium carbonate, sodium strontium oxide, or the like can be used. Potassium hydroxide, two Alcoholamine, tetramethylammonium hydroxide is equal to the present invention, and it is preferred to use an aqueous solution containing both an assay and a surfactant. The development is usually 10 to 50., preferably 20 to 4 (rc) The treatment at a treatment temperature is usually 30 to 6 sec., preferably 3 Torr to 12 sec. The cured product of the colored resin composition of the present invention is suitable as a liquid crystal display device, an organic EL display, or a digital camera. There is a color ray sheet such as a solid-state image sensor to be used, and the color filter has a patterned blue pixel containing a cured product of the colored resin composition of the present invention prepared as described above. The liquid crystal display device of the invention is produced, for example, by sequentially laminating (four) a light source, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a light sheet, a polarizing film, and the like. The device is fabricated on or under the multilayer organic light-emitting device according to the light sheet. The color is formed on any surface of the surface of the solid-state imaging device, for example, by moving the color filter on the surface of the color filter, and the light is The present invention is described in more detail below by providing the present invention with a layered microlens on the wafer. [Embodiment] 155795.doc • 22-201207559 The present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the examples, Γ%" means "% by mass" unless otherwise specified. Further, for the spectral characteristics, the spectral transmittance is measured by a spectrophotometer "Shimadzu Corporation UV-3 1 50". The chromaticity in the χγζ color system was calculated, and the tolerance of the coloring body was evaluated. Synthesis Example 1 (Synthesis of Compound 2-Α) [Chemical 2]

化合物1 (1)將 1-溴萘（12.42 g，0_06 mol)與環己胺（6.55 g , 0.06 mol)、第二丁氧化鈉（8 g，〇 m〇i)、pd2(dba)3 (東京化成工業製造，三（二亞苄基丙酮）二把（〇)，相對於溴萘為〇·〇〇3 q.)、BINAP(東京化成工業製造，（±)_22，_雙（二苯基膦基）-1，Γ-聯萘，相對於丨·溴萘為0 008 eq)溶解於甲苯 120 ml中，於65»C下攪拌3小時。其後回到室溫並對反應液進行管柱過濾，將濾液減壓蒸餾去除，藉此獲得上述化合物 1(12.8 g，94%)。 [化3]Compound 1 (1) 1-bromonaphthalene (12.42 g, 0_06 mol) with cyclohexylamine (6.55 g, 0.06 mol), sodium butoxide (8 g, 〇m〇i), pd2 (dba) 3 ( Manufactured by Tokyo Chemical Industry Co., Ltd., tris(dibenzylideneacetone), two (〇), relative to bromonaphthalene, BIN·〇〇3 q.), BINAP (manufactured by Tokyo Chemical Industry, (±)_22, _bis(diphenyl) The phosphinyl group-1, hydrazine-binaphthyl, which is 0 008 eq relative to the quinone bromonaphthalene, was dissolved in 120 ml of toluene and stirred at 65»C for 3 hours. Thereafter, the mixture was returned to room temperature, and the reaction liquid was subjected to column filtration, and the filtrate was evaporated under reduced pressure, whereby Compound 1 (12.8 g, 94%) was obtained. [Chemical 3]

