TW200931179A - Radiation-sensitive composition for blue color filter, color filter and liquid crystal display device - Google Patents

Radiation-sensitive composition for blue color filter, color filter and liquid crystal display device Download PDF

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TW200931179A
TW200931179A TW097140466A TW97140466A TW200931179A TW 200931179 A TW200931179 A TW 200931179A TW 097140466 A TW097140466 A TW 097140466A TW 97140466 A TW97140466 A TW 97140466A TW 200931179 A TW200931179 A TW 200931179A
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group
mass
acid
meth
methyl
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TW097140466A
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TWI467328B (en
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Hideyuki Yoshizawa
Shingo Naruse
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Abstract

A radiation-sensitive composition for a blue color filter contains (A) a colorant containing a blue colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator containing at least one selected from the group consisting of a compound represented by the following formula (3), an oxime ester compound and a biimidazole compound, and (E) an antioxidant containing at least one selected from the group consisting of a phenol antioxidant, a phosphorus antioxidant and a sulfur antioxidant, in which a total content of (E) is 1 to 100 parts by mass based on 100 parts by mass of the total content of (D): wherein the definitions of the symbols are the same as described in the specification. Based on this, photopolymerization initiators are selected from a further wider range and a radiation-sensitive composition for a blue color filter capable of forming blue pixels having high brightness is provided.

Description

200931179 九、發明說明 【發明所屬之技術領域】 本發明係有關藍色彩色濾光片用敏輻射線性組成物、 彩色濾光片及液晶顯示元件，更詳細係有關可用於製造彩 色攝像管元件、彩色液晶顯示裝置等所用之彩色濾光片的 藍色彩色濾光片用敏輻射線性組成物、具備由該敏輻射線 性組成物所形成之著色層的彩色濾光片及具備該彩色濾光 片的液晶顯示元件。 【先前技術】 使用著色敏輻射線性組成物形成彩色濾光片的方法， 已知方法包括在具有或預先形成所要之圖型之遮光層的基 板上，形成顏料分散型之著色敏輻射線性組成物的塗膜， 經由具有所定圖型之光罩，以放射線照射（以下稱爲「曝 光」）、顯像，以溶解除去未曝光部分，然後藉由後烘烤 ，得到具有各顏色之像素的方法（例如參考專利文獻1、 專利文獻2 )。 近年，爲了反映彩色攝像管元件、彩色液晶顯示裝置 等之高品質化及用途擴大化，強烈要求顯示面板之高亮度 化。因此，檢討提高藍色、紅色或綠色之各敏輻射線性組 成物之亮度（Y値）等。但是特別是關於提供藍色之像素 的敏輻射線性組成物，可利用的顏料限於銅酞菁藍，因此 提高亮度的手法也必然受限定。又，敏輻射線性組成物中 所含之光聚合起始劑或樹脂成分在後烘烤步驟之變黃成爲 -5- 200931179 藍色彩色濾光片之亮度降低的重要原因。 如以上之背景中，提高藍色彩色濾光片之亮度之手法 之一係提案在含有藍色著色劑、鹼可溶性樹脂、多官能性 單體及光聚合起始劑的藍色彩色濾光片用敏輻射線性組成 物中，光聚合起始劑使用具有特定構造之苯乙酮系化合物 及二苯甲酮系化合物（例如參照專利文獻3 )。 [專利文獻1]特開平2-144502號公報 Q [專利文獻2]特開平3 -5320 1號公報 [專利文獻3]特開200 1- 1 473 I5號公報 【發明內容】 [發明之開示] [發明欲解決的課題] 依據專利文獻3所記載之藍色彩色濾光片用敏輻射線 性組成物時，可提供高亮度，且具有充分之顏色再現範圍 Q 之顯示面板，但是使用其他光聚合起始劑取代上述特定之 光聚合起始劑時，無法得到足夠的亮度。又，試圖進一步 提高感度，倂用上述特定之光聚合起始劑與其他光聚合起 始劑時，感度雖提高，但是亮度明顯降低。因此，爲了實 現高亮度時，可使用上述特定之光聚合起始劑，但是光聚 合起始劑之選擇的寬度受限時，降低近年之曝光量很難縮 短產距時間（Takt Time )等。因此強烈要求開發一種使 用更多種類之光聚合起始劑，可形成亮度高之優異之藍色 像素的藍色彩色濾光片用敏輻射線性組成物。 -6- 200931179 本發明之課題係提供可更廣泛選擇光聚合起始劑，形 成亮度較高之優異之藍色像素的藍色彩色濾光片用敏輻射 線性組成物，具備由該敏輻射線性組成物所形成之著色層 的彩色濾光片及具備該彩色瀘光片之液晶顯示元件。 [解決課題的手段] 本發明人等發現在含有藍色著色劑、鹼可溶性樹脂、 多官能性單體及光聚合起始劑之藍色彩色濾光片用感放射 性組成物中，使用更多種類之光聚合起始劑，爲了實現提 供亮度高之優異的藍色像素時，使該組成物中含有特定的 氧化防止劑，同時將其含量限定在特定範圍。 換言之，本發明第一係提供一種藍色彩色濾光片用敏 輻射線性組成物，其特徵係含有： (A )含有藍色著色劑所成之著色劑、 (B) 鹼可溶性樹脂、 (C) 多官能性單體、 (D) 含有選自由下述式（3)表示之化合物、肟酯系 化合物及聯咪唑系化合物所成群之至少1種所成之光聚合 起始劑、 (E) 含有選自由酚系氧化防止劑、磷系氧化防止劑 及硫系氧化防止劑所成群之至少1種所成的氧化防止劑， 且（E)成分之合計含量爲對於（D)成分之合計100質量 份，含有1〜100質量份。 200931179 【化1】200931179 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a linear composition for sensitive radiation of blue color filters, a color filter, and a liquid crystal display element, and more specifically relates to a color camera element, a blue color filter for a color filter used in a color liquid crystal display device or the like, a linear composition for sensitive radiation, a color filter having a coloring layer formed of the linear composition of the sensitive radiation, and a color filter having the color filter Liquid crystal display element. [Prior Art] A method of forming a color filter using a coloring sensitive radiation linear composition, which comprises forming a pigment-dispersed color-sensitive radiation linear composition on a substrate having or pre-forming a desired pattern of a light-shielding layer The coating film is irradiated with radiation (hereinafter referred to as "exposure") and developed by a mask having a predetermined pattern to dissolve and remove the unexposed portion, and then post-baking to obtain pixels having respective colors. (For example, refer to Patent Document 1 and Patent Document 2). In recent years, in order to reflect the high quality and use of color image sensor components and color liquid crystal display devices, it is strongly required to increase the brightness of display panels. Therefore, it is reviewed to increase the brightness (Y値) of the linear composition of each sensitive radiation of blue, red or green. However, in particular, regarding the linear composition of the radiation which provides blue pixels, the usable pigment is limited to copper phthalocyanine blue, and therefore the method of improving the brightness is also inevitably limited. Further, the photopolymerization initiator or the resin component contained in the linear composition of the radiation radiation becomes yellow in the post-baking step to become an important cause of the decrease in the brightness of the blue color filter of -5-200931179. As in the above background, one of the methods for increasing the brightness of the blue color filter is proposed as a blue color filter containing a blue colorant, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. In the linear composition of the radiation radiation, the methacrylone-based compound and the benzophenone-based compound having a specific structure are used as the photopolymerization initiator (see, for example, Patent Document 3). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] According to the linear composition for sensitive radiation of the blue color filter described in Patent Document 3, a display panel having high brightness and having a sufficient color reproduction range Q can be provided, but other photopolymerization is used. When the initiator is substituted for the specific photopolymerization initiator described above, sufficient brightness cannot be obtained. Further, in an attempt to further improve the sensitivity, when the above specific photopolymerization initiator and other photopolymerization initiators are used, the sensitivity is improved, but the brightness is remarkably lowered. Therefore, in order to achieve high luminance, the above specific photopolymerization initiator can be used, but when the width of the selection of the photopolymerization initiator is limited, it is difficult to reduce the Takt Time and the like by reducing the exposure amount in recent years. Therefore, there has been a strong demand for the development of a linear radiation sensitive composition for blue color filters which uses a wider variety of photopolymerization initiators to form blue pixels having excellent brightness. -6- 200931179 The object of the present invention is to provide a linear composition for a blue color filter for a blue color filter which can be widely selected as a photopolymerization initiator to form a blue pixel having high brightness, and has a linearity of the sensitivity radiation. a color filter of a coloring layer formed by the composition and a liquid crystal display element including the color light-emitting sheet. [Means for Solving the Problem] The present inventors have found that more use is found in a radiation-sensitive composition for a blue color filter containing a blue colorant, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. In order to provide a blue pixel excellent in brightness, the photopolymerization initiator of the type contains a specific oxidation inhibitor in the composition, and the content thereof is limited to a specific range. In other words, the first aspect of the present invention provides a linear composition for a sensitive color of a blue color filter, characterized by: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) (a) a photopolymerization initiator containing at least one selected from the group consisting of a compound represented by the following formula (3), an oxime ester compound, and a biimidazole compound, (E) An oxidation preventing agent containing at least one selected from the group consisting of a phenolic oxidation preventing agent, a phosphorus-based oxidation preventing agent, and a sulfur-based oxidation preventing agent, and the total content of the component (E) is the component (D) A total of 100 parts by mass, and 1 to 100 parts by mass. 200931179 【化1】

