TW201142500A - Coloring composition for color filter, color filter and display element - Google Patents
Coloring composition for color filter, color filter and display element Download PDFInfo
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- TW201142500A TW201142500A TW100111732A TW100111732A TW201142500A TW 201142500 A TW201142500 A TW 201142500A TW 100111732 A TW100111732 A TW 100111732A TW 100111732 A TW100111732 A TW 100111732A TW 201142500 A TW201142500 A TW 201142500A
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201142500 六、發明說明: 【發明所屬之技術領域】 本發明關於一種彩色濾光片用著色組成物、彩色濾、光 片及顯示元件,更詳細地說,關於:可用於在彩色濾光片 形成有用的著色層的著色組成物,其中該彩色濾光片係用 於透過型或反射型的彩色液晶顯示元件、固體攝影元件、 有機EL顯示元件、電子紙等;具備使用該著色組成物所形 成之·著色層的彩色濾光片:及具傭該彩色濾光片的顯示元 件。 【先前技術】 #使用著色感放射線性組成物製造彩色濾光片時,已 知有藉由在基板上,塗布顏料分散型的著色感放射線性組 成物並加以乾燥後,將放射線以所要的圖案形狀照射在乾 燥塗膜(以下稱爲「曝光」)並加以顯影,來製得各色像 素的方法(專利文獻丨~2)。又,亦已知有利用使碳黑分 散之光聚合性組成物形成黑色矩陣的方法(專利文獻3 )。 進一步地’亦已知有使用顏料分散型的著色樹脂組成物利 用噴墨方式製得各色像素的方法(專利文獻。 然而’在用於液晶顯示元件或固體攝影元件的彩色濾 光片的領域中,隨著高輝度化或高對比化的要求,而傾向 逐漸將所使用的顔料予以微粒化。爲了實現經如此微粒化 的顏料之安疋且良好的分散性,已知使用分散劑是有效 的。已提出使用相關的分散劑改善顔料的分散性,不只使 201142500 對比或分散安定性提高也會使顯影性等提高的各種方法 (專利文獻5〜6)。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平2_144502號公報 [專利文獻2]日本特開平3_532〇1號公報 [專利文獻3]日本特開平6- 3 5 1 8 8號公報 [專利文獻4]日本特開2〇〇〇_31〇7〇6號公報 [專利文獻5]日本特開2003-26949號公報 [專利文獻6]日本特開2009-25813號公報 【發明內容】 [發明所欲解決的課題] 然而’即使依照這些專利文獻5 ~6記載的方法,仍難 以實現近年來對彩色液晶顯示元件的高對比化、高色純度 化及高輝度化的要求,而且也難謂能解決在量產彩色濾光 片中的顯影性等諸多問題。因此,強烈地追求實現近年來 的高對比化、高色純度化及高輝度化的要求,且顯影性等 優異的彩色濾光片用著色組成物的開發。 因此,本發明的課題在於提供一種彩色濾光片用著色 組成物,其色度特性優異,顯影性及保存安定性良好。再 者本發明的課題在於提供具備由上述著色組成物所形成之 著色層而成之彩色濾光片、及具備該彩色濾光片的顯示元 件。 201142500 [用以解決課題的手段] 鑑於實情’本發明人等進行銳意硏究後,發現能藉由 使用具有特定的重複單元的嵌段共聚物來解決上述課題, 完成本發明。 即’本發明提供一種彩色濾光片用著色組成物,其特 徵爲含有以下的成分(A) 、( B )、及(C); (A) 包含顏料的著色劑, (B) 包含以下述式(1)表示之重複單元(!)、以下 述式(2)表示之重複單元(2)、及含有酸性基之重複單 元(3) ’相對於前述重複單元(1)以外之重複單元的合 計’前述重複單元(2)的共聚合比例爲75質量%以上, 重量平均分子量Mw與數量平均分子量Μη之比(Mw/Mn) 爲1.0〜1.9的共聚物(以下,亦稱爲「(B)共聚物」。), 及 (C )交聯劑。201142500 VI. Description of the Invention: [Technical Field] The present invention relates to a coloring composition for a color filter, a color filter, a light sheet, and a display element, and more particularly, to: can be used for forming a color filter A coloring composition for a useful coloring layer for use in a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like; and a coloring composition is used A color filter of a colored layer: and a display element having the color filter. [Prior Art] When a color filter is produced using a coloring sensitizing radiation composition, it is known that a pigment-dispersed color-sensing radiation-linear composition is applied onto a substrate and dried, and then the radiation is in a desired pattern. A method in which a shape is irradiated on a dried coating film (hereinafter referred to as "exposure") and developed to obtain pixels of respective colors (Patent Document 丨~2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (Patent Document 3). Further, a method of producing a pixel of each color by an inkjet method using a pigment dispersion type coloring resin composition is known (Patent Literature. However, 'in the field of color filters for liquid crystal display elements or solid-state imaging elements With the requirement of high luminance or high contrast, it tends to gradually atomize the pigment used. In order to achieve the ampule and good dispersibility of the pigment thus fined, it is known that the use of a dispersant is effective. Various methods for improving the dispersibility of the pigment by using the dispersant in the related art, and improving the developability and the like not only by the comparison of 201142500 or the dispersion stability (Patent Documents 5 to 6) have been proposed. [Prior Art Document] [Patent Literature] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. 〇〇〇 〇 〇 2003 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 -26 However, even in accordance with the methods described in these Patent Documents 5 to 6, it is difficult to achieve high contrast, high color purity, and high luminance in recent years for color liquid crystal display elements, and it is difficult to solve the problem in mass production. There are many problems such as developability in the filter. Therefore, the coloring composition for color filters excellent in developability and the like is required to achieve high contrast, high color purity, and high luminance in recent years. In view of the above, an object of the present invention is to provide a coloring composition for a color filter which is excellent in chromaticity characteristics and has good developability and storage stability. Further, an object of the present invention is to provide a coloring composition. A color filter made of a color layer and a display element having the color filter. 201142500 [Means for Solving the Problem] In view of the facts, the inventors of the present invention conducted an intensive investigation and found that it can be used by using The present invention is accomplished by solving the above problems with a block copolymer of a specific repeating unit. That is, the present invention provides a coloring composition for a color filter, It is characterized by containing the following components (A), (B), and (C); (A) a coloring agent containing a pigment, and (B) comprising a repeating unit (!) represented by the following formula (1), having the following formula (2) The repeating unit (2) and the repeating unit (3) containing an acidic group are added to the total of repeating units other than the repeating unit (1). The copolymerization ratio of the repeating unit (2) is 75 mass. A copolymer having a ratio (Mw/Mn) of a weight average molecular weight Mw to a number average molecular weight Μη of 1.0% or more (hereinafter also referred to as "(B) copolymer"), and (C) a crosslinking agent.
[在式(1)中,R1表示氫原子或甲基,Z表示一 N+ R2R3R4Y_ (其中,r2〜R4係彼此獨立地表示氫原子或烴基,R、R4 當中2個以上亦可彼此鍵結而形成飽和雜環,表示相對 陰離子。)、或-NR5R6 (其中,R5及R6係彼此獨立地表 示氫原子或烴基,R5及R6亦可彼此鍵結而形成飽和雜 201142500 環。)’X1表示2價之連結基。] R7 —^-CH2—C-^- (2) COO——R8 [在式(2)中,R7表示氫原子或甲基,R8表示脂肪族 烴基或脂環式烴基。] 又,本發明提供具備使用上述著色組成物所形成之著 色層而成的彩色濾光片,及具備該彩色濾光片的顯示元 件。在此,「著色層」意指用於彩色濾光片之各色像素、 黑色矩陣、黑色間隙物等。 進一步地,本發明提供一種彩色濾光片用顏料分散 液,其特徵爲含有以下的成分(al) 、 (B)及(F); (a 1 )顏料, 上述(B )共聚物,及 (F)溶媒。 [發明的效果] 本發明之彩色濾光片用著色組成物,色度特性優異, 顯影性及保存安定性也優異。使用本發明的著色組成物, 便能製得具有對比高的各色像素的彩色濾光片。 因此,本發明之彩色濾光片用著色組成物,能極適合 使用在以彩色液晶顯示元件用彩色濾光片、固體攝影元件 之色分解用彩色濾光片、有機EL顯示元件用彩色濾光片、 電子紙用彩色濾光片爲首之各種彩色濾光片的製作。 【實施方式】 201142500 [用以實施發明的形態] 以下,就本發明詳細地說明。 彩色濾光片用著色組成物 以下’就本發明之彩色滤光片用著色組成物(以下簡 稱爲「者色組成物」)的構成成分加以說明。 -(A )著色劑- 本發明之著色組成物含有(a 1 )顏料作爲(a )著色劑。 作爲(al)顏料並無特別限定,可爲有機顔料、無機顔料 之任一者。在本發明中,(al)顏料能單獨或混合2種以 上使用。當然’亦能混合有機顏料與無機顔料使用。 作爲上述有機顏料,例如,可舉出在色彩索引(C I.; The Society of Dyers and Colourists 公司發行)中分類爲顏料 之化合物。具體而言’能舉出附有如下述的色彩索引(CI. (Color Index ))名稱者。 C.I.顏料黃12、C.I.顏料黃13、C.I.顏料黃14、c.I.顏 料黃17、C.I.顏料黃20、C.I.顏料黃24、C.I.顏料黃31、 C.I.顏料黃55、C.I.顔料黃83、c.I.顏料黃93、C.I.顔料黃 1〇9、(:.1.顏料黃110、(:.1.顏料黃138、<:.1.顏料黃139、(:.1. 顏料黃1 5 0、C · I ·顏料黃1 5 3、c _ I.顏料黃1 5 4、C . I.顔料黃 155、C.I.顏料黃 166、c.I.顏料黃 168'C.I·顏料黃 i8〇、c.I. 顏料黃21 1 ; C.I.顔料橙5、C.I.顏料橙13、C.I.顏料橙14、C.I.顏料 橙24、C.I.顔料橙34、c·〗.顏料橙36、C.I.顏料橙38、C.I. 201142500 顏料橙40、C.I.顏料橙43、C.I.顏料橙46、C.I.顔料橙49、 C.I.顏料橙61、C.I.顏料橙64、C.I.顏料橙68、C.I_顏料橙 70、C.I.顏料橙71、C.I.顏料橙72、C.I.顏料橙73、C.I.顏 料橙7 4 ; C.I.顏料紅1、C.I.顏料紅2、C.I·顏料紅5、C.I.顏料紅 17、C.I.顏料紅31、C.I.顏料紅32、C_I.顏料紅41、C.I.顏 料紅122、C.I.顏料紅123、C.I.顏料紅144、C.I.顏料紅149、 C.I.顏料紅166、C.I.顏料紅168、C.I.顏料紅170、C.I.顏料 紅1 7 1、C _ I.顏料紅1 7 5、C . I.顏料紅1 7 6、C . I.顏料紅1 7 7、 C.I.顏料紅178、C.I.顏料紅179、C.I.顏料紅180、C.I.顏料 紅185 ' C.I.顔料紅187、C.I.顏料紅202、C.I.顏料紅206、 C_I.顏料紅207、C.I.顏料紅209、C.I.顏料紅214、C.I.顏料 紅220、C.I.顏料紅221、C.I.顏料紅224、C.I.顏料紅242、 C.I_顏料紅243、C.I.顏料紅254、C.I.顏料紅255、C.I.顏料 紅2 6 2、C . I ·顏料紅2 6 4、c. I.顏料紅2 7 2 ; C.I.顏料紫1、C.I.顔料紫19、c.l顏料紫23、c.I.顏料 紫29、C.I.顏料紫32、C.I.顏料紫36、C.I.顏料紫38 ; C.I.顏料藍1、C.I.顏料藍15、c.l.顏料藍15: 3、c.I. 顏料藍15: 4、C_I·顏料藍15: 6、C.I.顏料藍60、C.I.顏料 藍80 ; C.I.顏料綠7、C.I.顏料綠%、c.I.顏料綠58; C.I.顏料褐23、C.I.顏料褐25; C_I·顏料黑1、C.I.顏料黑7。 -10- 201142500 又,作爲無機顏料’例如’可舉出:氧化鈦、硫酸鋇、 碳酸鈣、氧化鋅、硫酸鉛、黃色鉛、鋅黃、氧化鐵紅(紅 色氧化鐵(III )) '鎘紅、群青、普魯士藍、氧化鉻綠、 鈷綠、琥珀、鈦黑、合成鐵黑、碳黑等。 在本發明中’亦能將(a 1 )顏料利用再結晶法、再沉 澱法、溶劑洗滌法、昇華法、真空加熱法或它們的組合加 以精製而使用。又,(a 1 )顏料亦可依所需而將其粒子表 面以樹脂改質而使用。作爲將(a 1 )顏料之粒子表面改質 之樹脂,例如,可舉出日本特開2001-108817號公報記載之 載體樹脂(vehicle re sin)、或市售的各種顏料分散用的樹 脂。作爲碳黑表面之樹脂被覆方法,例如,能採用日本特 開平9-7 1733號公報、日本特開平9-95625號公報、日本特 開平9-124969號公報等記載的方法。又,有機顏料,較佳 爲利用所謂的鹽磨(s a· 11 m i 11 i n g ),將一次粒子微細化使 用。作爲鹽磨的方法,例如,能採用日本特開平〇8_179丨n 號公報所揭露的方法。 然而’在彩色濾光片用著色組成物中,藉由使用染料 作爲者色劑,可達成單獨使用顔料所不能達成的高輝度化 或高對比化。儘管如此’若使用(a2 )染料作爲著色劑, 則著色組成物的驗顯影性明顯惡化。相對於此,在本發明 之著色組成物中’藉由使用(B )共聚物作爲顏料分散劑, 即使是在組合(a 1 )顏料與(a 2 )染料使用作爲著色劑的 情況下,仍能製得鹼顯影性良好的著色組成物。 -11- 201142500 作爲(a2 )染料,例如,能舉出附有如下述的色彩索 引(C.I.)名稱的化合物。 C · I.酸性黃1卜C . I.酸性橙7、C · I.酸性紅3 7、c ·1 ·酸性 紅 180、C.I.酸性藍 29、C、I.直接紅 28(C_I,directred28)、 C.I.直接紅83、C.I.直接黃12、C.I.直接橙26、C.I.直接綠 2 8、C . I.直接綠5 9、C . I.反應性黃2、C · I.反應性紅1 7、C . I. 反應性紅120、C.I.反應性黑5、C.I.分散橙5、C.I.分散紅 58、C.I.分散藍 165、C.I.鹼性藍 41、C.I.鹼性紅 18、C.I. 媒介紅7、C_I.媒介黃5 ' C.I.媒介黑7等偶氮系染料; C.I.靛藍4、C.I.酸性藍40、C.I.酸性綠25、C.I.反應性 藍19、C.I.反應性藍49、C.I.分散紅60、C.I.分散藍56、 C.I.分散藍60等蒽醌系染料; C.I.旋藍5等駄青素(phthalocyanine)系染料; C.I.鹼性藍3、C.I.鹼性藍9等醌亞胺(quinone imine) 系染料; C.I.溶劑黃 33( C.I. solvent yellow 33)、C.I.酸性黃 3、 C.I.分散黃64等喹啉系染料; C.I·酸性黃1、C.I.酸性橙3、C.I.分散黃42等硝基系 染料; 分散黃201等次甲基系染料。 在本發明中使用(a2 )染料作爲著色劑的情況,(a2 ) 染料能單獨或混合2種以上來使用。 (A)著色劑的含有比例,從形成輝度高且色純度優異 -12- 201142500 的像素、或遮光性優異的黑色矩陣的觀點來看,通常爲在 著色組成物的固體成分中5〜70質量% ’較佳爲5〜60質量 %。在此’固體成分係丨曰後述丨谷媒以外的成分。 -(B)共聚物· 本發明中之(B)共聚物含有重複單元(1)、重複單 元(2)及重複單元(3) ’且相對於重複單元(1)以外之 重複單元的合計,重複單元(2)的共聚合比例爲75質量 %以上,重量平均分子量Mw與數量平均分子量Μη之比 (Mw/Mn)爲1.〇~1.9的共聚物,產生作爲(Α)著色劑的 分散劑的功能。又’在此所謂的Mw及Μη係指以凝膠滲透 層析法(GPC,洗提溶媒:DMF )測定之聚甲基丙烯酸甲酯 換算的重量平均分子量及數量平均分子量。 重複單元(1)係以上述式(1)表示者。 在上述式(1)中,作爲R、氫原子及甲基當中,甲基 是較佳的。 又,Ζ 表示一 n+r2r3r4y_ 或-NR5R6,R2~R6 係彼此獨 立地表示氫原子或烴基,在本發明中「烴基」係指包含脂 肪族烴基、脂環式烴基及芳香族烴基的槪念。可爲直鏈狀、 分枝狀及環狀之任何形態,又可爲飽和烴基亦可爲不飽和 烴基,亦可在分子內及末端之任一者具有不飽和鍵結。 作爲上述脂肪族烴基,較佳爲碳數1〜20(較佳爲1〜12) 之脂肪族烴基,更具體而言,可舉出碳數1〜20(較佳爲1〜1 2) 之烷基、碳數2~20(較佳爲2〜12)之烯基、碳數2〜20 (較 -13- 201142500 佳爲2〜12)之炔基。又’作爲上述脂環式烴基’較佳爲碳 數3〜20(較佳爲3〜12)之脂環式烴基’更具體而言’可舉 出碳數3〜20(較佳爲3~12)之環烷基。再者’作爲上述芳 香族烴基,較佳爲碳數6〜20(較佳爲6~10)之芳香族烴基, 更具體而言,可舉出碳數6〜20 (較佳爲6~10)之芳基、碳 數7~16(較佳爲7~12)之芳烷基。在此’在本發明中「芳 基」係指單環~ 3環式芳香族烴基。 其中,作爲R2〜R6中之烴基,較佳爲碳數1~12 (較佳 爲1〜6)之烷基、碳數7~16(較佳爲7〜12)之芳烷基’特 佳爲甲基、乙基、丙基、丁基、戊基。 又,在上述式(1)中’作爲R2~R4當中2個以上彼此 鍵結而形成之飽和雜環,可舉出例如下述者。[In the formula (1), R1 represents a hydrogen atom or a methyl group, and Z represents an N+R2R3R4Y_ (wherein, r2 to R4 each independently represent a hydrogen atom or a hydrocarbon group, and two or more of R and R4 may be bonded to each other. A saturated heterocyclic ring is formed to indicate a relative anion.) or -NR5R6 (wherein R5 and R6 independently represent a hydrogen atom or a hydrocarbon group, and R5 and R6 may be bonded to each other to form a saturated heterocyclic 201142500 ring.) 'X1 represents 2 The link of the price. R7 -^-CH2-C-^- (2) COO——R8 [In the formula (2), R7 represents a hydrogen atom or a methyl group, and R8 represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. Further, the present invention provides a color filter comprising a coloring layer formed using the coloring composition, and a display element including the color filter. Here, the "colored layer" means a color pixel, a black matrix, a black spacer, or the like for a color filter. Further, the present invention provides a pigment dispersion liquid for a color filter, which comprises the following components (al), (B) and (F); (a1) a pigment, the above (B) copolymer, and F) Solvent. [Effects of the Invention] The coloring composition for a color filter of the present invention is excellent in chromaticity characteristics and excellent in developability and storage stability. Using the colored composition of the present invention, a color filter having a relatively high contrast color pixel can be obtained. Therefore, the coloring composition for a color filter of the present invention can be suitably used for color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, and color filters for organic EL display elements. The production of various color filters, including color filters for electronic paper and electronic paper. [Embodiment] 201142500 [Mode for carrying out the invention] Hereinafter, the present invention will be described in detail. The coloring composition for a color filter is described below. The constituent components of the coloring composition for a color filter of the present invention (hereinafter referred to as "color composition") will be described. - (A) Colorant - The color composition of the present invention contains (a 1 ) a pigment as (a) a colorant. The (al) pigment is not particularly limited, and may be any of an organic pigment and an inorganic pigment. In the present invention, the (al) pigment can be used singly or in combination of two or more. Of course, it can also be used in combination with organic pigments and inorganic pigments. As the above-mentioned organic pigment, for example, a compound classified as a pigment in a color index (C I.; issued by The Society of Dyers and Colourists) can be cited. Specifically, the name of the color index (CI. (Color Index)) as described below can be cited. CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, cI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, cI Pigment Yellow 93, CI Pigment Yellow 1〇9, (:.1. Pigment Yellow 110, (:.1. Pigment Yellow 138, <:.1. Pigment Yellow 139, (:.1. Pigment Yellow 1 50, C · I · Pigment Yellow 1 5 3, c _ I. Pigment Yellow 1 5 4, C. I. Pigment Yellow 155, CI Pigment Yellow 166, cI Pigment Yellow 168'CI·Pigment Yellow i8〇, cI Pigment Yellow 21 1 ; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, c·〗. Pigment Orange 36, CI Pigment Orange 38, CI 201142500 Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46 , CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, C.I_Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 7 4 ; CI Pigment Red 1, CI Pigment Red 2, CI·Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, C_I. Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 1.7, C _ I. Pigment Red 175, C. I. Pigment Red 176, C. I Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185 'CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, C_I. Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, C.I_Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 2 6 2, C. I · Pigment Red 2 6 4, c. I. Pigment Red 2 7 2 ; CI Pigment Violet 1, CI Pigment Violet 19, Cl Pigment Violet 23, cI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 1, CI Pigment Blue 15, Cl Pigment Blue 15: 3, cI Pigment Blue 15: 4, C_I·Pigment Blue 15: 6, CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green %, cI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; C_I·Pigment Black 1, CI Pigment Black 7. -10- 201142500 Further, examples of the inorganic pigment 'e.g.' include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, and iron oxide red (red iron oxide (III)). Red, ultramarine, Prussian blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, and the like. In the present invention, the (a 1 ) pigment can also be used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating or a combination thereof. Further, the (a 1 ) pigment may be used by modifying the surface of the particles with a resin as needed. For example, a resin resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the particles of the (a1) pigment. For the method of coating the surface of the carbon black, for example, the method described in JP-A-9-7, 1733, JP-A-9-95625, and JP-A-9-124969 can be used. Further, as the organic pigment, it is preferred to use a so-called salt mill (s a·11 m i 11 i n g) to refine the primary particles. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179丨n can be employed. However, in the coloring composition for a color filter, by using a dye as a coloring agent, high luminance or high contrast which cannot be achieved by using a pigment alone can be achieved. However, if the (a2) dye is used as the colorant, the developability of the colored composition is remarkably deteriorated. In contrast, in the coloring composition of the present invention, by using the (B) copolymer as a pigment dispersant, even in the case where the (a 1 ) pigment and the (a 2 ) dye are used as a colorant, A colored composition having good alkali developability can be obtained. -11- 201142500 As the (a2) dye, for example, a compound having the name of the color index (C.I.) as described below can be cited. C · I. Acid Yellow 1 Bu C. I. Acid Orange 7, C · I. Acid Red 3 7 , c · 1 · Acid Red 180, CI Acid Blue 29, C, I. Direct Red 28 (C_I, directred28) , CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 2 8 , C. I. Direct Green 5 9 , C. I. Reactive Yellow 2, C · I. Reactive Red 1 7. C. I. Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Medium Red 7, C_I. Medium Yellow 5 'CI medium black 7 azo dyes; CI Indigo 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse blue 60 oxime dyes; CI cyclone 5 phthalocyanine dyes; CI basic blue 3, CI basic blue 9 quinone imine dyes; CI solvent yellow 33 ( CI solvent yellow 33), CI acid yellow 3, CI disperse yellow 64 and other quinoline dyes; CI·acid yellow 1, CI acid orange 3, CI disperse yellow 42 and other nitro dyes; disperse yellow 201 and other methine systems dye. In the case where the dye (a2) is used as the colorant in the present invention, the (a2) dye may be used singly or in combination of two or more. (A) The content ratio of the coloring agent is usually 5 to 70 mass in the solid content of the coloring composition from the viewpoint of forming a pixel having high luminance and excellent color purity, -12 to 201142500, or a black matrix having excellent light shielding properties. % ' is preferably 5 to 60% by mass. Here, the solid component is a component other than the glutinous rice. - (B) Copolymer · The (B) copolymer in the present invention contains the repeating unit (1), the repeating unit (2), and the repeating unit (3) 'and the total of the repeating units other than the repeating unit (1), The copolymerization ratio of the repeating unit (2) is 75 mass% or more, and the ratio of the weight average molecular weight Mw to the number average molecular weight Μη (Mw/Mn) is 1. 〇 to 1.9, which produces dispersion as a (Α) colorant. The function of the agent. Further, the terms Mw and Μη herein refer to a weight average molecular weight and a number average molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography (GPC, elution solvent: DMF). The repeating unit (1) is represented by the above formula (1). In the above formula (1), among R, a hydrogen atom and a methyl group, a methyl group is preferred. Further, Ζ represents an n+r2r3r4y_ or -NR5R6, and R2 to R6 represent a hydrogen atom or a hydrocarbon group independently of each other. In the present invention, "hydrocarbon group" means a group containing an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. . It may be any of a linear form, a branched form, and a cyclic form, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, or may have an unsaturated bond in either the molecule or the end. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms), and more specifically, a carbon number of 1 to 20 (preferably 1 to 1 2). An alkyl group, an alkenyl group having 2 to 20 carbon atoms (preferably 2 to 12), and an alkynyl group having 2 to 20 carbon atoms (better than 2 to 12, 2011 to 4,420,200, preferably 2 to 12). Further, 'the alicyclic hydrocarbon group' is preferably an alicyclic hydrocarbon group having a carbon number of 3 to 20 (preferably 3 to 12), and more specifically, a carbon number of 3 to 20 (preferably 3 to 3) 12) A cycloalkyl group. Further, 'the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having a carbon number of 6 to 20 (preferably 6 to 10), and more specifically, a carbon number of 6 to 20 (preferably 6 to 10) An aryl group having an aryl group having 7 to 16 carbon atoms (preferably 7 to 12 carbon atoms). Here, "aryl" means a monocyclic ? 3-ring aromatic hydrocarbon group in the present invention. Among them, as the hydrocarbon group in R2 to R6, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms) and an aralkyl group having 7 to 16 carbon atoms (preferably 7 to 12) are particularly preferable. It is methyl, ethyl, propyl, butyl or pentyl. In the above formula (1), the saturated heterocyclic ring formed by bonding two or more of R2 to R4 to each other may be, for example, the following.