化合物2 155795.doc 201207559 (2) 使將合成例1-(1)中所獲得之化合物i(4 5i g，〇〇2 m〇l)、4,4，-雙（二基乙胺基）二苯甲酮（6.49 g，0.02 mol)、氧氣化磷（3.37 g ’ 0.022 mol)溶解於曱苯8 ml中而成之混合溶液於60°C下反應4小時。回到室溫後，加水進行分液’於減壓下濃縮有機層，藉此獲得上述化合物2(1 i 3 g，99%) ° (3) 將合成例1-(2)中所獲得之化合物2(2.5 g，0.004 m〇l)溶解於水2 ml與曱醇30 ml之混合溶液中，一面授拌，一面添加於DMF 2 ml與甲醇1〇 ml之混合溶液中溶解有畚_三氟曱基續醯基甲基化物之铯鹽2.87 g而成之溶液。於6〇。〇下加熱授拌3小時後，濾取所析出之結晶，進行水洗、乾燥，獲得作為藍色結晶之化合物2之卷-三氟甲基磺醯基曱基化物鹽（三芳基曱烷化合物2-A)2.8 g。合成例2 (關於化合物4-A之合成） [化4]Compound 2 155795.doc 201207559 (2) The compound i (4 5 i g, 〇〇 2 m〇l) obtained in Synthesis Example 1-(1), 4,4,-bis (diethylethylamino) A mixed solution of benzophenone (6.49 g, 0.02 mol) and phosphorus oxide (3.37 g '0.022 mol) dissolved in 8 ml of toluene was reacted at 60 ° C for 4 hours. After returning to room temperature, water was added to carry out liquid separation', and the organic layer was concentrated under reduced pressure to obtain the above compound 2 (1 i 3 g, 99%) ° (3) obtained in Synthesis Example 1-(2) Compound 2 (2.5 g, 0.004 m〇l) was dissolved in a mixed solution of 2 ml of water and 30 ml of decyl alcohol, and mixed while being added to a mixed solution of 2 ml of DMF and 1 ml of methanol to dissolve 畚_3 A solution of 2.87 g of fluorenyl sulfonium thiol methoxide. At 6 〇. After heating for 3 hours under the armpits, the precipitated crystals were collected by filtration, washed with water, and dried to obtain a coil of the compound 2 as a blue crystal - trifluoromethylsulfonyl sulfhydryl salt (triaryl decane compound 2 -A) 2.8 g. Synthesis Example 2 (Synthesis of Compound 4-A) [Chemical 4]

(1)將 1-溴萘（12.42 g，0.06 mol)與 3-胺基戊烷（5 75 g，〇〇6 mol)、第三丁氧化納（8.07 g，0.08 mol)、Pd2(dba)3(相對於 1-溴萘為0.003 eq.)、BINAP(相對於1-溴萘為〇〇〇8 eq )溶解於甲苯120 ml中，於7(TC下攪拌5小時。其後回到室溫並對反應液進行管柱過濾，將濾液減壓蒸餾去除，藉此獲得 •24· 155795.doc ⑧ 201207559 上述化合物3(12.2 g，95%)。 [化5](1) 1-Bromonaphthalene (12.42 g, 0.06 mol) with 3-aminopentane (5 75 g, 〇〇6 mol), third butyl oxide (8.07 g, 0.08 mol), Pd2 (dba) 3 (0.003 eq. relative to 1-bromonaphthalene), BINAP (8 eq relative to 1-bromonaphthalene) was dissolved in 120 ml of toluene, stirred at 7 (TC for 5 hours), and then returned to the chamber. The reaction liquid was subjected to column filtration, and the filtrate was distilled off under reduced pressure to obtain the above compound 3 (12.2 g, 95%).

化合物3Compound 3

⑺使將合成例2-(1)中所獲得之化合物3(4 27 g，〇〇2 m〇l)、4,4，-雙（二乙基胺基）二苯甲酮（6.49 g，0.02 m〇1)、氧氯化磷（3_37 g，0.022 mol)溶解於甲苯8 ml中而成之混合溶液於60°C下反應3小時。回到室溫後，加水進行分液，於減壓下濃縮有機層，藉此獲得上述化合物丨丨〇】 g，99%) ° (3)使合成例2-(2)中所獲得之化合物4(3.0 g，〇·005 m〇1)溶解於水10 ml與甲醇40 ml之混合溶液中，一面授拌，一面添加於DMF 3 ml與曱醇20 ml之混合溶液中溶解有畚-三氟甲基確醯基曱基化物之絶鹽2.94 g而成之溶液。於6〇。〇下加熱攪拌3小時後，濾取所析出之結晶，進行水洗、乾燥’獲得作為藍色結晶之化合物4之叁·三氟甲基確醯基曱基化物鹽（三芳基甲烷化合物4-A)3.5 g。合成例3 (關於化合物8-A之合成） [化6] 155795.doc • 25· 201207559(7) Compound 3 (4 27 g, 〇〇2 m〇l) obtained in Synthesis Example 2-(1), 4,4,-bis(diethylamino)benzophenone (6.49 g, A mixed solution of 0.02 m〇1), phosphorus oxychloride (3_37 g, 0.022 mol) dissolved in 8 ml of toluene was reacted at 60 ° C for 3 hours. After returning to room temperature, water was added for liquid separation, and the organic layer was concentrated under reduced pressure to obtain the above compound 丨丨〇 g, 99%) ° (3) Compound obtained in Synthesis Example 2-(2) 4 (3.0 g, 〇·005 m〇1) dissolved in a mixed solution of 10 ml of water and 40 ml of methanol, and mixed while adding a mixture of DMF 3 ml and 20 ml of decyl alcohol to dissolve 畚-three. A solution of 2.94 g of a fluoromethyl group as a sulfhydryl compound. At 6 〇. After heating and stirring for 3 hours under the armpits, the precipitated crystals were collected by filtration, washed with water and dried to obtain a ruthenium trifluoromethyl decyl sulfhydryl salt of the compound 4 as a blue crystal (triarylmethane compound 4-A) ) 3.5 g. Synthesis Example 3 (Synthesis of Compound 8-A) [Chem. 6] 155795.doc • 25· 201207559