〔式（3)中，R6係互相獨立表示碳數1〜4之烷基，R7 及R8係互相獨立表示氫原子或碳數1〜4之烷基〕。 本發明第二係提供一種使用前述藍色彩色濾光片用敏 輻射線性組成物所形成的彩色濾光片。 本發明第三係提供一種具備前述彩色濾光片的液晶顯 示元件。 [發明之效果] 依據本發明時，即使使用以往不具有足夠亮度之光聚 合起始劑時，也可提供亮度高之優異的藍色像素。又，依 據本發明時，即使倂用提供高亮度之光聚合起始劑時，也 可抑制亮度降低，可提供兼具亮度及感度極高水準的藍色 像素。如此比以往可更寬廣地選擇光聚合起始劑，降低近 年之曝光量，縮短產距時間（Takt Time )等。 因此，本發明之藍色彩色濾光片用敏輻射線性組成物 極適用於電子工業領域之彩色液晶顯示面板用之彩色濾光 片及液晶顯示面板之製造。 -8- 200931179 [實施發明之最佳形態] 以下詳細說明本發明。 藍色彩色濾光片用敏輻射線性組成物 -(A )著色劑- 本發明之著色劑係將藍色著色劑作爲必須成分者。 藍色著色劑係依彩色濾光片之用途來適當選擇，可爲 顏料、染料或天然色素，可爲有機系或無機系。 彩色濾光片要求高精細的發色及耐熱性，因此本發明 之藍色著色劑係發色性高，且耐熱性高之著色劑，其中較 佳爲耐熱分解性高的著色劑。這種藍色著色劑通常可使用 有機顏料或無機顏料，特佳爲使用有機顏料。 本發明中使用的藍色有機顏料，例如有顏色指數（ C.I.; The Society of Dyers and Colourists 公司發行，以 下相同）分類成顏料藍（Pigment Blue)的化合物，具體 而言，例如有附上C.I·顏料藍15、C.I.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之顏色 指數（C.I.)編號者。這些藍色有機顏料中，特佳爲c.I. 顏料藍15 : 6。 又，藍色無機顏料例如有群青、深藍等。 又’本發明中’視需要可倂用藍色顏料與紫色顏料。 紫色顏料例如有顏色指數中，分類成顏料紫（ Pigment Violet )的化合物。具體例有附上C.I.顔料紫1、 200931179 匸丄顏料紫^^丄顏料紫^^丄顏料紫^^丄顏料 紫32、C.I.顏料紫36、（:丄顏料紫38之顔色指數（c」） 編號之有機顏料。這些紫色有機顔料中’特佳爲CI.顏料 紫23。 ’本發明中，藍色著色劑可單獨或組合兩種以上來使用 - 。又，可倂用有機顏料與無機顏料，但是形成像素時，較 佳爲使用1種以上之有機顏料。 〇 本發明之有機顏料必要時可藉硫酸再結晶法、溶劑清 洗法或此等方法之組合等純化後再使用。 各顏料必要時可使用聚合物將其粒子表面改質來使用 。將顏料之粒子表面改質的聚合物，例如有曰本特開平8_ 259876號公報等所記載之聚合物或市售之各種顏料分散用 之聚合物或寡聚物。 -(B)鹼可溶性樹脂- 〇 本發明之鹼可溶性樹脂係對於（A)著色劑具有黏合 月!ί作用’且製衫色濾光片時’對於該顯像處理步驟所使 用之顯像劑’特佳爲鹼顯像劑，具有可溶性的樹脂時，即 無特別限定。這種鹼可溶性樹脂較佳爲具有羧基之驗可溶 性樹脂，特佳爲具有1個以上之羧基之乙烯性不飽和單體 (以下稱爲「S竣基之不飽和單體」）及可.與此單體共聚 之其他之乙嫌丨生不飽和單體（以下稱爲「共聚性不飽和單 體」）之共聚物（以下稱爲「含羧基之共聚物」）。 具有羧基之不飽和單體，例如有 -10- 200931179 (甲基）丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等之 不飽和單羧酸類； 順丁烯二酸、順丁烯二酸酐、反丁烯二酸、衣康酸、 衣康酸酐、檸康酸、檸康酸酐、中康酸等之不飽和二羧酸 或其酸酐類； 三價以上之不飽和多價羧酸或其酸酐類； 琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、苯二甲酸單 0 [2-(甲基）丙烯醯氧乙基]酯等之二價以上之多價羧酸的 單[(甲基）丙烯醯氧烷基]酯類； ω-羧基聚己內酯單（甲基）丙烯酸酯等之於兩末端具 有羧基及羥基之聚合物的單（甲基）丙烯酸酯類等。 含羧基不飽和單體可單獨或二種以上摻合使用。 本發明中，含羧基之不飽和單體較佳爲（甲基）丙烯 酸、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、ω-羧基聚己 內酯單（甲基）丙烯酸酯等，特佳爲（甲基）丙烯酸。 φ 共聚性不飽和單體例如有下述者。 如Ν -苯基順丁烯二醯亞胺、Ν_鄰-羥基苯基順丁烯 二醯亞胺、Ν-間-羥基苯基順丁烯二醯亞胺、Ν-對-羥基 苯基順丁烯二醯亞胺、Ν-苄基順丁烯二醯亞胺、Ν-環己基 順丁烯二醯亞胺、Ν-琥珀亞胺基-3-順丁烯二醯亞胺苯酸 酯、Ν-琥珀亞胺基-4 -順丁烯二醯亞胺丁酸酯、Ν-琥珀亞 胺基-6-順丁烯二醯亞胺己酸酯、Ν_琥珀亞胺基-3 _順丁稀 二醯亞胺丙酸酯、Ν -(吖啶基）順丁烯二醯亞胺等之Ν _ 取代順丁烯二醯亞胺； -11 - 200931179 如苯乙烯、α-甲基苯乙烯、鄰-乙烯基甲苯、間〜乙 烯基甲苯、對-乙烯基甲苯、對一氯苯乙烯、鄰〜甲氧基 苯乙烯、間一甲氧基苯乙烯、對一甲氧基苯乙烯、鄰〜乙 稀基苯酌、間一乙嫌基苯酌、對-乙嫌基苯酌、對〜經基 α-甲基苯乙烯、 如鄰一乙烯基苄基甲醚、間-乙烯基苄基甲醚、對— 乙烯基苄基甲醚、鄰一乙烯基苄基縮水甘油醚、間一乙烯 基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚之芳香族 乙烯基化合物； 如茚、1 -甲基茚之茚； 如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲 基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙 烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第 二丁酯、（甲基）丙烯酸第三丁酯、（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2-羥基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸 2 -羥基丁酯、（甲基）丙烯酸3 -羥基丁酯、（甲基）丙烯 酸4 -羥基丁酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸 苄酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸苯酯、（ 甲基）丙烯酸2 -甲氧乙酯、（甲基）丙烯酸2_苯氧基乙酯 、甲氧基二（乙二醇）（甲基）丙烯酸酯、甲氧基三（乙 二醇）（甲基）丙烯酸酯、甲氧基丙二醇（甲基）丙烯酸 酯、甲氧基二（丙二醇）（甲基）丙烯酸酯、（甲基）丙 烯酸異冰片酯、（甲基）丙烯酸三環 -12- 200931179 (甲基）丙烯酸2-羥基-3-苯氧基丙酯、單（甲基）丙烯 酸甘油酯、（甲基）丙烯酸4-羥基苯酯、對枯基苯酚之環 氧乙烷改質（甲基）丙烯酸酯之不飽和羧酸酯； (甲基）丙烯酸2-胺基乙酯、（甲基）丙烯酸2-二甲 基胺基乙酯、（甲基）丙烯酸2-胺基丙酯、（甲基）丙烯 酸2-二甲基胺基丙酯、（甲基）丙烯酸3-胺基丙酯、（甲 基）丙烯酸3-二甲基胺基丙酯等不飽和羧酸胺基烷酯類； q (甲基）丙烯酸縮水甘油酯等不飽和羧酸縮水甘油酯 類； (甲基）丙烯腈、α-氯丙烯腈、亞乙基二氰等乙烯基 氰化合物類； (甲基）丙烯醯胺、α-氯丙烯醯胺、Ν-2-羥乙基（甲 基）丙烯醯胺等不飽和醯胺類； 乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯 酯等羧酸乙烯酯類； n 乙烯基甲醚、乙烯基乙醚、烯丙基縮水甘油醚等不飽 和醚類； 1，3-丁二烯、異戊二烯、氯丁二烯、異戊二烯磺酸等 脂肪族共軛二烯類； 聚苯乙烯、聚（甲基）丙烯酸甲酯、聚（甲基）丙烯 酸正丁酯、聚矽氧烷等聚合物分子鏈之末端含有單（甲基 )丙烯醯基的巨型單體類。 這些共聚性不飽和單體可單獨或混合2種以上使用。 本發明中’較佳共聚合性不飽和單體爲Ν-位取代順 -13- 200931179 丁烯二醯亞胺、芳香族乙烯基化合物、不飽和羧酸酯、聚 合物分子鏈之末端含有單（甲基）丙烯醯基的巨型單體等 ，特佳爲N-苯基順丁烯二醯亞胺、N_環己基順丁嫌二酿 亞胺、苯乙烯、α-甲基苯乙烯、對—羥基-α_甲基苯乙烯、 (甲基）丙烯酸甲酯、（甲基）丙烯酸正丁酯 '(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、單（甲基）丙嫌 Q 酸甘油酯、（甲基）丙烯酸4·羥基苯酯、對枯基苯酚之環 氧乙烷改質（甲基）丙烯酸酯、聚苯乙烯巨型單體、聚（ 甲基）丙烯酸甲酯巨型單體等。 含有羧基之共聚物的具體例如有下述者。 (甲基）丙铺酸/甲基（甲基）丙嫌酸醋共聚物、 (甲基）丙烯酸/苄基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/2 -羥基乙基（甲基）丙烯酸酯共聚物 、 〇 (甲基）丙烯酸/2-羥基乙基（甲基）丙烯酸酯/苄基 (甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/甲基（甲基）丙烯酸酯/聚苯乙烯巨 型單體共聚物、 (甲基）丙烯酸/甲基（甲基）丙烯酸酯/聚甲基甲基 丙烯酸酯巨型單體共聚物、 (甲基）丙烯酸/苄基（甲基）丙烯酸酯/聚苯乙烯巨 型單體共聚物、 (甲基）丙烯酸/苄基（甲基）丙烯酸酯/聚甲基（甲 -14- 200931179 基）丙烯酸酯巨型單體共聚物、 (甲基）丙燦酸/苄基（甲基）丙烯酸酯/甘油單（甲 基）丙烯酸酯共聚物、 (甲基）丙烯酸/苯乙烯/ 2_羥基乙基（甲基）丙烯酸 酯共聚物、 (甲基）丙烯酸/2_羥基乙基（甲基）丙烯酸酯/苄基 (甲基）丙烯酸酯共聚物、 0 (甲基）丙烯酸/2_羥基乙基（甲基）丙烯酸酯/苯基 (甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙烯/苄基 (甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-m-羥基苯基順丁烯二醯亞胺/苯乙 烯/苄基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-p-羥基苯基順丁烯二醯亞胺/苯乙 烯/苄基（甲基）丙烯酸酯共聚物、 ❿ (甲基）丙嫌酸環己基順丁嫌二酿亞胺/苯乙嫌/节 基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/心甲基苯乙 烯/苄基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙稀/正丁 基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙燒/2 _乙 基己基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺羥基_α_甲 -15- 200931179 基苯乙烯/苄基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙烯/正丁 基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙烯/對枯 基苯酣之環氧乙烷改質（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-苯基順丁烯二醯亞胺/苯乙烯/2-乙 基己基（甲基）丙烯酸酯/2-羥基乙基（甲基）丙烯酸酯/ Q 节基（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N_苯基順丁烯二醯亞胺/苯乙烯/2_羥 基乙基（甲基）丙烯酸酯/苄基（甲基）丙烯酸酯共聚物 、 (甲基）丙烯酸/N_苯基順丁烯二醯亞胺/苯乙烯/苄基 (甲基）丙烯酸酯/甘油單（甲基）丙烯酸酯共聚物、 (甲基）丙烯酸/N-p-羥基苯基順丁烯二醯亞胺/苯乙 烯/苄基（甲基）丙烯酸酯/甘油單（甲基）丙烯酸酯共聚 ❹ 物、 (甲基）丙烯酸/N_苯基順丁烯二醯亞胺/苯乙烯/苯基 (甲基）丙烯酸酯/2-羥基乙基（甲基）丙烯酸酯/聚苯乙 烯巨型單體共聚物、 (甲基）丙烯酸/N_苯基順丁烯二醯亞胺/苯乙烯/苯基 (甲基）丙烯酸酯/2_羥基乙基（甲基）丙烯酸酯/聚甲基 丙稀酸甲酯巨型單體共聚物、 (甲基）丙烯酸/琥珀酸單[2_(甲基）丙烯醯氧乙基] 酯/N-苯基順丁烯二醯亞胺/苯乙烯/苄基（甲基）丙烯酸酯 -16- 200931179 共聚物、 (甲基）丙烯酸/琥珀酸單u-(甲基）丙烯醯氧乙基] 酯/N-p-羥基苯基順丁烯二醯亞胺/苯乙烯/节基（甲基）丙 烯酸酯共聚物、 (甲基）丙烯酸/琥珀酸單[2-(甲基）丙烯醯氧乙基] 酯/N-苯基順丁烯二醯亞胺/苯乙烯/烯丙基（甲基）丙烯酸 酯共聚物、 (甲基）丙烯酸/琥珀酸單[2-(甲基）丙烯醯氧乙基] 酯/N-環己基順丁烯二醯亞胺/苯乙烯/烯丙基（甲基）丙稀 酸酯共聚物、 (甲基）丙嫌酸/㈣酸單[2-(甲基）_酿氧乙基] 酯/N-環己基順丁烯二醯亞胺/苯乙烯/苄基（甲基）丙烯酸 酯共聚物、 (甲基）丙烯酸/ω-羧基聚己內酯單（甲基）丙烯酸 ❹ 酯/N-m-羥基苯基順丁烯二醯亞胺/苯乙烯/苄基（甲基）丙 烯酸酯共聚物、 甲基）丙烯酸 (甲基）丙烯酸/ω-羧基聚己內醋單 酯/Ν-ρ-羥基苯基順丁烯二醯亞胺/苯乙烯/苄基（甲基）丙 烯酸酯共聚物、 (甲基）丙烯酸/ω-羧基聚己內酯單（甲 个盎）丙烯酸 酯/Ν-苯基順丁烯二醯亞胺/苯乙烯/苄 、 空k干基）丙烯酸酯 /甘油單（甲基）丙嫌酸醋共聚物、 (甲基）丙稀酸/ω -竣基聚己內醋單（甲发、 0曰早1甲基）丙烯酸 酯/Ν-ρ-羥基苯基順丁烯二醯亞胺/苯乙烯/苄基 、干基）丙 -17- 200931179 烯酸酯/甘油單（甲基）丙烯酸酯共聚物。 含羧基之共聚物中之含羧基不飽和單體之共聚比例， 通常爲5〜50質量％，較佳爲10〜40質量％。該共聚比例 未達5質量％時，所得之敏輻射線性組成物對鹼顯像液之 溶解性有降低的傾向。而超過5 0質量％時，對鹼顯像液之 溶解性過大，藉由鹼顯像液顯像時，有著色層容易由基板 上脫落或著色層表面之膜粗糙的傾向。 0 本發明之鹼可溶性樹脂之藉由凝膠滲透層析（GPC， 溶離溶劑：四氫呋喃）測量，並以聚苯乙烯換算之重量平 均分子量（以下稱爲「Mw」）通常爲3,000〜300,000, 更佳爲 5,000 〜100,000。 本發明之鹼可溶性樹脂之藉由凝膠滲透層析（GPC， 溶離溶劑：四氫呋喃）測量，並以聚苯乙烯換算之數平均 分子量（以下稱爲「Μη」）通常爲3,000〜60,000，更佳 爲 5,000〜25,000 ° ❹ 本發明中，藉由使用具有這種特定之Mw及Μη的鹼 可溶性樹脂’可得到具有優異顯像性之敏輻射線性組成物 ’藉以形成具有鮮明圖型邊緣之像素，同時在顯像時，在 未曝光部分之基板上及遮光層上不易發生殘渣、質地污染 、殘膜等。 此外，本發明之鹼可溶性樹脂之Mw與Μη之比例（ Mw/Mn )較佳係爲1〜5，更佳爲1〜4。 本發明中，鹼可溶性樹脂可單獨或混合兩種以上來使 用。 -18- 200931179 本發明中之鹼可溶性樹脂之含量（固形份換算）係對 於（A)著色劑100質量份，通常含有10〜1，000質量份 ，較佳爲20〜5 00質量份。當鹼溶性樹脂之含量未達10 質量份時，例如鹼顯像性可能會降低，或在未曝光部分之 基板上及遮光層上產生質地污染、殘膜。又超過1,000質 量份時，相對的，著色劑的濃度會降低，因此有時難以達 成作爲薄膜之目標的色濃度。 〇 -(C)多官能性單體- 本發明之多官能性單體係由具有2個以上之聚合性不 飽和鍵結之單體所構成。 多官能性單體例如有乙二醇、丙二醇等之烷二醇之二 (甲基）丙烯酸酯類； 聚乙二醇、聚丙二醇等之聚烷二醇之二（甲基）丙烯 酸酯類； 〇 甘油、三羥甲基丙烷、季戊四醇、二季戊四醇等之3 價以上之多元醇之聚（甲基）丙烯酸酯類或這些之二羧酸 改質物； 聚酯、環氧樹脂、胺基甲酸酯樹脂、醇酸樹脂、聚矽 氧樹脂、螺烷樹脂等之低聚（甲基）丙烯酸酯類； 兩末端羥基之聚-1,3-丁二烯、兩末端羥基之聚異戊二 烯、兩末端羥基之聚己內酯等之兩末端羥基化聚合物之二 (甲基）丙烯酸酯類； 三[2-(甲基）丙烯醯氧基乙基]磷酸酯等。 -19- 200931179 此等之多官能性單體中，較佳爲3價以上之多元醇之 聚（甲基）丙烯酸酯類或這些之二羧酸改質物。具體例有 三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯 、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊 四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇 五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六 丙烯酸酯、二季戊四醇六甲基丙嫌酸酯、以下式（4)所 示之化合物、下式（5)所不之化合物等爲佳。In the formula (3), R6 each independently represents an alkyl group having 1 to 4 carbon atoms, and R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The second aspect of the present invention provides a color filter formed using the above-described blue color filter with a linear composition of sensitive radiation. The third aspect of the present invention provides a liquid crystal display element comprising the above color filter. [Effects of the Invention] According to the present invention, even when a light polymerization initiator which does not have sufficient brightness in the past is used, it is possible to provide a blue pixel which is excellent in luminance. Further, according to the present invention, even when a photopolymerization initiator which provides high luminance is used, it is possible to suppress a decrease in luminance, and it is possible to provide a blue pixel having both a high level of brightness and sensitivity. In this way, the photopolymerization initiator can be selected more widely than in the past, and the exposure amount in recent years can be reduced, and the Takt Time can be shortened. Therefore, the linear color filter of the blue color filter of the present invention is extremely suitable for the manufacture of color filters and liquid crystal display panels for color liquid crystal display panels in the electronic industry. -8- 200931179 [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. Blue color filter using sensitive radiation linear composition - (A) colorant - The coloring agent of the present invention is a blue coloring agent as an essential component. The blue colorant is appropriately selected depending on the use of the color filter, and may be a pigment, a dye or a natural pigment, and may be an organic or inorganic system. The color filter of the present invention is required to have high-definition color development and heat resistance. Therefore, the blue coloring agent of the present invention is a coloring agent having high color developability and high heat resistance, and among them, a coloring agent having high heat decomposition resistance is preferable. Such a blue colorant can usually be an organic pigment or an inorganic pigment, and particularly preferably an organic pigment. The blue organic pigment used in the present invention is, for example, a compound having a color index (CI; issued by The Society of Dyers and Colourists, the same as the following) classified as Pigment Blue, and specifically, for example, a CI is attached. Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15:4, CI Pigment Blue 15: 6, CI·Pigment Blue 60 Color Index (CI) number. Among these blue organic pigments, it is particularly preferred to be c.I. Pigment Blue 15:6. Further, the blue inorganic pigment is, for example, ultramarine blue or dark blue. Further, in the present invention, a blue pigment and a violet pigment may be used as needed. The purple pigment is, for example, a compound classified into Pigment Violet in a color index. Specific examples include CI Pigment Violet 1, 200931179 匸丄 Pigment Violet ^^ 丄 Pigment Violet ^^ 丄 Pigment Violet ^^ 丄 Pigment Violet 32, CI Pigment Violet 36, (: 丄 Pigment Violet 38 Color Index (c") Numbered organic pigments. Among these purple organic pigments, 'excellently CI. Pigment Violet 23.' In the present invention, blue colorants may be used singly or in combination of two or more kinds. Further, organic pigments and inorganic pigments may be used. In the case of forming a pixel, it is preferred to use one or more kinds of organic pigments. The organic pigment of the present invention may be used after being purified by a sulfuric acid recrystallization method, a solvent cleaning method, or a combination of these methods, if necessary. In the case of using a polymer to modify the surface of the particles, the polymer of the surface of the pigment is modified, for example, a polymer described in JP-A-H08-259876 or a commercially available pigment dispersion. Polymer or oligomer. - (B) Alkali Soluble Resin - The alkali-soluble resin of the present invention has a bonding time for the (A) colorant and a 'wearing color filter' for the development process. The steps used by the steps The agent is particularly preferably an alkali developer, and is not particularly limited as long as it has a soluble resin. The alkali-soluble resin is preferably a soluble resin having a carboxyl group, and particularly preferably an ethylenic unsaturated group having one or more carboxyl groups. a monomer (hereinafter referred to as "S-group-unsaturated monomer") and another B-synthesized unsaturated monomer (hereinafter referred to as "co-unsaturated monomer") copolymerized with the monomer Copolymer (hereinafter referred to as "carboxyl-containing copolymer"). An unsaturated monomer having a carboxyl group, for example, an unsaturated single such as -10 200931179 (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid or the like Carboxylic acid; unsaturated dicarboxylic acid or anhydride thereof of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc. a trivalent or higher unsaturated polyvalent carboxylic acid or an anhydride thereof; succinic acid mono [2-(methyl) propylene oxiranyl] ester, phthalic acid mono 0 [2-(methyl) propylene oxime Mono[(meth)acryloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as ethyl]ester; ω-carboxylate A mono(meth)acrylate such as a polycaprolactone mono(meth)acrylate or the like having a carboxyl group and a hydroxyl group at both terminals. The carboxyl group-containing unsaturated monomer may be used singly or in combination of two or more kinds. In the present invention, the carboxyl group-containing unsaturated monomer is preferably (meth)acrylic acid, succinic acid mono [2-(methyl)acryloxyethyl ester], ω-carboxy polycaprolactone mono(methyl). Acrylate or the like is particularly preferably (meth)acrylic acid. φ The copolymerizable unsaturated monomer is, for example, the following: Ν-phenyl maleimide, Ν-o-hydroxyphenyl-butenylene醯imine, Ν-m-hydroxyphenyl maleimide, Ν-p-hydroxyphenyl maleimide, Ν-benzyl maleimide, Ν-cyclohexyl Maleimide, hydrazine-succinimido-3-methyleneimine benzoate, hydrazine-succinimido-4-m-butyleneimine butyrate, hydrazine- Succinimide-6-m-butyleneimine hexanoate, Ν_succinimide-3 _cis-butyl diimide propionate, Ν-(acridinyl) maleic acid Imine and the like _ 顺 substituted with maleimide; 11 - 200931179 Such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxy styrene, m-methoxy Styrene, p-methoxy styrene, o-ethylene bromide, m-ethyl benzene, p-ethyl benzene, p-amino-methyl styrene Vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl vinyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl benzyl Aromatic vinyl compound of glycidyl ether; such as hydrazine, 1-methyl hydrazine; such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (a Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) propyl 3-hydroxypropyl enoate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, Benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, Methoxy di(ethylene glycol) (meth) acrylate, methoxy tri (ethylene glycol) (meth) acrylate, methoxy propylene glycol (meth) acrylate, methoxy bis (propylene glycol) (meth) acrylate, isobornyl (meth) acrylate, tricyclo-12 (2009) methacrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, mono (meth) acrylate a glyceride, 4-hydroxyphenyl (meth)acrylate, an ethylene oxide-modified (meth) acrylate unsaturated carboxylic acid ester of p-cumylphenol; 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-di(meth)acrylate Aminoalkyl esters of unsaturated carboxylic acids such as propyl propyl ester, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate; q (meth)acrylic acid shrinkage Glycidyl esters of unsaturated carboxylic acid such as glycerides; vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile and ethylene dicyandiamide; (methyl) acrylamide, α-chloropropene oxime An unsaturated decylamine such as an amine or hydrazine-2-hydroxyethyl (meth) acrylamide; a vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; n ethylene An unsaturated ether such as methyl ether, vinyl ether or allyl glycidyl ether; an aliphatic conjugated 1,3-butadiene, isoprene, chloroprene or isoprene sulfonate a megamonomer containing a mono(meth)acrylonitrile group at the end of a polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene. class. These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types. In the present invention, the preferred copolymerizable unsaturated monomer is a fluorene-substituted cis-13-200931179 butenylenediamine, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a terminal of a polymer molecular chain. (Methyl) acrylonitrile-based megamonomers, etc., particularly preferably N-phenyl maleimide, N-cyclohexyl cis-butane, styrene, α-methyl styrene, p-Hydroxy-α-methylstyrene, methyl (meth)acrylate, n-butyl (meth)acrylate 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , allyl (meth) acrylate, benzyl (meth) acrylate, mono (methyl) propyl glycerate, 4 hydroxyphenyl (meth) acrylate, ethylene oxide of p-cumyl phenol Modified (meth) acrylate, polystyrene megamonomer, poly(methyl) methacrylate megamonomer, and the like. Specific examples of the copolymer containing a carboxyl group include the following. (Methyl)propionic acid/methyl(methyl)propyl citrate copolymer, (meth)acrylic acid/benzyl (meth) acrylate copolymer, (meth)acrylic acid/2-hydroxyethyl ( Methyl) acrylate copolymer, /2(meth)acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate copolymer, (meth) acrylate / methyl (methyl) Acrylate/polystyrene mega monomer copolymer, (meth)acrylic acid/methyl(meth)acrylate/polymethylmethacrylate megamonomer copolymer, (meth)acrylic acid/benzyl (A) Acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/benzyl (meth)acrylate/polymethyl (methyl-14-200931179) acrylate macromonomer copolymer, (a) (M) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylate / styrene / 2 - hydroxyethyl (meth) acrylate copolymer, ( Methyl)acrylic acid/2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, 0 (A Acrylic acid/2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / styrene / benzyl ( Methyl) acrylate copolymer, (meth)acrylic acid / Nm-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / Np - hydroxyl Phenyl maleimide / styrene / benzyl (meth) acrylate copolymer, ❿ (methyl) propylene succinic acid cyclohexyl cis succinimide / styrene Acrylate copolymer, (meth)acrylic acid / N-phenyl maleimide / heart methyl styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / N- Phenyl maleimide / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenyl maleimide / phenyl bromide / 2 _ Ethylhexyl (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide imine hydroxy _α_methyl-15- 200931179 styrene / benzyl (meth) acrylate Copolymer, ( Acrylic acid / N-phenyl maleimide / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenyl maleimide / benzene Ethylene/p-cumyl benzoquinone ethylene oxide modified (meth) acrylate copolymer, (meth) acrylate / N-phenyl maleimide / styrene / 2-ethylhexyl ( Methyl) acrylate/2-hydroxyethyl (meth) acrylate / Q-based (meth) acrylate copolymer, (meth) acrylate / N phenyl maleimide / styrene /2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / N phenyl maleimide / styrene / benzyl (methyl Acrylate/glycerol mono(meth)acrylate copolymer, (meth)acrylic acid/Np-hydroxyphenyl maleimide/styrene/benzyl (meth)acrylate/glycerol single (A) Acrylate copolymer, (meth)acrylic acid / N-phenyl maleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / Polystyrene Monomer Copolymer, (Meth)Acrylic/N_Phenylmethyleneimine/styrene/Phenyl (meth)acrylate/2-Hydroxyethyl (meth)acrylate/Polymethyl Methyl acrylate macromonomer copolymer, (meth)acrylic acid/succinic acid mono [2_(methyl) propylene oxiranyl] ester / N-phenyl maleimide / styrene / benzyl (meth) acrylate-16- 200931179 copolymer, (meth)acrylic acid / succinic acid mono u-(methyl) propylene oxiranyl ethyl ester / Np-hydroxyphenyl maleimide / Styrene / benzyl (meth) acrylate copolymer, (meth) acrylate / succinic acid [2-(methyl) propylene oxyethyl] ester / N-phenyl maleimide / Styrene/allyl (meth) acrylate copolymer, (meth)acrylic acid / succinic acid mono [2-(methyl) propylene oxyethyl] ester / N-cyclohexyl maleimide /styrene/allyl (meth) acrylate copolymer, (meth) propylene acid / (tetra) acid mono [2-(methyl) styroethoxy] ester / N-cyclohexyl cis Equinone imine/styrene/benzyl (meth) acrylate copolymer, (methyl Acrylic acid / ω-carboxy polycaprolactone ❹ (meth) acrylate / Nm - hydroxy phenyl maleimide / styrene / benzyl (meth) acrylate copolymer, methyl acrylate ( Methyl)acrylic acid/ω-carboxypolycaprolactone monoester/Ν-ρ-hydroxyphenyl maleimide/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/ Ω-carboxypolycaprolactone single (A ounce) acrylate / Ν-phenyl maleimide / styrene / benzyl, empty k-based acrylate / glycerol mono (methyl) propylene acid Vinegar copolymer, (meth)acrylic acid/ω-mercapto-polyhexyl vinegar single (methanoate, 0 曰 early 1 methyl) acrylate / Ν-ρ-hydroxyphenyl maleimide / Styrene / benzyl, dry basis C-17 - 200931179 enoate / glycerol mono (meth) acrylate copolymer. The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. When the copolymerization ratio is less than 5% by mass, the solubility of the obtained linear radiation sensitive composition tends to decrease in the solubility of the alkali developing solution. On the other hand, when it exceeds 50% by mass, the solubility in the alkali developing solution is too large, and when the alkali developing solution is developed, the colored layer tends to fall off from the substrate or the film on the surface of the colored layer tends to be rough. 0 The alkali-soluble resin of the present invention is measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene is usually 3,000 to 300,000, more Good for 5,000 to 100,000. The alkali-soluble resin of the present invention is measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the average molecular weight in terms of polystyrene (hereinafter referred to as "Μη") is usually 3,000 to 60,000, more preferably Between 5,000 and 25,000 ° ❹ In the present invention, by using an alkali-soluble resin having such a specific Mw and Μ, a sensitive radiation linear composition having excellent developing ability can be obtained, thereby forming a pixel having a sharp pattern edge. At the same time, at the time of development, residue, texture contamination, residual film, and the like are less likely to occur on the unexposed portion of the substrate and on the light shielding layer. Further, the ratio (Mw/Mn) of Mw to Μη of the alkali-soluble resin of the present invention is preferably from 1 to 5, more preferably from 1 to 4. In the present invention, the alkali-soluble resin may be used singly or in combination of two or more. -18- 200931179 The content of the alkali-soluble resin (in terms of solid content) in the present invention is usually 10 to 1,000 parts by mass, preferably 20 to 50,000 parts by mass, per 100 parts by mass of the (A) coloring agent. When the content of the alkali-soluble resin is less than 10 parts by mass, for example, alkali developability may be lowered, or texture contamination or residual film may be formed on the unexposed portion of the substrate and the light-shielding layer. When the amount is more than 1,000 parts by mass, the concentration of the coloring agent is lowered, so that it is sometimes difficult to achieve the color density as a target of the film. 〇 - (C) Polyfunctional monomer - The polyfunctional single system of the present invention is composed of a monomer having two or more polymerizable unsaturated bonds. The polyfunctional monomer is, for example, a di(meth)acrylate of an alkanediol such as ethylene glycol or propylene glycol; or a di(meth)acrylate of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol; a poly(meth) acrylate of a polyvalent alcohol having a valence of 3 or more, such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol, or a modified product of these dicarboxylic acids; polyester, epoxy resin, urethane Oligomeric (meth) acrylates such as ester resins, alkyd resins, polyoxyxylene resins, and spiro resins; poly-1,3-butadiene having hydroxyl groups at both terminals, and polyisoprene having hydroxyl groups at both terminals a di(meth)acrylate of two terminal hydroxylated polymers such as polycaprolactone at both terminal hydroxyl groups; tris[2-(methyl)acryloxyethyl)phosphate. -19- 200931179 Among these polyfunctional monomers, poly(meth)acrylates of polyvalent or higher polyvalent alcohols or modified dicarboxylic acids thereof are preferred. Specific examples are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate. The ester, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethylpropane acid ester, a compound represented by the following formula (4), a compound of the following formula (5), or the like is preferred.