在式(1-1)中,R表示氫原子或烴基,「*」表示連 接鍵,作爲R中之烴基可舉出與上述R2相同者。 又,在上述式(1 )中,作爲R5及R6彼此鍵結而形成 之飽和雜環,可舉出例如下述者。In the formula (1-1), R represents a hydrogen atom or a hydrocarbon group, and "*" represents a linkage, and examples of the hydrocarbon group in R are the same as those of the above R2. Further, in the above formula (1), the saturated hetero ring formed by bonding R5 and R6 to each other may, for example, be as follows.
-14- 201142500 在式(1-2)中,「*」表示連接鍵。 在上述式(1 )中,作爲2價的連結基(X1 ),例如’ 可舉出亞甲基、碳數2〜10 (較佳爲2~6)之伸烷基、伸芳 基、—CONH— R11—基、—COO— R12-基等。在此 ’ R"及 R12,係彼此獨立地表示單鍵、亞甲基、碳數2〜10(較佳爲 2~6)之伸烷基、或碳數2〜10之醚基(伸烷基氧化烯基-14- 201142500 In the formula (1-2), "*" indicates the connection key. In the above formula (1), the divalent linking group (X1) may, for example, be a methylene group, a C 2 to 10 (preferably 2 to 6) alkyl group, an aryl group, or CONH-R11-based, -COO-R12-based, etc. Here, 'R" and R12, independently of each other, represent a single bond, a methylene group, an alkylene group having a carbon number of 2 to 10 (preferably 2 to 6), or an ether group having a carbon number of 2 to 10 (alkylene). Base oxyalkylene
(alkyleneoxyalkylene))。其中,作爲 X1’ 較佳爲— COO 一 R12 —基,作爲R·2,較佳爲碳數2〜6之伸烷基。 在上述式(1)中,作爲Y—,可舉出Cl-、Br-、I·等 鹵素離子,ClCh-、BFr、CH3C0Cr、PF6-等之酸的相對陰 離子。 在上述式(2)中,作爲R7之氫原子及甲基當中’較 佳爲甲基。 作爲R8中之脂肪族烴基,例如,可舉出:烷基、嫌碁、 炔基等。其中,作爲R8,較佳爲碳數1~15(較佳爲1~12) 之烷基,特佳爲甲基、乙基、丙基、丁基、異丁基、t-丁 基、2-乙基己基、異癸基、十二烷基。 又,作爲R8中之脂環式烴基,例如,可舉出:環烷基、 環烯基、縮合多環烴基、交聯環烴基、螺烴基、環狀萜烯 烴基等。其中,作爲R8,較佳爲碳數3〜20 (較佳爲4~15 ) 的脂環式烴基,特佳爲環己基' t-丁基環己基、十氫-2-萘 基、三環[5. 2. 1. 02’6] -8-癸醇、金剛烷基、二環戊烯基、五 環十五烷基、三環戊烯基、異冰片基。 -15- 201142500 重複單元(3 )具有酸性基,作爲酸性基並無特別限定, 例如,可舉出酚性羥基、羧基 '磺酸基、—SO2NH2、- C(CF3): _ Ο Η等。在本發明中,作爲酸性基,從分散性及可獲得的 著色組成物的鹼顯影性的觀點來看,較佳爲酚性羥基、羧 基,特佳爲羧基。 作爲重複單元(3 ) ’例如,可舉出以下述式(3 )所 表示之重複單元。(alkyleneoxyalkylene)). Among them, X1' is preferably -COO-R12- group, and R2 is preferably an alkylene group having 2 to 6 carbon atoms. In the above formula (1), examples of Y- include halogen ions such as Cl-, Br-, and I, and relative anions of acids such as ClCh-, BFr, CH3C0Cr, and PF6-. In the above formula (2), among the hydrogen atom of R7 and the methyl group, 'preferably a methyl group. Examples of the aliphatic hydrocarbon group in R8 include an alkyl group, an anthracene group, and an alkynyl group. Wherein, as R8, an alkyl group having 1 to 15 carbon atoms (preferably 1 to 12) is preferred, and methyl, ethyl, propyl, butyl, isobutyl, t-butyl, and 2 are particularly preferred. -ethylhexyl, isodecyl, dodecyl. Further, examples of the alicyclic hydrocarbon group in R8 include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, a spirohydrocarbyl group, and a cyclic terpene hydrocarbon group. Among them, R8 is preferably an alicyclic hydrocarbon group having a carbon number of 3 to 20 (preferably 4 to 15), particularly preferably a cyclohexyl 't-butylcyclohexyl group, a decahydro-2-naphthyl group, a tricyclic ring. [5. 2. 1. 02'6] -8-nonanol, adamantyl, dicyclopentenyl, pentacyclopentadecyl, tricyclopentenyl, isobornyl. -15- 201142500 The repeating unit (3) has an acidic group, and the acidic group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group 'sulfonic acid group, —SO 2 NH 2 — and C (CF 3 ): _ Η Η. In the present invention, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group, and particularly preferably a carboxyl group, from the viewpoint of dispersibility and alkali developability of the coloring composition which can be obtained. The repeating unit (3)' is, for example, a repeating unit represented by the following formula (3).
在式(3)中,Rl()表示氫原子或甲基,a表示酸性基, X2表示單鍵或2價的連結基。 在上述式(3)中,作爲R1。,氫原子及甲基當中,較 佳爲甲基。 作爲2價的連結基(X2 ),例如,可舉出亞甲基、碳 數2〜10(較佳爲2〜6)之伸烷基、伸芳基、—CONH— R13 —基、一COO— R14 -基' —OCOR15 基一、-R16 - OCO - R17 —、一COO— (CmHuCOOh- CmH2m-基、一COO— R18— OCO _ R19-等。在此,Ri、R 17係彼此獨立地表示單鍵、亞甲基、 碳數2~10(較佳爲2〜6)之伸烷基、或碳數2~10之醚基(伸 烷基氧化烯基),m表示1〜10的整數,1表示1~4的整數, R18表示亞甲基或碳數2〜10(較佳爲2〜6)之伸烷基,R19 表示單鍵、亞甲基、碳數2〜10(較佳爲2~6)之伸烷基、 -16- 201142500 環己烷-1,2. 基)。 其中, 基、—COO —R 1 9 —。 (B ) i 稱爲「重複 子,可舉出 基、咪哩琳 飽和單體; 基)丙烯醯 以下述式(< 基)丙烯酸 ^-ch2— 在式( 之伸烷基, 在(B 部重複單元 又更佳爲1 對於重複單 以上,較佳 佳爲8 5 ~ 9 9 R20In the formula (3), R1() represents a hydrogen atom or a methyl group, a represents an acidic group, and X2 represents a single bond or a divalent linking group. In the above formula (3), it is R1. Among them, a hydrogen atom and a methyl group are preferably a methyl group. Examples of the divalent linking group (X2) include a methylene group, a C 2 to 10 (preferably 2 to 6) alkyl group, an aryl group, a —CONH—R 13 — group, and a COO. — R14 —基′ —OCOR15 基一, —R16 — OCO — R17 —, a COO—(CmHuCOOh- CmH2m-based, a COO—R18—OCO _ R19-, etc. Here, Ri and R 17 are independent of each other. And represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms (preferably 2 to 6), or an ether group having 2 to 10 carbon atoms (alkylene oxide group), and m represents 1 to 10 An integer of 1 represents an integer from 1 to 4, R18 represents a methylene group or an alkylene group having a carbon number of 2 to 10 (preferably 2 to 6), and R19 represents a single bond, a methylene group, and a carbon number of 2 to 10 (more) Preferably, it is 2~6) alkyl, -16- 201142500 cyclohexane-1, 2. base). Among them, the base, -COO - R 1 9 -. (B) i is called "repeat, which can be exemplified by a base, a sulfonium-saturated monomer; a propylene oxime" having the following formula (<-) acrylic acid ^-ch2- in the formula (in the alkyl group, in (B) The repeating unit is more preferably 1 for repeating more than one, preferably preferably 8 5 ~ 9 9 R20
-二基或伸苯基(例如,1,2 -伸苯基、1,4 -伸苯 作爲X2,較佳爲單鍵、伸苯基、一 COO—Rm_ (CmH^mCOO)! — CmΗ2m —基或—COO — R18 — 0 CΟ 专聚物,亦可具有上述以外的重複單元(以下, 單元(4)」)。作爲這種重複單元(4)的例 來自吡啶基、咪唑基、吡唑基、***基、四唑 基'四氫嘧啶基等含氮不飽和雜環之烯鍵性不 苯乙烯、ct-甲基苯乙烯等苯乙烯系單體;(甲 胺;醋酸乙烯酯;丙烯腈等單體的重複單元、 〇所表示之重複單元。在此,在本發明中,「(甲 酯」意指「丙烯酸酯或甲基丙烯酸酯」。 CO〇-fR21〇-^R22 4)中,R2°表示氫原子或甲基,R21表示碳數2~4 R22表示碳數1〜6之烷基。 )共聚物中,重複單元(1)的共聚合比例,全 中,較佳爲5〜70質量%,更佳爲10〜60質量%, 5〜40質量%。重複單元(2)的共聚合比例,相 元(1)以外的重複單元的合計,爲75質量% 爲75~99質量%,更佳爲80~99質量%,又更 質量%,特佳爲90〜99質量%。重複單元(3) -17- 201142500 的共聚合比例,相對於重複單元(1)以外的重複單元的合 計,較佳爲1〜20質量%,更佳爲1~15質量%,特佳爲卜10 質量%。藉由以這種比例來將各重複單元進行共聚合,能 製得分散性及鹼顯影性優異的著色組成物。 (B)共聚物的酸價,從保存安定性的觀點來看,較佳 爲5〜70 mgKOH/g,更佳爲10〜55 mgKOH/g,特佳爲15〜45 mgKOH/g。在此,在本發明中「酸價」係指爲了中和共聚 物溶液之除了溶媒以外的不揮發部分lg所需KOH的mg 數,具體而言,係指根據記載在後述實施例之方法所測定 者。 又,(B)共聚物的胺價,從保存安定性的觀點來看, 較佳爲10~200 mgK〇H/g,更佳爲30〜170mgKOH/g,特佳爲 50~150 mgKOH/g。在此,在本發明中「胺價」係指相當於 爲了中和共聚物溶液之除了溶媒以外的不揮發部分lg所 需的酸與當量之KOH的mg數,具體而言,係指根據記載 在後述實施例之方法所測定者。 (B)共聚物,只要是具有重複單元(1)~重複單元(3), 便無特別的限定,但從更加提高分散性的觀點來看,包含 不具有重複單元(2)及重複單元(3)但具有重複單元(1) 之A嵌段、與不具有重複單元(1)但具有重複單元(2) 及重複單元(3)之B嵌段的嵌段共聚物是較佳的。該嵌段 共聚物,較佳爲A-B嵌段共聚物或B-A-B嵌段共聚物。在 此情況,A嵌段嵌段的共聚合比(質量比),較佳爲 -18- 201142500 5/95〜70/30,更佳爲 10/90〜60/40,特佳爲 15/85〜40/60。 在A嵌段中,亦可在1個A嵌段中含有2種以上的重 複單元(1 ),在該情況下,亦可在該A嵌段中以隨機共聚 合、嵌段共聚合之任何態樣含有各個重複單元。 又,重複.單元(1)以外之重複單元,亦可被含有在A 嵌段中,作爲那種重複單元的例子,可舉出上述來自具有 含氮不飽和雜環基之烯鍵性不飽和單體的重複單元。 另一方面,在B嵌段中,亦可以隨機共聚合、嵌段共 聚合之任何態樣含有重複單元(2)及重複單元(3)。在 (B )共聚物爲B-A-B嵌段共聚物的情況,亦可爲具有B1 嵌段及B2嵌段之B1-A-B2嵌段共聚物,該B1嵌段係具有 重複單元(2)且不具有重複單元(3),該B2嵌段係具有 重複單元(3)且不具有重複單元(2)。又,重複單元(2) 及重複單元(3),亦可在1個B嵌段中分別含有2種以上, 在該情況,亦可以隨機共聚合、嵌段共聚合之任何態樣含 有各個重複單元。 亦可在B嵌段中含有重複單元(2)及重複單元(3) 以外之重複單元,作爲那種重複單元的例子,可舉出來自 苯乙烯、甲基苯乙烯等苯乙烯系單體;(甲基)丙烯醯 胺;醋酸乙烯酯;丙烯腈等單體的重複單元、以下述式(4) 所表示之重複單元。 Β嵌段中之重複單元(2)及重複單元(3)的合計共 聚合比例,較佳爲7 6質量%以上,更佳爲8 3質量%以上, 201142500 特佳爲100質量% ° (B)共聚物的分子量,以GPC (洗提溶媒:DMF)測 定之聚甲基丙烯酸甲酯換算的Mw,較佳爲1,000〜30,000, 特佳爲 5,000~15,0〇〇。 又,(B)嵌段共聚物的Mw與以GPC(洗提溶媒:DMF) 測定之聚甲基丙烯酸甲酯換算的Mn的比(Mw/Μη)爲 1.0~1.9,較佳爲1·〇〜1.8’更佳爲1.0-1.7,又更佳爲1.〇~1.5, 特佳爲1.0〜1.3。藉由將(Β)共聚物作成這種態樣,能製 得分散性及鹼顯影性優異的著色組成物。 (Β )共聚物,能利用熟知方法製造,在(Β )共聚物 爲嵌段共聚物的情況,例如,能藉由進行活性聚合(living polymerization)來製造導入上述各重複單兀的單體。作爲 活性聚合法,能採用下述文獻所記載之熟知方法:日本特 開平9-62002號公報;日本特開2002-3 1 7 1 3號公報;P. Lutz, P. Masson et al, Polym. Bull. 1 2, 79 ( 1 9 84) ; B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601(1981) K. Hatada, K. Ute, et al, Polym. J. 1 7, 977 ( 1 985 ) ; K. Hatada, K. Ute, et al,Polym. J. 18,1037(1986);右手浩一、畑田耕一, 高分子加工,36,366(1987);東村敏延、澤本光男,高分子 論文集,46,189(1989); M. Kuroki,T. Aida,J. Am. Chem. Soc, 1 09, 4737(1987);相田卓三、井上祥平,有機合成化學,43, 300( 1 985) ; D.Y. Sogoh, W.R. Hertler et al, Macromolecules, 20, 1 47 3 ( 1 9 87) ; J. Polym. Sci. Part A Polym. Chem., 47, -20- 201142500 3773-3794(2009); J. Polym. Sci. Part A Polym 3544-3557(2009)等。 作爲賦予重複單元(1 )之單體,例如,可 (甲基)丙烯醯基胺基丙基三甲基銨、氯化( 醯基氧基乙基三甲基銨、氯化(甲基)丙烯醯 三乙基銨、溴化(甲基)丙烯醯基氧基乙基( 基)二甲基銨、氯化(甲基)丙烯醯基氧基乙 基銨、氯化(甲基)丙烯醯基氧基乙基苄基二Z 基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸 乙酯、(甲基)丙烯酸二甲基胺基丙酯' (甲 二乙基胺基丙酯等。它們能單獨或混合2種以_ Z爲一N + R2R3R4Y -之重複單元(1),亦可將 之單體(例如,(甲基)丙烯酸二甲基胺基乙画 使氯化苄基(benzyl chloride )等鹵化烴化合物 合物,部分地使胺基4級化而製得。 作爲賦予重複單元(2 )之單體,例如,可 基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲 丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酵 基)丙烯酸異丁酯、(甲基)丙烯酸t-丁酯、 烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、( 酸異十二酯、(甲基)丙烯酸環己酯、三環[5 癸醇(甲基)丙烯酸酯、(甲基)丙烯酸異冰 基)丙烯酸金剛烷酯、(甲基)丙烯酸二環戊 .Chem., 4 7, 舉出:氯化 甲基)丙烯 基氧基乙基 4-苄醯基苄 基苄基二甲 :基銨、(甲 二乙基胺基 基)丙烯酸 t使用。又, z 爲-nr5r6 旨)聚合後, 反應至該聚 舉出:(甲 基)丙烯酸 ? 丁酯、(甲 (甲基)丙 甲基)丙烯 .2. 1. 02,6] -8-片酯、(甲 烯酯、(甲 -21- 201142500 基)丙烯酸十氫-2-萘酯、(甲基)丙烯酸五環十五烷酯、 (甲基)丙烯酸三環戊烯酯等。它們能單獨或混合2種以 上使用。 作爲賦予重複單元(3)之單體,例如,可舉出:(甲 基)丙烯酸、順丁烯二酸、無水順丁烯二酸、衣康酸、無 水衣康酸、(甲基)丙烯酸羧基甲酯、(甲基)丙烯酸2-羧基-乙酯、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、ω_ 竣基聚己內酯單(甲基)丙烯酸酯、ρ·乙烯基安息香酸、 Ρ -經基本乙稀、ρ -經基-α -甲基苯乙稀、2 -丙嫌醯氧基乙基 磺酸、2·甲基丙烯醯氧基乙基磺酸、2_丙烯醯氧基乙基磺 酸鈉、2 -丙烯醯氧基乙基磺酸鋰、2 -丙烯醯氧基乙基磺酸 銨、2 -丙烯醯氧基乙基磺酸咪唑鎗、2·丙烯醯氧基乙基磺 酸啶、2 -甲基丙烯醯氧基乙基磺酸鈉、2 -甲基丙烯醯氧基 乙基磺酸鋰、2-甲基丙烯醯氧基乙基磺酸銨、2_甲基丙烯 醯氧基乙基擴酸咪哩2 -甲基丙烧醯氧基乙基擴酸π定、 苯乙烯磺酸、苯乙烯磺酸鈉、苯乙烯磺酸鋰、苯乙烯磺酸 銨、苯乙烯磺酸咪唑鑰、苯乙烯磺酸啶等。它們能單獨或 混合2種以上使用。 又’賦予重複單元(4)之單體當中,作爲上述具有含 氮不飽和雜谭基之烯鍵性不飽和單體,例如,可舉出下述 化合物群α (單體1~18)、化合物群召(單體19〜20)所 示之單體等。 [化合物群a ] -22- 201142500 〔化合物群cr〕- a di- or phenyl group (for example, 1,2-phenylene, 1,4-benzene as X2, preferably a single bond, a phenylene group, a COO-Rm_(CmH^mCOO)! - CmΗ2m - Or a group of -COO - R18 - 0 CΟ, or a repeating unit other than the above (hereinafter, unit (4)"). Examples of such a repeating unit (4) are pyridyl, imidazolyl, pyrazole. a styrene monomer such as an ethylenic unsaturated heterocyclic ring such as a triazole group or a tetrazolyl 'tetrahydropyrimidinyl group; and a styrene monomer such as styrene or ct-methylstyrene; (methylamine; vinyl acetate; In the present invention, "(methyl ester) means "acrylate or methacrylate". CO〇-fR21〇-^R22 4 In the above, R2° represents a hydrogen atom or a methyl group, R21 represents a carbon number of 2 to 4, and R22 represents an alkyl group having 1 to 6 carbon atoms. In the copolymer, the copolymerization ratio of the repeating unit (1) is preferably all. 5 to 70% by mass, more preferably 10 to 60% by mass, 5 to 40% by mass. The copolymerization ratio of the repeating unit (2), the total of the repeating units other than the phase element (1), is 75 mass% % is 75 to 99% by mass, more preferably 80 to 99% by mass, and more preferably % by mass, particularly preferably 90 to 99% by mass. The copolymerization ratio of the repeating unit (3) -17 to 201142500 is relative to the repeating unit ( The total of the repeating units other than 1) is preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, particularly preferably from 10% by mass. By copolymerizing each repeating unit at such a ratio, A coloring composition excellent in dispersibility and alkali developability can be obtained. (B) The acid value of the copolymer is preferably from 5 to 70 mgKOH/g, more preferably from 10 to 55 mgKOH, from the viewpoint of storage stability. In the present invention, the "acid value" means the number of mg of KOH required to neutralize the non-volatile portion lg of the copolymer solution other than the solvent, specifically In other words, the amine valence of the copolymer (B) is preferably from 10 to 200 mg K 〇 H / g, more preferably from the viewpoint of preservation stability. It is 30 to 170 mgKOH/g, particularly preferably 50 to 150 mgKOH/g. Here, in the present invention, "amine price" means equivalent to the neutralization of the copolymer solution. The number of mg of the acid and the equivalent amount of KOH required for the non-volatile portion lg other than the solvent is specifically determined by the method described in the examples below. (B) Copolymer, as long as it has a repeating unit (1) The repeating unit (3) is not particularly limited, but includes an A block having no repeating unit (2) and repeating unit (3) but having a repeating unit (1) from the viewpoint of further improving dispersibility. A block copolymer with a B block having no repeating unit (1) but having a repeating unit (2) and a repeating unit (3) is preferred. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. In this case, the copolymerization ratio (mass ratio) of the A block block is preferably -18 to 201142500 5/95 to 70/30, more preferably 10/90 to 60/40, and particularly preferably 15/85. ~40/60. In the A block, two or more repeating units (1) may be contained in one A block, and in this case, any of random copolymerization or block copolymerization in the A block may be used. The pattern contains individual repeating units. Further, repeating units other than the unit (1) may be contained in the A block, and examples of the repeating unit include the above-mentioned ethylenic unsaturated group having a nitrogen-containing unsaturated heterocyclic group. A repeating unit of monomer. On the other hand, in the B block, the repeating unit (2) and the repeating unit (3) may be contained in any of the modes of random copolymerization and block copolymerization. In the case where the (B) copolymer is a BAB block copolymer, it may also be a B1-A-B2 block copolymer having a B1 block and a B2 block, the B1 block having a repeating unit (2) and not There is a repeating unit (3) having a repeating unit (3) and having no repeating unit (2). Further, the repeating unit (2) and the repeating unit (3) may be contained in one or more B blocks, respectively. In this case, any of the random copolymerization or block copolymerization may be included. unit. The repeating unit (2) and the repeating unit other than the repeating unit (3) may be contained in the B block, and examples of the repeating unit include styrene-based monomers such as styrene and methylstyrene; (Methyl) acrylamide; a repeating unit of a monomer such as vinyl acetate or acrylonitrile; and a repeating unit represented by the following formula (4). The total copolymerization ratio of the repeating unit (2) and the repeating unit (3) in the hydrazine block is preferably 76% by mass or more, more preferably 83% by mass or more, and 201142500 is preferably 100% by mass. The molecular weight of the copolymer, Mw in terms of polymethyl methacrylate measured by GPC (extraction solvent: DMF), is preferably from 1,000 to 30,000, particularly preferably from 5,000 to 15,0. Further, the ratio (Mw/Μη) of Mw of the (B) block copolymer to Mn in terms of polymethyl methacrylate measured by GPC (elution solvent: DMF) is 1.0 to 1.9, preferably 1·〇 ~1.8' is preferably 1.0-1.7, and more preferably 1.