(1)將 N-乙基苯胺（12.12 g，0.10 mol)、漠環己烧（97.83 g， 0.60 mol)、碳酸鉀（48.37 g，0.35 mol)、碘化銅（L90 g， 0.01 mol)溶解於DMF 10 ml中，於120°C下反應3天。回到室溫後’進行過濾並利用二氯甲烧清洗無機鹽。將滤液減壓濃縮’藉此獲得粗產物。藉由減壓蒸餾將該粗產物純化，獲得作為目標物之化合物5(11.45 g，56%)。 [化7](1) Dissolving N-ethylaniline (12.12 g, 0.10 mol), Molybdenum (97.83 g, 0.60 mol), potassium carbonate (48.37 g, 0.35 mol), copper iodide (L90 g, 0.01 mol) The reaction was carried out at 120 ° C for 3 days in 10 ml of DMF. After returning to room temperature, the mixture was filtered and the inorganic salt was washed with methylene chloride. The filtrate was concentrated under reduced pressure to thereby obtain a crude product. The crude product was purified by distillation under reduced pressure to yield Compound 5 (11.45 g, 56%). [Chemistry 7]

(2)於合成例3-(1)中所獲得之化合物5(11.20 g，〇〇6 mQlj 與濃鹽酸（2.54 g ’ 0.07 mol)之混合物中緩慢滴加福馬林 (2.35 g，0.03 mol)，於80。(：下反應12小時。添加二氣甲烧 10 m卜及水50 ml後，添加氫氧化鈉水溶液進行中和。萃取二氣曱烷層並進行減壓濃縮，藉此獲得上述化合物 6(12.09 g，96%)。 [化8](2) Slowly dropwise addition of formalin (2.35 g, 0.03 mol) to a mixture of compound 5 (11.20 g, 〇〇6 mQlj and concentrated hydrochloric acid (2.54 g '0.07 mol)) obtained in Synthesis Example 3-(1) , at 80: (: 12 hours under reaction. After adding 2 m of methane and 10 ml of water, 50 ml of water was added, and sodium hydroxide aqueous solution was added for neutralization. The dioxane layer was extracted and concentrated under reduced pressure, thereby obtaining the above. Compound 6 (12.09 g, 96%).

⑧ 201207559 (3)使合成例3-(2)中所獲得之化人鉍 <•化0 物 6(4.27 g , 0.02 mol)溶解於異丙醇140 ml中，禾一 mi +# Τ 添加四笨氣醌（3.16 g、0.013 m〇1)、25%次氣酸鈉水溶液9 35 g，於饥下反應7小時。回到至皿後將反應液減壓過渡而去除沈澱物。將滤液減壓 ’利用氫氧化鈉水溶液清洗藉此獲得上述化合物7(7.12 漠縮，將殘潰溶解於甲苯中後 4次。於減壓下濃縮甲苯層， g，55%)。 [化9]8 201207559 (3) The hydrazine obtained in Synthesis Example 3-(2) <•Chemical Compound 6 (4.27 g, 0.02 mol) was dissolved in 140 ml of isopropanol, and Hemi mi +# Τ added Four stupid gas (3.16 g, 0.013 m〇1), 25% sodium hypochlorite aqueous solution 9 35 g, reacted under starvation for 7 hours. After returning to the dish, the reaction solution was depressurized to remove the precipitate. The filtrate was depressurized and washed with an aqueous sodium hydroxide solution to obtain the above compound 7 (7.12, which was obtained by dissolving the residue in toluene four times. The toluene layer was concentrated under reduced pressure, g, 55%). [Chemistry 9]