-20- 200931179 【化3】-20- 200931179 【化3】

0==( JO -ο0==( JO -ο

o 〇\/〇-CH2·^—ch2och2— -ch2-oo 〇\/〇-CH2·^—ch2och2— -ch2-o

COOH (5) 、 P Q 〇=< ^=0COOH (5) , P Q 〇=< ^=0

OO

其中，特別是三經甲基丙院三丙烯酸酯、季戊四醇三 丙烯酸酯 '二季戊四醇六丙烯酸酯、及以上式（4)及（5 )所示之化合物因著色層之強度高，著色層之表面平滑性 優異’且未曝光部分之基板上及遮光層上不易產生質地汚 染、膜殘留等，故較佳。 多官能性單體可單獨或組合兩種以上來使用。 本發明中’多官能性單體之一部份可被取代爲具有一 個聚合性不飽和鍵結之單官能性單體。 這種單官能性單體例如有與（B )鹼可溶性樹脂中例 示之含羧基之不飽和單體或共聚性不飽和單體相同的化合 物或N-(甲基）丙烯醯基嗎啉、N -乙烯基吡咯烷酮' N-乙烯基-ε -己內醯胺及市售品M-5600 (商品名，東亞合成 (股）製）等。 此等單官能性單體可單獨或組合雨種以上來使用。 單官能性單體之使用比例係對於多官能性單體與單官 -21 - 200931179 能性單體之合計質量，通常使用9〇質量％以下’更佳5〇 質量％以下。單官能性單體之使用比例超過90質量％時， 所得之著色層的強度及表面平滑性可能不足。 本發明中’多官能性單體之含量係對於（B)鹼可溶 性樹脂100質量份（固形分換算），通常爲5〜500質量 份’較佳爲20〜3 00質量份。該含量未達5質量份時，著 色層之強度及表面平滑性有降低的傾向，另外，超過5〇〇 質量份時’例如鹼顯像性可能會降低，或在未曝光部分之 基板上或遮光層上容易產生質地污染、殘膜等的傾向。倂 用多官能性單體與單官能性單體時，單官能性單體之質量 係包含在多官能性單體之質量內。 -(D )光聚合起始劑_ 光聚合起始劑係曝照可見光、紫外線、遠紫外線、電 子射線' X射線’可產生使（C )多官能性單體及視需要 Q 使用之單官能性單體開始聚合之活性種的化合物。 本發明之光聚合起始劑係選自由上述式（3) 化合物（以下有時稱爲「苯乙酮系化合物」）、^ 」J ' fe酯系化 合物及聯咪唑系化合物之至少1種爲必須成分。 、 。错此可進 一步提高感度，因此即使以低曝光量也可得刹 守到有不會產生 底切之具有良好邊緣形狀的像素。 本發明中，光聚合起始劑之合計含量係對於（c $ # 官能性單體100質量份，通常爲0·01〜200暂壤/ 貝里份，較佳 爲1〜120質量份，特佳爲1〜1〇〇質量份。氺取八 %聚合起始劑 -22- 200931179 之合計含量未達0·01質量份時，藉由曝光之硬化 有時不易得到像素圖型以規則排列之圖型陣列。 200質量份時，形成之著色層在顯像時容易由基板 ’或在未曝光部分之基板上或遮光層上容易產生質 、殘膜等。倂用多官能性單體與單官能性單體時， 性單體之質量係包含在多官能性單體之質量內。 說明上述式（3)中之符號的定義。 ❹ R6、R7及R8之碳數1〜4之烷基可爲直鏈或支 例如有甲基、乙基、正丙基、異丙基、正丁基、異 第二丁基、第三丁基。 式（3)中，R6係甲基、乙基，特佳爲甲基，5 R8特佳爲氫原子、甲基、乙基。 式（3)表示之苯乙酮系化合物之具體例有、 2 -苄基-2-二甲基胺基-1- ( 4_嗎啉苯基）丁院_ 2 -节基-2 -二乙基胺基-1- ( 嗎啉苯基）丁院-i_酮 Q 4-甲基苄基）-2-(二甲基胺基）-1- ( 4-嗎啉苯基） 1-嗣、2-(4-乙基苄基）-2-(二甲基胺基） 基）乙院-1-酮' 2-(4-n -丙基节基）-2-(二甲基n 1-(4-嗎啉苯基）乙烷-卜酮、2-(4-n-丁基苄基）_ 甲基胺基）-1- ( 4-嗎啉苯基）乙烷-1-酮、2- ( 4-甲 )-2-(二乙基胺基）-1-( 4_嗎啉苯基）乙院-卜酮 4-乙基苄基）-2-(二乙基胺基）-1-(4-嗎啉苯基） 1-酮、2-(4-n -丙基节基）-2-( 一乙基胺基）-i_( 苯基）乙院-1-酮、2- (4_n -丁基节基）-2-(二乙 不足， 又超過 上脫落 地污染 單官能 鏈狀， 丁基、 :R7及 1- 酮、 、2-( 乙烷-嗎啉苯 5基）- 2- (二 基苄基 、2-( 乙烷-4 -嗎啉 基胺基 -23- 200931179 )-1-(4-嗎啉苯基）乙烷-丨-酮、2-(4_甲基苄基）-2_( 二甲基胺基）-1-(4-嗎啉苯基）丁烷-1-酮、2- (4-乙基苄 基）_2_(二甲基胺基）-1-(4-嗎啉苯基）丁烷-1-酮、2-(4-i-丙基苄基）_2-(二甲基胺基）-卜（4_嗎啉苯基）丁 院-1-酮' 2-(4-n-丁基苄基）-2-(二甲基胺基）-1-(4-嗎啉苯基）丁烷-1-酮、2- (4-i -丁基苄基）-2-(二甲基胺 基）-1-(4-嗎啉苯基）丁烷-酮、2_(4_丨_丙基苄基）-2_ Q 〔（正丁基）（甲基）胺基〕-1-(4-嗎啉苯基）丁烷-1-酮、2- ( 4·η-丁基苄基）-2-〔（正丁基）（甲基）胺基 〕-1-(4-嗎啉苯基）丁烷-丨_酮、2-(4“_丙基苄基）-2_( 二甲基胺基）-1-(4 -嗎啉苯基）戊烷-1-酮、2- (4-i -丁基 节基）-2-〔（正丁基）（甲基）胺基〕〕-1- ( 4-嗎啉苯 基）戊烷-1 -酮等。 這些苯乙酮系化合物中，較佳爲2-苄基-2-二甲基胺 基-1-(4-嗎啉苯基）丁烷·丨_酮、2_(4_甲基苄基）-2_( 〇 二甲基胺基）-1-(4 -嗎啉苯基）丁烷-1-酮等。 ^^酮系化合物可單獨或混合2種以上使用。 本發明中，光聚合起始劑使用苯乙酮系化合物時，其 含量係對於（C)多官能性單體100質量份，通常爲0.01 〜80質量份’較佳爲1〜質量份，更佳爲1〜60質量份 。倂用多官能性單體與單官能性單體時，單官能性單體之 質量係包含在多官能性單體之質量內。 月弓酯系化合物係指具有肟醋構造（>C = N-0-C0-)的 化合物。肟酯系化合物例如有下述式（n或（2 )表示之 -24- 200931179 化合物。 【化4】 〇 (R5);Among them, in particular, trimethyl methacrylate triacrylate, pentaerythritol triacrylate dipentaerythritol hexaacrylate, and compounds represented by the above formulas (4) and (5) have a high strength of the colored layer, and the surface of the colored layer It is preferable because it is excellent in smoothness, and it is less likely to cause texture contamination, film residue, and the like on the substrate and the light-shielding layer of the unexposed portion. The polyfunctional monomer may be used singly or in combination of two or more. In the present invention, a part of the 'polyfunctional monomer' may be substituted with a monofunctional monomer having a polymerizable unsaturated bond. Such a monofunctional monomer is, for example, the same compound as the carboxyl group-containing unsaturated monomer or copolymerizable unsaturated monomer exemplified in (B) the alkali-soluble resin, or N-(methyl)propenylmorpholine, N. -vinylpyrrolidone 'N-vinyl-ε-caprolactam and a commercial product M-5600 (trade name, manufactured by Toago Seisakusho Co., Ltd.). These monofunctional monomers can be used singly or in combination with rain. The ratio of the use of the monofunctional monomer to the total mass of the polyfunctional monomer and the mono----2009-11179 energy-sensitive monomer is usually 9% by mass or less and more preferably 5% by mass or less. When the use ratio of the monofunctional monomer exceeds 90% by mass, the strength and surface smoothness of the resulting colored layer may be insufficient. In the present invention, the content of the polyfunctional monomer is usually from 5 to 500 parts by mass, preferably from 20 to 30,000 parts by mass, per 100 parts by mass of the (B) alkali-soluble resin. When the content is less than 5 parts by mass, the strength and surface smoothness of the colored layer tend to be lowered, and when it exceeds 5 parts by mass, for example, alkali developability may be lowered, or on a substrate of an unexposed portion or There is a tendency that texture contamination, residual film, and the like are likely to occur on the light shielding layer. When a polyfunctional monomer and a monofunctional monomer are used, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer. -(D) Photopolymerization Initiator_ Photopolymerization initiators are exposed to visible light, ultraviolet light, far ultraviolet rays, and electron rays 'X-rays' to produce (C) polyfunctional monomers and monofunctional Qs as needed. A compound of an active species in which a monomer starts to polymerize. The photopolymerization initiator of the present invention is selected from at least one of the compound of the above formula (3) (hereinafter sometimes referred to as "acetophenone-based compound"), "J" fe-ester compound, and biimidazole-based compound. Must be a component. , . This can further improve the sensitivity, so that even with a low exposure amount, it is possible to hold the pixel with a good edge shape which does not cause undercut. In the present invention, the total content of the photopolymerization initiator is 100 parts by mass of the (c$# functional monomer, usually 0. 01 to 200, and preferably 1 to 120 parts by mass, preferably 1 to 120 parts by mass. Preferably, it is 1 to 1 part by mass. When the total content of the 8% polymerization initiator 22-200931179 is less than 0.101 parts by mass, it is sometimes difficult to obtain a pixel pattern by exposure hardening. Pattern array. When 200 parts by mass, the formed coloring layer is liable to produce mass, residual film, etc. from the substrate 'or on the unexposed portion of the substrate or on the light shielding layer during development. Polyfunctional monomer and single In the case of a functional monomer, the mass of the monomer is contained within the mass of the polyfunctional monomer. The definition of the symbol in the above formula (3) is explained. ❹ The alkyl group having 1 to 4 carbon atoms of R6, R7 and R8 It may be a straight chain or a branch, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a third butyl group. In the formula (3), the R6 group is a methyl group or an ethyl group. Particularly preferred is a methyl group, and 5 R8 is particularly preferably a hydrogen atom, a methyl group or an ethyl group. Specific examples of the acetophenone-based compound represented by the formula (3) include 2-benzyl-2-di Methylamino-1-(4_morpholinyl) butyl _ 2 -pyringyl-2-diethylamino-1-(morpholinylphenyl)-butyl-i-keto Q 4-methyl Benzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl) 1-indole, 2-(4-ethylbenzyl)-2-(dimethylamino)yl) B--1-keto' 2-(4-n-propyl)-2-(dimethyl n 1-(4-morpholinyl)ethane- ketone, 2-(4-n- Butylbenzyl)-methylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-methyl)-2-(diethylamino)-1-( 4_morpholinylphenyl)benz-butanone 4-ethylbenzyl)-2-(diethylamino)-1-(4-morpholinylphenyl) 1-one, 2-(4-n -propyl benzyl)-2-(ethylamino)-i-(phenyl) phenyl-1-one, 2-(4-n-butyl)-2-(2-diethyl sulphate) Peeling contaminated monofunctional chain, butyl, :R7 and 1-ketone, 2-(ethane-morpholinium-5-yl)-2-(diylbenzyl, 2-(ethane-4-morpholine) Aminoamino-23- 200931179 )-1-(4-morpholinylphenyl)ethane-fluorenone, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4) -morpholinylphenyl)butan-1-one, 2-(4-ethylbenzyl)_2-(dimethylamino)-1-(4-? Phenyl)butan-1-one, 2-(4-i-propylbenzyl)_2-(dimethylamino)-bu(4-morpholinyl)butan-1-one' 2- (4-n-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(4-i-butylbenzyl) -2-(Dimethylamino)-1-(4-morpholinylphenyl)butane-one, 2-(4-di-propylbenzyl)-2_Q[(n-butyl)(methyl) Amino]-1-(4-morpholinylphenyl)butan-1-one, 2-(4·η-butylbenzyl)-2-[(n-butyl)(methyl)amino]- 1-(4-morpholinylphenyl)butane-indole-ketone, 2-(4"-propylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)pentane 1-ketone, 2-(4-i-butyl)yl-2-((n-butyl)(methyl)amino]]-1-(4-morpholinylphenyl)pentan-1 Ketones, etc. Among these acetophenone-based compounds, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane·indolone and 2-(4-methylbenzyl) are preferred. -2_(decyldimethylamino)-1-(4-morpholinylphenyl)butan-1-one. The ketone compound may be used singly or in combination of two or more. In the present invention, when the acetophenone-based compound is used as the photopolymerization initiator, the content thereof is usually 0.01 to 80 parts by mass, preferably 1 to part by mass, based on 100 parts by mass of the (C) polyfunctional monomer. Preferably, it is 1 to 60 parts by mass. When a polyfunctional monomer and a monofunctional monomer are used, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer. The lupus ester compound refers to a compound having an vinegar structure (> C = N-0-C0-). The oxime ester compound is, for example, a compound of the following formula (n or (2) -24-200931179. [Chemical 4] 〇 (R5);