〇~1.5, especially preferably 1.0~1.3. By forming the (ruthenium) copolymer in such a manner, a colored composition excellent in dispersibility and alkali developability can be obtained. The (?) copolymer can be produced by a well-known method. When the (?) copolymer is a block copolymer, for example, a monomer introduced into each of the above repeating units can be produced by carrying out living polymerization. As the living polymerization method, a well-known method described in the following documents can be used: Japanese Patent Laid-Open Publication No. Hei 9-62002; Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2002-3 1 7 1 3; P. Lutz, P. Masson et al, Polym. Bull. 1 2, 79 (1 9 84) ; BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981) K. Hatada, K. Ute, et al, Polym. J. 1, 7, 977 ( 1 985 K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986); Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36, 366 (1987); Dong Cun Min Yan, Ze Benguang, Polymer Proceedings , 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 1 09, 4737 (1987); Xiangtian Zhuo San, Jing Shangxiang, Organic Synthetic Chemistry, 43, 300 (1 985); DY Sogoh, WR Hertler et al, Macromolecules, 20, 1 47 3 (1 9 87) ; J. Polym. Sci. Part A Polym. Chem., 47, -20- 201142500 3773-3794 (2009); J. Polym Sci. Part A Polym 3544-3557 (2009), etc. As the monomer which imparts the repeating unit (1), for example, (meth)acryloylaminopropyltrimethylammonium chloride, chlorinated (decyloxyethyltrimethylammonium, chlorinated (methyl)) Propylene 醯triethylammonium, brominated (meth) propylene decyloxyethyl dimethyl ammonium, chlorinated (meth) propylene decyl oxyethyl ammonium, chlorinated (methyl) propylene MercaptooxyethylbenzyldiZ-yl) dimethylaminoethyl acrylate, ethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate' (methyldiethylaminopropyl) Ester, etc. They can be used alone or in combination with two repeating units (1) of _Z as a N + R2R3R4Y - or a monomer (for example, dimethylaminosyl (meth) acrylate can be chlorinated A halogenated hydrocarbon compound such as benzyl chloride is obtained by partially quaternizing an amine group. As a monomer imparting the repeating unit (2), for example, methyl methacrylate or (meth)acrylic acid Ethyl ester, (methyl propyl ester, isopropyl (meth) acrylate, (meth) acryl based) isobutyl acrylate, t-butyl (meth) acrylate, 2-ethylhexyl acid, isodecyl (meth)acrylate, (isodecyl acid, cyclohexyl (meth)acrylate, tricyclo [5 decyl (meth) acrylate, (methyl) Isobutyl acrylate) adamantyl acrylate, dicyclopentan (meth) acrylate. Chem., 4 7, exemplified: methyl chloride acryloxyethyl 4-benzyl benzyl benzyl dimethyl : Glycolate, (methyldiethylamino)acrylic acid t used. Further, after z is a polymerization of -nr5r6, the reaction proceeds to the polycondensation: (meth)acrylic acid butyl ester, (methyl(methyl)propylmethyl) propylene. 2. 1. 02,6] -8- a tablet ester, (methene ester, (methyl-21-201142500)) decahydro-2-naphthyl acrylate, pentacyclopentadecyl (meth) acrylate, tricyclopentenyl (meth) acrylate, etc. It can be used alone or in combination of two or more. Examples of the monomer to which the repeating unit (3) is added include (meth)acrylic acid, maleic acid, anhydrous maleic acid, itaconic acid, and anhydrous. Itaconic acid, carboxymethyl (meth) acrylate, 2-carboxy-ethyl (meth) acrylate, mono [2-(methyl) propylene methoxyethyl] succinate, ω 竣 聚 聚Ester mono (meth) acrylate, ρ·vinyl benzoic acid, Ρ - via basic ethylene, ρ-pyridyl-α-methyl styrene, 2-propane decyloxyethyl sulfonic acid, 2· Methyl propylene methoxy oxy sulfonic acid, sodium 2-propylene oxy oxy sulfonate, lithium 2-propylene oxy oxy sulfonate, ammonium 2- propylene oxy oxy sulfonate, 2- propylene Methoxyethyl sulfonate Gun, 2, propylene oxy oxyethyl sulfonate, sodium 2-methacryloxy sulfonate, lithium 2-methyl propylene oxy sulfonate, 2-methyl propylene sulfoxy Ammonium ethyl sulfonate, 2-methylpropenyloxyethyl acid extended oxime 2-methylpropenyl oxime oxyethyl acid π ding, styrene sulfonic acid, sodium styrene sulfonate, styrene sulfonate Lithium acid, ammonium styrene sulfonate, imidazole sulfonic acid imidazole, styrene sulfonate, etc. These may be used alone or in combination of two or more. Further, among the monomers which are given to the repeating unit (4), Examples of the ethylenically unsaturated monomer of the nitrogen-unsaturated heterotyl group include a compound represented by the following compound group α (monomers 1 to 18) and a compound group (monomers 19 to 20). [Compound group a] -22- 201142500 [Compound group cr]
C%^H c=〇 O^CI H^· (單體2)C%^H c=〇 O^CI H^· (monomer 2)
CHj^ipH (ps=iQ (單體3)CHj^ipH (ps=iQ (monomer 3)
CHa C=D 〇-(CICHa C=D 〇-(CI
Hafe-O-fCHt). (單體5)Hafe-O-fCHt). (Monomer 5)
CHf=<pH :: (Will)CHf=<pH :: (Will)
ch3 GH— 0=0hL 陶 3-〇ν (單體10)Ch3 GH— 0=0hL Tao 3-〇ν (monomer 10)
CH2=C pH3 =0 9¾ V*令Π〇Ηώ-^ (單體14) (單體15)CH2=C pH3 =0 93⁄4 V* Π〇Ηώ-^ (monomer 14) (monomer 15)
9¾93⁄4
O'CHjpHCHi-N^ OH (單體]8) -23- 201142500O'CHjpHCHi-N^ OH (monomer) 8) -23- 201142500
(單體19 ) (單體20 ) 又,賦予上述重複單元(4)之單體當中,作爲賦 上述式(4)所表示之重複單元的單體’例如,可舉出: 基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸甲氧基二 醇酯、(甲基)丙烯酸甲氧基三乙二醇酯、(甲基) 酸甲氧基丙二醇酯、(甲基)丙烯酸甲氧基二丙二醇醋 (B)共聚物能單獨或混合2種以上使用。(B) 物的含有量,相對於(al)顏料100質量份,通常爲1 質量份,較佳爲5〜70質量份,更佳爲10〜50質量份。若 共聚物的含有量過多,則有顯影性受損的疑慮。 在本發明中,爲了提高分散性,亦能進一步使其 熟知的分散劑。作爲熟知的分散劑,例如,能舉出: 甲酸酯系分散劑、聚伸乙亞胺系分散劑、聚氧乙烯烷 系分散劑、聚氧乙烯烷基苯基醚系分散劑、聚乙二醇 系分散劑、山梨糖醇脂肪酸酯系分散劑、聚醋系分散 丙烯酸系分散劑、顏料衍生物等。 這種分散劑能在商業上購得,例如,作爲丙烯酸 予以 (甲 乙二 丙烯 等。 共聚 〜100 (B ) 含有 胺基 基醚 二酯 劑、 系分 -24- .201142500 散劑,能舉出 Disperbyk-2000 、 Disperbyk-2001 ' BYK-LPN6919、BYK-LPN 21116、BYK-LPN21324C 以上,BYK Chemie ( BYK)公司製);作爲胺基甲酸酯系分散劑,能 舉出 Disperbyk-161 、 Disperbyk-162 、 Disperbyk-165 、 Disperbyk-167、Disperbyk-170、Disperbyk-182 (以上,BYK Chemie ( BYK)公司製)、Solsperse 76500 ( Lubrizol(股) 公司製);作爲聚伸乙亞胺系分散劑,能舉出Sols perse 24000 (Lubrizol(股)公司製);作爲聚酯系分散劑,能舉出 AJISPERPB821、AJISPERPB822、AJISPERPB880、AJISPER PB881 (味之素Fine-Techno股份公司製)等。又,作爲顏 料衍生物之具體例,能舉出:銅酞菁、二酮吡咯并吡咯、 喹酞酮之磺酸衍生物等。 -(C )交聯劑- 在本發明中(C )交聯劑係指具有2個以上之可聚合的 基的化合物。作爲可聚合的基,例如,能舉出:烯鍵性不 飽和基、環氧乙基(Oxiranyl)、氧雜環丁烷基、N-烷氧基 甲基胺基等。在本發明中,作爲(C )交聯劑,較佳爲具有 2個以上之(甲基)丙烯醯基的化合物、或具有2個以上 之N-烷氧基甲基胺基的化合物。 作爲上述具有2個以上之(甲基)丙烯醯基的化合物 的具體例,能舉出:使脂肪族聚羥基化合物與(甲基)丙 烯酸反應所製得之多官能(甲基)丙烯酸酯、己內酯改質 之多官能(甲基)丙烯酸酯、環氧烷改質之多官能(甲基) -25- 201142500 丙燦酸醋、使具有羥基之(甲基)丙烯酸酯與多官能異氰 酸醋反應所製得之多官能胺基甲酸酯(甲基)丙烯酸酯、 使具有經基之(甲基)丙烯酸酯與酸酐反應所製得之具有 羧基之多官能(甲基)丙烯酸酯等, 在此’作爲上述脂肪族聚羥基化合物,例如,能舉出: 如乙二醇、丙二醇、聚乙二醇、聚丙二醇之2價脂肪族聚 羥基化合物,如丙三醇、三羥甲基丙烷、新戊四醇、二新 戊四醇之3價以上之脂肪族聚羥基化合物。作爲上述具有 經基之(甲基)丙烯酸酯,例如,能舉出:(甲基)丙烯 酸2 -羥基乙酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊 四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸 醋、丙三醇二甲基丙烯酸酯等。作爲上述多官能異氰酸酯, 例如,能舉出:甲苯二異氰酸酯、六亞甲基二異氰酸酯、 二苯基亞甲基二異氰酸酯、異佛酮二異氰酸酯等。作爲酸 酐’例如’能舉出:如琥珀酸酐、順丁烯二酸酐、戊二酸 酐、衣康酸酐、酞酸酐、六氫酞酸酐之二鹼基酸酐,焦蜜 石酸酐、聯苯基四羧酸二酐、二苯甲酮四羧酸二酐之四鹼 基二酸酐。 又,作爲上述己內酯改質之多官能(甲基)丙烯酸酯, 例如’能舉出日本特開11-44955號公報段落[0015]〜[0018] 所記載之化合物。作爲上述環氧烷改質之多官能(甲基) 丙烯酸酯,能舉出:雙酚A之環氧乙烷及/或環氧丙烷改質 二(甲基)丙烯酸酯、三聚異氰酸之瓌氧乙烷及/或環氧丙 -26- 201142500 烷改質三(甲基)丙烯酸酯、三羥甲基丙烷之環氧乙烷及/ 或環氧丙烷改質三(甲基)丙烯酸酯 '新戊四醇之環氧乙 烷及/或環氧丙烷改質三(甲基)丙烯酸酯、新戊四醇之環 氧乙烷及/或環氧丙烷改質四(甲基)丙烯酸酯、二新戊四 醇之環氧乙烷及/或環氧丙烷改質五(甲基)丙烯酸酯、二 新戊四醇之環氧乙烷及/或環氧丙烷改質六(甲基)丙烯酸 酯等。 又’作爲上述具有2個以上之N -烷氧基甲基胺基之化 合物,例如’能舉出具有三聚氰胺結構、苯并胍胺結構、 尿素結構之化合物等。又,三聚氰胺結構、苯并胍胺結構, 係指具有以1個以上之三畊環或苯基取代三畊環作爲基本 骨架的化學結構’亦包含三聚氰胺、苯并胍胺或它們的縮 合物的槪念。作爲具有2個以上之N -烷氧基甲基胺基之化 合物的具體例,能舉出:N,N,N,N,N,N-六(烷氧基甲基) 三聚氰胺、N,N,N,N-四(烷氧基甲基)苯并胍胺、N,N,N,N-四(院氧基甲基)甘脲(N,N,N,N-tetra ( alkoxylmethyl) glycoluril )等。 這些多官能性單體當中,使3價以上之脂肪族聚羥基 化合物與(甲基)丙烯酸反應所製得之多官能(甲基)丙 烯酸酯、己內酯改質之多官能(甲基)丙烯酸酯、多官能 胺基甲酸酯(甲基)丙烯酸酯、具有羧基之多官能(甲基) 丙烯酸酯、N,N,N,N,N,N-六(烷氧基甲基)三聚氰胺、 叱叱叱1^四(烷氧基甲基)苯并胍胺是較佳的。在使3價 -27- 201142500 以上之脂肪族聚羥基化合物與(甲基)丙烯酸反應所製得 之多官能(甲基)丙烯酸酯當中之三羥甲基丙烷三丙烯酸 酯、新戊四醇三丙烯酸酯 '二新戊四醇五丙烯酸酯、二新 戊四醇六丙烯酸酯,具有羧基之多官能(甲基)丙烯酸酯 當中之使新戊四醇三丙烯酸酯與琥珀酸酐反應所製得之化 合物、使二新戊四醇五丙烯酸酯與琥珀酸酐反應所製得之 化合物,在著色層的強度高、著色層表面平滑性優異、且 難以在未曝光部之基板上及遮光層上發生油污 (greasing )、殘膜等方面上是特佳的。 在本發明中,(C )交聯劑能單獨或混合2種以上使用。 本發明中之(C)交聯劑的含有量,相對於(A)著色 劑100質量份,較佳爲1〇~ 1,〇〇〇質量份,特佳爲20〜5 00質 量份。在此情況,若多官能性單體的含有量過少,則有無 法獲得足夠的硬化性的疑慮。另一方面,若多官能性單體 的含有量過多,則在將鹼顯影性賦予本發明之著色組成物 的情況下,鹼顯影性降低,有成爲容易在未曝光部之基板 上或遮光層上發生油污、殘膜等的傾向。 • ( D )結合劑樹脂- 本發明之著色組成物,能使其含有(D)結合劑樹脂。 藉此’能提高著色組成物之鹼顯影性或對基板的結合附著 性。作爲這種結合劑樹脂,並無特別限定,但較佳爲具有 殘基、酚性羥基等酸性官能基的樹脂。其中,較佳爲具有 竣基之聚合物(以下稱爲「含羧基聚合物」),例如,能 -28- 201142500 舉出:具有1個以上羧基之烯鍵性不飽和單體(以下稱爲 「不飽和單體(dl)」)與其他的可共聚合的烯鍵性不飽 和單體(以下稱爲「不飽和單體(d2 )」)的共聚物。 作爲上述不飽和單體(d 1 ),例如,能舉出:(甲基) 丙烯酸、順丁烯二酸、順丁烯二酸酐、琥珀酸單[2-(甲基) 丙稀醯氧基乙基]醋、ω-殘基聚己內醋單(甲基)丙嫌酸 酯、ρ_乙烯基安息香酸等。 這些不飽和單體(dl)能單獨或混合2種以上使用。 又,作爲上述不飽和單體(d 2 ),例如,能舉出: 如N -苯基順丁烯二醯亞胺、N -環己基順丁烯二醯亞胺 之N-取代順丁烯二醯亞胺;如苯乙烯、α -甲基苯乙烯、p_ 鞋基本乙嫌、p -經基-α-甲基苯乙煉、p -乙烧基节基縮水甘 油基醚、苊烯之之芳香族乙烯化合物; 如(甲基)丙烯酸甲酯、(甲基)丙烯酸η-丁酯、(甲 基)丙烯酸2 -乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲 基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、聚乙二醇(η =2〜10)甲基醚(甲基)丙烯酸酯、聚丙二醇(η=2〜10) 甲基醚(甲基)丙烯酸酯、聚乙二醇(η=2~10)單(甲基) 丙烯酸酯、聚丙二醇(η=2〜10)單(甲基)丙烯酸酯、(甲 基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、三環[5,2. 1. 0 2’6 ]癸-8-基(甲基)丙烯酸酯、(甲基)丙烯酸二環 戊酯、甘油單(甲基)丙烯酸酯、4-羥基苯基(甲基)丙 烯酸酯、對異丙苯基酚之環氧乙烷改質(甲基)丙烯酸酯、 -29- 201142500 (甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環 己基甲酯、3 -[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3_ [(甲 基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷之(甲基)丙烯酸 酯: 如環己基乙烯基醚、異冰片基乙烯基醚、三環[5.2. ΙΟ2’6] 癸 -8-基乙 烯基醚 、戊環十五烷基乙烯基醚、 3-( 乙烯 基氧基甲基)-3-乙基氧雜環丁烷之乙烯基醚; 在如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基) 丙烯酸-η-丁酯、聚矽氧烷之聚合物分子鏈的末端具有單 (甲基)丙烯醯基的巨大單體等。 這些不飽和單體(d2 )能單獨或混合2種以上使用。 在不飽和單體(dl)與不飽和單體(d2)的共聚物中, 該共聚物中的不飽和單體(dl )的共聚合比例,較佳爲5~50 質量%,更佳爲10〜40質量%。藉由在這種範圍下使不飽 和單體(d 1 )進行共聚合,能製得鹼顯影性及保存安定性 優異的著色組成物。 作爲不飽和單體(dl)與不飽和單體(d2)的共聚物 的具體例,例如’能舉出:日本特開平7」4〇654號公報、 曰本特開平8-259876號公報、日本特開平10_3 1 3 08號公 報、日本特開平1 0-300922號公報、日本特開平1 1 - 1 74224 號公報、日本特開平1 1 -25 84 1 5號公報、日本特開 2000-56118號公報、日本特開2004-101728等所揭示之共聚 物。 -30- 201142500 又,在本發明中,例如,亦能使用如日本特I 號公報、日本特開平6-230212號公報、日本特開 號公報、日本特開平09-325494號公報、| U-140144號公報、日本特開2008-181095號 示’在側鏈具有(甲基)丙烯醯基等之聚合性不 含羧基聚合物,作爲結合劑樹脂使用。 本發明中之結合劑樹脂,以GPC (洗提溶 喃)測定之聚苯乙烯換算的重量平均分子量( 常爲 1,000〜100,000,較佳爲 3,000〜50,000。若 則有所製得之被膜的殘膜率等降低,圖案形狀 受損,又電性特性惡化的疑慮,另一方面若過 晰度降低,圖案形狀受損,又當利用狹縫噴嘴 成爲乾燥異物容易發生的疑慮。 又,本發明中之結合劑樹脂的重量平均分 與數量平均分子量(Μη,)的比(Mw,/ Μη’ 1.0〜5·0,更佳爲1.0〜3.0。又,在此所謂之Mw’ GPC (洗提溶媒:四氫呋喃)測定之聚苯乙烯 平均分子量及數量平均分子量。 本發明中之結合劑樹脂,能利用熟知的方 亦能藉由例如日本特開 2003-2227 1 7號公報 2006-2596 80號公報、國際公開第07/029 87 1號 示之方法來控制其構造或Mw、Mw/Mn。 在本發明中,結合劑樹脂,能單獨或混合 圍平 5 - 1 9 4 6 7 平 7-207211 3本特開平 公報等所揭 飽和鍵結的 媒:四氫呋 Mw,),通 M w ’過小, 、耐熱性等 大,則有解 方式塗布時 子量(M w ’) ),較佳爲 及 Μ η ’係以 換算的重量 法製造,但 、曰本特開 手冊等所揭 2種以上使 -31- 201142500 用。 在本發明中’結合劑樹脂的含有量,相對於(A )著色 劑100質量份,通常爲1〇~ 1,〇〇〇質量份,較佳爲20〜500質 量份。若結合劑樹脂的含有量過少,則有例如,鹼顯影性 降低’製得之著色組成物的保存安定性降低的疑慮,另一 方面若過多’則有因著色劑濃度相對地降低,而變得難以 以薄膜來達成想要的色濃度的疑慮。 -(E)光聚合起始劑- 本發明之著色組成物,能使其含有(E)光聚合起始劑。 藉此,能將感放射線性賦予著色組成物。本發明使用的(E ) 光聚合起始劑’係藉由可見光線、紫外線、遠紫外線、電 子線、X線等放射線的曝光,產生可開始上述(C )交聯劑 的聚合之活性種的化合物。 作爲這種光聚合起始劑,例如,可舉出:9 -氧硫卩山d星 系化合物、苯乙酮系化合物、聯咪唑系化合物、三哄系化 合物' 〇 -醯基肟系化合物、鑰鹽系化合物、苯偶姻系化合 物、二苯基酮系化合物、〇:-二酮系化合物、多核醌系化合 物、重氮系化合物、亞胺磺酸鹽(imido-sulfonate )系化合 物等。 在本發明中’光聚合起始劑’能單獨或混合2種以上 使用。作爲光聚合起始劑,較佳爲從9 -氧硫灿唱系化合物、 本乙嗣系化合物、聯味哗系化合物、二哄系化合物、Q__ 基肟系化合物之群組所選出的至少1種。 -32- 201142500 本發明中之較佳的光聚合起始劑當中,作爲9-氧硫口山 嗤系化合物之具體例,能舉出:9-氧硫卩[II哩、2-氯9-氧硫 口山喂、2-甲基9-氧硫卩ill·、2-異丙基9-氧硫灿嘎、心異丙 基9-氧硫卩山I]星、2,4-二氯9-氧硫卩山唱、2,4-二甲基9-氧硫口山 !]星、2,4-二乙基9-氧硫卩山卩星、2,4-二異丙基9-氧硫卩山唱等。 又,作爲上述苯乙酮系化合物之具體例,能舉出:2-甲基-1·[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲 基胺基-1-(4-嗎啉基苯基)·1-丁酮、2-(4-甲基苄基)-2-(二甲 基胺基)-1-(4-嗎啉基苯基)-1-丁酮等。 又,作爲上述聯咪唑系化合物之具體例,能舉出:2,2’ -雙(2-氯苯基)-4,4’ ,5,5’ -四苯基-1,2’ -聯咪唑、2,2’ - 雙(2,4-二氯苯基)-4,4’ ,5,5’ -四苯基-1,2’ -聯咪唑、2,2’ -雙(2,4,6-三氯苯基)-4,4’ ,5,5’ -四苯基·1,2’ -聯咪唑等。 又,在使用聯咪唑系化合物作爲光聚合起始劑的情 況,倂用氫予體,在能改善感度方面是較佳的。在此所謂 的「氫予體」,係指對藉由曝光而從聯咪唑系化合物產生 的自由基,能供給氫原子之化合物。作爲氫予體,例如, 能舉出:2-锍基苯并噻唑、2-毓基苯并噁唑等之硫醇系氫 予體;4,4’-雙(二甲基胺基)二苯基酮、4,4’_雙(二乙基 胺基)二苯基酮等之胺系氫予體。在本發明中,氫予體, 能單獨或混合2種以上使用,但將1種以上硫醇系氫予體 與1種以上胺系氫I予體組合使用’在能進一步改善感度方 面是較佳的。 -33- 201142500 又,作爲上述三阱系化合物之具體例,能舉出:2,4,6-參(三氯甲基)-s-三阱、2-甲基·4,6-雙(三氯甲基)-s-三 阱' 2-[2-( 5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基) -5-三阱、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-5-三阱、2-[2-( 4-二乙胺基-2-甲苯基)乙烯基]-4,6-雙(三氯 甲基)-3-三畊、2-[2-(3,4-二甲氧苯基)乙烯基]-4,6-雙(三 氯甲基)-s-三阱、2-(4-甲氧苯基)-4,6-雙(三氯甲基) -5-三畊、2-(4-乙氧苯乙烯基)-4,6-雙(三氯甲基)-5-三 阱、2-(4-!1-丁氧苯基)-4,6-雙(三氯甲基)-5-三阱等具 有鹵甲基之三畊系化合物。 又,作爲◦-醯基肟系化合物之具體例,能舉出:1,2 -辛二酮,1-[4·(苯硫基)苯基]-,2-(0-苯甲醯基肟)、乙 酮,1-[9-乙基-6-(2-甲基苯甲醯基)-911-咔唑-3-基]-,1-(〇· 乙醯基肟)、乙酮,1·[9·乙基-6- (2 -甲基-4 -四氫呋喃基甲 氧基苯甲醯基)_9Η_咔唑·3-基]-,1-(〇-乙醯基肟)、乙 酮,1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二環氧乙烷基) 甲氧基苯甲醯基} _9Η_咔唑-3-基]· ,1-(0-乙醯基肟)等。 在本發明中,在使用苯乙酮系化合物等之聯咪唑系化 合物以外的光聚合起始劑的情況,亦可倂用增感劑。作爲 這種增感劑,例如,能舉出:4,4’ -雙(二甲胺基)二苯基酮、 4,4’ -雙(二乙胺基)二苯基酮、4-二乙胺基苯乙酮、4-二甲 胺基苯丙酮、4 -二甲胺基安息香酸乙酯、4 -二甲胺基安息 香酸2-乙基己酯' 2,5-雙(4-二乙胺基亞苄基)環己酮、7-二 -34- 201142500 乙胺基-3-(4-二乙胺基苄醯基)香豆素、4-(二乙胺基)查酮 等。 在本發明中,光聚合起始劑之含有量,相對於(C)交 聯劑100質量份,較佳爲0.0卜120質量份,特佳爲1~1〇〇 質量份。在此情況,若光聚合起始劑之含有量過少,便會 有利用曝光之硬化成爲不充分的疑慮,另一方面,若過多, 則有所形成之著色層在顯影時成爲容易從基板脫落的傾 向。 -(F )溶媒- 本發明之著色組成物,通常,將包含(A)顏料之著色 劑,在(F)溶媒中’連同(B)共聚物及依需要之其他分 散劑或(D )結合劑樹脂的一部分,使用例如珠磨(beads mill)、輥磨(r ο Π m i 11 )等’加以粉碎同時混合、分散而 作成顏料分散液’接著,在此顏料分散液,藉由添加、混 合(C )交聯劑、及依需要之(d )結合劑樹脂、(E )光 聚合起始劑、進一步追加的(F)溶媒等方法,來予以調製。 作爲(F)溶媒’只要是將構成著色組成物的成分(.a)〜 (C)或其他成分分散或溶解,且不會與這些成分反應,具 有適度的揮發性者,便能適宜地選擇使用。但是,在調製 上述顏料分散液之際,從分散性及安定性的觀點來看,較 佳爲倂用(f!)具有羥基的溶媒(以下,亦稱爲「溶媒(f丨)」) 與(Π)不具有羥基的溶媒(以下,亦稱爲「溶媒(f2)」)。 &種溶媒當中’作爲溶媒(f 1 ),例如,能舉出: -35- 201142500 乙二醇單甲醚、乙二醇單***、乙二醇單- η-丙醚、乙 二醇單-η-丁醚、二乙二醇單甲醚、二乙二醇單***、二乙 二醇單-η-丙醚、二乙二醇單-η-丁醚、三乙二醇單甲醚、三 乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單 -η-丙醚、丙二醇單-η-丁醚、二丙二醇單甲醚、二丙二醇單 ***、二丙二醇單-η-丙醚、二丙二醇單-η-丁醚、三丙二醇 單甲醚、三丙二醇單***等之(聚)伸烷基二醇單烷基醚 類; 乳酸甲酯、乳酸乙酯等之乳酸烷基酯類; 甲醇、乙醇、丙醇、丁醇、異丙醇、異丁醇、t-丁醇、 辛醇、2-乙基己醇、環己醇等之(環)烷基醇; 二丙酮醇等之酮醇類等。 