化合物3Compound 3

(4)使將合成例2-(1)中所獲得之化合物3(1 % g , 〇〇〇6 mol)、合成例3-(3)中所獲得之化合物7(2 55 g，〇〇〇6 mol)、氧氯化磷（1.〇 g，0.0065 m〇1)溶解於甲苯3 ml中而成之混合溶液於6(TC下反應7小時。回到室溫後’加水進行分液，於減壓下濃縮有機層，藉此獲得上述化合物8(3 g，98%)。 (5)將合成例3-(4)中所獲得之化合物8(3.93 g，〇⑼6 may 溶解於水10 ml與甲醇40 ml之混合溶液中，一面授摔，一面添加於DMF 3 ml與甲醇20 ml之混合溶液中溶解有叁_三氟甲基石黃醯基曱基化物之絶鹽3.21 g而成之溶液。授掉3小時後，滤取所析出之結晶，進行水洗、乾燥，獲得作為藍色結晶之化合物8之叁-三氟甲基磺醯基甲基化物鹽（三芳基 155795.doc •27· 201207559 甲烷化合物8-A)1.62 g » 合成例4 (黏合樹脂（共聚物）之製備）於500 ml之四口燒瓶中添加甲基乙基酮16〇§、甲基丙烯酸1〇 g、甲基丙烯酸苄酯33 g、α，α，-偶氮雙（異丁腈）1 g，一面授拌一面向燒瓶内流入氮氣3〇分鐘。其後，升溫至 80°C ’於保持於80〜85。(：之狀態下攪拌4小時。反應結束後，冷卻至室溫，獲得無色透明且均勻之共聚物溶液。使該共聚物溶液於異丙醇與水之1 ·〗混合溶液十沈澱，進行過濾而取出固體成分，乾燥而獲得共聚物（A)。所獲得之共聚物（A)之以聚苯乙烯換算之重量平均分子量為18〇〇〇，酸值為152。實施例1 將作為黏合樹脂之共聚物（A) 5 4 g、作為光聚合性單體之Kayarad DPHA(日本化藥製造）6 g、作為光聚合起始劑之 Irgacure 907(BASF JAPAN製造 M 5 g&Kayacure 〇ΕΤχ_ S(曰本化藥製造）0.6 g、作為染料之合成例卜⑺中所獲得之化合物2-A 1.2 g、作為溶劑之環己酮2〇 g及丙二醇單甲喊乙酸醋8.6 g分別混合，獲得藍色之本發明之著色樹脂組合物。實施例2〜4如下。實施例2:除了將化合物2-A變更為合成例2·(3)之化合物心 Α以外，設定為與實施例1相同之組成。實施例3:除了將化合物2-A變更為合成例3_(5)之化合物8· A以外，設定為與實施例1相同之組成。 155795.doc -28- 201207559 實施例4 :於實施例2中添加下述比較例1之藍色顏料分散液19 g，獲得本發明之藍色著色樹脂組合物。比較例1 以 C.I.顏料藍 15:6/Ajisper PB821/Solsperse 5000/PGMEA= 15.0/6.0/1.0/78.0(質量比）之組成比混合後，添加03111111氧化錯珠400質量份’利用塗料振盪器進行6〇分鐘之處理，進行過濾’藉此獲得藍色顏料分散液。比較例2 :除了將化合物2-a變更為Basic Blue 7(驗性藍7) 以外，設定為與實施例丨相同之組成。將上述所獲得之著色樹脂組合物（實施例1~4)塗佈於上述基板上，於80。(： xl 00秒之條件下進行預烘烤後，介隔光罩藉由曝光進行硬化後，利用含有界面活性劑之鹼性水溶液進行顯影，以水沖洗後，於2〇(rc下加熱而獲得藍色圖案。所獲得之藍色圖案於線與間隙中具有5 μηι見方之解析性，未確認到殘渣、像素之剝落等。作為固體攝像元件用之彩色濾光片而確認到之高解析性之性能。關於耐熱性之評價耐熱性評價用之基板係與上述同樣地於玻璃基板上塗佈各組合物後，進行整個面曝光，於2〇〇<>c下進行5分鐘之後火、烤處理而製成。其後，如下所記載般進行評價。首先，藉由分光光度計測定評價用基板之分光透射率，計算出xyz表色系統中之色度。其次，於2〇〇。。下對評價用基板進行60分鐘之處理後，再次測定分光透射率，計算出色差（AEab)而評價耐熱性。 155795.doc -29- 201207559 將耐熱性之結果示於表1中。 [表1] 表1耐熱性之評價結果 (△Eab) 實施例1 2.6 實施例2 2.9 實施例3 2.5 實施例4 1.7 比較例11 0.7 比較例2 41.9 表1係耐熱性之評價結果，本發明之實施例W與相同染料之比較例2相比較，均顯示良好之結果。比較m由於為顏料故可謂理所當然之社黑。麻# , ^ 田、·〇果。貫施例4由於為與顏料之混合’故同樣地成為对性良好之結果。然而，即便與顏料混合亦不特別析出而成為良好之結果，顯示出本發明之染料系有色材料化合物之廣泛之適用性。由以上可知，本發明可藉由使用特定之藍色染料系有色材料化合物之藍色著色樹脂組合物形成彩色濾光片，所獲得之彩色濾光片由於亮度較高、且具有充分之耐性，故可獲得高品質且可靠性較高之鮮明之藍色像素。又，視用途不同而與顏料亦良好地混合使用，顯示出廣泛之適用性，故產業上之價值較高。 155795.doc(4) Compound 3 obtained in Synthesis Example 2-(1) (1% g, 〇〇〇6 mol), and Compound 7 obtained in Synthesis Example 3-(3) (2 55 g, 〇〇〇6 mol), phosphorus oxychloride (1.〇g, 0.0065 m〇1) dissolved in 3 ml of toluene mixed solution was reacted at 6 (TC for 7 hours. After returning to room temperature), water was added for liquid separation. The organic layer was concentrated under reduced pressure to give the compound 8 (3 g, 98%). (5) Compound 8 (3.93 g, 〇(9)6 may be dissolved in water. In a mixed solution of 10 ml and 40 ml of methanol, one side of the mixture was added to a mixed solution of 3 ml of DMF and 20 ml of methanol to dissolve 3.21 g of strontium trifluoromethyl sulphate ruthenium salt. After the solution was allowed to stand for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain a fluorene-trifluoromethylsulfonylmethylate salt of the compound 8 as a blue crystal (triaryl 155795.doc • 27 · 201207559 Methane Compound 8-A) 1.62 g » Synthesis Example 4 (Preparation of Adhesive Resin (Copolymer)) Add methyl ethyl ketone 