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TW200949437A - Radiation-sensitive composition for forming coloring layer, color filter and color liquid crystal display element - Google Patents

Radiation-sensitive composition for forming coloring layer, color filter and color liquid crystal display element Download PDF

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Publication number
TW200949437A
TW200949437A TW098108117A TW98108117A TW200949437A TW 200949437 A TW200949437 A TW 200949437A TW 098108117 A TW098108117 A TW 098108117A TW 98108117 A TW98108117 A TW 98108117A TW 200949437 A TW200949437 A TW 200949437A
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weight
pigment
compound
composition
radiation
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TW098108117A
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Chinese (zh)
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TWI493281B (en
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Yoshitaka Yamada
Fumiko Yonezawa
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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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention provides a radiation-sensitive composition for forming coloring layer which is capable of forming a suitable foward-taper shape and a pixel having excellent residual-film rate and adherence even under low exposure amount. A radiation-sensitive composition for forming coloring layer is characterized by comprising (A) colorant, (B) alkali-soluble resin, (C) multi-functional monomer and (D) photo-polymerization initiator, in which the composition contains 100 to 300 weight parts of a compound having a caprolactone structure and two or more polymeric unsaturated bond as (C) multi-functional monomer relative to 100 weight parts of (B) alkali-soluble resin.

Description

200949437 六、發明說明： 【發明所靥之技術領域】 本發明係有關於一種著色層形成用感放射線性組成 物、彩色濾光片及彩色液晶顯示元件，更詳言之，係有關 於一種能夠在透射型或反射型的彩色液晶顯示裝置、彩色 攝像管元件等所使用的彩色濾光片形成有用的著色層所使 用的感放射線性組成物、具有由該感放射線性組成物所形 成的著色層之彩色濾光片及具備該彩色濾光片之彩色液晶 〇 顯示元件。 【先前技術】 使用著色感放射線性組成物來形成彩色濾光片之方 法，已知有藉由在基板上或預先形成有需要圖案的遮光層 之基板上，形成著色感放射性組成物的塗膜，並透過具有 規定圖案的光罩照射放射線（以下，稱爲「曝光」）’顯像 且溶解除去未曝光部，隨後進行後烘烤來得到各色的像素 〇 之方法（例如，參照專利文獻1及2)。 而且，近年來，在彩色濾光片的技術領域’降低曝光 量並縮短產出時間成爲主流’而且爲了因應對彩色液晶顯 示元件要求高色純度化，在著色感放射性組成物中所佔有 的顏料之含有比率有逐漸提高的傾向。如此’在著色感放 射性組成物中所佔有的顔料之含有比率提高之同時’若形 成像素圖案時之曝光量降低時’像素圖案的剖面形狀有變 爲逆錐（突出；overhang)之傾向。結果’在像素圖案上所形 成的ITO等透明電極斷線之問題顯在化。 200949437 針對圖案形狀的剖面形狀成爲逆錐的問題，例如，專 利文獻3、4提案揭示使用含有鏈轉移劑之組成物。但是此 種手法時，若曝光量變低時形成殘膜率或黏附性充分的像 素圖案係困難的。