3R \ 錢 63R \ money 6

\ \ .CIO\ \ .CIO

2R /Nnc vn/ 1A /-\ 【化5】 ❹ R5—(CH2)^-〇2R /Nnc vn/ 1A /-\ 【化5】 ❹ R5—(CH2)^-〇

2 R \n/ 2 /n\ 〔式（1)及（2)中，R1係互相獨立表示碳數1〜20之烷 基、碳數3〜8之環烷基或苯基， R2及R3係互相獨立表示氫原子、碳數1〜20之烷基 、碳數3〜8之環烷基、可被取代之苯基或碳數7〜20之1 -25- 200931179 價脂環基（但是前述環烷基除外）， R4係互相獨立表示碳數1〜12之烷基、碳數3〜8之 環烷基、碳數1〜12之烷氧基或碳數3〜8之環烷氧基， R5係互相獨立表示碳數4〜20之1價含氧雜環基、碳 數4〜20之1價含氮雜環基或碳數4〜20之1價含硫雜環 基， k係表示1〜5之整數， ^ j、m及η係互相獨立表示0〜5之整數， ρ係表示〇〜6之整數。 但是（n+j ) S5，( m + k) S5〕 說明上述式（1)及（2)中之符號的定義。 R】、R2及R3之碳數1〜20之烷基可爲直鏈或支鏈狀 ，碳數1〜12(更佳爲1〜4)之烷基。具體例如有甲基、 乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、 正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正 ^ -f--基、正十二基等。 R1〜R4之碳數3〜8之環烷基，較佳爲碳數5〜6之環 烷基，具體例有環戊基、環己基等。 R2及R3之苯基之取代基，例如有甲基、乙基、正丙 基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正 己基等之碳數1〜6之烷基；環戊基、環己基等之碳數3〜 6之環烷基：甲氧基、乙氧基、正丙氧基、異丙氧基、正 丁氧基 '第三丁氧基等之碳數1〜6之烷氧基；環戊氧基 、環己氧基等之碳數3〜6之環烷氧基；苯基；氟原子、 -26- 200931179 氯原子等之鹵原子等。 R2及R3之碳數7〜20之1價脂環基（但是前述環烷 基除外）例如有具有1-烷基環鏈烷骨架之基、具有雙環鏈 烷骨架之基、具有三環鏈烷骨架之基 '具有螺鏈烷骨架之 基、具有萜烯骨架之基、具有金剛烷骨架之基等。 R4之碳數1〜12之烷基可爲直鏈狀或支鏈狀，較佳爲 碳數1〜6(更佳爲1〜4)之烷基。 R4之碳數1〜12之烷氧基，較佳爲碳數1〜6(更佳 爲1〜4)之烷氧基。具體例有甲氧基、乙氧基、正丙氧基 、異丙氧基、正丁氧基、第三丁氧基、正戊氧基、正己氧 基、正庚氧基、正辛氧基、正壬氧基、正癸氧基、正十一 氧基、正十二氧基等。 R4之碳數3〜8之環烷氧基較佳爲碳數5〜6之環烷氧 基。具體例有環戊氧基、環己氧基等。 R5之碳數4〜20之1價含氧雜環基、碳數4〜20之1 價含氮雜環基或碳數4〜20之1價含硫雜環基，例如有四 氫噻吩基、吖庚因基、二氫吖庚因基、二氧雜環戊基、三 嗪基、噁嗪基、噻唑啉基、噁二嗪基、二氧雜茚滿基、二 硫萘基、呋喃基、噻吩基、吡咯基、噁唑基、異噁唑基、 噻唑基、異噻唑基、吡唑基、呋咱基、吡喃基、吡咯基、 噠嗪基、嘧啶基、吡嗪基、吡咯烷基、嗎啉基、哌嗪基、 奎寧環基、吲哚基、異吲哚基、苯并呋喃基、苯并噻吩基 、中氮茚基、色烯基、喹啉基、異喹啉基、嘌呤基、喹唑 啉基、噌啉基、酞嗪基' 喋啶基、咔唑基、吖啶基、菲啶 -27- 200931179 基、噻噸基、吩曉基、吩噻嗪基、吩嘆噁基、吩噁噻基、 噻蒽基、四氫呋喃基、四氫吡喃基等。 式（1)及式（2)中’ R1特佳爲甲基、乙基等，r2 及R3特佳爲氫原子、甲基、乙基等。又，R4特佳爲甲基 、乙基、正丙基、異丙基、正丁基、甲氧基、乙氧基等， R4較佳爲芳香環之〇 -位進行取代。R5較佳爲四氫呋喃基 、四氫吡喃基等。 式（1)中，η較佳爲0、1或2’特佳爲1。』較佳爲 〇或1，特佳爲〇。 式（2)中，m較佳爲〇、1或2’特佳爲1。又，k較 佳爲1，P較佳爲〇、1或2，特佳爲1。 式（1 )表示之肟酯系化合物之具體例’例如有下述 者。 1-〔 9-乙基-6-苯醯- 9H-咔哩-3-基〕-丨，2-壬烷-2-肟- 0-苯甲酸酯、：! -〔 9 -乙基-苯醯·9Η -咔唑-3-基〕-1,2 -壬烷-2 -肟-〇-乙酸酯、卜〔9 -乙基-6-苯醯- 9H -咔唑-3 -基〕-i，2-戊烷-2-肟-〇-乙酸酯、卜〔9_乙基-6-苯醯-9H-咔唑-3-基 〕-辛烷-1-酮聘-〇-乙酸酯、 1-〔9-乙基-6-(2-甲基苯醯）-9H-昨哩-3-基〕-乙烷_ 1_酮肟〇_苯甲酸酯、卜〔9 -乙基-6-(2_甲基苯酶）-9H -味 唑-3-基〕-乙烷-1-酮肟-〇-乙酸醋、卜〔9-n-丁基-6- ( 2-乙 基苯酸）-9Η -味哩-3-基〕-乙院_1-酮目弓_0_苯甲酸醋、 乙酮，1-[9 -乙基-6_(2_甲基-4_四氫呋喃基苯醯）-9Η -昨哩-3-基]-，1- ( 〇 -乙醯基目弓）、乙酮’ 1-〔 9 -乙基- 200931179 6-(2-甲基-4-四氫吡喃基苯醯）_9H•咔唑-3-基〕.，丨_( 〇-乙醯基蔣）、乙酮’1-〔9-乙基-6-(2-甲基-5-四氫呋喃 基苯醯）-9H -咔唑-3-基〕-，；[_(〇_乙醯基肟）、乙酮， 1-〔 9 -乙基- 6-( 2 -甲基-5-四氫吡喃基苯醯）-9H -咔唑-3-基〕1-(0 -乙醯基肟）、乙酮，l-〔9 -乙基- 6- {2 -甲基-4-(2,2-二甲基-1，3-二氧雜環戊基）苯醯}-9Η·咔唑-3-基 〕-，1- ( 0-乙醯基肟）、 Q 又’式（2 )表示之肟酯系化合物之具體例，例如有 下述者。 乙酮，1-[9 -乙基-6- (2 -甲基-4-四氫呋喃基甲氧基苯 醯）-9Η -咔唑-3-基]1-(〇_乙醯基肟）、乙酮，丨_〔9-乙基-6- (2 -甲基-4-四氫吡喃基甲氧基苯醯）-9Η-昨唑- 3-基〕1-(0 -乙醯基肟）、乙酮，卜〔9 -乙基- 6-(2 -甲 基-5-四氫呋喃基甲氧基苯醯）_9H_咔唑-3-基〕_，^(o· 乙醯基肟）、乙酮’ 1-〔 9 -乙基-6- ( 2 -甲基-5-四氫吡喃基 〇 甲氧基苯醯）-9H -咔唑-3 -基〕-，l-(〇 -乙醯基肟）、乙 酮，1-〔 9-乙基- 6-{2-甲基-4- (2,2-二甲基-1，3-二氧雜環 戊基）甲氧基苯醯}-9H-咔唑基〕-，1-(〇_乙醯基肟） 〇 式（1)或（2)表示之化合物以外之肟酯系化合物， 例如有下述者。 1，2-辛烷二酮，1-〔4-(苯硫基）苯基〕-，2-(0-苯 醯肟）、1,2-丁烷二酮，1-〔4-(苯硫基）苯基〕_，2-( 〇-苯醯肟）、1，2-丁烷二酮，1-〔4-(苯硫基）苯基〕·， -29- 200931179 2- (0-乙醯基肟）、1,2-辛烷二酮，1-〔4-(甲基硫基） 苯基〕-，2-(0 -苯醯肟）、1,2 -辛烷二酮，1-〔4-(苯硫 基）苯基〕-，2-(0-( 4-甲基苯醯肟））。 這些肟酯系化合物中，較佳爲式（1)或（2)表示之 化合物，特佳爲1-〔9-乙基- 6-(2-甲基苯醯）-9H-咔唑- 3- 基〕-乙烷-1-酮肟乙酸酯、乙酮，1-〔 9-乙基- 6-( 2-甲基-4-四氫呋喃基甲氧基苯醯）-9H-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-1，3-二氧雜環戊基）甲氧基苯醯}-9H-咔唑-3-基〕 1- ( 〇-乙醯基肟）等。 這些肟酯系化合物係感度非常高，即使低曝光量也可 形成無邊緣缺損及底切的圖型 肟酯系化合物可單獨或組合兩種以上來使用。 本發明中，光聚合起始劑使用目弓酯系化合物時，其含 量係對於（c )多官能性單體1 00質量份，較佳爲〇 〇丨〜 60質量份’更佳爲1〜50質量份，特佳爲1〜40質量份。 倂用多官能性單體與單官能性單體時，單官能性單體之質 量係包含在多官能性單體之質量內。 聯咪唑系化合物係指具有至少一種以下述式（6 )、 式（7)或式（8)表示之骨架的化合物。 -30- 2009311792 R \n/ 2 /n\ [In the formulae (1) and (2), R1 independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, R2 and R3. Respectively, independently of each other, represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted, or a 1 to 25-200931179 valence alicyclic group having a carbon number of 7 to 20 (but R4 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cycloalkane having 3 to 8 carbon atoms independently of each other. The R5 group independently represents a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, k It is an integer of 1 to 5, ^ j, m, and η are independent of each other to represent an integer of 0 to 5, and ρ is an integer of 〇 to 6. However, (n+j) S5, (m + k) S5] defines the definition of the symbols in the above formulas (1) and (2). The alkyl group having 1 to 20 carbon atoms of R, R2 and R3 may be a linear or branched alkyl group having 1 to 12 carbon atoms (more preferably 1 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, Positive 癸 group, positive ^ -f-- base, positive twelve base, etc. The cycloalkyl group having 3 to 8 carbon atoms of R1 to R4 is preferably a cycloalkyl group having 5 to 6 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. The substituent of the phenyl group of R2 and R3, for example, the number of carbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl, etc. Alkyl group of 1 to 6; cycloalkyl group having a carbon number of 3 to 6 such as a cyclopentyl group or a cyclohexyl group: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group 'third Alkoxy group having a carbon number of 1 to 6 such as a butoxy group; a cycloalkoxy group having a carbon number of 3 to 6 such as a cyclopentyloxy group or a cyclohexyloxy group; a phenyl group; a fluorine atom, -26-200931179, a chlorine atom, etc. Halogen atoms and the like. The monovalent alicyclic group having 7 to 20 carbon atoms of R 2 and R 3 (except for the aforementioned cycloalkyl group) is, for example, a group having a 1-alkylcycloalkane skeleton, a group having a bicycloalkane skeleton, and a tricyclic alkane. The base of the skeleton 'has a base of a helical alkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like. The alkyl group having 1 to 12 carbon atoms of R4 may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). The alkoxy group having 1 to 12 carbon atoms of R4 is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). Specific examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy , n-decyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy and the like. The cycloalkoxy group having 3 to 8 carbon atoms of R4 is preferably a cycloalkoxy group having 5 to 6 carbon atoms. Specific examples are a cyclopentyloxy group, a cyclohexyloxy group and the like. a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms of R5, a nitrogen-containing heterocyclic group having a carbon number of 4 to 20 or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, for example, a tetrahydrothiophenyl group , azepine, dihydroazepine, dioxolyl, triazinyl, oxazinyl, thiazolinyl, oxadiazinyl, dioxaindanyl, dithionaphthyl, furan Base, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, pyranyl, pyrrolyl, pyridazinyl, pyrimidinyl, pyrazinyl, Pyrrolidinyl, morpholinyl, piperazinyl, quinuclidinyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, mesoindolyl, chromenyl, quinolinyl, iso Quinolinyl, fluorenyl, quinazolinyl, porphyrinyl, pyridazinyl 'acridinyl, oxazolyl, acridinyl, phenanthryl-27-200931179, thioxanthyl, phenoxy, phenothiazine Zinyl, octyl, thiophenyl, thioxyl, tetrahydrofuranyl, tetrahydropyranyl and the like. In the formulae (1) and (2), R1 is particularly preferably a methyl group or an ethyl group, and r2 and R3 are particularly preferably a hydrogen atom, a methyl group or an ethyl group. Further, R4 is particularly preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a methoxy group or an ethoxy group, and R4 is preferably substituted with a fluorene-position of the aromatic ring. R5 is preferably tetrahydrofuranyl, tetrahydropyranyl or the like. In the formula (1), η is preferably 0, 1 or 2' particularly preferably 1. 』It is preferably 〇 or 1, especially good. In the formula (2), m is preferably 〇, 1 or 2' is particularly preferably 1. Further, k is preferably 1, and P is preferably 〇, 1 or 2, and particularly preferably 1. Specific examples of the oxime ester compound represented by the formula (1) are as follows. 1-[9-ethyl-6-benzoquinone-9H-indol-3-yl]-indole, 2-decane-2-indole- 0-benzoate, :! -[ 9 -ethyl- Benzoquinone·9Η-carbazol-3-yl]-1,2-decane-2-indole-indole-acetate, [9-ethyl-6-benzoquinone-9H-carbazole-3-yl -i,2-pentane-2-indole-indole-acetate, bis[9-ethyl-6-benzoquinone-9H-indazol-3-yl]-octane-1-one- -acetate, 1-[9-ethyl-6-(2-methylphenylhydrazine)-9H-indolyl-3-yl]-ethane_1_ketooxime-benzoate, 9-ethyl-6-(2-methylphenylase)-9H-isoxazole-3-yl]-ethane-1-one oxime-indole-acetic acid vinegar, [9-n-butyl-6- (2-ethylbenzoic acid)-9Η-Miso-3-yl]-B-Yin-1-ketone eye bow__benzoic acid vinegar, ethyl ketone, 1-[9-ethyl-6_(2_A -4-tetrahydrofuranylbenzoquinone)-9Η-哩哩-3-yl]-,1-(〇-acetamidine), ethyl ketone ' 1-[ 9 -ethyl- 200931179 6-(2- Methyl-4-tetrahydropyranylphenylhydrazine)_9H•carbazol-3-yl].,丨_(〇-acetamido), ethyl ketone '1-[9-ethyl-6-(2) -methyl-5-tetrahydrofuranylphenylhydrazone-9H-indazol-3-yl]-,;[_(〇_乙醯基肟), ethyl ketone, 1-[9-ethyl-6-(2 -methyl -5-tetrahydropyranylphenylhydrazine)-9H-oxazol-3-yl]1-(0-acetamidopurine), ethyl ketone, 1-[9-ethyl-6-{2-methyl -4-(2,2-Dimethyl-1,3-dioxolanyl)benzoquinone}-9Η·carbazol-3-yl]-,1-(0-ethylindenyl), Q Further, specific examples of the oxime ester compound represented by the formula (2) include the following. Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9Η-carbazol-3-yl]1-(〇_乙醯基肟), Ethyl ketone, 丨_[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoquinone)-9Η-isozolyl-3-yl]1-(0-ethenyl)肟), ethyl ketone, benzo[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoquinone)_9H_indazol-3-yl]_,^(o· ethoxylated oxime Ethylketone ' 1-[ 9 -ethyl-6-( 2 -methyl-5-tetrahydropyranyl methoxybenzoquinone)-9H-indazole-3-yl]-, l-( 〇-acetamidine, ethyl ketone, 1-[ 9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) The oxime ester compound other than the compound represented by the formula (1) or (2), for example, is exemplified by the following: oxybenzoquinone}-9H-carbazolyl]-, 1-(indole-ethenyl). 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(0-benzoquinone), 1,2-butanedione, 1-[4-(benzene Thio)phenyl]-, 2-(indole-benzoquinone), 1,2-butanedione, 1-[4-(phenylthio)phenyl]·, -29- 200931179 2- (0 -Ethyl hydrazide), 1,2-octanedione, 1-[4-(methylthio)phenyl]-, 2-(0-benzoquinone), 1,2-octanedione , 1-[4-(phenylthio)phenyl]-, 2-(0-(4-methylphenylhydrazine)). Among these oxime ester-based compounds, a compound represented by the formula (1) or (2) is preferred, and 1-[9-ethyl-6-(2-methylbenzoquinone)-9H-carbazole-3 is particularly preferred. -yl]-ethane-1-one oxime acetate, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9H-carbazole- 3-yl]-, 1-(indole-ethenyl), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3 -Dioxolyl)methoxybenzoquinone}-9H-carbazol-3-yl] 1-(indo-ethenylhydrazine). These oxime ester-based compounds have a very high sensitivity, and can form a pattern having no edge defects and undercuts even at a low exposure amount. The oxime ester-based compounds can be used singly or in combination of two or more. In the present invention, when the photopolymerization initiator is a mycophenolate-based compound, the content thereof is 100 parts by mass of the (c) polyfunctional monomer, preferably 〇〇丨~60 parts by mass, more preferably 1~ 50 parts by mass, particularly preferably 1 to 40 parts by mass. When a polyfunctional monomer and a monofunctional monomer are used, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer. The biimidazole-based compound means a compound having at least one skeleton represented by the following formula (6), formula (7) or formula (8). -30- 200931179