16 〇, methacrylic acid 1 〇 g, in a 500 ml four-necked flask Benzyl acrylate 33 g, α,α,-azobis(isobutyronitrile) 1 g, one side of the flask was introduced into the flask for nitrogen gas for 3 minutes. Thereafter, the temperature was raised to 80 ° C 'maintained at 80 to 85 After stirring for 4 hours, the reaction mixture was cooled to room temperature to obtain a colorless transparent and uniform copolymer solution. The copolymer solution was precipitated in a mixed solution of isopropyl alcohol and water. The solid component was taken out by filtration, and dried to obtain a copolymer (A). The obtained copolymer (A) had a weight average molecular weight of 18 Å in terms of polystyrene and an acid value of 152. Example 1 Resin copolymer (A) 5 4 g, Kayarad DPHA (manufactured by Nippon Kasei Co., Ltd.) as photopolymerizable monomer 6 g, Irgacure 907 as photopolymerization initiator (M5 g & Kayacure 〇ΕΤχ_ S manufactured by BASF JAPAN) (manufactured by Sakamoto Chemical Co., Ltd.) 0.6 g, as a synthetic example of the dye, compound 2-A 1.2 g obtained in (7), cyclohexanone 2 〇g as a solvent, and propylene glycol monoacetic acid vinegar 8.6 g were separately mixed. Blue colored resin composition of the present invention. Example 2~ 4. Example 2: The composition was the same as that of Example 1 except that the compound 2-A was changed to the compound of the compound of Example 2 (3). Example 3: In addition to changing the compound 2-A to In the same manner as in Example 1 except for the compound 8_(5), the same composition as in Example 1. 155795.doc -28-201207559 Example 4: In Example 2, the following blue pigment dispersion of Comparative Example 1 was added. 19 g of a liquid was obtained to obtain a blue colored resin composition of the present invention. Comparative Example 1 After mixing with a composition ratio of CI Pigment Blue 15:6/Ajisper PB821/Solsperse 5000/PGMEA=15.0/6.0/1.0/78.0 (mass ratio), 40011 parts of 03111111 oxidized wrong beads was added' using a paint shaker After 6 minutes of treatment, filtration was carried out 'by this to obtain a blue pigment dispersion. Comparative Example 2: The composition was the same as that of Example 以外 except that the compound 2-a was changed to Basic Blue 7 (inspective blue 7). The colored resin compositions (Examples 1 to 4) obtained above were applied onto the above substrate at 80. (: After pre-baking under xl 00 seconds, the mask is cured by exposure, developed with an alkaline aqueous solution containing a surfactant, rinsed with water, and heated at 2 Torr (rc) A blue pattern was obtained, and the obtained blue pattern had a resolution of 5 μηι square in the line and the gap, and no residue or pixel peeling was observed, and high resolution was confirmed as a color filter for a solid-state image sensor. Performance of the heat resistance evaluation The substrate for heat resistance evaluation was applied to the glass substrate in the same manner as described above, and then exposed to the entire surface, and fired at 2 〇〇 <>c for 5 minutes. This was prepared by baking, and was evaluated as follows. First, the spectral transmittance of the substrate for evaluation was measured by a spectrophotometer, and the chromaticity in the xyz color system was calculated. Secondly, at 2〇〇 After the evaluation substrate was treated for 60 minutes, the spectral transmittance was measured again, and the excellent difference (AEab) was calculated to evaluate the heat resistance. 