又，即便剖面形狀爲順錐，若該錐角太 平緩時，像素圖案的傾斜部分變長，致使在像素的邊緣產 生膜厚度變薄的部分，亦會引起無法再現需要的色彩之不 良。 ^ 而且，在彩色濾光片的量產過程，在各式各樣的製程 〇 所產生的異物或顏色不均等使檢查製程遲滞並使生產效率 低落的問題亦會顯在化。 [先前技術文獻] [專利文獻1]特開平2-144502號公報 [專利文獻2]特開平3 -5 3 20 1號公報 [專利文獻3]特開平2002- 1 67404號公報 [專利文獻4]特開平2002-2873 3 7號公報 〇 【發明內容】 [發明所欲解決之課題] 本發明係基於以上的情形而進行，其課題係提供一種 即便低曝光量亦能夠形成適當的順錐形狀且殘膜率或黏附 性都優良的像素之新穎的著色層形成用感放射線性組成 物。 而且，本發明的目的係提供一種具備由該著色層形成 用感放射線性組成物所形成的像素之彩色濾光片，及具備 該彩色濾光片之彩色液晶顯示元件。 200949437 [解決課題之手段] 鑒於此種情形，本發明者等進行專心硏究時，發現特 定量含有在分子內具有己內酯結構及2個以上的聚合性不 飽鍵之化合物作爲多官能性單體之著色層形成用感放射線 性組成物能夠解決上述課題，而完成了本發明。 亦即，本發明係一種著色層形成用感放射線性組成 物，其特徵係含有（A)著色劑、（B)鹼可溶性聚合物、（C)多 ^ 官能性單體及（D)光聚合引發劑之著色層形成用感放射線 性組成物，其中相對於100重量份（B)鹼可溶性聚合物，含 有100〜300重量份在分子內具有己內酯結構及2個以上的 聚合性不飽鍵之化合物作爲（C)多官能性單體。 又，本發明係提供一種具備使用該感放射線性組成物 所形成的像素，及具備該彩色濾光片之彩色液晶顯示元件。 [發明之效果] 依照本發明的感放射線性組成物’能夠降低曝光量 〇並縮短產出時間，而且即便在著色感放射性組成物中所 佔有的顏料之含有比率有變高，亦能夠形成適當的順錐 狀且殘膜率或黏附性都優良的像素圖案。而且依本發明 的感放射線性組成物’能夠以高生產效率來製造彩色濾 光片。 因此，本發明的感放射線性組成物非常適合使用於製 造在電子工業領域爲首之彩色液晶顯示元件用彩色濾光 片、彩色攝像管元件、彩色傳感器等各種用途的彩色濾光 片。 200949437 【實施方式】 [實施發明之最佳形態] 著色層形成用感放射線性組成物 本發明的著色層形成用感放射線性組成物（以下，會有 簡稱爲「感放射線性組成物」之情形）之「著色層」係意味 著使用於彩色濾光片之由像素及/或黑色矩陣所構成的層。 以下，說明本發明的著色層形成用感放射線性組成物 ^ 之構成成分。 -(A)著色劑- 本發明之（A)著色劑沒有特別限定，可以是有機顏料、 無機顏料之任一者。 有機顏料可舉出的有例如在色指數（C.I.;染色師及著 色師學會（The Society of Dyers and Colourists)公司發行） 分類爲顏料的化合物，具體上，可以舉出的有附加下述的 色指數（C.I.)號碼者。但是，本發明未限定於此等。 〇 C.I.顔料黃12、C.I.顏料黃13、C.I.顏料黃14、C.I. 顏料黃17、C.I.顔料黃20、C.I.顏料黃24、C.I.顏料黃31、 C.I.顏料黃55、C.I.顏料黃83、C.I.顏料黃93、C.I·顏料黃 109、C.I.顏料黃 ll〇、C.I_ 顏料黃 138、C.I.顏料黃 139、 C.I.顏料黃150、C.I.顏料黃153、C.I.顏料黃154、C.I.顔 料黃155、C.I.顏料黃166、C.I.顔料黃168、C.I.顏料黃211; C.I.顏料橙5、C.I·顏料橙13、C.I.顏料橙14、C.I.顏 料橙24、C.I.顔料橙34、C.I.顔料橙36、C.I.顏料橙38、 C.I.顔料橙40' C.I.顔料橙43、C.I.顏料橙46、C.I.顏料橙 200949437 49、C.I·顏料橙 61、C.I.顏料橙 64、C.I.顔料橙 68、C.I. 顏料橙70、C.I.顏料橙71、C.I·顔料橙72、C.I.顏料橙73、 C.I.顏料橙74 ; C.I.顔料紅1、C.I.顏料紅2、C.I.顏料紅5、C.I.顏料 紅17、C.I.顏料紅31、C.I.顏料紅32、C.I.顏料紅41、C.I· 顏料紅122、C.I.顔料紅123、C.I.顏料紅144、C.I·顏料紅 149、C.I.顏料紅 166、C.I.顏料紅 168、C.I.顏料紅 170、 ◎ C_I.顔料紅171、C.I·顔料紅175、C.I.顏料紅176、C.I·顔 料紅177、〇.1.顔料紅178、<：丄顏料紅179、（：.1.顏料紅180、 C.I·顏料紅185、C.I.顏料紅187、C.I.顏料紅202、C.I.顏 料紅206、（：.1.顏料紅207、（：.1.顏料紅209、（：.1.顏料紅214、 C.I.顏料紅22〇、C.I_顏料紅221、C.I.顔料紅224、C.I.顏 料紅242、（：.1.顏料紅243、（：.1.顔料紅254、（：.1.顏料紅25 5、 C.I.顏料紅262、C.I.顏料紅264、C.I.顔料紅272; C·!·顏料紫1、C_I·顔料紫19、C.I.顏料紫23、C.I.顏 Ο 料紫29、C_I·顏料紫32、C.I·顔料紫36、C.I.顏料紫38 ; C.I.顔料藍15、C.I.顔料藍15: 3、C.I.顏料藍15: 4、 C.I·顏料藍15: 6、C.I·顏料藍60、C.I.顏料藍80; C.I_顏料綠7、C.I.顔料綠36、C.I.顏料綠58; C.I_顔料棕23、C.I·顔料棕25 ; C.I.顔料黑i、c·〗.顏料黑7。 在本發明，有機顏料亦能夠藉由再結晶法、再沈澱法、 溶劑洗淨法、昇華法、真空加熱法或該等的組合來精製。 又’上述無機顔料可舉出例如氧化鈦、硫酸鋇、碳酸 200949437 鈣、鋅白、硫酸鉛、黃色鉛、鋅黃、氧化鐵紅（紅色氧化鐵 (III))、鎘紅、群青、紺青、氧化鉻綠、鈷綠、琥珀、鈦黑、 合成鐵黑、及碳黑等。 該等著色劑亦可按照需要，使用聚合物將其粒子表面 改性而使用。