【化6】【化6】

其具體例，例如有 2,2’-雙（2-氯苯基）-4,4’，5,5’-四（4-乙氧羰基苯基 )-1，2’-聯咪唑、2,2’-雙（2-溴苯基）-4,4’，5,5’-四（4-乙 氧羰基苯基）-1，2’-聯咪唑等之雙（鹵取代苯基）四（烷 氧羰基苯基）聯咪唑； 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 、2,2’-雙（2-溴苯基）-4,4’，5,5’ -四苯基-1，2’-聯咪唑、 2,2’-雙（2,4-二溴苯基）-4,4’，5,5’-四苯基-1,2’-聯咪唑、 2,2’-雙（2,4,6-三溴苯基）-4,4’，5,5’-四苯基-1，2’-聯咪唑 -31 - 200931179 等之雙（鹵取代苯基）四苯基聯咪唑。 這些聯咪唑系化合物中，較佳爲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’-聯咪唑及2,2’-雙（2,4,6-三氯苯 基）-4,4’，5,5’-四苯基-1，2’-聯咪唑等，特佳爲2,2’-雙（2-氯苯基）-4,4’，5，5’-四苯基-1,2’-聯咪唑。 聯咪唑系化合物對溶劑之溶解性優異，不會產生未溶 0 解物、析出物質等異物，且感度高。聯咪唑系化合物係以 小量能量曝光可充分進行硬化反應，同時對比高，未曝光 部分不會產生硬化反應。因此，曝光後之塗膜可明確區分 爲對顯像液不溶性之硬化部分及對於顯像液具高溶解性的 未硬化部分。藉此可形成無底切之像素圖案依所定排列配 置的高精細的圖型陣列。 聯咪唑系化合物可單獨或混合二種以上來使用。 本發明中，光聚合起始劑使用聯咪唑系化合物時，其 〇 含量係對於（C)多官能性單體100質量份，通常爲0.01 〜40質量份，較佳爲1〜30質量份，更佳爲1〜20質量份 。倂用多官能性單體與單官能性單體時，單官能性單體之 質量係包含在多官能性單體之質量內。 本發明中，光聚合起始劑使用聯咪唑系化合物時，較 佳爲倂用下述之氫供給體可進一步改良感度。 此「氫供給體」係指對於藉由曝光提供氫原子給聯咪 唑系化合物所產生之自由基的化合物。 本發明之氫供給體較佳爲下述定義之硫醇系化合物、 -32- 200931179 胺系化合物等。 硫醇系化合物係以苯環或雜環爲母核，且含有1個以 上’較佳爲1〜3個’更佳爲1〜2個直接與該母核鍵結之 硫醇基的化合物（以下稱爲「硫醇系氫供給體」）。 前述胺系化合物係以苯環或雜環爲母核，且含有1個 以上’較佳爲1〜3個’更佳爲1〜2個直接與該母核鍵結 之胺基的化合物（以下稱爲「胺系氫供給體」）。 這些氫供給體可同時含硫醇基與胺基。 以下更具體說明氫供給體。 硫醇系氫供給體可具有一個以上之苯環或雜環，也可 含有苯環與雜環兩者，含有兩個以上之這些環時，可形成 縮合環。 硫醇系氫供給體含有兩個以上之硫醇基時，至少一個 之游離硫醇基殘留時，剩餘之硫醇基之1個以上可被烷基 、芳烷基或芳基取代。而至少一個之游離硫醇基殘留時， 可具有兩個硫原子介於伸烷基等之二價有機基鍵結的結構 單元’或兩個硫原子以二硫化物的形態鍵結的結構單元。 硫醇系氫供給體係在硫醇基以外的位置，可被羧基、 烷氧羰基、經取代之烷氧羰基、苯氧羰基、經取代的苯氧 裁基、腈基等所取代。 這種硫醇系氫供給體之具體例有2-硫醇基苯并噻唑、 2-硫醇基苯并噁唑、2-硫醇基苯并咪唑、2,5-二硫醇基-1 ，3,4-噻二唑、2·硫醇基-2,5-二甲基胺基吡啶等之硫醇基 取代雜環化合物。 -33- 200931179 這些硫醇系氫供給體中，較佳爲2 -硫醇基苯并噻唑、 2·硫醇基苯并噁唑，特佳爲2 -硫醇基苯并噻唑。 又’胺系氫供給體可含有苯環或雜環各一個以上，或 含有苯環與雜環兩者。含有兩個以上之這些環時，可形成 縮合環。 胺系氫供給體係胺基之一個以上可被烷基或取代烷基 所取代’在胺基以外的位置也可被羧基、烷氧羰基、經取 Q 代的院氧羰基、苯氧羰基、經取代的苯氧羰基、腈基等所 取代。 這種胺系氫供給體之具體例有4,4’-雙（二甲基胺基 )二苯甲酮、4,4，-雙（二乙基胺基）二苯甲酮等之胺基取 代二苯甲酮類；4_二乙基胺基二苯甲酮、4-二甲基胺基苯 丙酮、乙基-4-二甲基胺基苯甲酸酯、4-二甲基胺基苯甲酸 、4-二甲基胺基苯甲腈等。 這些胺系氫供給體中，較佳爲4,4’-雙（二甲基胺基 〇 )二苯甲酮、4,4’-雙（二乙基胺基）二苯甲酮，特佳爲 4,4’·雙（二乙基胺基）二苯甲酮。 胺系氫供給體即使爲聯咪唑系化合物以外的光聚合起 始劑時，也爲具有增感劑的作用者。 本發明中，氫供給體可單獨或混合二種以上來使用。 特別是從所形成之著色層在顯像時不易由基板上掉落，且 著色層強度高及感度高的觀點，較佳爲組合一種以上之硫 醇系氫供給體與一種以上之胺系氫供給體使用。 硫醇系氫供給體與胺系氫供給體之組合的具體例有2 - -34- 200931179 硫醇基苯并噻唑Μ，4’-雙（二甲基胺基）一 逆；一本甲酮、2-硫 Ο 醇基苯并嚷哩/4,4’-雙（二乙基胺基）二苯甲酮、2_硫醇 基苯并嚼哩/4,4’-雙（二甲基胺基）二苯甲酮' 八硫醇^ 苯并嚼哩M，4，-雙（二乙基胺基）二苯甲酮等。其中較佳 之組合爲2-硫醇基苯并噻哗/4,4’-雙（二乙基胺基）二苯 甲酮、2-硫醇基苯并嚼哩M，4’-雙（二乙基胺基）二苯甲 酮，特佳爲2-硫醇基苯并噻唑/4,4，-雙（二甲基胺基）— 苯甲酮。 硫醇系氫供給體與胺系氫供給體之铂a出今e p < 組口中之硫醇系氫 :4 ’較佳 供給體與胺系氫供給體的質量比通常爲丨：i ~ 爲 1 : 1 〜1 : 3。 本發明中’氫供給體與聯咪哩系化合物倂用時，氫供 給體之調配量係對於（C )多官能性單體1〇〇質胃丨分，^ 佳爲0.0 1〜40質量份’更佳爲1〜30質量份，特佳爲1〜 2〇質量份。氫供給體之調配量未達〇.〇1質量份時，感度 〇 之改良效果有降低的傾向。超過40質量份時，所形成的 著色層在顯像時容易從基板掉落的傾向。併用多官能彳生單 體與單官能性單體時，單官能性單體之質量係包含在多官 能性單體之質量內。 又，本發明中，可倂用前述光聚合起始劑與其他之光 聚合起始劑（以下有時稱爲「其他之光聚合起始劑」）作 爲（D )光聚合起始劑可。其他之光聚合起始劑例如有式 (3)表示之化合物以外的苯乙酮系化合物、苯偶姻系化 合物、α -二酮系化合物、多核醌系化合物、咕噸酮系化合 -35- 200931179 物、膦系化合物、三嗪系化合物等。 本發明中，這些其他之光聚合起始劑可單獨使用或混 合二種以上使用。 式（3 )表示之化合物以外的苯乙酮系化合物，例如 有2,2-二甲氧基苯乙酮、2,2-二乙氧基苯乙酮、2，2-二甲 氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮、4- (2-羥基 乙氧基）苯基-(2-羥基-2-丙基）酮、1-羥基環己基苯基 酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等之外，尙有2_甲 基-1-( 4-甲基硫苯基）-2-嗎啉基丙烷-1-酮等之具有嗎啉 基之苯乙酮系化合物。 這些苯乙酮系化合物中，較佳爲2 -甲基-(4 -甲基硫 苯基）-2-嗎啉基-1-丙烷-1-酮、4-(2-羥基乙氧基）苯基-(2-羥基-2-丙基）酮等。 苯偶姻系化合物，例如有苯偶姻、苯偶姻甲醚、苯偶 姻乙醚、苯偶姻異丙醚、苯偶姻異丁醚、2-苯甲醯苯甲酸 甲酯等。 α-二酮系化合物例如有丁二酮、聯苯酮、甲基苯甲醯 基甲酸酯等。 多核醌系化合物例如有蒽醌、2 -乙基蒽醌、2 -第三丁 基蒽醌、1，4-萘醌等。 咕噸酮系化合物例如有咕噸酮、噻噸酮、2,4 -二乙基 噻噸酮、2 -氯噻噸酮等之咕噸嗣類。 膦系化合物例如有雙（2,4,6 -三甲基苯甲醯）苯基氧 -36 - 200931179 化膦、2,4,6-三甲基苯甲醯二苯基氧化膦等。 三嗪系化合物例如有2,4,6-參（三氯甲基）_s•三_、 2-甲基-4,6·雙（三氯甲基）_s_三嗪、' 2_[2_ (呋喃-2_基 )乙嫌基]-4,6-雙（二氯甲基）_8_三曉'2_[2-(5-甲基咲 喃-2-基）乙烯基]-4,6-雙（三氯甲基）-3_三嗪、2_[2_(4_ 二乙基胺基-2-甲基苯基）乙稀基]-4,6 -雙（三氯甲基）-s-三嗪、2-[2-(3,4 -二甲氧基苯基）乙烯基]_4,6_雙（三氯 ^ 甲基）-s-二曉、2- (4 -甲氧基苯基）-4,6 -雙（三氯甲基 )-3-三嗪、2-(4-乙氧基苯乙烯基）-4,6_雙（三氯甲基 )-3-三嗪、2-(4-正丁氧基苯基）_4,6-雙（三氯甲基）-5-三嗪等之含鹵甲基之化合物等。 這些三嗪系化合物中，較佳爲2-[2-( 3,4-二甲氧基苯 基）乙烯基]-4,6-雙（三氯甲基）-s-三嗪等。 -(E )氧化防止劑- Q 本發明中’ （E)氧化防止劑爲含有選自由酚系氧化 防止劑、磷系氧化防止劑及硫系氧化防止劑所成群之至少 1種所成的氧化防止劑。這些特定之氧化防止劑與上述特 定之光聚合起始劑組合，可抑制以往使用上述特定之光聚 合起始劑時，產生亮度降低的問題，使用特定之光聚合起 始劑所形成之像素可展現最大限度的亮度。此乃是特定之 氧化防止劑抑制因後烘烤步驟造成特定之光聚合起始劑變 黃的緣故。本發明人等發現這種效果係在這些特定之氧化 防止劑與上述特定之光聚合起始劑組合時，始能奏效，與 -37- 200931179 上述其他之光聚合起始劑組合時，對於亮度等沒有任何影 響。 酚系氧化防止劑可使用公知的化合物。具體而言，例 如有 3,9-雙[2-〔3- (3-t-丁基-4-羥基-5-甲基苯基）丙醯 氧基〕-1,1-二甲基乙氧基]-2,4,8,10-四氧雜螺[5.5]十一烷 、季戊四醇•四[3- (3，5-二-t-丁基-4-羥基苯基）丙酸酯] 等具有螺環骨架的酚化合物； 1，3,5-三甲基-2,4,6-三（3’5’-二-t-丁基-4-羥基苄基） 苯、三乙二醇-雙[3-( 3-t-丁基-5-甲基-4-羥基苯基）丙酸 酯]、4,4’-硫雙（6-t-丁基-3-甲基酚）、三-(3,5-二-t-丁 基-4-羥基苄基）-三聚異氰酸酯、1,3,5-三（4-t-丁基-3-羥 基-2,6-二甲基苄基）-三聚異氰酸酯、1,6-己二醇-雙[3-( 3，5-二-t-丁基-4-羥基苯基）丙酸酯]、2,2-硫-二乙撐雙[3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]、Ν,Ν’-六甲撐雙（ 3,5-二-t-丁基-4-羥基-氫化肉桂醯胺）、1，3,5-三甲基-2,4,6-三（3,5-二-t-丁基-4-羥基苄基）苯、2,4-雙[(辛基 硫）甲基]-〇-甲酚、1，6-己二醇-雙-[3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯]、十八烷基-[3- (3，5-二-t-丁基-4-羥基 苯基）丙酸酯、2,2’-甲撐雙（4-甲基- 6-t-丁基酚）、4,4'-丁叉-雙（3-甲基-6-t-丁基酚）、1,1,3-三（2-甲基-4-羥 基-5-1-丁基苯基）丁烷、1,3,5-三（4-羥基苄基）苯及四[ 甲撐-3- ( 3,5'-二-t-丁基-4'-羥基苯基丙酸酯）]甲烷等。 這些中，從耐熱性及耐熱變色防止的觀點，較佳爲 3,9-雙[2-〔 3- ( 3-t-丁基-4-羥基-5-甲基苯基）丙醯氧基 -38- 200931179 〕-1,1-二甲基乙氧基]-2,4,8,10-四氧雜螺[5.5]i--烷、 1,3,5，-二甲基-2,4,6，-三（3’5’-一 - t-丁基-4-經基卞基） 苯、季戊四醇•四[3- (3,5-二-t-丁基-4-羥基苯基）丙酸酯 ]、三乙二醇-雙[3- (3-t-丁基-5-甲基-4-羥基苯基）丙酸酯 ]、4,4’-硫雙（6-t-丁基-3-甲基酚）、三-(3,5-二-t-丁基-4-經基节基）-三聚異氰酸醋、1，3,5-二（4-卜丁基-3-經基-2,6-二甲基苄基）-三聚異氰酸酯、1,6-己二醇-雙[3- (3，5-一 -t -丁基-4 -經基苯基）丙酸醋]、2,2 -硫-一·乙撐雙[3-( 3.5- 二-t-丁基-4-羥基苯基）丙酸酯]、Ν,Ν’-六甲撐雙（ 3.5- 二-t-丁基-4-羥基-氫化肉桂醯胺）、1,3,5-三甲基-2，4,6-三（3，5-二-t-丁基-4-羥基苄基）苯、2,4-雙[(辛基 硫）甲基]-0 -甲酚等。 酚系氧化防止劑可單獨或組合兩種以上來使用。 磷系氧化防止劑可使用公知的化合物。具體而言，例 如有 3,9-雙（2,6-二-tert-丁基-4-甲基苯氧基）-2,4,8,10-四氧雜-3,9-二磷酸螺[5.5]十一烷、二異癸基季戊四醇二亞 磷酸酯、雙（2,4-二-t-丁基苯基）季戊四醇二亞磷酸酯等 具有螺環骨架的亞磷酸酯化合物； 2,2’ -甲撐雙（4,6 - 一 - t-丁基-1-苯氧基）（2 -乙基己氧 基）磷、6-[3-(3-t-丁基-4-羥基-5 -甲基苯基）丙氧基]-2,4,8，10-四-t- 丁基二苯并[d，f][l，3,2]二氧雜膦（ phosphepine)、三苯基亞磷酸酯、二苯基異癸基亞磷酸酯 、苯基二異癸基亞磷酸酯、4,4’-丁叉-雙（3-甲基-6-t-丁基 苯基二-十三烷基）亞磷酸酯、十八烷基亞磷酸酯、三（ -39- 200931179 壬基苯基）亞磷酸酯、9，1 0 -二氫-9 -氧雜-1 0 -磷雜菲-1 〇 ·氧 化物、10- ( 3,5-二-t-丁基-4-羥基苄基）·9, 10-二氫-9-氧 雜-10-磷雜菲-10-氧化物、10-癸氧基-9，10_二氫-9-氧雜_ 10-磷雜菲-10-氧化物、三（2,4-二-t-丁基苯基）亞磷酸酯 、環狀季戊四醇雙（2,4-二-t-丁基苯基）亞磷酸酯、環狀 季戊四醇雙（2,6-二-t-丁基苯基）亞磷酸酯、2,2 -甲撐雙 (4,6_二-t-丁基苯基）辛基亞磷酸酯、三（2,4-二-t-丁基 苯基）亞磷酸酯、四（2,4-二-t-丁基苯基）[1，1-聯苯基]-4,4’-二基雙亞膦酸酯、雙[2,4-雙（l，l-二甲基乙基）-6-甲 基苯基]乙酯、膦酸等。 這些磷系氧化防止劑中，從耐熱性及耐熱變色防止的 觀點，較佳爲2,2’-甲撐雙（4,6-二-t-丁基-1-苯氧基）（ 2 -乙基己氧基）磷、3,9-雙（2,6-二-tert-丁基-4-甲基苯氧 基）-2,4,8,10-四氧雜-3,9-二磷酸螺[5.5]十一烷、6-[3-( 3-1-丁基-4-羥基-5-甲基苯基）丙氧基]-2,4,8,10-四-t-丁基 二苯并[d，f][l，3,2]二氧雜膦（phosphepine)等。 磷系氧化防止劑可單獨或組合兩種以上來使用。 硫系氧化防止劑可使用公知的化合物。具體而言，例 如有2,2-雙（{[3-(十二烷基硫）丙醯基]氧基}甲基）-1,3-丙烷二基-雙[3-(十二烷基硫）丙酸酯]、2-氫硫基苯 并咪唑、二月桂基-3，3’-硫二丙酸酯、二十四基-3,3’-硫二 丙酸酯、二硬脂-3，3’-硫二丙酸酯、季戊四醇-四（3-月桂 基硫丙酸酯）等具有硫醚結構的化合物；2-氫硫基苯并咪 唑等。 -40- 200931179 這些硫系氧化防止劑中，從耐熱性及耐熱變色防止的 觀點，較佳爲 2,2-雙（{[3-(十二烷基硫）丙醯基丨氧基）甲基）· 1，3-丙烷二基-雙[3-(十二烷基硫）丙酸酯）、2-氫硫基苯 并咪唑等。 硫系氧化防止劑可單獨或組合兩種以上來使用。 本發明從抑制亮度降低與兼具亮度及感度的觀點，氧 化防止劑較佳爲使用下述（E-1 )或（E-2 )。 (E-1 )選自由磷系氧化防止劑及硫系氧化防止劑所 成群之至少1種、 (E-2 )磷系氧化防止劑或硫系氧化防止劑與酚系氧 化防止劑之組合。 本發明之氧化防止劑之合計含量係對於（D )光聚合 起始劑之合計100質量份，通常爲1〜100質量份，較佳 爲2〜80質量份，特佳爲4〜60質量份。此合計含量未達 1質量份時’無法得到所要的效果。而超過100質量份時 ，可能有不溶物或顯像後產生殘渣。 -添加劑- 本發明之敏輻射線性組成物，必要時可添加各種的添 加劑。 前述添加劑例如有機酸或有機胺基化合物（不包括前 述氫供給體）等。這些化合物係進一步改善敏輻射線性組 成物對於鹼顯像液之溶解特性，且顯示進一步抑制顯像後 -41 - 200931179 之未溶解物之殘留的作用等的成分。 有機酸較佳爲分子中具有1個以上之羧基之脂肪 酸或含苯基之羧酸。 前述脂肪族羧酸例如有甲酸、乙酸、丙酸、丁酸 酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸等之脂 單羧酸類； 草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二 辛二酸、壬二酸、癸二酸、巴西二酸、甲基丙二酸、 丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸 己烷二羧酸、依康酸、檸康酸、順丁烯二酸、反丁烯 、中康酸等之二羧酸類；丙三甲酸、烏頭酸、樟腦三 三羧酸類等。 此外，前述含苯基之羧酸，例如有羧基直接鍵結 基的化合物及羧基經由碳鏈與苯基鍵結的羧酸等。 含苯基之羧酸例如有苯甲酸、甲苯酸、枯茗酸、 三酸、二甲基苯甲酸之芳香族單羧酸類； 苯二甲酸、間苯二甲酸、對苯二甲酸、肉桂叉丙 等之芳香族二羧酸類； 苯偏三酸、苯三甲酸、苯偏四酸、均苯四甲酸之 以上之芳香族多羧酸類；及 苯基乙酸、氫化阿托酸、氫化肉桂酸、扁桃酸、 琥珀酸、阿托酸、肉桂酸、肉桂叉乙酸、香豆酸、傘 等。 此等有機酸中，從鹼溶解性、對後述之溶劑的溶 族羧 、戊 肪族 酸、 乙基 、環 二酸 酸之 於苯 苯連 二酸 3價 苯基 形酸 解性 -42- 200931179 、防止未曝光部之基板上或遮光層上之質地污染及膜殘留 等的觀點，較佳爲脂肪族羧酸之脂肪族二羧酸類，特佳爲 丙二酸、己二酸、依康酸、檸康酸、反丁烯二酸、中康酸 等。含苯基之羧酸較佳爲芳香族二羧酸類，特佳爲苯二甲 酸。 前述有機酸可單獨或混合二種以上來使用。 有機酸之含量係對於敏輻射線性組成物之全質量（固 0 形份換算），通常爲15質量％以下，較佳爲10質量％以 下。有機酸之含量超過15質量％時，著色層對基板之密著 性有降低的傾向。 有機胺基化合物較佳爲分子中具有1個以上之胺基之 脂肪族胺或含苯基之胺。 前述脂肪族胺例如有下述者。 脂肪族胺例如有正丙胺、i-丙胺、正丁胺、i-丁胺、 第二-丁胺、t - 丁胺、正戊胺、正己胺、正庚胺 '正辛胺、 Q 正壬胺、正癸胺、正十一胺、正十二胺、環己胺、2-甲基 環己胺、3 -甲基環己胺、4 -甲基環己胺、2 -乙基環己胺、 3 -乙基環己胺、4_乙基環己胺等之單（環）烷胺類； 甲基乙胺、二乙胺、甲基正丙胺、乙基正丙胺、二_ 正丙胺、二-i-丙胺、二-正丁胺、二小丁胺、二-第二-丁 胺、二-t-丁胺、二-正戊胺、二-正己胺、甲基環己胺、乙 基環己胺、二環己胺等之二（環）烷胺類； 二甲基乙胺、甲基二乙胺、三乙胺、二甲基正丙胺、 二乙基正丙胺、甲基二-正丙胺、乙基二-正丙胺、三-正丙 -43- 200931179 胺、三小丙胺、三-正丁胺、三小丁胺、三-第二-丁胺、 三-t-丁胺 '三-正戊胺、三·正己胺、二甲基環己胺、二乙 基環己胺、甲基二環己胺、乙基二環己胺、三環己胺等之 三（環）烷胺類； 2-胺基乙醇、3-胺基-1-丙醇、1-胺基-2-丙醇、4-胺 基-1-丁醇、5 -胺基-1-戊醇、6 -胺基-1-己醇、4 -胺基-1-環 己醇等之單（環）烷醇胺類； 〇 二乙醇胺、二·正丙醇胺、二-i-丙醇胺、二-正丁醇胺 、二-i-丁醇胺、二-正戊醇胺、二-正己醇胺、二（4-環己 醇）胺等之二（環）烷醇胺類； 三乙醇胺、三-正丙醇胺、三-i-丙醇胺、三-正丁醇胺 、三-i-丁醇胺、三-正戊醇胺、三-正己醇胺、三（4-環己 醇）胺等之三（環）烷醇胺類； 3 -胺基-1，2 -丙二醇、2 -胺基-1,3 -丙二醇、4 -胺基-1，2-丁二醇、4 -胺基-1，3 -丁二醇、4 -胺基-1,2 -環己二醇、4 -胺 基-1，3 -環己—醇、3 - 一甲胺基-1，2 -丙二醇、3 -二乙胺基-1，2-丙二醇、2-二甲胺基-1，3-丙二醇、2-二乙胺基-1，3-丙 二醇等之胺基（環）烷二醇類； 1-胺基環戊烷甲醇、4-胺基環戊烷甲醇、1-胺基環己 烷甲醇' 4-胺基環己烷甲醇、4-二甲胺基環戊烷甲醇、4-二乙胺基環戊烷甲醇、4-二甲胺基環己烷甲醇、4_二乙胺 基環己烷甲醇等之含胺基之環烷甲醇類； β-丙胺酸、2-胺基丁酸、3-胺基丁酸、4_胺基丁酸、 2 -胺基異丁酸、3 -胺基異丁酸、2 -胺基戊酸、5_胺基戊酸 -44- 200931179 、6-胺基己酸、1-胺基環丙烷羧酸、1_胺基環己烷羧酸、 4 -胺基環己烷羧酸等之胺基羧酸類。 此外’含苯基之胺例如有胺基直接鍵結於苯基之化合 物、胺基介於碳鏈與苯基鍵結的化合物等。 含苯基之胺例如有苯胺、2 -甲基苯胺、3 -甲基苯胺、 4-甲基苯胺、4-乙基苯胺、4-正丙基苯胺、4-i-丙基苯胺、 4-正丁基苯胺、4-t-丁基苯胺、1-萘胺、2-萘胺、Ν,Ν-二 甲基苯胺、Ν，Ν-二乙基苯胺、4-甲基-Ν,Ν-二甲基苯胺等 之芳香族胺類； 2-胺基苄醇、3-胺基苄醇、4-胺基苄醇、4-二甲胺基 苄醇、4-二乙胺基苄醇等之胺基苄醇類； 2-胺基酚、3-胺基酚、4-胺基酚、4-二甲胺基酚、4-二乙胺基酚等之胺基酚類等。 這些有機胺基化合物中，從對後述溶劑之溶解性、防 止在未曝光之部分之基板上或遮光層上之質地污染或膜殘 留的觀點，脂族胺較佳爲單（環）烷醇胺類及胺基（環） 烷二醇類，特佳爲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。含苯基的胺較佳爲胺基酚類，特佳爲2-胺 基酚、3-胺基酚、4-胺基酚等。 有機胺基化合物可單獨或組合兩種以上來使用。 有機胺基化合物之含量係對於敏輻射線性組成物之全 質量（固形份換算），通常爲1 5質量％以下，較佳爲10 質量％以下。有機胺基化合物之含量超過1 5質量％時，著 -45- 200931179 色層對基板之密著性有降低的傾向。 前述以外之添加劑成分，例如： 銅酞菁衍生物之藍色顏料衍生物或黃色顏料衍生物等 之分散助劑； 玻璃、二氧化鋁等之塡充劑； 聚乙烯醇、聚乙二醇單烷醚、聚（氟烷基丙烯酸酯） 類等之高分子化合物； 非離子系、陽離子系、陰離子系等之界面活性劑； 乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷' 乙烯基 三（2-甲氧基乙氧基）矽烷、N- (2-胺基乙基）-3-胺基丙 基甲基二甲氧基矽烷、N- (2-胺基乙基）-3-胺基丙基三甲 氧基砂院、3 -胺基丙基二乙氧基砂院、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 丙基三甲氧基矽烷、3 -氫硫基丙基三甲氧基矽烷等之密著 促進劑； 2- (3-t -丁基-5-甲基-2 -經基苯基）-5 -氯苯並三哩、 烷氧基二苯甲酮類等之紫外線吸收劑； 聚丙烯酸鈉等之凝集防止劑； -偶氮雙（環己院_卜膳）、2 -本基偶氮-4-甲氧基-2，4-二甲基戊腈等之熱自由基產生劑等。 -溶劑- -46 - 200931179 本發明之敏輻射線性組成物係以上述成分（A )〜（E )作爲必要成分，有時含有上述添加劑，通常與溶劑混合 以製備成液狀組成物。 溶劑只要是可分散或溶解構成敏輻射線性組成物之各 成分，且不與這些成分反應，具有適當的揮發性者，皆可 適當選擇使用。 這種溶劑例如有下述者。 ^ 乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙 Ό 二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙 二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三 乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單 正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單 乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇 單甲醚、三丙二醇單乙醚等之（聚）烷二醇單烷醚類； 乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二 Q 醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚 乙酸酯、丙二醇單乙醚乙酸酯等之（聚）烷二醇單院醚乙 酸酯類； 二乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙 醚、四氫呋喃等之其他醚類；甲基乙基酮、環己酮、2-庚 酮、3-庚酮等之酮類； 乳酸甲酯、乳酸乙酯等之乳酸烷酯類； 2-羥基-2-甲基丙酸乙酯、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 -47- 200931179 氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基 3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧 酯、乙酸乙酯、乙酸正丙酯、乙酸i-丙酯、乙 乙酸i-丁酯、甲酸正戊酯、乙酸i-戊酯、丙酸 酸乙酯、丁酸正丙酯、丁酸i-丙酯、丁酸正丁 甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸 乙酸乙酯、2-氧代丁酸乙酯等之其他酯類； 甲苯、二甲苯等之芳香族烴類； N，N-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、 烷酮等之醯胺或內醯胺類。 這些溶劑當中，從溶解性、顏料分散性、 點而言，較佳爲丙二醇單甲醚、乙二醇單甲醚 二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、二 醚、二乙二醇甲基乙醚、環己酮、2-庚酮、3-乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯 丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸 酸i-丁酯、甲酸正戊酯、乙酸i-戊酯、丙酸正 乙酯、丁酸i-丙酯、丁酸正丁酯、丙酮酸乙酯彳 溶劑可單獨或組合兩種以上來使用。 又，上述溶劑可與苄基乙醚、二-正己醚 、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、 苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸 丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙二醇單 等之高沸點溶劑倂用。 丁酸甲酯、 基丁基丙酸 酸正丁酯、 正丁酯、丁 酯、丙酮酸 甲酯、乙醯 N-甲基吡咯 塗佈性的觀 乙酸酯、丙 乙二醇二甲 庚酮、乳酸 、3-乙氧基 正丁酯、乙 丁酯、丁酸 等。 、乙醯丙嗣 苄醇、乙酸 二乙酯、γ-苯醚乙酸酯 -48- 200931179 這些高沸點溶劑可單獨或組合雨種以上來使用 溶劑之含量無特別限制’但從所得之敏輻射線 物之塗佈性、穩定性的觀點而言’該組成物除去溶 各成分的總量濃度通常爲5〜50質量％’較佳爲1〇 量％ 〇 -製造方法- 0 本發明之敏輻射線性組成物可藉由適當的方法 例如使用著色劑時，將該顏料在溶媒中、分散劑的 ，使用球磨機、輥磨機等，經粉碎混合•分散，形 分散液，再將此分散液與（B )成分、（C )成分、 成分及（E)成分，以及必要時所追加之溶劑或其 劑，進行混合調製爲佳。 分散劑例如有胺基甲酸酯系分散劑、聚乙烯亞 散劑、聚氧乙烯烷醚系分散劑、聚氧乙烯烷基苯醚 ❿ 劑、聚乙二醇二酯系分散劑、山梨糖醇脂肪酸酯系 、經脂肪酸修飾之聚酯系分散劑、丙烯酸系分散劑; 這種分散劑之具體例有商品名 efka( Chemicals ( EFKA )公司製）、Disperbyk ( BYK (BYK )公司製）、Disbaron (楠本化成（股）公 、Solsperse ( Lubrizol 公司製）、：KP (信越化學工 )製）、P〇iy flow (共榮社化學（股）製）、F Tokem Products (股）製）、Megafac (大日本油墨 業（股）製）、Florade (住友3M (股）製）. 性組成 劑外的 〜40質 製備， 存在下 成顏料 (D ) 他添加 胺系分 系分散 分散劑 等。 EFKA Chemie 司製） 業（股 Top ( 化學工 As ahi -49- 200931179Specific examples thereof include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2 , 2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, etc. Tetrakis(alkoxycarbonylphenyl)biimidazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2 Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-four Phenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole-31 - 200931179 Phenyl) tetraphenylbiimidazole. Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' is preferred. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc., particularly preferably 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole. The biimidazole-based compound is excellent in solubility in a solvent, and does not cause foreign matter such as an undissolved solution or a precipitated substance, and has high sensitivity. The biimidazole compound is sufficiently hardened by exposure with a small amount of energy, and at the same time, the contrast is high, and the unexposed portion does not cause a hardening reaction. Therefore, the film after exposure can be clearly distinguished into a hardened portion which is insoluble to the developing liquid and an unhardened portion which has high solubility to the developing liquid. Thereby, a high-definition pattern array in which the undercut pixel patterns are arranged in a predetermined arrangement can be formed. The biimidazole compound can be used singly or in combination of two or more. In the present invention, when the photopolymerization initiator is a biimidazole compound, the content of ruthenium is usually 0.01 to 40 parts by mass, preferably 1 to 30 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. More preferably, it is 1 to 20 parts by mass. When a polyfunctional monomer and a monofunctional monomer are used, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer. In the present invention, when the photopolymerization initiator is a biimidazole compound, it is preferred to further improve the sensitivity by using the hydrogen donor described below. The "hydrogen donor" means a compound which radicals are generated by supplying a hydrogen atom to a bisimidazole compound by exposure. The hydrogen donor of the present invention is preferably a thiol compound as defined below, an -32-200931179 amine compound or the like. The thiol compound is a compound having a benzene ring or a hetero ring as a core and containing one or more 'preferably 1 to 3', more preferably 1 to 2, thiol groups directly bonded to the core ( Hereinafter, it is referred to as "thiol-based hydrogen donor"). The amine compound is a compound having a benzene ring or a heterocyclic ring as a core and containing one or more 'preferably 1 to 3', more preferably 1 to 2, amine groups directly bonded to the core (hereinafter It is called "amine-based hydrogen donor"). These hydrogen donors may contain both a thiol group and an amine group. The hydrogen donor will be described more specifically below. The thiol-based hydrogen donor may have one or more benzene rings or heterocyclic rings, and may contain both a benzene ring and a heterocyclic ring. When two or more of these rings are contained, a condensed ring may be formed. When the thiol-based hydrogen donor contains two or more thiol groups, when at least one of the free thiol groups remains, one or more of the remaining thiol groups may be substituted with an alkyl group, an aralkyl group or an aryl group. When at least one of the free thiol groups remains, there may be two structural units in which a sulfur atom is bonded to a divalent organic group such as an alkyl group or a structural unit in which two sulfur atoms are bonded in a disulfide form. . The thiol-based hydrogen supply system may be substituted at a position other than the thiol group by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxy group, a nitrile group or the like. Specific examples of such a thiol-based hydrogen donor are 2-thiolbenzothiazole, 2-thiolbenzoxazole, 2-thiol benzimidazole, 2,5-dithiol-1 A thiol group-substituted heterocyclic compound such as 3,4-thiadiazole or 2·thiol-2,5-dimethylaminopyridine. -33- 200931179 Among these thiol-based hydrogen donors, 2-thiolbenzothiazole and 2. thiol benzoxazole are preferred, and 2-thiolbenzothiazole is particularly preferred. Further, the amine-based hydrogen donor may contain one or more of a benzene ring or a hetero ring, or both a benzene ring and a hetero ring. When two or more of these rings are contained, a condensed ring can be formed. One or more amine groups of the amine-based hydrogen supply system may be substituted by an alkyl group or a substituted alkyl group. 'The position other than the amine group may also be a carboxyl group, an alkoxycarbonyl group, a Q-substituted oxycarbonyl group, a phenoxycarbonyl group, a Substituted by a substituted phenoxycarbonyl group, a nitrile group or the like. Specific examples of such an amine-based hydrogen donor include amine groups such as 4,4'-bis(dimethylamino)benzophenone and 4,4,-bis(diethylamino)benzophenone. Substituted benzophenones; 4_diethylaminobenzophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylamine Benzoic acid, 4-dimethylaminobenzonitrile, and the like. Among these amine-based hydrogen donors, 4,4'-bis(dimethylaminopurine)benzophenone and 4,4'-bis(diethylamino)benzophenone are preferred. It is 4,4'-bis(diethylamino)benzophenone. When the amine-based hydrogen donor is a photopolymerization initiator other than the biimidazole-based compound, it is also a person having a sensitizer. In the present invention, the hydrogen donor may be used singly or in combination of two or more. In particular, it is preferable to combine one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogens from the viewpoint that the formed color layer is less likely to fall from the substrate during development, and the color layer has high strength and high sensitivity. The supplier is used. Specific examples of the combination of the thiol-based hydrogen donor and the amine-based hydrogen donor are 2 - -34- 200931179 thiol benzothiazole, 4'-bis(dimethylamino)-inverse; one ketone , 2-thiononanol benzopyrene/4,4'-bis(diethylamino)benzophenone, 2-thiolbenzopyrene/4,4'-bis(dimethyl Amino) benzophenone 'octanol> benzo oxime M, 4,-bis(diethylamino)benzophenone and the like. A preferred combination thereof is 2-thiol benzothiazepine/4,4'-bis(diethylamino)benzophenone, 2-thiol benzoxanthene M, 4'-double (two Ethylamino)benzophenone, particularly preferably 2-thiolbenzothiazole/4,4,-bis(dimethylamino)-benzophenone. The platinum a of the thiol-based hydrogen donor and the amine-based hydrogen donor is ep < thiol-based hydrogen in the mouth of the group: 4' The mass ratio of the preferred donor to the amine-based hydrogen donor is usually 丨: i ~ 1 : 1 ~ 1 : 3. In the present invention, when the hydrogen donor and the hydrazine compound are used, the amount of the hydrogen donor is (1) for the (C) polyfunctional monomer, and is preferably from 0.01 to 40 parts by mass. 'More preferably 1 to 30 parts by mass, particularly preferably 1 to 2 parts by mass. When the amount of the hydrogen donor is less than 1 part by mass, the effect of improving the sensitivity 有 tends to decrease. When the amount is more than 40 parts by mass, the formed colored layer tends to fall from the substrate at the time of development. When polyfunctional twins and monofunctional monomers are used together, the quality of the monofunctional monomer is included in the mass of the multifunctional monomer. Further, in the present invention, the photopolymerization initiator and other photopolymerization initiator (hereinafter sometimes referred to as "other photopolymerization initiator") may be used as the (D) photopolymerization initiator. Other photopolymerization initiators include, for example, an acetophenone-based compound, a benzoin-based compound, an α-diketone-based compound, a polynuclear oxime-based compound, and a xanthone-based compound-35- other than the compound represented by the formula (3). 