這些溶媒(Π)當中,較佳爲(聚)伸烷基二醇單烷 基醚類,特佳爲丙二醇單甲醚、丙二醇單***。溶媒(Π), 能單獨或混合2種以上使用。 又,作爲溶媒(f2 ),例如,能舉出: 乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二 醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚 乙酸酯、丙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、 3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等之 (聚)伸烷基二醇單烷基醚乙酸酯類; 二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二 ***、四氫呋喃等之其它的醚類; -36- 201142500 甲基乙基酮、環己酮、2-庚酮、3-庚酮等之酮類; 丙二醇二乙酸酯、1,3-丁二醇二乙酸酯' 1,6-己二醇二 乙酸酯等之二乙酸酯類; 3-甲氧基丙酸甲酯' 3-甲氧基丙酸乙酯、3-乙氧基丙酸 甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、3-甲基.-3-甲 氧基丁基丙酸酯等之烷氧基羧酸酯類; 乙酸乙醋、乙酸η-丙酯、乙酸i-丙醋、乙酸η-丁醋、 乙酸i-丁酯、甲酸η-戊酯、乙酸i-戊酯、丙酸η-丁酯、丁 酸乙酯、丁酸丙酯、丁酸i-丙酯、丁酸η-丁酯、丙酮酸 甲酯、丙酮酸乙酯、丙酮酸η-丙酯、乙醯乙酸甲酯、乙醯 乙酸乙酯、2-氧丁酸乙酯等之其它的酯類; 甲苯、二甲苯等之芳香族烴類; Ν,Ν-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、Ν-甲基吡咯 啶酮等之醯胺或內醯胺類等。 這些溶媒(f2)當中,較佳爲(聚)伸烷基二醇單烷 基醚乙酸酯類、醚類、酮類、二乙酸酯類、烷氧基羧酸酯 類,特佳爲乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、 丙二醇單***乙酸酯、3 -甲氧基丁基乙酸酯、二丙二醇單 甲醚乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、環 己酮、1,3· 丁二醇二乙酸酯、1,6-己二醇二乙酸酯、3-甲氧 基丙酸乙酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯。溶 媒(f2 ),能單獨或混合2種以上使用。 在本發明中,著色劑分散液中之溶媒(f 1 )與溶媒(f2 ) -37- 201142500 的含有質量比(fl/f2) ’較佳爲〇.5/99.5~40/60,更佳爲 1/99〜30/70 ,特佳爲 5/95〜25/75 。 溶媒的含有量’並無特別限定,但不論是顏料分散液 或著色組成物,除了該顏料分散液或著色組成物的溶媒以 外之各成分的合計濃度’較佳地成爲5 ~5〇質量%的量,特 佳地成爲10〜40質量%的量.。藉由作成這種態樣,能製得 分散性、安定性良好的著色劑分散液,以及塗布性、安定 性良好的著色組成物。 -添加劑- 本發明之著色組成物’依需要,亦能含有各種添加劑。 作爲添加劑’例如,能舉出:玻璃、氧化鋁等之塡充 劑;聚乙烯醇、聚(氟烷基丙烯酸酯)類等之高分子化合 物;氟系界面活性劑、矽系界面活性劑等之界面活性劑; 乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2_ 甲氧基乙氧基)矽烷、N-(2 -胺基乙基)-3 -胺基丙基甲基 —甲氧基砂院、N-( 2 -胺基乙基)-3 -胺基丙基三甲氧基砂 烷、3 -胺基丙基三乙氧基矽烷、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 氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基 矽烷、3 -氯丙基三甲氧基矽烷、3 -甲基丙烯醯氧基丙基三 甲氧基矽烷、3-锍基丙基三甲氧基矽烷等之密著促進劑; 2,2·硫基雙(4-甲基-6-t-丁基酚)、2,6-二-t-丁基酚等之抗 氧化劑;2-( 3-t-丁基-5-甲基-2-羥基苯基)-5-氯苯并***、 -38- 201142500 院氧基二苯基酮類等之紫外線吸收劑;聚丙烯酸鈉等之抗 凝集劑;丙二酸、己二酸、衣康酸、檸康酸、富馬酸、中 康酸(mesaconic acid) 、2-胺基乙醇、3-胺基-1-丙醇、5- 胺基-1-戊醇、3-胺基-1,2 -丙二醇、2 -胺基-1,3-丙二醇、4-胺基-1,2-丁二醇等之殘渣改善劑;琥珀酸單[2_ (甲基)丙 烯醯氧基乙基]酯、苯二甲酸單[2-(甲基)丙烯醯氧基乙基] 酯、羧基聚己內酯單(甲基)丙烯酸酯等之顯影性改善 劑等。 彩色濾光片及其製造方法 本發明之彩色濾光片係具備使用本發明之著色組成物 所形成的著色層者。 作爲製造彩色濾光片之方法,第一可舉出以下的方 法。首先,在基板表面上,依需要以劃分形成像素的部分 的方式形成遮光層(黑色矩陣)。接著,在此基板上,例如, 在塗布已分散紅色顔料之感放射線性組成物的液狀組成物 之後,進行預烘烤使溶媒蒸發,形成塗膜。接著,在對此 塗膜透過光罩進行曝光之後,使用鹼顯影液進行顯影,將 塗膜之未曝光部溶解除去。之後,藉由進行後烘烤,形成 將紅色的像素圖案以既定的排列予以配置之像素陣列。 接著,使用綠色或藍色之各著色感放射線性組成物, 與上述同樣地進行,進行各著色感放射線性組成物之塗 布、預烘烤、曝光、顯影以及後烘烤,依序在同一基板上 形成綠色之像素陣列及藍色之像素陣列。藉此,可製得將 -39- 201142500 紅色、綠色及藍色之三原色的像素陣列配置在基板上之彩 色濾光片。但是,在本發明中,各色像素之形成順序,並 未限定於上述者。 又’黑色矩陣,能藉由將以濺鍍或蒸鍍成膜之鉻等的 金屬薄膜’利用光微影法作成所要之圖案來形成,亦能使 用分散有黑色顏料的著色感放射線性組成物,與形成上述 像素的情況同樣地形成。 作爲在形成彩色濾光片之際所使用之基板,例如,能 舉出:玻璃、矽、聚碳酸酯 '聚酯、芳香族聚醯胺、聚醯 胺醯亞胺、聚醯亞胺等。 又’在這些基板’亦能依所需’而先實施矽烷耦合劑 等之藥品處理、電漿處理、離子鏟敷、濺鍍、氣相反應法、 真空蒸鍍等之適宜的前處理。 在將著色感放射線性組成物塗布在基板上之際,能採 用噴霧法(spray method)、輥塗法、旋轉塗布法(spinc〇at method)、狹縫模塗布法、棒塗布法等適宜的塗布法,但特 佳爲旋轉塗布法、狹縫模塗布法。 預烘烤’通常是組合減壓乾燥與加熱乾燥進行。減壓 乾無,通吊疋進订至達到50~200Pa爲止。又,加熱乾燥之 條件,通常是在70-110 °C下進行1〜1〇分鐘左右。 塗布厚度’作爲乾燥後之膜厚,通常是〇.6〜8 ()" m, 較佳爲1.2〜5.0# m。 作爲在形成像素及/或黑色矩陣之際所使用之放射線 -40- 201142500 光源,例如,能舉出:氙燈、鹵素燈、鎢燈、高壓水銀燈、 超高壓水銀燈、金屬鹵素燈、中壓水銀燈、低壓水銀燈等 之燈光源或氬離子雷射、YAG雷射、XeCl準分子雷射、氮 雷射等之雷射光源等,但較佳爲波長位於190〜450nm範圍 之放射線。 放射線之曝光量,一般而言,較佳爲10~ 1 0,000〗/m2。 又,作爲上述鹼顯影液,例如,較佳爲碳酸鈉、氫氧 化鈉、氫氧化鉀、氫氧化四甲基銨、膽鹼(choline ) 、l,8-二氮雜雙環-[5·4.0^7-十一烯、l,5-二氮雜雙環-[4·3·0]-5-壬烯等之水溶液。 在上述鹼顯影液,例如,亦能適量添加甲醇、乙醇等 水溶性有機溶劑或界面活性劑等。又,鹼顯影後,通常進 行水洗。 · 作爲顯影處理法,能應用噴淋顯影法、噴霧顯影法、 浸漬(dip )顯影法、混拌(puddle )(盛液)顯影法等。 顯影條件,較佳爲常溫下5〜3 0 0秒。 後烘烤的條件,通常是在180〜280°C下進行10〜60分鐘 左右。 依此方式所形成之像素的膜厚,通常爲〇.5~5.0y m, 較佳爲1.0〜3.0ym。 又’作爲製造彩色濾光片之第二方法,能採用揭示於 曰本特開平7 - 3 1 8 7 2 3號公報、日本特開2000-3 1 0706號公 報等之利用噴墨方式製得各色像素的方法。在此方法中, -41- 201142500 首先,在基板表面上,形成兼具遮光功能的隔牆。接著’ 在所形成之隔牆內,例如,將已分散紅色顏料之著色組成 物之液狀組成物,利用噴墨裝置吐出後,進行預烘烤使溶 媒蒸發。接著,依需要,將此塗膜曝光後,藉由後烘烤使 其硬化,形成紅色的像素圖案。 接著,使用綠色或藍色之各著色組成物,與上述同樣 地進行,依序在同一基板上形成綠色像素圖案及藍色像素 圖案。藉此,可製得將紅色、綠色及藍色之三原色的像素 圖案配置在基板上之彩色濾光片。但是,在本發明中,形 成各色像素的順序不限定於上述者。 又,上述隔牆,不僅有遮光功能,亦發揮讓已吐出在 劃分區域內之各色著色組成物不會混色之功能,因此相較 於在上述第一方法所使用之黑色矩陣,膜厚厚。因此,隔 牆,通常是使用黑色感放射線性組成物形成。 在形成彩色濾光片之際所使用之基板或放射線的光 源,又,預烘烤或後烘烤之方法或條件,係與上述第一方 法相同。依此方式,利用噴墨方式所形成之像素的膜厚, 係與黑色矩陣的厚度相同程度。 在依此方式所製得之像素圖案上,依需要在形成保護 膜後,利用濺鍍形成透明導電膜。亦能在形成透明導電膜 後’進一歩形成間隙物(spacer)作成彩色濾光片。間隙物, 通常是使用感放射線性組成物形成,亦能作成具有遮光性 之間隙物(黑色間隙物(b 1 a c k s p a c e r ))。在此情況,可 -42- 201142500 用分散有黑色著色劑之著色感放射線性組成物,但本發明 之著色組成物,亦能適合使用於黑色間隙物之形成。 依此方式所製得之本發明的彩色濾光片,輝度及色純 度極高,因此對於彩色液晶顯示元件、彩色攝像管元件、 彩色感測器、有機EL顯示元件、電子紙等而言極爲有用。 顯示元件 本發明之顯示元件,係具備本發明之彩色濾光片者。 作爲顯示元件,能舉出彩色液晶顯示元件、有機EL顯示元 件、電子紙等。 本發明之具備彩色濾光片之彩色液晶顯示元件,能採 取適宜的構造。例如,能採取將彩色濾光片形成在與配置 有薄膜電晶體(TFT )之驅動用基板不同的基板上,驅動用 基板與形成有彩色濾光片的基板,透過液晶層對向的構 造’再者亦能採取將在配置有薄膜電晶體(TFT )之驅動用 基板的表面上形成彩色瀘光片的基板、與形成有ITO (掺 雜錫的氧化銦)電極,透過液晶層對向的構造。後者的構 造’具有·能使開口率顯著提高,可製得明亮且高精細的液 晶顯示元件的優點。 本發明之具備彩色濾光片之彩色液晶顯示元件,除了 冷陰極蛋光管(CCFL: Cold Cathode Fluorescent Lamp)以 外’能具備以白色LED作爲光源的背光單元。作爲白色 LED ’例如’能舉出:使用具有獨立光譜的紅色led、綠色 LED芨藍色LED獲得白色光的白色LED ;藉由組合紅色 -43- 201142500 LED、綠色LED及藍色LED而加以混色來獲得白色光的白 色LED ;藉由組合藍色LED、紅色LED及綠色螢光體而加 以混色來獲得白色光的白色LED ;藉由組合藍色LED、紅 色發光螢光體及綠色發光螢光體而加以混色來獲得白色光 的白色LED;藉由藍色LED及YAG系螢光體的混色來獲得 白色光的白色LED ;藉由組合藍色LED、橙色發光螢光體 及綠色發光螢光體而加以混色來獲得白色光的白色LED: 藉由組合紫外線LED、紅色發光螢光體、綠色發光螢光體 及藍色發光螢光體而加以混色來獲得白色光的白色LED 等。 具備本發明之彩色濾光片的彩色液晶顯示元件,能應 用於 TN( Twisted Nematic,扭曲向列)型、STN( Super Twisted Nematic,超扭曲向列)型、IPS (In-Planes Switching,面 內切換)型、VA ( Vertical Alignment,垂直配向)型、OCB (Optically Compensated Birefringence,光學補償式雙折射) 型等適宜的液晶模式。 又’具備本發明之彩色濾光片的有機EL顯示元件,能 採取適宜的構造,例如,能採取日本特開平1 1 -307242號 公報所揭示的構造。 又,具備本發明之彩色濾光片的電子紙,能採取適宜 的構造,例如,能採取日本特開2 0 0 7 - 4 1 1 6 9號公報所揭示 的構造。 [實施例] -44- 201142500 以下,舉出實施例,進一步具體地說明本發明的實施 形態。但是,本發明不限定於下述實施例。 <(B)共聚物的合成> 以下,使用在「(B)共聚物的合成」的原料的11胃@ 如下所示》 THF :四氫呋喃 EEMA :甲基丙烯酸1-乙氧基乙酯 MA :甲基丙烯酸 nBMA :甲基丙烯酸正丁酯 MMA :甲基丙烯酸甲酯 AIBN : 2,2’-偶氮雙異丁腈 DAM A :甲基丙烯酸二甲基胺基乙酯 EHMA :甲基丙烯酸2-乙基己酯(Monomer 19) (Monomer 20) Further, among the monomers to which the repeating unit (4) is added, the monomer which is a repeating unit represented by the above formula (4) is exemplified by: -methoxyethyl ester, methoxy glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, (meth)acrylic acid The oxydipropylene glycol vinegar (B) copolymer can be used alone or in combination of two or more. The content of the substance (B) is usually 1 part by mass, preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the (al) pigment. If the content of the copolymer is too large, there is a concern that the developability is impaired. In the present invention, in order to improve the dispersibility, a dispersing agent which is well known can be further provided. Examples of the well-known dispersing agent include a formate dispersant, a polyethylenimine dispersant, a polyoxyethylene alkyl dispersant, a polyoxyethylene alkylphenyl ether dispersant, and polyethylene. A glycol-based dispersant, a sorbitol fatty acid ester-based dispersant, a polyacetated-dispersed acrylic dispersant, a pigment derivative, and the like. Such a dispersant can be commercially obtained, for example, as acrylic acid (methylenedipropylene, etc. copolymerization ~100 (B) containing an amino ether diester agent, a fraction -24-. For the 201142500 powder, please refer to Disperbyk-2000, Disperbyk-2001 'BYK-LPN6919, BYK-LPN 21116, BYK-LPN21324C or higher, BYK Chemie (BYK)); as a urethane dispersant, it can be cited Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol); For the imide-based dispersing agent, Sols perse 24000 (manufactured by Lubrizol Co., Ltd.), and the polyester-based dispersing agent, AJISPERPB821, AJISPERPB822, AJISPERPB880, and AJISPER PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) Wait. Further, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone. - (C) Crosslinking Agent - In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. The polymerizable group may, for example, be an ethylenically unsaturated group, an epoxy group (Oxiranyl), an oxetanyl group or an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups. Specific examples of the compound having two or more (meth) acrylonitrile groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, Caprolactone-modified polyfunctional (meth) acrylate, alkylene oxide modified polyfunctional (methyl) -25- 201142500 propylene vinegar, (hydroxy) methacrylate and polyfunctional The polyfunctional urethane (meth) acrylate obtained by the reaction of cyanic acid and vinegar, and the polyfunctional (meth)acrylic acid having a carboxyl group obtained by reacting a transbasic (meth) acrylate with an acid anhydride The ester or the like, as the above-mentioned aliphatic polyhydroxy compound, for example, a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol, such as glycerol or trishydroxyl An aliphatic polyhydroxy compound having a trivalent or higher valence of methyl propane, neopentyl alcohol, and dipentaerythritol. Examples of the (meth) acrylate having a trans group include, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol. Acrylate, dipentaerythritol penta (meth) acrylate vinegar, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. As the acid anhydride 'for example, there can be mentioned, for example, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dibasic acid anhydride, pyrogallic anhydride, biphenyl tetracarboxylic acid A tetrabasic dianhydride of acid dianhydride and benzophenone tetracarboxylic dianhydride. Further, as the polyfunctional (meth) acrylate which is modified by the above-mentioned caprolactone, for example, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 can be mentioned. Examples of the polyfunctional (meth) acrylate modified by the above alkylene oxide include ethylene oxide and/or propylene oxide modified di(meth)acrylate of bisphenol A, and isocyanuric acid. Ethylene oxide and/or epoxy propylene-26- 201142500 alkane modified tri(meth) acrylate, trimethylolpropane ethylene oxide and / or propylene oxide modified tri (meth) acrylate Ethylene oxide and/or propylene oxide modified tris(meth)acrylate of ester 'nepentaerythritol, ethylene oxide and/or propylene oxide modified tetra(meth)acrylic acid of pentaerythritol Ethyl ester of diester pentaerythritol and/or propylene oxide modified penta (meth) acrylate, ethylene oxide of dipentaerythritol and/or propylene oxide modified hexamethyl ) Acrylate and the like. Further, the compound having two or more N-alkoxymethylamino groups, for example, may be a compound having a melamine structure, a benzoguanamine structure or a urea structure. Further, the melamine structure and the benzoguanamine structure refer to a chemical structure having a three-till ring or a phenyl-substituted three-till ring as a basic skeleton, and also includes melamine, benzoguanamine or a condensate thereof. Mourning. Specific examples of the compound having two or more N-alkoxymethylamino groups include: N,N,N,N,N,N-hexa(alkoxymethyl)melamine, N,N ,N,N-tetrakis(alkoxymethyl)benzoguanamine, N,N,N,N-tetra(alkoxylmethyl) glycoluril )Wait. Among these polyfunctional monomers, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having three or more valences with (meth)acrylic acid, and a polyfunctional (methyl) modified by caprolactone Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N, N, N, N-hexa(alkoxymethyl) melamine Further, 叱叱叱1^tetrakis(alkoxymethyl)benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound of 3 to 27-201142500 or more with (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol Acrylic acid: dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, a polyfunctional (meth) acrylate having a carboxyl group, which is obtained by reacting pentaerythritol triacrylate with succinic anhydride The compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride has high strength in the colored layer, excellent surface smoothness of the colored layer, and difficulty in oil staining on the substrate of the unexposed portion and on the light shielding layer. (greasing), residual film, etc. are particularly good. In the present invention, the (C) crosslinking agent can be used singly or in combination of two or more. The content of the (C) crosslinking agent in the present invention is preferably from 1 Å to 1 part by mass, particularly preferably from 20 to 50,000 parts by mass, based on 100 parts by mass of the (A) coloring agent. In this case, if the content of the polyfunctional monomer is too small, there is a concern that sufficient curability can be obtained. On the other hand, when the content of the polyfunctional monomer is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and it is easy to be on the substrate of the unexposed portion or the light shielding layer. There is a tendency for oil stains, residual film, and the like to occur. • (D) binder resin - The coloring composition of the present invention can contain (D) a binder resin. Thereby, the alkali developability of the colored composition or the adhesion to the substrate can be improved. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a residue or a phenolic hydroxyl group. Among them, a polymer having a mercapto group (hereinafter referred to as a "carboxyl group-containing polymer") is preferred. For example, -28-201142500 exemplifies an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as A copolymer of "unsaturated monomer (dl)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (d2)"). Examples of the unsaturated monomer (d 1 ) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl) acrylonitrile. Ethyl] vinegar, ω-residue polycaprolactone mono(methyl)propionate, ρ-vinylbenzoic acid, and the like. These unsaturated monomers (dl) can be used individually or in mixture of 2 or more types. Further, as the unsaturated monomer (d 2 ), for example, N-substituted cis-butene such as N-phenylmaleimide and N-cyclohexylmethyleneimine may be mentioned. Diterpenoid imine; such as styrene, α-methylstyrene, p_ shoes, basic b, p-carbyl-α-methylbenzene ethyl sulphate, p-ethyl sulfhydryl glycidyl ether, terpene An aromatic vinyl compound; such as methyl (meth)acrylate, η-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (a) Allyl acrylate, benzyl (meth) acrylate, polyethylene glycol (η = 2~10) methyl ether (meth) acrylate, polypropylene glycol (η = 2~10) methyl ether (A Acrylate, polyethylene glycol (η=2~10) mono(meth)acrylate, polypropylene glycol (η=2~10) mono(meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, tricyclic [5, 2. 