將顏料的粒子表面改性之聚合物可舉出例如 特開平8-25987 6號公報所記載之聚合物、或市售的各種顏 料分散用之聚合物或低聚物等。碳黑表面之被覆聚合物的 0 方法係例如特開平9-7 1 73 3號公報、特開平9-9 5 62 5號公 報、特開平9-124969號公報等所揭示。 前述著色劑可單獨或組合使用2種以上。 將本發明的感放射線性組成物使用於形成像素時，因 爲像素被要求高精細的發色及耐熱性，所以（A)著色劑係以 發色性高且耐熱性高的著色劑、特別是耐熱分解性高的著 色劑爲佳，具體上以有機著色劑爲佳，以使用有機顏料爲 特佳。 〇 另一方面，將本發明的感放射線性組成物使用於形成 黑色矩陣時，因爲黑色矩陣被要求遮光性，所以（A)著色劑 以使用有機顏料或碳黑爲佳。 本發明的感放射線性組成物之著色劑的含量係即便在 感放射線性組成物的總固體成分中爲3 0重量％以上時’亦 能夠形成適當的順錐狀且殘膜率或黏附性都優良的像素。 又，在本發明，從確保顯像性的觀點，著色劑的含量係在 感放射線性組成物的總固體成分中，以7〇重量％以下爲 佳，以6 0重量％以下爲特佳。在此，固體成分係後述溶劑 200949437 以外的成分。 在本發明之著色劑能夠按照需要與分散劑、分散助劑 一同使用。 上述分散劑可使用例如陽離子系、陰離子系、非離子 系或兩性等適當的分散劑，以聚合物分散劑爲佳。具體上， 可舉出改性丙烯酸系共聚物、丙烯酸系共聚物、聚胺基甲 酸酯、聚酯、高分子共聚物的烷基銨鹽或磷酸酯鹽、陽離 0 子性梳子型接枝聚合物等。在此，陽離子性梳子型接枝聚 合物係意指在具有複數個鹼性基（陽離子性的官能基）之幹 聚合物1分子，接枝鍵結2分子以上的分枝聚合物而成的 結構之聚合物，例如幹聚合物部可舉出聚伸乙亞胺、分枝 聚合物可舉出由ε -己內酯的開環聚合物所構成之聚合 物。該等分散劑之中，以改性丙烯酸系共聚物、聚胺基甲 酸酯、陽離子性梳子型接枝聚合物爲佳。 此種分散劑能夠商業性地取得，例如改性丙烯酸系共 〇 聚物可舉出 Disperbyk-2000 、 D i s p e r b y k - 2 0 0 1 BYK-LPN6919、BYK-LPN21116(以上爲 BYK-Chemie(BYK) 公司製），聚胺基甲酸酯可舉出 Disperbyk-161、 Disperbyk-162 、 Disperbyk-165 、 Disperbyk-167 、 D i s p e rb y k-1 7 0、D i s p e r b y k -1 8 2 (以上爲 BYK-Chemie(BYK) 公司製），SOLSPERSE765 00(LUBRIZOL(股）製）、陽離子性 梳子型接枝聚合物可舉出SOLSPERSE24000(LUBRIZOL(股） 製）、AJISPER PB821 、 AJISPER PB 822(Aj inomoto -Fine-Techno(股）製）等。 -10- 200949437 該等分散劑可單獨或混合使用2種以上。就使顯像性 等良好而言，分散劑的含量係相對於100重量份（A)著色 劑，通常爲100重量份以下’以0.5〜100重量份爲佳，以 1〜70重量份爲更佳，以10〜50重量份爲特佳。 上述分散助劑可舉出例如藍色顏料衍生物、黃色顏料 衍生物等，具體上，可舉出例如銅酞菁衍生物等。 -(B)鹼可溶性樹脂- 在本發明的感放射線性組成物所有的（B)鹼可溶性樹 脂，若是對在形成著色層時之顯像處理製程所使用的鹼性 顯像液具有可溶性時沒有特別限定，通常係具有羧基、酚 性羥基等的酸性官能基之聚合物。其中以含有具有羧基之 聚合物者爲佳，以具有1個以上的羧基之乙烯性不飽和單 體（以下，稱爲「含羧基的不飽和單體」與其他能夠共聚合 的乙烯性不飽和單體（以下，稱爲「共聚合性不飽和單體」） 之共聚物（以下，稱爲「含羧基的共聚物」）爲特佳。又， Ο 在本說明書，（甲基）丙烯酸係表示甲基丙烯酸或丙烯酸。 含羧基的不飽和單體可舉出例如 如（甲基）丙烯酸、巴豆酸、0：-氯丙烯酸、桂皮酸之不 飽和一元羧酸； 順丁烯二酸、順丁烯二酸酐、反丁烯二酸、伊康酸、 伊康酸酐、檸康酸、檸康酸酐、中康酸之不飽和二元羧酸 或其酐； 如琥珀酸一 [2-(甲基）丙烯醯氧基乙基]酯、酞酸一 [2-(甲基）丙烯醯氧基乙基]酯之二元以上的多元羧酸的一 -11- 200949437 [(甲基）丙烯醯氧基烷基]酯； 如ω-羧基聚己內酯一（甲基）丙烯酸酯之在兩末端具有 羧基及羥基之聚合物的一（甲基）丙烯酸酯。 在本發明，含羧基的不飽和單體以（甲基）丙烯酸、琥 珀酸一 [2-(甲基）丙烯醯氧基乙基]酯、ω-羧基聚己內酯一 (甲基）丙烯酸酯等爲佳，以（甲基）丙烯酸爲特佳。 該等含羧基的不飽和單體可單獨或混合使用 2種以 〇上° 又，共聚合性不飽和單體可舉出例如 Ν-苯基順丁烯二醯亞胺、Ν·鄰羥苯基順丁烯二醯亞 胺、Ν-間羥苯基順丁烯二醯亞胺、Ν-對羥苯基順丁烯二醯 亞胺、Ν-苄基順丁烯二醯亞胺、Ν-環己基順丁烯二醯亞胺、 Ν-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、Ν-琥珀醯亞 胺基-4順丁烯二醯亞胺丁酸酯、Ν -琥珀醯亞胺基-6-順丁烯 二醯亞胺己酸酯、Ν-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸 Ο 酯、Ν-(吖啶基）順丁烯二醯亞胺之Ν -位置取代順丁烯二醯 亞胺； 如苯乙烯、〇：-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基 甲苯、對乙烯基甲苯、對氯苯乙烯、鄰甲氧基苯乙烯、間 甲氧基苯乙嫌、對甲氧基苯乙嫌、鄰乙烯苯酚、間乙嫌苯 酚、對乙烯苯酚、對羥基-α-甲基苯乙烯、鄰乙烯基苄基甲 基醚、間乙烯基苄基甲基醚、對乙烯基节基甲基醚、鄰乙 烯基苄基環氧丙基醚、間乙烯基苄基環氧丙基醚、對乙烯 基苄基環氧丙基醚之芳香族乙烯化合物； -12- 