200931179 A compound, a phosphine compound, a triazine compound, and the like. In the present invention, these other photopolymerization initiators may be used singly or in combination of two or more. An acetophenone-based compound other than the compound represented by the formula (3), for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy- 2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2- In addition to diphenylethane-1-one, etc., hydrazine has a morpholinyl group such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one An ketone compound. Among these acetophenone-based compounds, 2-methyl-(4-methylthiophenyl)-2-morpholinyl-1-propan-1-one and 4-(2-hydroxyethoxy) are preferred. Phenyl-(2-hydroxy-2-propyl) ketone and the like. The benzoin-based compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether or 2-benzylidenebenzoic acid methyl ester. The α-diketone-based compound may, for example, be butanedione, biphenyl ketone or methyl benzhydrylcarboxylate. The polynuclear lanthanide compound is, for example, anthracene, 2-ethylanthracene, 2-tributylguanidine, 1,4-naphthoquinone or the like. The xanthone-based compound is, for example, a xanthene such as xanthone, thioxanthone, 2,4-diethylthioxanthone or 2-chlorothioxanthone. The phosphine-based compound may, for example, be bis(2,4,6-trimethylbenzhydrazide)phenyloxy-36 - 200931179 phosphine, 2,4,6-trimethylbenzimidium diphenylphosphine oxide or the like. The triazine-based compound is, for example, 2,4,6-paran (trichloromethyl)_s•tris-, 2-methyl-4,6-bis(trichloromethyl)_s_triazine, '2_[2_ ( Furan-2-yl)ethyl]-4,6-bis(dichloromethyl)_8_三晓'2_[2-(5-methylindol-2-yl)vinyl]-4,6 - bis(trichloromethyl)-3_triazine, 2_[2_(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s -Triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]_4,6-bis(trichloro(methyl)-s-di-, 2-(4-methoxy) Phenyl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-3-triazine And a halogen-containing methyl group compound such as 2-(4-n-butoxyphenyl)_4,6-bis(trichloromethyl)-5-triazine. Among these triazine-based compounds, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine or the like is preferable. - (E) Oxidation preventing agent - Q In the present invention, the (E) oxidation preventing agent is composed of at least one selected from the group consisting of a phenolic oxidation preventing agent, a phosphorus-based oxidation preventing agent, and a sulfur-based oxidation preventing agent. Oxidation inhibitor. The combination of the specific oxidation preventing agent and the specific photopolymerization initiator described above can suppress the problem of lowering the brightness when the above-mentioned specific photopolymerization initiator is used, and the pixel formed by using the specific photopolymerization initiator can be used. Show maximum brightness. This is because the specific oxidation preventing agent inhibits the yellowing of the specific photopolymerization initiator due to the post-baking step. The present inventors have found that such an effect is effective when these specific oxidation preventing agents are combined with the above specific photopolymerization initiator, and when combined with the above other photopolymerization initiators of -37-200931179, Waiting for no effect. As the phenolic oxidation inhibitor, a known compound can be used. Specifically, for example, there is 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1-dimethyl B. Oxy]-2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol•tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate a phenolic compound having a spiro skeleton; 1,3,5-trimethyl-2,4,6-tris(3'5'-di-t-butyl-4-hydroxybenzyl)benzene, triethyl Glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-3-methyl Phenol), tris-(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6 -Dimethylbenzyl)-trimeric isocyanate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 - sulfur-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], hydrazine, Ν'-hexamethylene bis(3,5-di-t- Butyl-4-hydroxy-hydrocinnamylamine), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-anthracene-cresol, 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate] Octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene bis(4-methyl-6-t-butyl Phenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-1-butyl Phenyl)butane, 1,3,5-tris(4-hydroxybenzyl)benzene and tetrakis[3,5'-di-t-butyl-4'-hydroxyphenylpropionic acid Ester)] methane and the like. Among these, from the viewpoint of heat resistance and prevention of heat discoloration, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy group is preferred. -38- 200931179]-1,1-Dimethylethoxy]-2,4,8,10-tetraoxaspiro[5.5]i--alkane, 1,3,5,-dimethyl-2 , 4,6,-tris (3'5'-mono-t-butyl-4-ylhydrazino) benzene, pentaerythritol, tetrakis[3-(3,5-di-t-butyl-4-hydroxyl) Phenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-sulfur double (6 -t-butyl-3-methylphenol), tris-(3,5-di-t-butyl-4-alkyl)-trimeric isocyanate, 1,3,5-di ( 4-Bubutyl-3-transyl-2,6-dimethylbenzyl)-trimeric isocyanate, 1,6-hexanediol-bis[3-(3,5-mono-t-butyl-4 Phenylphenyl)propionic acid vinegar], 2,2-sulfo-ethylidene bis[3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate], hydrazine, Ν'- Hexamethylene bis(3.5-di-t-butyl-4-hydroxy-hydrocinnamylamine), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl Alkyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-0-cresol, and the like. The phenolic oxidation inhibitor may be used singly or in combination of two or more. As the phosphorus-based oxidation preventing agent, a known compound can be used. Specifically, for example, there is 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphate. a phosphite compound having a spiro ring skeleton such as spiro[5.5]undecane, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite; , 2'-Methylene bis(4,6-mono-t-butyl-1-phenoxy)(2-ethylhexyloxy)phosphorus, 6-[3-(3-t-butyl-4 -hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][l,3,2]dioxaphosphine (phosphepine , triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butyl Phenyl ditridecyl phosphite, octadecyl phosphite, tris(-39-200931179 nonylphenyl) phosphite, 9,10-dihydro-9-oxa-1 0-phosphaphenanthrene-1 〇·oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)·9, 10-dihydro-9-oxa-10-phosphaphenanthrene -10-Oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-p-phenanthrene-10-oxide, tris(2,4-di-t-butylphenyl Phosphite, cyclic pentaerythritol bis(2,4-di-t-butylphenyl) phosphite, cyclic pentaerythritol bis(2,6-di-t-butylphenyl) phosphite, 2, 2-Methylene bis(4,6-di-t-butylphenyl)octyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tetra(2,4- Di-t-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, bis[2,4-bis(l,l-dimethylethyl) -6-methylphenyl]ethyl ester, phosphonic acid, and the like. Among these phosphorus-based oxidation inhibitors, 2,2'-methylenebis(4,6-di-t-butyl-1-phenoxy)(2 - is preferred from the viewpoint of heat resistance and prevention of discoloration resistance. Ethylhexyloxy)phosphorus, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Spirulinaphosphate [5.5] undecane, 6-[3-( 3-1-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t -butyldibenzo[d,f][l,3,2]phosphine and the like. The phosphorus-based oxidation inhibitors may be used singly or in combination of two or more. As the sulfur-based oxidation preventing agent, a known compound can be used. Specifically, for example, there are 2,2-bis({[3-(dodecylthio)propenyl)oxy}methyl)-1,3-propanediyl-bis[3-(dodecane) Base thio)propionate], 2-hydrothiobenzimidazole, dilauryl-3,3'-thiodipropionate, tetracosyl-3,3'-thiodipropionate, di-hard a compound having a thioether structure such as a lipid-3,3'-thiodipropionate or pentaerythritol-tetrakis(3-laurylthiopropionate); 2-hydrothiobenzimidazole or the like. -40- 200931179 Among these sulfur-based oxidation inhibitors, 2,2-bis({[3-(dodecylthio)propenyl fluorenyloxy)) is preferred from the viewpoint of heat resistance and prevention of heat discoloration. Base) · 1,3-propanediyl-bis[3-(dodecylthio)propionate), 2-hydrothiobenzimidazole, and the like. The sulfur-based oxidation inhibitors may be used singly or in combination of two or more. In the present invention, from the viewpoint of suppressing the decrease in brightness and the combination of brightness and sensitivity, it is preferred to use the following (E-1) or (E-2) as the oxidation preventing agent. (E-1) is at least one selected from the group consisting of a phosphorus-based oxidation inhibitor and a sulfur-based oxidation inhibitor, and a combination of the (E-2) phosphorus-based oxidation inhibitor or the sulfur-based oxidation inhibitor and the phenol-based oxidation inhibitor . The total content of the oxidation preventing agent of the present invention is usually from 1 to 100 parts by mass, preferably from 2 to 80 parts by mass, particularly preferably from 4 to 60 parts by mass, per 100 parts by mass of the total of (D) photopolymerization initiator. . When the total content is less than 1 part by mass, the desired effect cannot be obtained. When it exceeds 100 parts by mass, there may be insoluble matter or residue after development. - Additive - The linear composition of the sensitive radiation of the present invention may be added with various additives as necessary. The aforementioned additives are, for example, organic acids or organic amine based compounds (excluding the aforementioned hydrogen donor) and the like. These compounds further improve the solubility characteristics of the linear composition of the radiation sensitive agent to the alkali imaging solution, and exhibit components which further suppress the action of the residual of the undissolved substance after the development -41 - 200931179. The organic acid is preferably a fatty acid having one or more carboxyl groups in the molecule or a carboxylic acid having a phenyl group. The aliphatic carboxylic acid is, for example, a lipid monocarboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid or octanoic acid; oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, heptanedioic acid, azelaic acid, sebacic acid, malic acid, methylmalonic acid, malonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl a carboxylic acid such as succinic acid hexane dicarboxylic acid, isaconic acid, citraconic acid, maleic acid, transbutene or mesaconic acid; glycerin tricarboxylic acid, aconitic acid, camphor tricarboxylic acid, and the like. Further, the phenyl group-containing carboxylic acid may, for example, be a compound having a carboxyl group direct bond group or a carboxylic acid having a carboxyl group bonded to a phenyl group via a carbon chain. The phenyl group-containing carboxylic acid is, for example, an aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumanoic acid, tricarboxylic acid or dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, and cinnamidine Or aromatic dicarboxylic acids; aromatic polycarboxylic acids of trimellitic acid, trimellitic acid, pyromellitic acid, and pyromellitic acid; and phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, almond Acid, succinic acid, atropic acid, cinnamic acid, cinnamon fork acetic acid, coumaric acid, umbrella, and the like. Among these organic acids, the solubility in alkali, the solvent of a solvent to be described later, a pentane aliphatic acid, an ethyl group, a dicarboxylic acid to a benzene benzoic acid trivalent phenyl acidolysis-42- 200931179 The viewpoint of preventing texture contamination and film residue on the substrate or the light-shielding layer of the unexposed portion is preferably an aliphatic dicarboxylic acid of an aliphatic carboxylic acid, particularly preferably malonic acid, adipic acid, and Yikang. Acid, citraconic acid, fumaric acid, mesaconic acid, etc. The phenyl group-containing carboxylic acid is preferably an aromatic dicarboxylic acid, particularly preferably a phthalic acid. The above organic acids may be used singly or in combination of two or more. The content of the organic acid is usually 15% by mass or less, preferably 10% by mass or less, based on the total mass of the linear composition of the radiation radiation (in terms of solid content). When the content of the organic acid exceeds 15% by mass, the adhesion of the colored layer to the substrate tends to be lowered. The organic amine-based compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amine groups in the molecule. The above aliphatic amine is, for example, the following. The aliphatic amines are, for example, n-propylamine, i-propylamine, n-butylamine, i-butylamine, second-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine 'n-octylamine, Q-negral Amine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexane a mono(cyclo)alkylamine such as an amine, 3-ethylcyclohexylamine or 4-ethylcyclohexylamine; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine , di-i-propylamine, di-n-butylamine, dibutylamine, di-second-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, a bis(cyclo)alkylamine such as ethylcyclohexylamine or dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyl Di-n-propylamine, ethyldi-n-propylamine, tri-n-propyl-43- 200931179 amine, trisamine, tri-n-butylamine, tributylamine, tri-second-butylamine, tri-t-butyl Amine 'tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyl bicyclic a tri(cyclo)alkylamine such as an amine or tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butane a mono(cyclo)alkanolamine such as an alcohol, 5-amino-1-pentanol, 6-amino-1-hexanol or 4-amino-1-cyclohexanol; hydrazine diethanolamine, di-positive Propylamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, bis(4-cyclohexanol)amine, etc. Di(cyclo)alkanolamines; triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, a tri(cyclo)alkanolamine such as tri-n-hexanolamine or tris(4-cyclohexanol)amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4- Amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexane- Alcohol, 3-methylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1, Amino (cyclo)alkanediols such as 3-propanediol; 1-aminocyclopentane methanol, 4-aminocyclopentane methanol , 1-Aminocyclohexanemethanol' 4-Aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexane An amine group-containing cycloalkane methanol such as methanol or 4-diethylaminocyclohexane methanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2 -Aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid-44-200931179, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1 An aminocarboxylic acid such as aminocyclohexanecarboxylic acid or 4-aminocyclohexanecarboxylic acid. Further, the phenyl group-containing amine is, for example, a compound in which an amine group is directly bonded to a phenyl group, a compound in which an amine group is bonded to a phenyl group, and the like. Phenyl-containing amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4- n-Butylaniline, 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, anthracene, fluorene-dimethylaniline, anthracene, fluorene-diethylaniline, 4-methyl-indole, hydrazine- Aromatic amines such as dimethylaniline; 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol, etc. Aminobenzyl alcohols; 2-aminophenols, 3-aminophenols, 4-aminophenols, 4-dimethylaminophenols, aminophenols such as 4-diethylaminophenol, and the like. Among these organic amine-based compounds, the aliphatic amine is preferably a mono(cyclo)alkanolamine from the viewpoints of solubility to a solvent to be described later, prevention of texture contamination on a substrate or an unexposed portion or a film residue on an unexposed portion. And alkane (cyclo) alkanediols, particularly preferably 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2- Propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, and the like. The phenyl group-containing amine is preferably an aminophenol, and particularly preferably a 2-aminophenol, a 3-aminophenol, a 4-aminophenol or the like. The organic amine-based compounds may be used singly or in combination of two or more. The content of the organic amine-based compound is usually 15% by mass or less, preferably 10% by mass or less, based on the total mass of the linear composition of the radiation radiation (in terms of solid content). When the content of the organic amine-based compound exceeds 15% by mass, the adhesion of the color layer to the substrate tends to decrease from -45 to 200931179. The additive component other than the above, for example, a dispersing aid such as a blue pigment derivative or a yellow pigment derivative of a copper phthalocyanine derivative; a chelating agent such as glass or alumina; a polyvinyl alcohol or a polyethylene glycol single A polymer compound such as an alkyl ether or a poly(fluoroalkyl acrylate); a surfactant such as a nonionic, cationic or anionic surfactant; vinyl trimethoxy decane, vinyl triethoxy decane' vinyl Tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxy sand, 3-aminopropyldiethoxylate, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldi Methoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3- a adhesion promoter such as methacryloxypropyltrimethoxydecane or 3-hydrothiopropyltrimethoxydecane; 2-(3-t-butyl-5-methyl-2-phenylbenzene) -5-chlorobenzophenone Ultraviolet absorbers such as hydrazine, alkoxybenzophenone, etc.; agglutination inhibitors such as sodium polyacrylate; - azobis (cyclohexylamine _), 2-n-azo azo-4-methoxy a thermal radical generator such as 2,4-dimethylvaleronitrile or the like. - Solvent - -46 - 200931179 The sensitive radiation linear composition of the present invention contains the above components (A) to (E) as essential components, and sometimes contains the above additives, and is usually mixed with a solvent to prepare a liquid composition. The solvent can be appropriately selected as long as it can disperse or dissolve the components constituting the linear composition of the radiation radiation, and does not react with these components, and has appropriate volatility. Such a solvent is, for example, the following. ^ Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, (poly)alkylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (poly)alkylene glycol monoester ether acetates such as acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; a ketone such as ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl lactate or ethyl lactate; Ethyl 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, B-47- 200931179 Ethyl oxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy ester Ethyl acetate, n-propyl acetate, i-propyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, ethyl propionate, n-propyl butyrate, butyrate i- Other esters such as propyl ester, n-butyl butyrate, ethyl pyruvate, n-propyl pyruvate, ethyl acetate, ethyl 2-oxobutanoate, etc.; aromatics such as toluene and xylene Hydrocarbons; decylamines or indoleamines such as N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, alkanones and the like. Among these solvents, from the viewpoints of solubility, pigment dispersibility, and point, propylene glycol monomethyl ether, ethylene glycol monomethyl ether glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diether, and second are preferable. Ethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-ethyl ester, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl propionate, 3-methyl- 3-methoxybutyl propionate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-ethyl propionate, i-propyl butyrate, n-butyl butyrate, pyruvic acid The ethyl ester oxime solvent may be used singly or in combination of two or more. Further, the above solvent may be combined with benzyl ether, di-n-hexyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl ester, ethyl benzoate, diethyl oxalate, and cis. A high boiling point solvent such as butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol. Methyl butyrate, n-butyl butyl propyl propionate, n-butyl ester, butyl ester, methyl pyruvate, acetamidine N-methylpyrrole coated acetate, propylene glycol Ketone, lactic acid, 3-ethoxy n-butyl ester, ethyl butyl ester, butyric acid, and the like. , acetamyl benzyl alcohol, diethyl acetate, γ-phenyl ether acetate-48- 200931179 These high-boiling solvents can be used alone or in combination with rain. The content of the solvent is not particularly limited 'but the sensitive radiation obtained from From the viewpoint of coatability and stability of the wire, the total concentration of the components to be dissolved and dissolved is usually 5 to 50% by mass, preferably 1% by volume. 制造 - Manufacturing method - 0 The radiation linear composition can be pulverized, mixed, dispersed, dispersed, and dispersed by a suitable method, for example, when a coloring agent is used, in a solvent, a dispersing agent, using a ball mill, a roll mill, or the like. It is preferred to mix and prepare the component (B), the component (C), the component, and the component (E), and the solvent or the agent added thereto as necessary. Examples of the dispersant include a urethane dispersant, a polyethylene dispersion, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether oxime, a polyethylene glycol diester dispersant, and sorbitol. a fatty acid ester-based, fatty acid-modified polyester-based dispersant, or an acrylic-based dispersant; specific examples of such a dispersing agent include efka (manufactured by Chemicals (EFKA) Co., Ltd.) and Disperbyk (manufactured by BYK (BYK) Co., Ltd.). Disbaron (Nanmoto Chemical Co., Ltd., Solsperse (manufactured by Lubrizol), KP (Shin-Etsu Chemical Co., Ltd.), P〇iy flow (Kyoei Chemical Co., Ltd.), F Tokem Products (share) system, Megafac (Daily Ink Co., Ltd.), Florade (Sumitomo 3M (stock) system). ~40 quality preparation outside the composition of the composition, the presence of the pigment (D), the addition of an amine-based dispersion dispersant. EFKA Chemie Division) Industry (Shares Top (Chemistry As ahi -49- 200931179