1. 0 2'6 ]癸-8-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, dihed Ethylene oxide modified (meth) acrylate of propofol, -29- 201142500 glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3 -[ (Meth) propylene methoxymethyl] oxetane, (meth) acrylate of 3-[(meth) propylene methoxymethyl]-3-ethyl oxetane: such as a ring Hexyl vinyl ether, isobornyl vinyl ether, tricyclic [5. 2. ΙΟ2'6] 癸-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3-(vinyloxymethyl)-3-ethyloxetane; Polystyrene, poly(methyl) methacrylate, poly(meth)acrylic acid-η-butyl ester, polyoxymethane, polymer monomer chain having a single (meth) acrylonitrile group at the end . These unsaturated monomers (d2) can be used individually or in mixture of 2 or more types. In the copolymer of the unsaturated monomer (dl) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (dl) in the copolymer is preferably from 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (d 1 ) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained. Specific examples of the copolymer of the unsaturated monomer (dl) and the unsaturated monomer (d2), for example, Japanese Patent Application Laid-Open No. Hei. No. Hei. Japanese Patent Publication No. 10_3 1 3 08, Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymer disclosed in Japanese Laid-Open Patent Publication No. 2004-101728. -30- 201142500 In the present invention, for example, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. 6-230212, Japanese Patent Laid-Open Publication No. Hei 09-325494, and U- In the case of a polymerizable non-carboxyl polymer having a (meth)acryl fluorenyl group or the like in the side chain, it is used as a binder resin, as disclosed in JP-A-2008-181095. The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (usually 1,000 to 100,000, preferably 3,000 to 50,000) as measured by GPC (eluent elution). When the film rate or the like is lowered, the shape of the pattern is impaired, and the electrical characteristics are deteriorated. On the other hand, if the degree of deterioration is lowered, the shape of the pattern is impaired, and the use of the slit nozzle is likely to cause dry foreign matter to occur. The ratio of the weight average of the binder resin to the number average molecular weight (Μη,) (Mw, / 'η' 1. 0~5·0, more preferably 1. 0~3. 0. Further, the average molecular weight and the number average molecular weight of the polystyrene measured by Mw' GPC (extraction solvent: tetrahydrofuran) herein. The binder resin of the present invention can be controlled by a method known in the art, for example, in the method disclosed in Japanese Patent Laid-Open Publication No. 2003-2227 No. 2006-259680, No. 07/029 87 No. Construction or Mw, Mw / Mn. In the present invention, the binder resin can be used alone or in a mixture to form a mixture of 5 - 1 9 4 6 7 7-207211 3 , which is disclosed in the Japanese Patent Laid-Open Publication No. 4: THF, Mw, and Mw. 'If it is too small, heat resistance, etc., there is a solution amount (M w ')), and it is preferable to use 换算 η ' to be produced by the weight method. However, the manual is published in the manual. The above is used for -31- 201142500. In the present invention, the content of the binder resin is usually from 1 to 1 part by mass, preferably from 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the binder resin is too small, for example, the alkali developability is lowered, and the storage stability of the colored composition obtained is lowered. On the other hand, if the amount is too large, the concentration of the colorant is relatively lowered. It is difficult to achieve the desired color density with a film. - (E) Photopolymerization initiator - The color composition of the present invention can contain (E) a photopolymerization initiator. Thereby, the sensory radiation can be imparted to the coloring composition. The (E) photopolymerization initiator used in the present invention is exposed to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays to produce an active species capable of starting polymerization of the above (C) crosslinking agent. Compound. Examples of such a photopolymerization initiator include a 9-oxosulfonium d-star compound, an acetophenone-based compound, a biimidazole-based compound, a triterpenoid compound, a fluorene-fluorenyl compound, and a key. A salt compound, a benzoin compound, a diphenyl ketone compound, a fluorene-diketone compound, a polynuclear oxime compound, a diazo compound, an imido-sulfonate compound, or the like. In the present invention, the "photopolymerization initiator" can be used singly or in combination of two or more. The photopolymerization initiator is preferably at least 1 selected from the group consisting of a 9-oxosulfanyl compound, an acetamidine compound, a conjugated quinone compound, a diterpenoid compound, and a Q__ quinone compound. Kind. -32- 201142500 Among the preferred photopolymerization initiators in the present invention, as a specific example of the 9-oxosulfanyl sulphate compound, 9-oxopurine [II哩, 2-chloro 9- Oxygen sulphate feed, 2-methyl 9-oxosulfonium ill, 2-isopropyl 9-oxosulfanthine, isopropyl 9-oxosulfonate I] star, 2,4-dichloro 9-oxosulfonate sing, 2,4-dimethyl 9-oxosulfuron mountain!] star, 2,4-diethyl 9-oxosulfonate, comet, 2,4-diisopropyl 9 - Oxygen sulphur sings and so on. Further, specific examples of the acetophenone-based compound include 2-methyl-1·[4-(methylthio)phenyl]-2-morpholinyl-1-propanone and 2-benzyl group. -2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(4-methylbenzyl)-2-(dimethylamino)-1-( 4-morpholinylphenyl)-1-butanone and the like. Further, specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked. Imidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4,6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Further, in the case where a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor to improve the sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include a thiol-based hydrogen donor such as 2-mercaptobenzothiazole or 2-mercaptobenzoxazole; and 4,4'-bis(dimethylamino)di An amine-based hydrogen donor such as phenylketone or 4,4'-bis(diethylamino)diphenyl ketone. In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, but one or more thiol-based hydrogen donors may be used in combination with one or more amine-based hydrogen I precursors. Good. Further, as specific examples of the above-described triple well-based compound, 2,4,6-parade(trichloromethyl)-s-tripper, 2-methyl-4,6-bis ( Trichloromethyl)-s-tripper '2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-5-trimole, 2- [2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-5-trimole, 2-[2-(4-diethylamino-2-methyl)ethene 4-[6,6-bis(trichloromethyl)-3-trin, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl) )-s-tripper, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-5-triturate, 2-(4-ethoxystyryl)-4,6 - bis(trichloromethyl)-5-tripper, 2-(4-!1-butoxyphenyl)-4,6-bis(trichloromethyl)-5-triad, etc. Three tillage compounds. Further, specific examples of the fluorene-fluorenyl fluorene-based compound include 1,2-octanedione, 1-[4·(phenylthio)phenyl]-, 2-(0-benzylidene fluorenyl).肟), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-911-oxazol-3-yl]-, 1-(〇· 醯 醯 肟), B Ketone, 1·[9·ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzylidene)_9Η_carbazole-3-yl]-,1-(〇-ethenylhydrazine Ethylketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxiranyl) methoxybenzimidyl } _9Η_oxazol-3-yl]·, 1-(0-ethylindenyl) and the like. In the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound, a sensitizer may be used. As such a sensitizer, for example, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-di Ethyl acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate 2,5-bis (4- Diethylaminobenzylidene)cyclohexanone, 7-di-34- 201142500 ethylamino-3-(4-diethylaminobenzylidene) coumarin, 4-(diethylamino) ketone Wait. In the present invention, the content of the photopolymerization initiator is preferably 0% by mass based on 100 parts by mass of the (C) crosslinking agent. 0 Bu 120 parts by mass, especially preferably 1 to 1 part by mass. In this case, if the content of the photopolymerization initiator is too small, there is a concern that the curing by exposure is insufficient. On the other hand, if the amount is too large, the colored layer formed is likely to fall off from the substrate during development. Propensity. - (F) Solvent - a colored composition of the present invention, usually, a coloring agent comprising (A) a pigment, in combination with (B) a copolymer and optionally other dispersing agents or (D) in (F) a solvent A part of the resin is pulverized by using, for example, a bead mill, a roll mill (r ο Π mi 11 ), or the like, and is mixed and dispersed to form a pigment dispersion liquid. Next, the pigment dispersion liquid is added and mixed by the pigment dispersion liquid. (C) a crosslinking agent, and if necessary, (d) a binder resin, (E) a photopolymerization initiator, and a further addition (F) solvent, etc., are prepared. The (F) solvent 's' is a component that will constitute a colored composition (. a) ~ (C) or other components are dispersed or dissolved, and do not react with these components. If they have moderate volatility, they can be suitably used. However, when preparing the above-mentioned pigment dispersion liquid, from the viewpoint of dispersibility and stability, it is preferred to use (f!) a solvent having a hydroxyl group (hereinafter also referred to as "solvent (f)") and (Π) A solvent having no hydroxyl group (hereinafter also referred to as "solvent (f2)"). 'As a solvent (f 1 ) in a kind of solvent, for example, -35- 201142500 ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-η-propyl ether, ethylene glycol single -η-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-η-propyl ether, diethylene glycol mono-η-butyl ether, triethylene glycol monomethyl ether , triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, propylene glycol mono-η-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-η- (poly)alkylene glycol monoalkyl ethers such as propyl ether, dipropylene glycol mono-η-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; lactated alkyl lactate, ethyl lactate, etc. Esters; (cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol; Keto alcohols such as alcohols. Among these solvents (Π), preferred are (poly)alkylene glycol monoalkyl ethers, particularly preferably propylene glycol monomethyl ether or propylene glycol monoethyl ether. The solvent (Π) can be used alone or in combination of two or more. Further, examples of the solvent (f2) include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl (poly)alkyl glycol monoalkyl ether acetates such as diacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Other ethers; -36- 201142500 Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate 'Diacetate such as 1,6-hexanediol diacetate; methyl 3-methoxypropionate 3-ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 - ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl. Alkoxycarboxylates such as 3-methoxybutylpropionate; ethyl acetate, η-propyl acetate, i-propyl acetate, η-butyl vinegar, i-butyl acetate, formic acid Η-amyl ester, i-amyl acetate, η-butyl propionate, ethyl butyrate, propyl butyrate, i-propyl butyrate, η-butyl butyrate, methyl pyruvate, pyruvate Other esters such as ester, η-propyl pyruvate, methyl acetoacetate, ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; A decylamine or an indoleamine such as dimethylformamide, hydrazine, hydrazine-dimethylacetamide or hydrazine-methylpyrrolidone. Among these solvents (f2), preferred are (poly)alkylene glycol monoalkyl ether acetates, ethers, ketones, diacetates, alkoxycarboxylates, particularly preferably ethylene. Alcohol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether , diethylene glycol methyl ethyl ether, cyclohexanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate, 3 - Methyl ethoxypropionate, ethyl 3-ethoxypropionate. The solvent (f2) can be used singly or in combination of two or more. In the present invention, the mass ratio (fl/f2) of the solvent (f 1 ) to the solvent (f2 ) -37 to 201142500 in the colorant dispersion is preferably 〇. 5/99. 5~40/60, more preferably 1/99~30/70, especially good 5/95~25/75. The content of the solvent is not particularly limited, and the total concentration of each component other than the pigment dispersion or the coloring composition is preferably 5 to 5 % by mass, regardless of the pigment dispersion or the coloring composition. The amount is particularly preferably 10 to 40% by mass. . By forming such a form, a colorant dispersion having good dispersibility and stability can be obtained, and a coloring composition having good coatability and stability can be obtained. - Additive - The colored composition of the present invention can also contain various additives as needed. Examples of the additive include, for example, a chelating agent such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a fluorine-based surfactant, a lanthanoid surfactant, and the like. Surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Methyl-methoxy sand, N-(2-aminoethyl)-3-aminopropyltrimethoxysane, 3-aminopropyltriethoxydecane, 3-epoxypropane Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl a adhesion promoter such as methyl dimethoxy decane, 3-chloropropyl trimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane or 3-mercaptopropyl trimethoxy decane; 2,2·thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, etc.; 2-(3-t-butyl-5- Methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, -38- 201142500 Ultraviolet absorber such as diphenyl ketone; anti-aggregating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2 -Aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amine Residue improver for keto-1,2-butanediol; etc.; succinic acid mono [2-(meth) propylene oxiranyl ethyl] ester, phthalic acid mono [2-(methyl) propylene oxiranyl ethyl A developability improving agent such as an ester or a carboxypolycaprolactone mono(meth)acrylate. Color filter and method for producing the same The color filter of the present invention is provided with a coloring layer formed using the coloring composition of the present invention. As a method of manufacturing a color filter, the first method is as follows. First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to divide the portion where the pixels are formed. Next, on the substrate, for example, after applying a liquid composition in which the radiation-sensitive composition of the red pigment has been dispersed, pre-baking is performed to evaporate the solvent to form a coating film. Next, after the coating film was exposed to the reticle, development was carried out using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by performing post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Next, using a coloring composition of green or blue coloring, the coating, prebaking, exposure, development, and post-baking of each coloring radiation composition are carried out in the same manner as described above, sequentially on the same substrate. A green pixel array and a blue pixel array are formed thereon. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue of -39 to 201142500 is disposed on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above. Further, a 'black matrix can be formed by forming a desired pattern by a photolithography method using a metal thin film of chromium or the like which is formed by sputtering or vapor deposition, and a color-sensing radioactive composition in which a black pigment is dispersed can also be used. This is formed in the same manner as the case of forming the above-described pixels. Examples of the substrate used in forming the color filter include glass, enamel, polycarbonate 'polyester, aromatic polyamine, polyamidimide, polyimine, and the like. Further, in these substrates, an appropriate pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion coating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition can be carried out as needed. When the coloring sensitizing radiation composition is applied onto a substrate, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or the like can be used. The coating method is particularly preferably a spin coating method or a slit die coating method. The pre-baking is usually carried out by a combination of vacuum drying and heat drying. Decompression is dry, and the sling is ordered until it reaches 50~200Pa. Further, the conditions of heat drying are usually carried out at 70 to 110 ° C for about 1 to 1 minute. Coating thickness 'as the film thickness after drying, usually 〇. 6~8 ()" m, preferably 1. 2~5. 0# m. As the radiation source of the radiation-40-201142500 used in forming the pixel and/or the black matrix, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A light source such as a low-pressure mercury lamp or a laser source such as an argon ion laser, a YAG laser, a XeCl excimer laser, or a nitrogen laser, but preferably a radiation having a wavelength in the range of 190 to 450 nm. The exposure amount of the radiation is, in general, preferably 10 to 10,000 Å/m2. Further, as the alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5·4 is preferred. . An aqueous solution of 0^7-undecene, l,5-diazabicyclo-[4·3·0]-5-decene. In the above alkali developing solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkali development, water washing is usually carried out. As the development processing method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at normal temperature. The post-baking conditions are usually carried out at 180 to 280 ° C for about 10 to 60 minutes. The film thickness of the pixel formed in this way is usually 〇. 5~5. 0y m, preferably 1. 0~3. 0ym. In addition, the second method of producing a color filter can be obtained by an inkjet method, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2000-3. The method of each color pixel. In this method, -41- 201142500 First, a partition wall having a light-shielding function is formed on the surface of the substrate. Then, in the partition wall formed, for example, a liquid composition in which the colored composition of the red pigment has been dispersed is discharged by an ink jet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a red pixel pattern. Then, each of the colored compositions of green or blue was used in the same manner as described above, and a green pixel pattern and a blue pixel pattern were sequentially formed on the same substrate. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate can be obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above. Further, the partition wall has a function of not only a light-shielding function but also a coloring composition of each color which has been discharged in the divided area, and the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation linear composition. The method or condition for pre-baking or post-baking of the substrate or the radiation source used in forming the color filter is the same as the first method described above. In this manner, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the black matrix. In the pixel pattern obtained in this manner, a transparent conductive film is formed by sputtering after forming a protective film as needed. It is also possible to form a color filter by forming a spacer after forming a transparent conductive film. The spacers are usually formed using a radiation-sensitive composition, and can also be formed into a light-shielding spacer (b 1 a c k s p a c e r ). In this case, the color-sensitive linear composition in which the black colorant is dispersed may be used in the case of -42 to 201142500, but the colored composition of the present invention can also be suitably used for the formation of a black spacer. The color filter of the present invention produced in this manner has extremely high luminance and color purity, and thus is extremely excellent for a color liquid crystal display element, a color image pickup device element, a color sensor, an organic EL display element, an electronic paper, and the like. it works. Display Element The display element of the present invention is provided with the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper. The color liquid crystal display element having the color filter of the present invention can adopt a suitable structure. For example, it is possible to adopt a configuration in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, a substrate for driving and a substrate on which a color filter is formed, and a liquid crystal layer is opposed to each other. Further, it is also possible to adopt a substrate in which a color light-receiving sheet is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode is formed to face the liquid crystal layer. structure. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. The color liquid crystal display element having the color filter of the present invention can be provided with a backlight unit using a white LED as a light source, in addition to a cold cathode fluorescent lamp (CCFL: Cold Cathode Fluorescent Lamp). As a white LED 'for example', it is possible to use a red LED with a separate spectrum, a green LED, a blue LED to obtain white light, and a white LED by combining red-43-201142500 LED, green LED and blue LED. White LED for white light; white LED by combining blue LED, red LED and green phosphor to obtain white light; by combining blue LED, red illuminating phosphor and green luminescent fluorescent a white LED that is mixed with color to obtain white light; a white LED that obtains white light by color mixing of a blue LED and a YAG-based phosphor; by combining a blue LED, an orange-emitting phosphor, and a green-emitting fluorescent A white LED that is mixed with a color to obtain white light: a white LED that obtains white light by combining an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor to obtain a white LED. The color liquid crystal display element having the color filter of the present invention can be applied to TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes Switching). A suitable liquid crystal mode such as a switching type, a VA (Vertical Alignment) type, or an OCB (Optically Compensated Birefringence) type. Further, the organic EL display element having the color filter of the present invention can have a suitable structure. For example, the structure disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. Further, the electronic paper comprising the color filter of the present invention can adopt a suitable structure. For example, the structure disclosed in Japanese Patent Laid-Open Publication No. WO 07-41 1 169 can be employed. [Embodiment] - 44 - 201142500 Hereinafter, embodiments of the present invention will be specifically described by way of examples. However, the invention is not limited to the following examples. <Synthesis of (B) Copolymer> The following is the use of the material of "(B) copolymer synthesis] 11 stomach @ as shown below" THF: tetrahydrofuran EEMA: 1-ethoxyethyl methacrylate MA : methacrylic acid nBMA : n-butyl methacrylate MMA : methyl methacrylate AIBN : 2,2'-azobisisobutyronitrile DAM A : dimethylaminoethyl methacrylate EHMA : methacrylic acid 2-ethylhexyl ester
BzMA :甲基丙烯酸苄酯 PME-2 00 :甲氧基聚乙二醇單甲基丙烯酸酯(日油股份 公司製) 合成例1 將600.30g之THF、10.80g之氯化鋰(濃度3.63質量 %之THF溶液)、3.84g之二苯乙烯添加在反應容器,冷卻 至-60°C。之後,添加9.60g之η-丁基鋰(濃度15.36質量 %之己院溶液),進行10分鐘熟成。 接著,花30分鐘滴下1 03.84g之nBMA、13.45g之ΕΕΜΑ 的混合液,滴下後繼續反應1 5分鐘。然後測定氣相層析法 -45- 201142500 (以下,簡稱爲「GC」),確認單體消失。 接著,滴下32.25g之DMMA,滴下後繼續反應 然後測定GC ’確認單體消失後,添加3.42g之甲 應。 將所製得之共聚物之濃度50質量%的丙二 乙酸酯溶液220g,加溫至160°C使其熟成3小時 調整成濃度40質量%的丙二醇單甲醚乙酸酯溶液 式,製得由具有來自DAMA之重複單元的A嵌段 來自MA及nBMA之重複單元的B嵌段所構成的 物。將所製得之嵌段共聚物定爲「共聚物(B-1) 合成例2 將5 5.7g之THF、4.65g之氯化鋰(濃度4·54 THF溶液)、〇.45g之二苯乙烯添加在反應容器’) °C。之後,添加1.22g之η-丁基鋰(濃度15.36質 烷溶液),進行1 〇分鐘熟成。 接著,花120分鐘滴下1.66g之EEMA、9.9g I 4.14g之MMA的混合液,滴下後繼續反應15分鐘 定GC,確認單體消失。 接著,滴下3.96g之DMMA,滴下後繼續反應 然後測定GC,確認單體消失後’添加0.41g之甲 )]¾ 。 在所製得之前驅物聚合物之濃度25質量% 單甲醚乙酸酯溶液6 5.6 4g中,添加16.44g之水,加 30分鐘。 醇停止反 醇單甲酸 。之後, :。依此方 、及具有 嵌段共聚 j 。 質量%之 令卻至-60 量%之己 匕 nBMA、 。然後測 3 0分鐘。 醇停止反 的丙二醇 丨溫至100 -46- 201142500 °C使其反應8小時。蒸餾除去水分,調整成濃度40質量% 的丙二醇單甲醚乙酸酯溶液。依此方式,製得由具有來自 DAM A之重複單元的A嵌段、及具有來自M A、nBM A及MM A 之重複單元的B嵌段所構成的嵌段共聚物。將所製得之嵌 段共聚物定爲「共聚物(B-2)」。 合成例3 在具備攪拌子的燒瓶內,將4.8g之 MA、11.2g之 nBMA、5.0g 之 MMA、302mg 之 AIBN、及 778mg 之吡唑-1-二硫基羧酸氰基(二甲基)甲基酯,溶解在3 OmL之甲苯, 進行30分鐘的氮起泡。之後緩慢地攪拌,使反應溶液的溫 度上升至60°C,將此溫度保持24小時進行活性自由基聚合 (living radical polymerization ) ° 接著,把已將364mg之AIBN與7.0g之DAMA溶解在 2 OmL之甲苯進行30分鐘氮取代的溶液,添加至上述反應 溶液,在60°C下進行24小時活性自由基聚合。之後,藉由 減壓濃縮,調整成20質量%之丙二醇單甲基醚溶液。依此 方式,製得由具有來自DAMA之重複單元的A嵌段、及具 有來自ΜΑ、nBMA及MMA之重複單元的B嵌段所構成的 嵌段共聚物。將所製得之嵌段共聚物定爲「共聚物(B-3)」。 合成例4 在具備攪拌子的燒瓶內,將3.4g之MA、2.2g之nBMA、 14.0g 之 MMA、318mg 之 AIBN、及 821mg 之 D比哩-1-二硫基 羧酸氰基(二甲基)甲基酯’溶解在3 0mL之甲苯’進行 -47- 201142500 3 0分鐘的氮起泡。之後緩慢地攪拌’使反應溶液的溫度上 升至60°C,將此溫度保持24小時進行活性自由基聚合。 接著,把已將437mg之AIBN與8.4g之DAMA溶解在 20mL之甲苯進行30分鐘氮取代的溶液,添加至上述反應 溶液,在60°C下進行24小時活性自由基聚合。之後,藉由 減壓濃縮,調整成20質量%之丙二醇單甲基醚乙酸酯溶 液。依此方式,製得由具有來自DAMA之重複單元的A嵌 段、及具有來自ΜΑ、nBMA及MMA之重複單元的B嵌段 所構成的嵌段共聚物。將所製得之嵌段共聚物定爲「共聚 物(B-4)」。 合成例5 在具備攪拌子的燒瓶內,將1.4g之 MA、12.6g之 nBMA、5.6g 之 EHMA、218mg 之 AIBN、及 561mg 之吡唑-1-二硫基羧酸氰基(二甲基)甲基酯,溶解在3 OmL之甲苯, 進行30分鐘的氮起泡。之後緩慢地攪拌,使反應溶液的溫 度上升至60°C,將此溫度保持24小時進行活性自由基聚 合。 接著,把已將437mg之AIBN與8.4g之DAMA溶解在 20mL之甲苯進行30分鐘氮取代的溶液,添加至上述反應 溶液,在60°C下進行24小時活.性自由基聚合。之後,藉由 減壓濃縮,調整成40質量%之丙二醇單甲基醚乙酸酯溶 液。依此方式,製得由具有來自DAM A之重複單元的A嵌 段、及具有來自ΜΑ、PME-200、nBMA及EHMA之重複單 -48- 201142500 元的B嵌段所構成的嵌段共聚物。將所製得之嵌段共聚物 定爲「共聚物(B-5 )」。 比較合成例1 將568.08g之THF、ii.56g之氯化鋰(濃度3.63質量 %之THF溶液)、3.25g之二苯乙烯添加至反應容器,冷卻 至-60 °C。之後,添加7.16g之η-丁基鋰(濃度15.36質量 %之環己烷溶液),進行10分鐘熟成。 接著,花30分鐘滴下33.72g之MMA、15.52g之ηΒΜΑ、 13.14g 之 BzMA、15.79g 之 EHMA、ll_94g 之 ΡΜΕ-200 的混 合液,滴下後繼續反應15分鐘。測定GC,確認單體消失。 接著,滴下30.09g之DMMA,滴下後繼續反應30分鐘。 然後,測定GC,確認單體消失後,添加2.5 2g之甲醇停止 反應。之後,藉由減壓蒸餾,調整成濃度40質量%之丙二 醇單甲基醚乙酸酯溶液。依此方式,製得由具有來自DAM A 之重複單元的A嵌段、及具有來自MMA、PME-200、nBMA、 BzMA及EHMA之重複單元的B嵌段所構成的嵌段共聚物。 將所製得之嵌段共聚物定爲「共聚物(b-1)」。 比較合成例2 將626.56g之THF、10.26g之氯化鋰(濃度3.63質量 %之THF溶液)、3.23g之二苯乙烯添加至反應容器,冷卻 至-60°C。之後,添加6.95g之n-丁基鋰(濃度15.36質量 %之環己烷溶液),進行10分鐘熟成。 接著,花30分鐘滴下26_52g之MMA、62.13g之ηΒΜΑ、 -49- 201142500 的混合液,滴下後繼續反應.15分鐘。然後測定GC ’確認 單體消失。 接著,滴下42_19g之DMMA’滴下後繼續反應30分鐘。 然後,測定GC,確認單體消失後’添加3.79g之甲醇停止 反應。之後,藉由減壓蒸餾’調整成濃度40質量%之丙二 醇單甲基醚乙酸酯溶液。依此方式,製得由具有來自DAMA 之重複單元的A嵌段、及具有來自MMA及nBMA之重複單 元的B嵌段所構成的嵌段共聚物。將所製得之嵌段共聚物 定爲「共聚物(b-2)」。 比較合成例3 在具備攪拌子的燒瓶內,添加30g之丙二醇單甲基醚 乙酸酯,一邊注入氮氣一邊加溫至80 °C。在同溫度下,花 2 小時把已使 1.4g 之 MA、12.6g 之 nBMA、5.6g 之 EHMA 及8.4g之DAM A溶解在16g之丙二醇單甲基醚乙酸酯的溶 液,和已使1.2g之AIBN溶解在10g之丙二醇單甲基醚乙 酸酯的溶液同時滴下。之後,使反應溶液的溫度上升至1 00 °C,保持此溫度1小時進行聚合。之後,藉由減壓蒸餾, 調整成濃度40質量%之丙二醇單甲基醚乙酸酯溶液。依此 方式,製得ΜΑ、nBMA、EHMA及DAMA的隨機共聚物。 將所製得之隨機共聚物定爲「共聚物(b-3 )」。 <Mw及Mw/Mn之測定> 在上述各合成例所製得之(B )共聚物的Mw及Μη, 係利用下述規格的GPC測定。將測定結果,連同(Β )共 -50- 201142500 聚物中之各單體的共聚合比例(質量%)—起顯示在表丄。 裝置:GPC-104(昭和電工股份公司製)。 管柱·結合 KD-G、KF-603、KF-602、KF-601 (昭和電 工股份公司製)使用。 移動相:DMF。 <酸價之測定> 以下述要領測定在上述各合成例所製得之(B )共聚物 的酸價。將測定結果顯示在表1。 精密秤量0.5g之共聚物溶液至img的單位爲止,分到 玻璃容器。以丙二醇單甲基醚乙酸酯稀釋至5 OmL後,添加 酚酞(phenolphthalein ),以0.1N乙醇性氫氧化鉀的水溶 液進行滴定’以著色成粉紅色的點作爲終點。同樣地進行 空白試驗。從(B)共聚物與空白試驗之〇.1N乙醇性氫氧 化鉀水溶液滴下量算出酸價(單位·· mgK〇H/g )。 <胺價之測定> 以下述要領測定在上述各合成例所製得之(B )共聚物 的胺價。將測定結果顯示在表i。 精密坪量0.5g之共聚物溶液至的單位爲止,分到 玻璃容器。添加、溶解20ml之無水乙酸/乙酸= 9/1 (體積 比)’在室溫下放置3小時。之後,進一步添加30mL之乙 酸後’使用電位差測定裝置AT-5 10 (京都電子工業股份公 司製)’以〇」moUL過氯酸·乙酸溶液進行滴定。同樣地 進行空白試驗。從(B)共聚物與空白試驗之〇.imol/L過 -51- 201142500 氯酸·乙酸溶液滴下量算出胺價(單位:mgKOH/g )。 -52- 201142500 [表1 ] 合成例 比較合成例 1 2 3 4 5 1 2 3 共聚物名稱 B-1 B-2 B-3 B-4 B-5 b —1 b-2 b -3 MA 5 5 17 12 5 6 MMA 23 18 50 28 20 nBMA 73 50 40 8 45 13 48 46 EHMA 20 13 17 BzMA 11 PME-200 10 DAMA 22 22 25 30 30 25 32 31 Mw/Mn 1.21 1.19 1.68 1.70 1.64 1.19 1.21 1.96 Mw 8500 8100 8200 8500 8300 8000 7900 8900 酸價] 33 33 111 78 33 0 0 39 胺價 79 79 89 107 107 89 114 111 <顏料分散液之調製> 調製例1 使用作爲著色劑之9質量份之C.I.顏料綠58 ( DIC公 司製)及6質量份之C.I.顏料黃150、12.5質量份之共聚物 (B-1)(不揮發部分=40質量%)、作爲溶媒之64.5質 量份之丙二醇單甲基醚乙酸酯及8質量份之丙二醇單甲基 酸’利用珠磨加以處理,調製著色劑分散液(1 )。 調製例2〜8及比較調製例1〜7 在調製例1中,除了將著色劑、(B)共聚物及溶媒的 種類及量如表2所示般變更以外,與調製例1同樣地進行, 調製顔料分散液(A-2)~(A-15)。 -53- 201142500 <顏料分散液之評價> 使用E型黏度計(東京計器製),測定所製得之顏料 分散液的黏度。又,將所製得之著色劑分散液塡充至遮光 玻璃容器,在密閉狀態下以23 °C靜置14天後,使用E型 黏度計(東京計器製)再度測定黏度。然後,算出保存14 天後之黏度對剛調製後之黏度的增加率,增加率低於5 % 的情況評價爲「A」,5 %以上、低於1 0 %的情況評價爲「B」’ 1 0 %以上的情況評價爲「C」。