200949437 如茚、1 -甲基茚之茚類； 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）丙嫌酸2 -乙基己醋、（甲基）丙嫌酸2 -徑 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 0 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-甲氧基乙酯、（甲基）丙烯酸2-苯氧基乙酯、 甲氧基二甘醇（甲基）丙烯酸酯、甲氧基三甘醇（甲基）丙烯酸 酯、甲氧基丙二醇（甲基）丙烯酸酯、甲氧基二伸丙二醇（甲 基）丙烯酸酯、（甲基）丙烯酸異莰酯、三環[5.2.1.02’6]癸烷 -8-基（甲基）丙烯酸酯、（甲基）丙烯酸2-羥基-3-苯氧基丙 酯、甘油一（甲基）丙烯酸酯、（甲基）丙烯酸4-羥基苯酯、對 〇異丙苯基苯酚之環氧乙烷改性（甲基）丙烯酸酯之不飽和羧 酸酯； 如（甲基）丙烯酸環氧丙酯之不飽和羧酸環氧丙酯； 如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙 烯酯之羧酸乙烯酯； 如乙烯基甲基醚、乙烯基乙基醚、烯丙基環氧丙基醚 之其他的不飽和醚； 如（甲基）丙烯腈、α-氯丙烯腈、氰化亞乙烯基之氰化 乙烯系化合物； -13- 200949437 如（甲基）丙烯醯胺、α-氯丙烯醯胺、N-2-羥乙基（甲基） 丙烯醯胺之不飽和醯胺； 如1,3-丁二烯、異戊二烯、氯丁二烯之脂肪族共轭二 烯； 如聚苯乙烯、聚（甲基）丙烯酸甲酯、聚（甲基）丙烯酸正 丁酯、聚矽氧烷之在聚合物分子鏈的末端具有一（甲基）丙 烯醯基之大分子單體等。 0 該等共聚合性不飽和單體可單獨或混合使用2種以 上。 在本發明，共聚合性不飽和單體係以含有選自由N-位 置取代的順丁烯二醯亞胺、芳香族乙烯系化合物、不飽和 羧酸酯及在聚合物分子鏈的末端具有一（甲基）丙烯醯基之 大分子單體所組成群組之至少1種者爲佳，以含有選自N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、苯乙烯、 α-甲基苯乙烯、對羥基-α-甲基苯乙烯、（甲基）丙烯酸甲 Ο 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、丙烯酸烯丙酯、（甲基）丙烯酸苄酯、 甘油一（甲基）丙烯酸酯、（甲基）丙烯酸4-羥基苯酯、對異丙 苯基苯酚之環氧乙烷改性（甲基）丙烯酸酯、聚苯乙烯大分 子單體、聚甲基丙烯酸甲酯大分子單體所組成群組之至少 1種爲更佳，以選自由Ν-苯基順丁烯二醯亞胺、Ν_環己基 順丁嫌二醯亞胺、苯乙嫌、<2-甲基苯乙嫌、（甲基）丙嫌酸 甲酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸2-乙基己酯、（甲 基）丙烯酸苄酯、甘油一（甲基）丙烯酸酯、及對異丙苯基苯 -14- 200949437 酚之環氧乙烷改性（甲基）丙烯酸酯所組成群組之至少1種 爲特佳。 在本發明，例如藉由使（甲基）丙烯酸2-羥基乙酯等具 有羥基的共聚合性不飽和單體共聚合而成的丙烯酸可溶性 樹脂，與2-(甲基）丙烯醯氧基乙基異氰酸酯等的不飽和異 氰酸酯化合物反應，能夠在丙烯酸可溶性樹脂的側鏈導入 聚合性不飽和鍵。 π 在含羧基的共聚物，含羧基的不飽和單體之共聚合比 〇 率，以5〜50重量％爲佳，以10〜40重量％爲更佳。該共 聚合比率太少時，所得到感放射線性組成物對鹼性顯像液 的溶解度會有低落的傾向，另一方面，太多時對鹼性顯像 液的溶解度變爲太大，在使用鹼性顯像液進行顯像時，會 有容易造成像素從基板脫落或像素表面容易膜粗糙之傾 向。 在本發明之鹼可溶性樹脂之使用凝膠滲透色譜儀 〇 (GPC、溶出溶劑：四氫呋喃））所測定換算成聚苯乙烯的重 量平均分子量（以下，亦稱爲「Mw」），係通常爲1，000〜 45,000 >以3,000〜20,000爲佳。Mw太小時，所得到被膜 的殘膜率等會降低、或是圖案形狀、耐熱性等會受到損害， 又，會有電特性變差之可能性，另一方面，Mw太大時，解 像度降低、或圖案形狀受到損害，又，使用狹縫噴嘴方式 塗布時會有容易產生乾燥異物之傾向》 又，本發明之鹼可溶性樹脂之使用凝膠滲透色譜儀 (GPC、溶出溶劑：四氫呋喃）所測定換算成聚苯乙烯的數量 -15- 200949437 平均分子量（以下’亦稱爲「Μη」），係通常爲1，〇〇〇〜 45,000，以 3,000 〜20,000 爲佳。 又，在本發明之鹼可溶性樹脂之Mw與Μη的比（Mw/ Μη)以1.0〜5.0爲佳，以1.0〜4.0爲更佳。 在本發明之鹼可溶性樹脂能夠使用眾所周知的方法製 造，例如藉由特開2003-222717號公報、特開2006-259680 號公報、國際公開第07/029871號小冊子等所揭示之方法， φ 亦能夠控制其結構或Mw、Mw/ Μη。 在本發明，鹼可溶性樹脂可單獨或混合使用2種以上。 在本發明，（Β)鹼可溶性樹脂的含量係相對於（Α)著色 劑100質量份，通常以10〜1，000質量份爲佳，以20〜500 質量份爲特佳。鹼可溶性樹脂的含量太少時，會有例如鹸 顯像性低落，或是在未曝光部的基板上或遮光層上產生殘 渣或表面污染之可能性。相對地，太多時，因爲相對地著 色劑濃度降低，會有難以達成薄膜的目標色濃度之可能性。 〇 -(C)多官能性單體- 在本發明之多官能性單體係由具有2個以上的聚合性 不飽鍵之單體所構成，且相對於（Β)鹼可溶性樹脂1〇〇重量 份，含有100〜300重量份在分子內具有己內酯結構及2個 以上的聚合性不飽鍵之化合物（以下，會有稱爲「含己內酯 結構的多官能性單體」之情形），以含有100〜250重量份 者爲佳。己內酯改性多官能性單體的含量小於100重量份 時，會有損害希望效果之可能性，另一方面，大於300重 量份時，會有對基板的黏附性低落之可能性。 -16- 200949437 含己內酯結構的多官能性單體係例如藉由將三經甲基 乙烷、二·三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙 烷、新戊四醇、二新戊四醇、三新戊四醇、甘油、雙甘油、 三羥甲基三聚氰胺等的多元醇、與（甲基）丙烯酸及ε -己內 酯酯化而得到。可舉出含ε-己內酯結構的多官能（甲基）丙 烯酸酯。其中，從即便低曝光量亦能夠形成適當的順錐狀 的像素之觀點，以下述式（1)所示之含e -己內酯結構的多官 _ 能性單體爲佳。200949437 VI. Description of the Invention: [Technical Field] The present invention relates to a radiation sensitive composition for forming a coloring layer, a color filter, and a color liquid crystal display element. More specifically, it relates to a A color filter used in a transmissive or reflective type color liquid crystal display device, a color image sensor element, or the like forms a radiation sensitive composition for use in a useful coloring layer, and has a coloring formed by the radiation sensitive composition. A color filter of a layer and a color liquid crystal display device having the color filter. [Prior Art] A method of forming a color filter using a coloring sensitizing radiation composition is known, and a coating film of a color sensitizing radioactive composition is formed on a substrate or a substrate on which a light shielding layer requiring a pattern is formed in advance. And a method of irradiating radiation (hereinafter referred to as "exposure") to develop a light through a mask having a predetermined pattern and dissolving and removing the unexposed portion, followed by post-baking to obtain pixel defects of respective colors (for example, refer to Patent Document 1) And 2). In addition, in recent years, in the technical field of color filters, 'reducing the amount of exposure and shortening the production time has become the mainstream', and in order to cope with the high color purity required for color liquid crystal display elements, the pigments in the coloring sensitizing radioactive composition are occupied. The content ratio tends to increase gradually. When the content ratio of the pigment occupied by the coloring radiation-receiving composition is increased, and the amount of exposure when the pixel pattern is formed is lowered, the cross-sectional shape of the pixel pattern tends to become a reverse cone (overhang). As a result, the problem that the transparent electrode such as ITO formed on the pixel pattern is broken is conspicuous. 