Guard、Surflon (以上爲旭硝子（股）製）等。 這些分散劑可單獨或組合兩種以上來使用。 調製顏料分散液時之分散劑的使用量係對於顔料1〇〇 質量份’通常爲100質量份以下，較佳爲0.5〜1〇〇質量 份’更佳爲1〜70質量份，特佳爲10〜50質量份。分散 劑之使用量太多時，可能會影響顯像性等。 又，調製顏料分散液時使用之溶劑，例如有與上述溶 Λ 媒相同者。 調製顏料分散液時使用之溶劑的使用量係對於顏料 100質量份，通常爲200〜1,200質量份，較佳爲3〇〇〜 1，000質量份。 利用球磨機製備顏料分散液時，使用例如0.5〜i 〇 mm直徑的玻璃珠或氧化鈦珠等，將由顔料、溶劑及分散 劑所構成之顏料分散液較佳爲採用冷卻水等冷卻，同時進 行混合、分散的方法。 〇 此時，珠粒之塡充率較佳爲硏磨機容量之50〜8〇體 積/。，顔料混合液之注入量較佳爲硏磨機容量的2〇〜5〇體 積％。處理時間通常爲2〜50小時，較佳爲2〜25小時。 利用輥磨機製備時，使用例如三滾筒硏磨機或雙滾筒 硏磨機帛，較佳爲將顏料混合液利用&卻水等冷卻的狀態 下’進行處理的方法。 此時，滾筒間隔較佳爲1〇 μιη以下，剪切力通常爲 108dyn/秒。處理時間通常爲2〜5〇小時’更佳爲2〜25小 時。 -50- 200931179 彩色濾光片 本發明之彩色濾光片係使用本發明之藍色彩色濾光片 用敏輻射線性組成物形成者。 以下說明形成本發明之彩色濾光片的方法。 首先，視情況於基板表面上形成遮光層以區分形成像 素之部分，此基板上塗佈本發明之藍色彩色濾光片用敏輻 射線性組成物之液狀組成物後，進行預烘烤使溶劑蒸發， 形成塗膜。 接著，此塗膜介由光罩曝光後，使用鹼顯像液顯像， 溶解除去塗膜之未曝光的部分。然後，藉由後烘烤形成藍 色像素圖型依所定之排列配置的像素陣列。 然後，使用含有綠色或紅色之著色劑所構成之各敏輻 射線性組成物之液狀組成物，與前述相同對於各液狀組成 物進行塗佈、預烘烤、曝光、顯像及後烘烤，於相同基板 上依序形成綠色像素陣列及紅色像素陣列，而得到在基板 上配置紅色、綠色及藍色之三原色之像素陣列的彩色濾光 片。然而’本發明中，各顏色之像素的形成順序不限於前 述者。 用於形成彩色濾光片時所用的基板，例如有玻璃、砂 、聚碳酸酯、聚酯、芳族聚醯胺、聚醯胺醯亞胺、聚醯亞 胺等。 此等基板可視情況施予使用矽烷偶合劑等之藥品處理 、電槳處理、離子電鍍、濺鍍、氣相反應法、真空蒸鍍法 -51 - 200931179 等之適當的前處理。 將敏輻射線性組成物之液狀組成物塗佈於基板時，可 採用噴霧塗覆法、輥塗法、旋轉塗佈法、縫隙模塗佈法、 棒塗法、噴墨法等適當的塗佈法，特佳係旋轉塗佈法、縫 隙模塗佈法。 塗佈厚度係以乾燥後之膜厚，通常爲0.1〜ΙΟμηι，較 佳爲〇 · 2〜8 0 μ m ’特佳係0.2〜6.0μηι。 用以形成彩色濾光片之輻射，可使用例如可見光、紫 外線、遠紫外線、電子線、X-射線等，較佳爲波長爲190 〜450nm之輻射。 輻射之曝光量較佳爲10〜l〇,〇〇〇J/m2。 此外’鹼顯像液較佳爲例如碳酸鈉、氫氧化鈉、氫氧 化鉀、氫氧化四甲基銨、膽鹼、1，8-二氮雜雙環-[5.4.0]-7-十一碳烯、1，5-二氮雜雙環-[4.3.0]-5-壬烯等的水溶液。 鹼顯像液中可添加適量之例如甲醇、乙醇等之水溶性 有機溶劑或界面活性劑。鹼顯像後，通常進行水洗。 顯像處理方法可採用例如噴啉式顯像法、噴霧式顯像 法、浸漬式顯像法、攪拌顯像法等。顯像條件較佳係於室 溫進行5〜3 0 0秒。 後烘烤的條件較佳爲180〜230 °C，20〜40分鐘。 如此形成之像素的膜厚通常爲〇_ 5〜5.0 μηι，較佳爲 1 . 5 〜3.0 μηι。 如此所得之本發明之彩色濾光片非常適用於例如透過 型或反射型之彩色液晶顯示元件、彩色攝像管元件、彩色 -52- 200931179 感知器等。 液晶顯示元件 本發明之液晶顯示元件係具備本發明之彩色濾光片者 〇 此外’本發明之液晶顯示元件之一的實施形態爲使用 本發明之藍色彩色濾光片用敏輻射線性組成物，於薄膜電 晶體基板陣列上如前述形成像素及/或黑色矩陣，可製備 具有特別優異特性的液晶顯示元件。 【實施方式】 [實施例] 以下，舉實施例更具體說明本發明之實施形態。但是 本發明不限於述實施例者。 本實施例使用的光聚合起始劑及氧化防止劑如下所示 ❿ 光聚合起始劑 (d-Ι) : 2-甲基-1·(4-甲基苯硫基）-2-嗎啉基丙烷- 1·銅（商品名 Ir g ac ur e 9 0 7，C i b a · Sp e e i al i ty · Chemi e al s 公司製） (d-2) :2,2’-雙（2-氯苯基）-4,5,4’，5’-四苯基- 1，2’-聯咪唑 (d-3) :2,4 -二乙基噻噸酮 -53- 200931179 (d-4 ) : 2-氫硫基苯并噻唑 (d-5 ) : 2-苄基-2-二甲基胺基-1- ( 4-嗎啉苯基）-丁 院-1-嗣（IRUGACURE 369、Ciba · Speciality · Chemicals 公司製） (d-6) : 1-〔 9 -乙基-6- ( 2 -甲基苯醯）-9H -咔唑- 3- 基〕-乙烷-1-酮肟-0-乙酸酯（IRUGACURE OXE-02、 Ciba · Speciality · Chemicals 公司製） 氧化防止劑 (e-1 ) : 2,2’-甲撐雙（4,6-二-t-丁基-1-苯氧基）（ 2-乙基己氧基）磷（商品名ADK STAB HP-10、股份公司 ADEKA 製） (e-2 ) : 3,9-雙（2,6-二-tert-丁基-4-甲基苯氧基）- 2,4,8,10-四氧雜-3,9-二磷酸螺[5.5]十一烷（ADK STABPEP-36、股份公司 ADEKA 製） (e-3 ) : 3,9-雙[2-〔 3- ( 3-t-丁基-4-羥基-5-甲基苯 基）丙醯氧基〕-1,1-二甲基乙氧基]-2,4,8，10-四氧雜螺 [5.5]十一烷（ADKSTABAO-80、股份公司 ADEKA 製） (e-4 ) :2,2-雙（{[3-(十二烷基硫）丙醯基]氧基} 甲基}-1，3-丙烷二基-雙[3-(十二烷基硫）丙酸酯](ADK STABAO-412S、股份公司 ADEKA 製） (B)鹼可溶性樹脂之製造例 合成例1 -54- 200931179 在具備冷卻管、攪拌機之燒瓶中裝入2,2，_偶氮雙（ 2,4 -一甲基戊腈）1質量份及丙二醇單甲醚乙酸酯2〇〇質 量份’接著裝入甲基丙烯酸15質量份、苄基甲基丙烯酸 酯35質量份、甘油單甲基丙烯酸酯1〇質量份、N_苯基順 丁嫌二酿亞胺25質量份及α_甲基苯乙烯二聚物（鏈轉移 劑）2.5質量份’經氮取代後，緩緩攪拌，使反應溶液升 溫至8 0 °C，保持此溫度進行3小時聚合。其後，將反應溶 0 液之溫度升溫至l〇〇°C’添加2,2，-偶氮雙（2,4-二甲基戊 腈）〇. 5質量份，再聚合1小時，得到（b )鹼可溶性樹脂 之溶液（固形分濃度=3 3 · 0 % )。 此（B)鹼可溶性樹脂係]viw=10,000、Mn = 6,000。此 (B )鹼可溶性樹脂作爲「樹脂（b )」。 實施例1 將（A)著色劑：C.I.顏料藍15: 6/C.I.顏料紫 23 = 80/20 (質量比）之混合物12質量份、分散劑： BYK2001 ( Disperbyk ： BYK Chemie ( BYK)社製）3.8 質 量份（固形分換算）、Solsperse12000: 0.8質量份及溶媒 :丙二醇單甲醚乙酸酯83.4質量份藉由珠磨機處理，調 製顏料分散液。 接著，將此顏料分散液360質量份、（B )鹼可溶性 樹脂：樹脂（b ) 70質量份（固形分換算）、（C )多官 能性單體：二季戊四醇六丙烯酸酯80質量份、（D)光聚 合起始劑：（d-Ι ) 30質量份、（d-2 ) 3質量份、（d-3 ) -55- 200931179 10質量份及（d-4 ) 1 .5質量份、（E )氧化防止劑：（e-l )2.5質量份、添加劑：含有全氟烷基之寡聚物（商品名 Megafac R08-MH、大日本油墨（股）製）0.3質量份及3-甲基丙烯氧基丙基三甲氧基矽烷（商品名SILA-ACE S710 、窒素（股）製）0.4質量份及溶劑：丙二醇單甲醚乙酸 酯900質量份予以混合，調製液狀之敏輻射線性組成物（ B 1 )。 〇 像素陣列之形成 使用旋轉塗佈機將敏輻射線性組成物（B 1 )塗佈於表 面形成防止鈉離子溶離之Si02膜的鈉鈣玻璃基板上，改 變轉數塗佈3片後，在8 (TC之潔淨烤箱內進行1 0分鐘預 烘烤，形成膜厚爲1.5〜2.5 μιη之範圍，且不同之3片的 塗膜。 接著，將此基板冷卻至室溫後，使用高壓水銀燈，經 q 由光罩，對塗膜以含有365nm、405nm及43 6nm之各波長 之輻射線以5,OOOJ/m2之曝光量曝光。接著，將基板浸漬 於25。(：之〇. 1質量％氫氧化四甲銨水溶液中1分鐘，進行 顯像處理，以超純水洗淨、風乾。然後’以2 3 0 °C進行3 0 分鐘後供烤，製作形成各邊之大小之藍色之 像素圖型的像素陣列。 色度之評價 對於製得之像素’使用彩色分析器（東京電色（股） -56- 200931179 製TC- 1 800M)，以C光源、2度視野測定CIE表色系之 色度座標値（X，y)及亮度（Y)，得到在（X，y)=( 0.141 ’ 0.089)的亮度（Y) 。Y値越大表示亮度越高。評 價結果如表1所示。 實施例2 除了使用氧化防止劑（e-2 ) 2.5質量份取代氧化防止 0 劑（e-Ι) 2.5質量份外’與實施例1同様在基板上形成藍 色的像素，進行評價。結果如表1所示。 實施例3 除了使用氧化防止劑（e-3) 2.5質量份取代氧化防止 劑（e-1) 2.5質量份外’與實施例1同樣在基板上形成 藍色的像素’進行評價。結果如表1所示。 φ 實施例4 除了使用氧化防止劑（e -1 ) 1.9質量份及氧化防止劑 (e-3 ) 0.6質量份取代氧化防止劑（）2.5質量份外， 與實施例1同樣在基板上形成藍色的像素，進行評價。結 果如表1所示。 實施例5 除了使用氧化防止劑（e-3) 〇_6質量份及氧化防止劑 (e-4) 1.9質量份取代氧化防止劑（e_〇 2 5質量份外， -57- 200931179 評價。結 與實施例1同様在基板上形成藍色的像素，進 果如表1所示。 實施例6 劑（d-ι ) 丨樣在基板 除了使用起始劑（d-5 ) 20質量份取代起始 、（d-2) 、（d-3)及（d-4)外，與實施例 上形成藍色的像素’進行評價。結果如表i所示 ❹ 實施例7 化防止劑 量份外， 評價。結 除了使用氧化防止劑（e-3) 0.6質量份及氧 (e-4) 1.9質量份取代氧化防止劑（) 2.5質 與實施例6同樣在基板上形成藍色的像素，進行 果如表1所示。 實施例8 劑（d -1 ) 様在基板 0 除了使用起始劑（d-6 ) 1 0質量份取代起始 、（d - 2 ) 、（ d - 3 )及（d - 4 )外，與實施例5同 上形成藍色的像素，進行評價。結果如表1所示 比較例1 ’與實施 結果如表 除了不含氧化防止劑（e-Ι ) 2.5質量份除外 例1同様在基板上形成藍色的像素，進行評價。 1所示。 200931179 比較例2 除了不含氧化防止劑（e -1 ) 2.5質量份外，與實施例 6同様在基板上形成藍色的像素，進行評價。結果如表1 所示。 比較例3 除了不含氧化防止劑（e-3 ) 1質量份及氧化防止劑（ e-4) 1_9質量份除外’與實施例8同樣在基板上形成藍色 的像素，進彳了評價。結果如表1所示。 参考例 僅使用光聚合起始劑（d-1 ) 3 0質量份及不含氧化防 止劑（e-Ι ) 2.5質量份外，與實施例1同樣在基板上形成 藍色的像素，進行評價。結果如表1所示。 [表 1] __ 光聚合起始劑 氧化防止劑 γ値 d-1 d-2 d-3 d-4 d-5 d-6 e-1 e-2 e-3 e-4 實施例1 30 3 10 1.5 2.5 9.5 實施例2 30 3 10 1.5 2.5 9.5 實施例3 30 3 10 1.5 2.5 9.5 實施例4 30 3 10 1.5 1.9 0.6 9.6 實施例5 30 3 10 1.5 0.6 1.9 9.6 實施例ό 20 2.5 9.5 實施例7 20 0.6 1.9 9.5 實施例8 10 0.6 1.9 9.4 比較例1 30 3 10 1.5 9.4 比較例2 20 9.2 比較例3 10 9.0 參考例 30 9.6 -59- 200931179 参考例係使用專利文獻3之光聚合起始劑（d-l)的 高亮度化藍色像素’該藍色像素之Y値爲9·6。爲了進— 步提高感度，使此光聚合起始劑（d·1)與3種之光聚合 起始劑（d-2 )〜（d-4 )組合時，得知Y値會降低至9.4 (比較例1 )。 然而，實施例1〜5係爲了進一步提高感度’將光聚 合起始劑（d-Ι )與3種之光聚合起始劑（d-2 )〜（d-4 ) 組合，再組合特定之氧化防止劑者’確認可得到與参考例 相較，毫不遜色的Y値（9.5〜9.6)。如此’實施例1〜5 組合特定之光聚合起始劑與特定之氧化防止劑，可得到抑 制亮度降低，且以高水準兼具亮度及感度的藍色像素。 對於在比較例2〜3中單獨使用時，無法得到足夠亮 度（Y値）的光聚合起始劑，在實施例6〜7中藉由將光 聚合起始劑與特定之氧化防止劑組合，可得到高亮度之藍 色像素。 -60-Guard, Surflon (above is Asahi Glass Co., Ltd.). These dispersing agents can be used individually or in combination of 2 or more types. The amount of the dispersant to be used in the preparation of the pigment dispersion is usually 100 parts by mass or less, preferably 0.5 to 1 part by mass, more preferably 1 to 70 parts by mass, more preferably 1 to 70 parts by mass. 10 to 50 parts by mass. When the amount of the dispersant used is too large, it may affect the development property and the like. Further, the solvent used in the preparation of the pigment dispersion liquid is, for example, the same as the above solvent. The solvent used in the preparation of the pigment dispersion liquid is usually used in an amount of from 200 to 1,200 parts by mass, preferably from 3 to 1,000 parts by mass, per 100 parts by mass of the pigment. When the pigment dispersion liquid is prepared by a ball mill, the pigment dispersion liquid composed of a pigment, a solvent, and a dispersant is preferably cooled by cooling water or the like using, for example, glass beads having a diameter of 0.5 to 100 mm or titanium oxide beads. , the method of dispersion. 〇 At this time, the beading rate of the beads is preferably 50 to 8 〇 volume of the honing machine. The amount of the pigment mixture to be injected is preferably 2 〇 to 5 〇 of the volume of the honing machine. The treatment time is usually from 2 to 50 hours, preferably from 2 to 25 hours. In the preparation by the roll mill, for example, a three-roll honing machine or a double-roll honing machine 使用 is used, and it is preferred to carry out the treatment of the pigment mixed liquid in a state of being cooled by water. At this time, the roller interval is preferably 1 〇 μηη or less, and the shear force is usually 108 dyn/sec. The processing time is usually 2 to 5 hours', more preferably 2 to 25 hours. -50- 200931179 Color filter The color filter of the present invention is formed by using the blue color filter of the present invention with a radiation sensitive linear composition. The method of forming the color filter of the present invention will be described below. First, a light-shielding layer is formed on the surface of the substrate to distinguish the portion forming the pixel, and the liquid composition of the linear composition for sensitive radiation of the blue color filter of the present invention is coated on the substrate, and then pre-baked. The solvent is evaporated to form a coating film. Next, after the film was exposed through a photomask, it was developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, the pixel array in which the blue pixel pattern is arranged in accordance with the predetermined arrangement is formed by post-baking. Then, using a liquid composition of a linear composition of each sensitive radiation composed of a green or red coloring agent, coating, prebaking, exposing, developing, and post-baking the respective liquid compositions are carried out in the same manner as described above. A green pixel array and a red pixel array are sequentially formed on the same substrate, and a color filter in which pixel arrays of three primary colors of red, green, and blue are disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above. The substrate used for forming the color filter is, for example, glass, sand, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimine or the like. These substrates may be subjected to an appropriate pretreatment such as a drug treatment such as a decane coupling agent, an electric paddle treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition method -51 - 200931179. When the liquid composition of the linear composition of the radiation radiation is applied to the substrate, a suitable coating such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method may be employed. The cloth method is a spin coating method or a slit die coating method. The coating thickness is usually 0.1 to ΙΟμηι after drying, and more preferably 〇 2 to 80 μm Å to 0.2 to 6.0 μm. For the radiation for forming the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of 190 to 450 nm is preferable. The exposure amount of the radiation is preferably 10 to 1 Torr, 〇〇〇 J/m 2 . Further, the 'alkali developing solution is preferably, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7- eleven An aqueous solution of carbene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developing solution. After alkali imaging, it is usually washed with water. The development processing method may be, for example, a spray-type development method, a spray-type development method, an immersion-type development method, a stirring development method, or the like. The development condition is preferably carried out at room temperature for 5 to 300 seconds. The post-baking conditions are preferably 180 to 230 ° C for 20 to 40 minutes. The film thickness of the pixel thus formed is usually 〇 5 to 5.0 μηι, preferably 1.5 to 3.0 μηι. The color filter of the present invention thus obtained is very suitable for, for example, a transmissive or reflective type color liquid crystal display element, a color image pickup device element, a color -52-200931179 sensor, and the like. Liquid crystal display element The liquid crystal display element of the present invention is provided with the color filter of the present invention. Further, an embodiment of one of the liquid crystal display elements of the present invention is a linear composition for sensitive radiation using the blue color filter of the present invention. A liquid crystal display element having particularly excellent characteristics can be prepared by forming a pixel and/or a black matrix on the thin film transistor substrate array as described above. [Embodiment] [Embodiment] Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited to the embodiments described. The photopolymerization initiator and the oxidation inhibitor used in the present embodiment are as follows: a photopolymerization initiator (d-Ι): 2-methyl-1·(4-methylphenylthio)-2-morpholine Propane- 1 · copper (trade name Ir g ac ur e 9 0 7, C iba · Sp eei al ty · manufactured by Chemi e al s) (d-2) : 2,2'-bis (2-chloro Phenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (d-3): 2,4-diethylthioxanthone-53- 200931179 (d-4) : 2-Hydroxythiobenzothiazole (d-5) : 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl-1-pyrene (IRUGACURE 369, Ciba · Speciality · Chemicals Co., Ltd.) (d-6) : 1-[9-Ethyl-6-(2-methylphenylhydrazine)-9H-carbazole-3-yl]-ethane-1-one oxime- 0-acetate (IRUGACURE OXE-02, manufactured by Ciba · Speciality · Chemicals) Oxidation inhibitor (e-1) : 2,2'-methylene bis(4,6-di-t-butyl-1- Phenoxy)(2-ethylhexyloxy)phosphorus (trade name: ADK STAB HP-10, manufactured by the company ADEKA) (e-2) : 3,9-bis(2,6-di-tert-butyl 4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphate spiro[5.5]undecane (ADK STABPEP-36, ADEKA, a joint stock company) (e-3) : 3,9-bis[2-[ 3-( 3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1 -Dimethylethoxy]-2,4,8,10-tetraoxaspiro[5.5]undecane (ADKSTABAO-80, manufactured by the company Adeka) (e-4): 2,2-double ({ [3-(dodecylthio)propanyl]oxy}methyl}-1,3-propanediyl-bis[3-(dodecylthio)propionate] (ADK STABAO-412S, (B) Manufacture of alkali-soluble resin Synthesis Example 1 -54- 200931179 A flask equipped with a cooling tube and a stirrer was charged with 2,2,-azobis(2,4-methylpentanenitrile). 1 part by mass and 2 parts by mass of propylene glycol monomethyl ether acetate' followed by 15 parts by mass of methacrylic acid, 35 parts by mass of benzyl methacrylate, 1 part by mass of glycerol monomethacrylate, and N _Phenyl cis-butyl succinimide 25 parts by mass and α-methyl styrene dimer (chain transfer agent) 2.5 parts by mass 'after nitrogen substitution, slowly stirring, the reaction solution is heated to 80 ° C This temperature was maintained for 3 hours of polymerization. Thereafter, the temperature of the reaction solution was raised to 10 ° C to add 2,2,-azobis(2,4-dimethylvaleronitrile) oxime. 5 parts by mass, and polymerization was further carried out for 1 hour. (b) A solution of an alkali-soluble resin (solid content concentration = 3 3 · 0 %). This (B) alkali-soluble resin system] viw = 10,000, Mn = 6,000. This (B) alkali-soluble resin is referred to as "resin (b)". Example 1 (A) Colorant: CI Pigment Blue 15: 6/CI Pigment Violet 23 = 80/20 (mass ratio) mixture 12 parts by mass, dispersant: BYK2001 (Disperbyk: BYK Chemie (BYK)) 3.8 parts by mass (solid content conversion), Solsperse 12000: 0.8 parts by mass and solvent: propylene glycol monomethyl ether acetate 83.4 parts by mass was prepared by a bead mill to prepare a pigment dispersion. Next, 360 parts by mass of the pigment dispersion liquid, (B) 70% by mass of the alkali-soluble resin: resin (b) (calculated as solid content), and (C) 80 parts by mass of polyfunctional monomer: dipentaerythritol hexaacrylate ( D) photopolymerization initiator: (d-Ι) 30 parts by mass, (d-2) 3 parts by mass, (d-3) -55 to 200931179 10 parts by mass, and (d-4) 1.5 parts by mass, (E) Oxidation inhibitor: (el) 2.5 parts by mass, additive: a perfluoroalkyl group-containing oligomer (trade name: Megafac R08-MH, manufactured by Dainippon Ink Co., Ltd.) 0.3 parts by mass and 3-methylpropene 0.4 parts by mass of oxypropyltrimethoxydecane (trade name: SILA-ACE S710, manufactured by Alizarin Co., Ltd.) and solvent: 900 parts by mass of propylene glycol monomethyl ether acetate are mixed to prepare a linear composition of liquid sensitive radiation (B 1 ). Formation of 〇 pixel array The sensitizing radiation linear composition (B 1 ) was applied to a soda lime glass substrate having a surface on which a sodium ion-dissolved SiO 2 film was formed using a spin coater, and after changing the number of revolutions, 3 sheets were coated. (Pre-baking in a clean oven of TC for 10 minutes to form a film having a film thickness of 1.5 to 2.5 μm and different three sheets. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is used. q By a photomask, the coating film is exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J/m 2 . Next, the substrate is immersed in 25. (: 〇. 1% by mass of hydrogen After immersing in an aqueous solution of tetramethylammonium chloride for 1 minute, it was subjected to development treatment, washed with ultrapure water, and air-dried. Then, it was baked at 30 ° C for 30 minutes and then baked to form a blue pixel of each side. Pixel array of pattern. Evaluation of chromaticity For the obtained pixel 'using color analyzer (Tokyo Electric Co., Ltd. -56-200931179 TC-1800M), CIE color system is measured by C light source and 2 degree field of view The chromaticity coordinates 値(X,y) and brightness (Y) are obtained at (X,y)=( 0.141 The brightness (Y) of 0.089). The larger the Y値, the higher the brightness. The evaluation results are shown in Table 1. Example 2 In addition to the use of the oxidation preventing agent (e-2) 2.5 parts by mass, the oxidation prevention agent 0 (e-Ι) 2.5 parts by mass of the same as in Example 1 and blue pixels were formed on the substrate and evaluated. The results are shown in Table 1. Example 3 In addition to the use of the oxidation preventing agent (e-3) 2.5 parts by mass of the substitution oxidation preventing agent (e-1) 2.5 parts by mass of the same thing as in Example 1 except that a blue pixel was formed on the substrate. The results are shown in Table 1. φ Example 4 except that an oxidation preventing agent (e -1 ) was used. In the same manner as in Example 1, a blue pixel was formed on the substrate in the same manner as in Example 1 except that the oxidation inhibitor (e-3) was replaced by 0.6 parts by mass of the oxidation inhibitor (e-3). The results are shown in Table 1. 5 In addition to the oxidation inhibitor (e-3) 〇 6 parts by mass and the oxidation inhibitor (e-4) 1.9 parts by mass of the substitution oxidation inhibitor (e_〇 2 5 parts by mass, -57- 200931179 evaluation. In Example 1, the blue pixels were formed on the substrate, and the results are shown in Table 1. Example 6 D-ι ) 丨 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The color pixel ' was evaluated. The results are shown in Table i. Example 7 In addition to the dose-preventing portion, the evaluation was carried out except that 0.6 parts by mass of the oxidation preventing agent (e-3) and 1.9 parts by mass of oxygen (e-4) were used. Oxidation inhibitor () 2.5 A blue pixel was formed on the substrate in the same manner as in Example 6, and the results are shown in Table 1. Example 8 Agent (d-1) 様 On the substrate 0, except that the starting agent (d-6) was substituted with 10 parts by mass of the starting, (d - 2 ), (d - 3 ) and (d - 4 ), A blue pixel was formed in the same manner as in Example 5, and evaluation was performed. The results are shown in Table 1. Comparative Example 1' and the results of the evaluation are as follows. Except that 2.5 parts by mass of the oxidation preventing agent (e-Ι) is not contained, the blue pixel is formed on the substrate in the same manner as in the example 1 and evaluated. 1 is shown. 200931179 Comparative Example 2 A blue pixel was formed on the substrate in the same manner as in Example 6 except that 2.5 parts by mass of the oxidation preventing agent (e -1 ) was not contained, and the evaluation was carried out. The results are shown in Table 1. Comparative Example 3 A blue pixel was formed on the substrate in the same manner as in Example 8 except that 1 part by mass of the oxidation preventing agent (e-3) and 1 to 9 parts by mass of the oxidation preventing agent (e-4) were not contained. The results are shown in Table 1. In the reference example, a blue pixel was formed on the substrate in the same manner as in Example 1 except that the photopolymerization initiator (d-1) was used in an amount of 30 parts by mass and the oxidation inhibitor (e-Ι) was not contained in an amount of 2.5 parts by mass. . The results are shown in Table 1. [Table 1] __ Photopolymerization initiator oxidation inhibitor γ値d-1 d-2 d-3 d-4 d-5 d-6 e-1 e-2 e-3 e-4 Example 1 30 3 10 1.5 2.5 9.5 Example 2 30 3 10 1.5 2.5 9.5 Example 3 30 3 10 1.5 2.5 9.5 Example 4 30 3 10 1.5 1.9 0.6 9.6 Example 5 30 3 10 1.5 0.6 1.9 9.6 Example ό 20 2.5 9.5 Example 7 20 0.6 1.9 9.5 Example 8 10 0.6 1.9 9.4 Comparative Example 1 30 3 10 1.5 9.4 Comparative Example 2 20 9.2 Comparative Example 3 10 9.0 Reference Example 30 9.6 -59- 200931179 The reference example uses the photopolymerization start of Patent Document 3. The high-luminance blue pixel of the agent (dl)' Y蓝色 of the blue pixel is 9.6. In order to further improve the sensitivity, when the photopolymerization initiator (d·1) is combined with three kinds of photopolymerization initiators (d-2) to (d-4), it is known that Y値 is lowered to 9.4. (Comparative Example 1). However, in Examples 1 to 5, in order to further improve the sensitivity, a photopolymerization initiator (d-Ι) was combined with three kinds of photopolymerization initiators (d-2) to (d-4), and the combination was specified. The oxidation inhibitor "confirmed that Y値 (9.5 to 9.6) which is inferior to the reference example can be obtained. Thus, in the first to fifth embodiments, a specific photopolymerization initiator and a specific oxidation inhibitor are combined to obtain a blue pixel which suppresses the decrease in brightness and which has a high level of brightness and sensitivity. When used alone in Comparative Examples 2 to 3, a photopolymerization initiator having sufficient brightness (Y値) could not be obtained, and in Examples 6 to 7, by combining a photopolymerization initiator with a specific oxidation inhibitor, High-brightness blue pixels are available. -60-