將評價結果顯示在表2 ° -54- 201142500 匕較調製例 r^· A-15 νη ο 卜 Ο > Η u A-14 αν MD OO Ο τ—Η ο u A-13 Ό cvi ι Η 寸 CN δ OO ο 异 PQ 寸 A-12 ι 1 . OO ο oo » '< PQ cn A-ll ν〇 ι i ί〇 s r-~ ο oo m CM A-10 Ό 52 〇 ο 异 CQ r H 〇\ < α\ oo ο oo P '< 〇q 調製例 oo OO < νη ο 汔 r- Ο 卜 < c— < \〇 Csi »—Η Η oo ο oo < \o vo < σ\ JO ο cs CN PQ to to < σ> Ό \〇 oo 〇 oo < 寸 寸 < in oo PQ cn cn < ο ON t—H PQ CM <N < ο MD oo ο OO < i 1 i H < ΟΝ 64.5 oo CN » < oo < 顏料分散液 G58 Υ150 Β15:6 V23 Υ179 PGMEA PGME ι—1 1 m c\] 1 CQ 00 1 PQ 寸 1 CQ LO 1 ω »—Η 1 X) b-2 cn 初期黏度(mPa · s) 保存安定性 著色劑 溶媒 (B)共聚物溶液 to v〇 201142500 在表2中’ 「G58」係指c.I.顔料綠58,「Y150」係指 C.I.顏料黃150,「B15 : 6」係指C.I.顏料藍15 : 6,「V23」 係指C.I.顏料紫23’ 「Y179」係指有機染料之C.I.溶劑黃 179, 「PGMEA」係指丙二醇單甲基醚乙酸酯,「PGME」 係指丙二醇單甲基醚。 <結合劑樹脂之合成> 合成例6 在具備冷卻管及攪拌機之燒瓶,將44.0g之P-乙烯基 苄二醇醚、40.0g之N-苯基順丁烯二醯亞胺、16.0g之BzMA 溶解至300g之丙二醇單甲基醚乙酸酯,進一步投入8.0g 之AIBN及8.0g之α-甲基苯乙烯二聚物,之後進行15分 鐘之氮沖洗(purge)。氮沖洗之後,將反應溶液一邊擅拌 及氮起泡一邊加熱至80t進行5小時的聚合。 接著,將17.0g之MA、0.5g之P-甲氧基酚、及4.4g 之四丁基溴化銨添加至此反應溶液,在1 20°C下使其反應9 小時。進一步地,添加18.5g之無水琥珀酸,在100°C下使 其反應6小時後,在將液溫保持在85 °C下進行2次水洗, 減壓濃縮,藉以製得包含33質量%之結合劑樹脂(D-1 ) 的溶液。此結合劑樹脂(D-1 ),以GPC (洗提溶媒··四氫 呋喃)測定之聚苯乙烯換算之重量平均分子量=7,800,以 GPC (洗提溶媒:四氫呋喃)測定之聚苯乙烯換算之重量 平均分子量與數量平均分子量的比=2.8° 合成例7 -56- 201142500 在具備冷卻管及攪拌機之燒瓶,將30.0g之BzMA、 20.0g之nBMA、15.0g之甲基丙烯酸羥基乙酯、20.0g之苯 乙烯、及15.0g之MA溶解至2 00g之丙二醇單甲基醚乙酸 酯,進一步投入3.0g之AIBN及5.0g之α-甲基苯乙烯二聚 物,之後進行15分鐘之氮沖洗。氮沖洗之後,將反應液一 邊攪拌及氮起泡一邊加熱至80°C進行5小時的聚合,藉以 製得包含33質量%之結合劑樹脂(D-2 )的溶液。此結合 劑樹脂(D-2),以GPC (洗提溶媒:四氫呋喃)測定之聚 苯乙烯換算之重量平均分子量=1 〇,〇〇〇,以GPC (洗提溶 媒:四氫呋喃)測定之聚苯乙烯換算之重量平均分子量與 數量平均分子量的比=2.5。 合成例8 在具備冷卻管及攪拌機之燒瓶,將25.0g之3-甲基丙 烯醯氧甲基-3-乙基氧雜環丁烷、18.0g之MA、9.0g之琥珀 酸單2-丙烯醯氧基乙酯、10.0g之N-苯基順丁烯二醯亞胺、 24.0g之BzMA、.14.0g之甲基丙烯酸羥基乙酯溶解至300g 之丙二醇單甲基醚乙酸酯,進一步投入6.0g之AIBN及6.0g 之α -甲基苯乙烯二聚物,之後進行15分鐘之氮沖洗。氮 沖洗之後,將反應液一邊攪拌及氮起泡一邊加熱至80 °C進 行5小時的聚合,藉以製得前驅物共聚物溶液。 在所製得之200g的前驅物共聚物溶液,添加13.4g之 2-甲基丙烯醯氧基異氰酸乙酯、作爲聚合禁止劑之0.2g的 4-甲氧基酚,在9(TC下使其反應2小時。就此反應液,以 -57- 201142500 每1次75g之離子交換水進行2次水洗,減壓濃縮,藉以 製得包含33質量%之結合劑樹脂(D-3 )的溶液。結合劑 樹脂(D-3 ),以GPC (洗提溶媒:四氫呋喃)測定之聚苯 乙烯換算之重量平均分子量=11,0 00,以GPC (洗提溶媒: 四氫呋喃)測定之聚苯乙烯換算之重量平均分子量與數量 平均分子量的比=1.9。 <著色組成物之調製及評價> 著色組成物之調製 實施例1 混合100質量份之顏料分散液(A-1 )、31.5質量份之 作爲結合劑樹脂之結合劑樹脂(D-2 )、1 0.4質量份之作爲 交聯劑之東亞合成股份公司製之M-402C二新戊四醇六丙 烯酸酯爲主成分)、4.3質量份之作爲光聚合起始劑之2-苄基-2-二甲基胺基-1- ( 4-嗎啉基苯基)-1-丁酮(商品名: IRGACURE 369,Ciba. Specialty· Chemicals 公司製)、及 80.0質童份之作爲溶劑之3 -乙氧基丙酸乙酯,調製液狀的 著色組成物。 脫落時間之評價 將所製得之液狀組成物,使用旋轉塗布機塗布在玻璃 基板上後,以1 0 0 °C之加熱板進行2分鐘的預烘烤,形成膜 厚2.的塗膜。接著,將此基板冷卻至室溫後,對基板 上的塗膜,使用高壓水銀燈將包含3 65 nm、405nm、及43 6nm 之各波長的放射線,透過光罩以l,〇〇〇〗/m2的曝光量曝光至 -58- 201142500 各塗膜。之後,對基板上的塗膜,藉由以1.0kgf/cm2的顯 影壓(噴嘴徑1mm )吐出23°C之0.04質量%之氫氧化鉀水 溶液來進行淋浴顯影。此時,測定到未曝光部的塗膜完全 剝離的時間(脫落時間)。然後,將脫落時間低於60秒的 情況評價爲「A」,將60秒以上、低於90秒的情況評價爲 「B」,將90秒以上、低於120秒的情況評價爲「C」,將 1 20秒以上的情況評價爲「D」》此時間越短顯影速度越快, 有縮短彩色濾光片製造的節拍時間(tact time)的優點。將 評價結果顯示在表3。 色度特性之評價 將所製得之著色組成物,使用旋轉塗布機塗布在玻璃 基板上後,以1 00°C之加熱板進行2分鐘的預烘烤,形成膜 厚不同的3片塗膜。接著,將這些基板冷卻至室溫後,對 基板上的塗膜,使用高壓水銀燈將包含3 65 nm、405 nm、及 436nm之各波長的放射線,不透過光罩而以l,000J/m2的曝 光量曝光至各塗膜。之後,以220 °C進行20分鐘後烘烤, 在基板上形成硬化膜。針對所製得之3片硬化膜,使用色 彩分析儀(coloranalyzer,大塚電子(股)製MCPD2000), 以C光源、2度視野,測定CIE表色系中之色度座標値(X, y)及刺激値(Y)。由測定結果,求出色度座標値y = 0.590 時之色度座標値X及刺激値(Y )。將評價結果顯示在表3。 對比之評價 針對在上述「色度特性之評價」所製得之3片硬化膜, -59- 201142500 使用對比計(壺板電機製對比測定器c Τ -1 ), 根據測疋結果’求出色度座標値y = 0.590時之 價結果顯示在_表3。 實施例2〜8及比較例1〜7 除了將實施例1中’顏料分散液、結合劑 劑、光聚合起始劑及溶媒的種類及量如表3所 外’與實施例1同樣地進行,進行著色組成物 價。將評價結果顯示在表3。又,關於藍色的 (實施例8及比較例3〜4 ),係求出在色度座標 之色度座標値X、刺激値(Y )、及對比。將評 在表3。 定對比。 比。將評 脂、交聯 般變更以 調製及評 色組成物 y = 0.090 結果顯不 -60- 201142500 【£椒】 比較例 卜 ο —Η 丨 57.9 1 o < ! 24.9 οο 244.3 pq οο cK 0.152 3900 VO ο 21.8 14.4 85.4 PQ 59.8 0.299 9200 ID Ο ί 4 :32.7 CN CO VO 78.1 Q 61.7 0.152 14700 寸 Ο r Η 57.9 1 4 24.9 to οό 244.3 U 10.4 0.152 6500 cn ο 57.9 1 H 24.9 οο 244.3 U 0.152 6600 CO ο ί < ι i CO CN ν〇 !〇 75.2 〇 60.4. 0.299 13200 ο ι Η 1 32.7 1 CN CO M3 78·1 〇 60.2 0.299 13000 實施例 〇〇 ο 57.9 1 i 24.9 \Τ) οό 244.3 < 10.4 0.152 7000 卜 ο ·—Η i 32.7 Oi ν〇 ΙΟ ΟΟ CQ 61.7 0.299 15100 ο :32.7 CN CO ν〇 V) οο < οο cK νη 0.299 13100 to ο ι ·Ι οο CS U-J 85.4 < 60.3 0.299 13900 寸 ο 1 ' < 32.7 OO 〇 ι I ΟΟ < 60.4 0.299 13200 m Ο ' * ON r Ή * 嶙 as οο CN 41.8 < 60.2 0.299 13100 CO Ο r^H 1 32.7 ι CN cn νο I _ , οο < 60.5 0.299 14300 1 t ο ΓΟ 80.0 < ι—Η 0.299 14000 ι Η < CN < CO < 寸 <i to < \〇 < 卜 < οο < σ\ < 1 Α40 1 1 Α-11 1 Α-12 1 1 Α-13 1 1 Α-14 1 Α-15 1 I < ά CN Q cn Q 嫜 ύ CN ύ _< ώ CM ώ ΕΕΡ MBA 脫落時間 Υ値 iM X 對比 著色劑 分散液 結合劑 樹脂溶液 交聯劑 光聚合 起始劑 溶媒 s-19- 201142500 表3之中各成分如下所示。 C-1:二新戊四醇六丙烯酸酯與二新戊四醇五丙烯酸醋 的混合物(商品名M-402,東亞合成股份公司製) C-2:二新戊四醇五丙烯酸酯與琥珀酸的單酯化物、二 新戊四醇六丙烯酸酯與二新戊四醇五丙烯酸酯的混合物 (商品名TO- 1 3 82,東亞合成股份公司製) E-1:乙醇、1-[9-乙基- 6-(2-甲基苯甲醯基)-9H-咔唑 -3-基]-,1-(〇-乙醯基肟)(商品名 IRGACUREOX02, Ciba· Specialty · Chemicals 公司製) E-2: 2-苄基-2-二甲基胺基-1-( 4-嗎啉基苯基)-1-丁 酮(商品名 IRGACURE 369,Ciba . Specialty · Chemicals 公司製) EEP : 3-乙氧基丙酸乙酯 MBA : 3-甲氧基丁基乙酸酯 【圖式簡單說明】 〇 /»w 【主要元件符號說明】 〇 y»\\ -62-BzMA: benzyl methacrylate PME-2 00: methoxypolyethylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd.) Synthesis Example 1 600.30 g of THF, 10.80 g of lithium chloride (concentration of 3.63 mass) A solution of 3.64 g of stilbene was added to the reaction vessel and cooled to -60 °C. Thereafter, 9.60 g of η-butyllithium (concentration of 15.36% by mass of a hospital solution) was added and aging was carried out for 10 minutes. Next, a mixture of 1 03.84 g of nBMA and 13.45 g of hydrazine was dropped over 30 minutes, and the reaction was continued for 15 minutes after dropping. Then, gas chromatography -45-201142500 (hereinafter, abbreviated as "GC") was measured, and it was confirmed that the monomer disappeared. Subsequently, 32.25 g of DMMA was dropped, and the reaction was continued after dropping, and after measuring GC' to confirm the disappearance of the monomer, 3.42 g of the methyl group was added. 220 g of a malonate solution having a concentration of the obtained copolymer of 50% by mass was heated to 160 ° C to be aged for 3 hours, and adjusted to a concentration of 40% by mass of a propylene glycol monomethyl ether acetate solution. An article consisting of a B block having a repeating unit derived from DAMA from the repeating unit of MA and nBMA. The obtained block copolymer was designated as "copolymer (B-1). Synthesis Example 2 5 5.7 g of THF, 4.65 g of lithium chloride (concentration of 4·54 THF solution), and 4545 g of diphenyl Ethylene was added to the reaction vessel ') ° C. Thereafter, 1.22 g of η-butyllithium (concentration of 15.36 massane solution) was added and aging was carried out for 1 Torr. Then, 1.66 g of EEMA and 9.9 g of I 4.14 were dropped for 120 minutes. The mixture of g MMA was mixed and the reaction was continued for 15 minutes to confirm the disappearance of the monomer. Then, 3.96 g of DMMA was dropped, and the reaction was continued after the dropwise addition, and then the GC was measured to confirm that 0.41 g of the methyl group was added after the disappearance of the monomer] 3⁄4. In the obtained precursor polymer concentration of 25% by mass of monomethyl ether acetate solution 6 5.6 4g, 16.44 g of water was added for 30 minutes. The alcohol stopped the inverse alcohol monocarboxylic acid. Thereafter, This side, and the block copolymerization j. The mass% of the order is up to -60% by volume of 匕nBMA, then measured for 30 minutes. The alcohol stops the reverse propylene glycol 丨 temperature to 100 -46- 201142500 °C to make the reaction 8 hours. The water was distilled off and adjusted to a concentration of 40% by mass of a propylene glycol monomethyl ether acetate solution. A block copolymer composed of an A block having a repeating unit derived from DAM A and a B block having a repeating unit derived from MA, nBM A, and MM A was prepared. The obtained block copolymer was copolymerized. The substance was defined as "copolymer (B-2)". Synthesis Example 3 In a flask equipped with a stir bar, 4.8 g of MA, 11.2 g of nBMA, 5.0 g of MMA, 302 mg of AIBN, and 778 mg of pyrazole-1-dithiocarbamic acid cyano (dimethyl group) The methyl ester was dissolved in 30 mL of toluene and subjected to nitrogen foaming for 30 minutes. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization. Then, 364 mg of AIBN and 7.0 g of DAMA were dissolved in 2 OmL. The toluene was subjected to a nitrogen substitution solution for 30 minutes, added to the above reaction solution, and subjected to living radical polymerization at 60 ° C for 24 hours. Thereafter, the mixture was adjusted to a 20% by mass solution of propylene glycol monomethyl ether by concentration under reduced pressure. In this manner, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from hydrazine, nBMA and MMA was obtained. The obtained block copolymer was designated as "copolymer (B-3)". Synthesis Example 4 In a flask equipped with a stirrer, 3.4 g of MA, 2.2 g of nBMA, 14.0 g of MMA, 318 mg of AIBN, and 821 mg of D are 哩-1-dithiocarbamic acid cyano (dimethyl The base methyl ester 'dissolved in 30 mL of toluene' was subjected to -47 - 201142500 for 30 minutes of nitrogen foaming. Thereafter, the mixture was slowly stirred to raise the temperature of the reaction solution to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization. Next, a solution in which 437 mg of AIBN and 8.4 g of DAMA were dissolved in 20 mL of toluene for 30 minutes of nitrogen substitution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, the solution was adjusted to a 20% by mass solution of propylene glycol monomethyl ether acetate by concentration under reduced pressure. In this manner, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having repeating units derived from hydrazine, nBMA and MMA was obtained. The obtained block copolymer was designated as "copolymer (B-4)". Synthesis Example 5 In a flask equipped with a stirrer, 1.4 g of MA, 12.6 g of nBMA, 5.6 g of EHMA, 218 mg of AIBN, and 561 mg of pyrazole-1-dithiocarbamic acid cyano (dimethyl group) were placed. The methyl ester was dissolved in 30 mL of toluene and subjected to nitrogen foaming for 30 minutes. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 60 ° C, and the temperature was maintained for 24 hours to carry out living radical polymerization. Next, a solution in which 437 mg of AIBN and 8.4 g of DAMA were dissolved in 20 mL of toluene for 30 minutes of nitrogen substitution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C for 24 hours. Thereafter, the mixture was adjusted to a 40% by mass solution of propylene glycol monomethyl ether acetate by concentration under reduced pressure. In this manner, a block copolymer composed of an A block having a repeating unit derived from DAM A and a B block having a repeating mono-48-201142500 element derived from hydrazine, PME-200, nBMA, and EHMA was obtained. . The obtained block copolymer was designated as "copolymer (B-5)". Comparative Synthesis Example 1 568.08 g of THF, ii.56 g of lithium chloride (concentration of 3.63% by mass in THF), and 3.25 g of stilbene were added to a reaction vessel, and the mixture was cooled to -60 °C. Thereafter, 7.16 g of η-butyllithium (concentration: 15.36% by mass in a cyclohexane solution) was added, followed by aging for 10 minutes. Next, a mixture of 33.72 g of MMA, 15.52 g of ηΒΜΑ, 13.14 g of BzMA, 15.79 g of EHMA, and ll_94 g of ΡΜΕ-200 was added dropwise for 30 minutes, and the reaction was continued for 15 minutes after dropping. The GC was measured to confirm the disappearance of the monomer. Next, 30.09 g of DMMA was dropped, and the reaction was continued for 30 minutes after dropping. Then, GC was measured to confirm the disappearance of the monomer, and then 2.5 2 g of methanol was added to stop the reaction. Thereafter, the solution was adjusted to a concentration of 40% by mass of a propylene glycol monomethyl ether acetate solution by distillation under reduced pressure. In this manner, a block copolymer composed of an A block having a repeating unit derived from DAM A and a B block having repeating units derived from MMA, PME-200, nBMA, BzMA, and EHMA was produced. The obtained block copolymer was designated as "copolymer (b-1)". Comparative Synthesis Example 2 626.56 g of THF, 10.26 g of lithium chloride (concentration of 3.63% by mass of a THF solution), and 3.23 g of stilbene were added to a reaction vessel, and the mixture was cooled to -60 °C. Thereafter, 6.95 g of n-butyllithium (concentration: 15.36% by mass of a cyclohexane solution) was added, followed by aging for 10 minutes. Next, a mixture of 26-52 g of MMA, 62.13 g of ηΒΜΑ, and -49-201142500 was dropped for 30 minutes, and the reaction was continued after dropping for 15 minutes. Then, GC ' was determined to confirm that the monomer disappeared. Next, 42_19 g of DMMA' was dropped and the reaction was continued for 30 minutes. Then, GC was measured to confirm that the monomer disappeared, and 3.79 g of methanol was added to stop the reaction. Thereafter, the solution was adjusted to a concentration of 40% by mass of a propylene glycol monomethyl ether acetate solution by distillation under reduced pressure. In this manner, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having repeating units derived from MMA and nBMA was obtained. The obtained block copolymer was designated as "copolymer (b-2)". Comparative Synthesis Example 3 In a flask equipped with a stir bar, 30 g of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C while injecting nitrogen gas. At the same temperature, a solution of 1.4 g of MA, 12.6 g of nBMA, 5.6 g of EHMA and 8.4 g of DAM A in 16 g of propylene glycol monomethyl ether acetate was dissolved for 2 hours, and 1.2 was made. The AIBN of g was dissolved in 10 g of a solution of propylene glycol monomethyl ether acetate while dropping. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and the temperature was maintained for 1 hour to carry out polymerization. Thereafter, the solution was adjusted to a concentration of 40% by mass of a propylene glycol monomethyl ether acetate solution by distillation under reduced pressure. In this manner, random copolymers of hydrazine, nBMA, EHMA and DAMA were obtained. The obtained random copolymer was designated as "copolymer (b-3)". <Measurement of Mw and Mw/Mn> The Mw and Μη of the (B) copolymer obtained in each of the above Synthesis Examples were measured by GPC of the following specifications. The measurement results are shown in Table 连同 together with the copolymerization ratio (% by mass) of each monomer in (Β) -50- 201142500. Device: GPC-104 (made by Showa Denko Co., Ltd.). The pipe column is used in combination with KD-G, KF-603, KF-602, and KF-601 (made by Showa Denko Co., Ltd.). Mobile phase: DMF. <Measurement of Acid Value> The acid value of the (B) copolymer obtained in each of the above Synthesis Examples was measured in the following manner. The measurement results are shown in Table 1. Weigh the 0.5g copolymer solution to the unit of img and divide it into a glass container. After diluting to 500 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was carried out with an aqueous solution of 0.1 N ethanolic potassium hydroxide. A blank test was performed in the same manner. The acid value (unit··mgK〇H/g) was calculated from the amount of the (B) copolymer and the blank test. The amount of the 1N ethanolic potassium hydroxide aqueous solution was dropped. <Measurement of amine valence> The amine valence of the (B) copolymer obtained in each of the above Synthesis Examples was measured in the following manner. The measurement results are shown in Table i. The unit is placed in a glass container with a precision of 0.5 g of the copolymer solution. 20 ml of anhydrous acetic acid/acetic acid = 9/1 (volume ratio) was added and dissolved, and allowed to stand at room temperature for 3 hours. After the addition of 30 mL of acetic acid, the potentiometric apparatus AT-5 10 (manufactured by Kyoto Electronics Co., Ltd.) was used to titrate with a moUL perchloric acid/acetic acid solution. The blank test was performed in the same manner. The amine valence (unit: mgKOH/g) was calculated from (B) copolymer and blank test im.imol/L over -51- 201142500 chloric acid·acetic acid solution. -52- 201142500 [Table 1] Synthesis Example Comparative Synthesis Example 1 2 3 4 5 1 2 3 Copolymer Name B-1 B-2 B-3 B-4 B-5 b-1 b-2 b -3 MA 5 5 17 12 5 6 MMA 23 18 50 28 20 nBMA 73 50 40 8 45 13 48 46 EHMA 20 13 17 BzMA 11 PME-200 10 DAMA 22 22 25 30 30 25 32 31 Mw/Mn 1.21 1.19 1.68 1.70 1.64 1.19 1.21 1.96 Mw 8500 8100 8200 8500 8300 8000 7900 8900 Acid value] 33 33 111 78 33 0 0 39 Amine price 79 79 89 107 107 89 114 111 <Preparation of pigment dispersion> Preparation Example 1 9 parts by mass as a coloring agent was used. CI Pigment Green 58 (manufactured by DIC Corporation) and 6 parts by mass of CI Pigment Yellow 150, 12.5 parts by mass of copolymer (B-1) (nonvolatile content = 40% by mass), and 64.5 parts by mass of propylene glycol as a solvent The methyl ether acetate and 8 parts by mass of propylene glycol monomethyl acid' were treated by bead milling to prepare a colorant dispersion (1). Preparation Examples 2 to 8 and Comparative Preparation Examples 1 to 7 In the same manner as in Preparation Example 1, except that the type and amount of the colorant, the (B) copolymer, and the solvent were changed as shown in Table 2, the preparation example 1 was carried out. , Modulate the pigment dispersion (A-2) ~ (A-15). -53- 201142500 <Evaluation of Pigment Dispersion> The viscosity of the obtained pigment dispersion liquid was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Further, the obtained colorant dispersion was placed in a light-shielding glass container, and allowed to stand at 23 ° C for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity after the storage for 14 days was calculated, and the increase rate was less than 5%, and it was evaluated as "A", and when it was 5% or more and less than 10%, it was evaluated as "B". The case of 10% or more was evaluated as "C". The evaluation results are shown in Table 2 ° -54 - 201142500 匕Comparative Example r^· A-15 νη ο Ο Ο > Η u A-14 αν MD OO Ο τ—Η ο u A-13 Ό cvi ι Η inch CN δ OO ο 异 PQ inch A-12 ι 1 . OO ο oo » '< PQ cn A-ll ν〇ι i 〇 r r-~ ο oo m CM A-10 Ό 52 〇ο 异 CQ r H 〇\ < α\ oo ο oo P '< 〇q Modulation example oo OO < νη ο 汔r- Ο 卜 < c— < \〇Csi »—Η Η oo ο oo < \o vo < σ\ JO ο cs CN PQ to to <σ> Ό \〇oo 〇oo < inch inch< in oo PQ cn cn < ο ON t-H PQ CM <N < ο MD oo ο OO <; i 1 i H < ΟΝ 64.5 oo CN » < oo < pigment dispersion G58 Υ150 Β15:6 V23 Υ179 PGMEA PGME ι—1 1 mc\] 1 CQ 00 1 PQ inch 1 CQ LO 1 ω »—Η 1 X) b-2 cn initial viscosity (mPa · s) preservation stability colorant solvent (B) copolymer solution to v 201142500 In Table 2 'G58' means cI pigment green 58, "Y150" means CI Pigment Yellow 150, "B15: 6" means CI Pigment Blue 15: 6, "V23" means CI Pigment Violet 23' "Y179" means CI Solvent Yellow 179 for organic dyes, "PGMEA" means propylene glycol monomethyl ether acetate, and "PGME" means propylene glycol monomethyl ether. <Synthesis of binder resin> Synthesis Example 6 In a flask equipped with a cooling tube and a stirrer, 44.0 g of P-vinylbenzyl glycol ether and 40.0 g of N-phenyl maleimide, 16.0 were used. The BzMA of g was dissolved in 300 g of propylene glycol monomethyl ether acetate, and 8.0 g of AIBN and 8.0 g of α-methylstyrene dimer were further charged, followed by nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was heated to 80 t for 5 hours while being mixed with nitrogen and bubbling. Next, 17.0 g of MA, 0.5 g of P-methoxyphenol, and 4.4 g of tetrabutylammonium bromide were added to the reaction solution, and the mixture was reacted at 1,200 ° C for 9 hours. Further, 18.5 g of anhydrous succinic acid was added, and the mixture was reacted at 100 ° C for 6 hours, and then washed with water twice while maintaining the liquid temperature at 85 ° C, and concentrated under reduced pressure to obtain 33% by mass. A solution of the binder resin (D-1). The binder resin (D-1) has a weight average molecular weight of 7,800 in terms of polystyrene measured by GPC (extraction solvent·tetrahydrofuran), and a polystyrene equivalent weight measured by GPC (elution solvent: tetrahydrofuran). Ratio of average molecular weight to number average molecular weight = 2.8° Synthesis Example 7 -56- 201142500 In a flask equipped with a cooling tube and a stirrer, 30.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g Styrene and 15.0 g of MA were dissolved in 200 g of propylene glycol monomethyl ether acetate, and further 3.0 g of AIBN and 5.0 g of α-methylstyrene dimer were added, followed by nitrogen flushing for 15 minutes. . After the nitrogen rinsing, the reaction solution was stirred while stirring with nitrogen and heated to 80 ° C for 5 hours to obtain a solution containing 33% by mass of the binder resin (D-2 ). The binder resin (D-2), a polystyrene-equivalent weight average molecular weight measured by GPC (eluent solvent: tetrahydrofuran) = 〇, 聚, polystyrene measured by GPC (eluent solvent: tetrahydrofuran) The ratio of the weight average molecular weight to the number average molecular weight in terms of ethylene = 2.5. Synthesis Example 8 In a flask equipped with a cooling tube and a stirrer, 25.0 g of 3-methacryloxymethyl-3-ethyloxetane, 18.0 g of MA, and 9.0 g of succinic acid mono-2-propene were placed.醯 methoxyethyl ester, 10.0 g of N-phenyl maleimide, 24.0 g of BzMA, .14.0 g of hydroxyethyl methacrylate dissolved in 300 g of propylene glycol monomethyl ether acetate, further 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were charged, followed by nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was heated to 80 ° C for 5 hours while stirring with nitrogen to obtain a precursor copolymer solution. To 200 g of the precursor copolymer solution obtained, 13.4 g of 2-methylpropenyloxy isocyanate, 0.2 g of 4-methoxyphenol as a polymerization inhibiting agent, and 9 (TC) were added. The reaction mixture was allowed to react for 2 hours, and the reaction liquid was washed twice with 75 g of ion-exchanged water at -57 to 201142500, and concentrated under reduced pressure to obtain a binder resin (D-3) containing 33% by mass. Solution: binder resin (D-3), polystyrene-equivalent weight average molecular weight measured by GPC (eluent solvent: tetrahydrofuran) = 11,0 00, polystyrene measured by GPC (eluent solvent: tetrahydrofuran) The ratio of the weight average molecular weight to the number average molecular weight was 1.9. <Preparation and evaluation of coloring composition> Preparation of coloring composition Example 1 100 parts by mass of the pigment dispersion liquid (A-1) and 31.5 parts by mass were mixed. As a binder resin (D-2) of a binder resin, 0.4 parts by mass of M-402C dipentaerythritol hexaacrylate (as a component of East Asia Synthetic Co., Ltd. as a crosslinking agent), and 4.3 parts by mass 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator Phenylphenyl)-1-butanone (trade name: IRGACURE 369, manufactured by Ciba. Specialty Chemicals Co., Ltd.), and 80.0 ethoxylated ethyl ester as a solvent for the liquid coloring Composition. Evaluation of the detachment time The liquid composition thus obtained was applied onto a glass substrate using a spin coater, and then prebaked for 2 minutes on a hot plate at 100 ° C to form a coating film having a film thickness of 2. . Next, after cooling the substrate to room temperature, the coating film on the substrate is irradiated with radiation of wavelengths of 3 65 nm, 405 nm, and 43 6 nm using a high-pressure mercury lamp, and passed through a reticle to be 〇〇〇 / / m 2 The exposure was exposed to -58- 201142500 for each film. Then, the coating film on the substrate was subjected to shower development by discharging a 0.04 mass% aqueous solution of potassium hydroxide at 23 ° C at a developing pressure of 1.0 kgf/cm 2 (nozzle diameter: 1 mm). At this time, the time (falling time) at which the coating film of the unexposed portion was completely peeled off was measured. Then, the case where the fall-off time is less than 60 seconds is evaluated as "A", the case of 60 seconds or more and less than 90 seconds is evaluated as "B", and the case of 90 seconds or more and less than 120 seconds is evaluated as "C". The case where the temperature is 10 seconds or longer is evaluated as "D". The shorter the time, the faster the development speed, and the advantage of shortening the tact time of the color filter manufacturing. The evaluation results are shown in Table 3. Evaluation of chromaticity characteristics The obtained coloring composition was applied onto a glass substrate using a spin coater, and then prebaked for 2 minutes on a hot plate at 100 ° C to form three coating films having different film thicknesses. . Next, after cooling the substrate to room temperature, the coating film on the substrate was irradiated with radiation of wavelengths of 3 65 nm, 405 nm, and 436 nm using a high-pressure mercury lamp, and was passed through the reticle at 10,000 J/m 2 . The exposure amount was exposed to each coating film. Thereafter, post-baking was carried out at 220 ° C for 20 minutes to form a cured film on the substrate. For the three cured films obtained, a color analyzer (coloranalyzer, MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinates 値(X, y) in the CIE color system using a C light source and a 2 degree field of view. And stimulating 値 (Y). From the measurement results, the chromaticity coordinates 値X and the stimulus 値(Y) at the chromaticity coordinate 値y = 0.590 are obtained. The evaluation results are shown in Table 3. The comparison was evaluated for the three cured films obtained in the above "Evaluation of Chroma Characteristics", -59- 201142500 using a comparison meter (pot plate electromechanical contrast measuring device c Τ -1 ), and determining the color based on the measured results. The price of the coordinate 値 y = 0.590 is shown in _ Table 3. Examples 2 to 8 and Comparative Examples 1 to 7 The same procedures as in Example 1 were carried out except that the types and amounts of the pigment dispersion liquid, the binder agent, the photopolymerization initiator, and the solvent were the same as in Example 1 in Example 1. , the coloring composition price. The evaluation results are shown in Table 3. Further, regarding blue (Example 8 and Comparative Examples 3 to 4), the chromaticity coordinates 値X, the stimulus 値(Y), and the contrast at the chromaticity coordinates were obtained. It will be evaluated in Table 3. Contrast. ratio. The fat and cross-linking changes are made to modulate and evaluate the composition y = 0.090. The result is not -60- 201142500 [£椒] Comparative example ο - Η 7.9 57.9 1 o < ! 24.9 οο 244.3 pq οο cK 0.152 3900 VO ο 21.8 14.4 85.4 PQ 59.8 0.299 9200 ID Ο ί 4 : 32.7 CN CO VO 78.1 Q 61.7 0.152 14700 inch Ο r Η 57.9 1 4 24.9 to οό 244.3 U 10.4 0.152 6500 cn ο 57.9 1 H 24.9 οο 244.3 U 0.152 6600 CO ο ί < ι i CO CN ν〇!〇75.2 〇60.4. 0.299 13200 ο ι Η 1 32.7 1 CN CO M3 78·1 〇60.2 0.299 13000 Example 〇〇ο 57.9 1 i 24.9 \Τ) οό 244.3 < 10.4 0.152 7000 ο —— Η i 32.7 Oi ν〇ΙΟ ΟΟ CQ 61.7 0.299 15100 ο : 32.7 CN CO ν〇V) οο < οο cK νη 0.299 13100 to ο ι ·Ι οο CS UJ 85.4 < 60.3 0.299 13900 Inch ο 1 ' < 32.7 OO 〇ι I ΟΟ < 60.4 0.299 13200 m Ο ' * ON r Ή * 嶙as οο CN 41.8 < 60.2 0.299 13100 CO Ο r^H 1 32.7 ι CN cn νο I _ , οο < 60.5 0.299 14300 1 t ο ΓΟ 80.0 < ι—Η 0.299 14000 ι Η < CN < CO < inch <i to <\〇<卜< οο < σ\ < 1 Α40 1 1 Α-11 1 Α-12 1 1 Α-13 1 1 Α-14 1 Α-15 1 I < ά CN Q cn Q 嫜ύ CN ύ _< ώ CM ώ MBA MBA shedding time Υ値iM X contrast colorant dispersion binder Resin solution crosslinking agent Photopolymerization initiator solvent s-19- 201142500 The components in Table 3 are as follows. C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.) C-2: dipentaerythritol pentaacrylate and amber a mixture of an acid monoester, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO- 1382, manufactured by Toagosei Co., Ltd.) E-1: ethanol, 1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(anthracene-ethenylhydrazine) (trade name: IRGACUREOX02, manufactured by Ciba· Specialty · Chemicals) E-2: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone (trade name: IRGACURE 369, manufactured by Ciba. Specialty Chemicals Co., Ltd.) EEP: Ethyl 3-ethoxypropionate MBA : 3-methoxybutyl acetate [Simple description] 〇/»w [Main component symbol description] 〇y»\\ -62-
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