155795.doc -29-201207559 The results of heat resistance are shown in Table 1. 1] Table 1 Evaluation results of heat resistance (ΔEab) Example 1 2.6 Example 2 2.9 Example 3 2.5 Example 4 1.7 Comparative Example 11 0.7 Comparative Example 2 41.9 Table 1 Evaluation results of heat resistance, practice of the present invention Example W shows good results compared with Comparative Example 2 of the same dye. Comparing m as a pigment, it can be taken for granted. It is a natural matter. Ma #, ^田,·〇果. By example 4 is a mixture with pigment In the same way, it is a result of good compatibility. However, even if it is mixed with a pigment, it does not precipitate particularly and is a good result, and shows the wide applicability of the dye-based coloring material compound of the present invention. A color filter is formed by using a blue colored resin composition of a specific blue dye-based coloring material compound, and the obtained color filter is high in quality and reliable because of high brightness and sufficient resistance. The bright blue pixel is higher in character. Moreover, it is well mixed with the pigment depending on the application, showing a wide applicability, so the value in the industry is high. 155795.d Oc

Claims

201207559 VII. Patent application scope:

A color filter using a colored material compound [Chemical Formula 1] A color resin composition containing a binder resin, a solvent, and a hardener according to the following formula (1).

(In the formula (1), R1 to R6 each independently represent a hydrogen atom, an alkyl group having a carbon number of W, a phenyl group or a benzyl group, and at least _翩&, a coix seed to a branched alkyl group, or a cyclic alkyl group, R7 to R2 each independently represent a hydrogen atom, an alkyl group of carbon number 6, a dentate atom; an anion moiety X- represents a fluorene-trifluoromethylsulfonyl methide or a bis-trifluoromethylsulfonimide ). 2. The colored resin composition of claim 1, which comprises a copper phthalocyanine-based pigment. 3. A coloring cured film for color filters, which is obtained by patterning using the colored resin composition of claim 2 or 2. A color filter comprising a color hardening film for a color filter according to claim 3. 5. A liquid crystal display device and an organic E]L display, which are provided with a color filter as claimed in claim I55795.doc 201207559. A solid-state image pickup element which is obtained by mounting a color filter as in claim 4. 155795.doc 8 201207559 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the characteristics that can best display the invention. Chemical formula:

(1) 155795.doc ·2· 8