Claims (1)

200931179 十、申請專利範圍 1 · 一種藍色彩色濾光片用敏輻射線性組成物’其特徵 係含有： (A) 含有藍色著色劑所成之著色劑、 (B) 鹼可溶性樹脂、 (C )多官能性單體、 (D)含有選自由下述式（3)表示之化合物、肟酯系 化合物及聯咪唑系化合物所成群之至少1種所成的光聚合 起始劑、 (E )含有選自由酣系氧化防止劑、碟系氧化防止劑 及硫系氧化防止劑所成群之至少1種所成的氧化防止劑， 且（E)成分之合計含量爲對於（D)成分之合計1〇〇質量 份，含有1〜1〇〇質量份，200931179 X. Patent application scope 1 · A linear composition for sensitive radiation of blue color filters' is characterized by: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) (a) a photopolymerization initiator containing at least one selected from the group consisting of a compound represented by the following formula (3), an oxime ester compound, and a biimidazole compound, (E) An oxidation preventing agent containing at least one selected from the group consisting of a lanthanum oxidation inhibitor, a dish oxidation inhibitor, and a sulfur-based oxidation inhibitor, and the total content of the component (E) is for the component (D) A total of 1 part by mass, containing 1 to 1 part by mass, 【化7】【化7】 〔式中，R6係互相獨立表示碳數1〜4之烷基，R7及 R8係互相獨立表示氫原子或碳數1〜4之烷基〕。 2.如申請專利範圍第1項之藍色彩色濾光片用敏輻射 -61 - 200931179 線性組成物，其中（E ) 硫系氧化防止劑所成群之 之組合所構成。 3 . —種彩色濾光片， 或2項之藍色彩色濾光片 4·—種液晶顯示元件 3項之彩色濾光片。 成分爲選自由磷系氧化防止劑及 至少1種或其與酚系氧化防止劑 其特徵係使用申請專利範圍第1 用敏輻射線性組成物所形成。 ，其特徵係具備申請專利範圍第 〇 -62- 200931179 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無Wherein R6 independently represents an alkyl group having 1 to 4 carbon atoms, and R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2. The blue color filter of claim 1 is composed of a linear composition, wherein (E) a combination of sulfur-based oxidation inhibitors. 3 . A color filter, or 2 blue color filters 4 - a liquid crystal display element 3 color filters. The component is selected from the group consisting of a phosphorus-based oxidation preventing agent and at least one of them or a phenolic oxidation preventing agent. Its characteristics are in the scope of patent application 〇 -62- 200931179 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple Description: None 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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