200949437 The cross-sectional shape of the pattern shape becomes a problem of the inverse cone. For example, Patent Document 3 and 4 propose the use of a composition containing a chain transfer agent. However, in such a technique, it is difficult to form a pixel pattern having a sufficient residual film ratio or adhesion when the amount of exposure is lowered. Further, even if the cross-sectional shape is a straight cone, if the taper angle is too gentle, the inclined portion of the pixel pattern becomes long, so that a portion where the film thickness is thinned at the edge of the pixel causes a defect in which the desired color cannot be reproduced. ^ Moreover, in the mass production process of color filters, the foreign matter or color unevenness generated in various processes 使 makes the inspection process sluggish and the production efficiency is low. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide an appropriate tapered shape even at a low exposure amount. A novel coloring layer of a pixel having excellent residual film ratio or adhesion is formed with a radiation sensitive composition. Further, an object of the present invention is to provide a color filter including a pixel formed of the radiation-sensitive composition for forming a colored layer, and a color liquid crystal display element including the color filter. 200949437 [Means for Solving the Problem] In view of such a situation, the present inventors have found that a specific amount contains a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in a molecule as a polyfunctional property. The present invention has been accomplished by solving the above problems with a radiation sensitive linear composition for forming a color layer of a single body. That is, the present invention is a radiation sensitive composition for forming a coloring layer, which comprises (A) a coloring agent, (B) an alkali-soluble polymer, (C) a polyfunctional monomer, and (D) photopolymerization. a radiation-sensitive composition for coloring layer formation of an initiator, wherein 100 to 300 parts by weight of a base having a caprolactone structure and two or more polymerizable unsaturated states per 100 parts by weight of the (B) alkali-soluble polymer The compound of the bond is used as the (C) polyfunctional monomer. Moreover, the present invention provides a pixel including the pixel formed using the radiation sensitive composition and a color liquid crystal display element including the color filter. [Effects of the Invention] The radiation sensitive composition of the present invention can reduce the exposure amount 〇 and shorten the production time, and can form an appropriate amount even if the content ratio of the pigment occupied by the coloring sensitizing radioactive composition becomes high. A pixel pattern that is tapered and has excellent residual film rate or adhesion. Further, the radiation sensitive composition according to the present invention can manufacture a color filter with high production efficiency. Therefore, the radiation sensitive composition of the present invention is very suitable for use in color filters for various applications such as color filters for color liquid crystal display elements, color image sensor elements, and color sensors, which are used in the electronics industry. [Brief Description of the Invention] [Best Mode for Carrying Out the Invention] The radiation sensitive composition for forming a colored layer is a radiation sensitive composition for forming a colored layer of the present invention (hereinafter, abbreviated as "radiosensitive linear composition") The "colored layer" means a layer composed of a pixel and/or a black matrix for use in a color filter. Hereinafter, the constituent components of the radiation sensitive composition for coloring layer formation of the present invention will be described. - (A) Colorant - The coloring agent (A) of the present invention is not particularly limited, and may be any of an organic pigment and an inorganic pigment. The organic pigment may, for example, be a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), and specifically, the following color may be mentioned. Index (CI) number. However, the present invention is not limited to this. 〇CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93 , CI·Pig Yellow 109, CI Pigment Yellow ll〇, C.I_ Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 211; CI Pigment Orange 5, CI·Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40 'CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 200949437 49, CI·Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI·Pig Orange 72, CI Pigment orange 73, CI pigment orange 74; CI pigment red 1, CI pigment red 2, CI pigment red 5, CI pigment red 17, CI pigment red 31, CI pigment red 32, CI pigment red 41, CI · pigment red 122, CI Pigment Red 123, CI Pigment Red 144, CI·Pigment Red 149, CI Pigment Red 166, CI Pigment 168, CI Pigment Red 170, ◎ C_I. Pigment Red 171, CI·Pigment Red 175, CI Pigment Red 176, CI·Pigment Red 177, 〇.1. Pigment Red 178, <: 丄 Pigment Red 179, (:. 1. Pigment Red 180, CI·Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, (:.1. Pigment Red 207, (:.1. Pigment Red 209, (:.1. Pigment Red 214, CI Pigment Red 22〇, C.I_Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, (:.1. Pigment Red 243, (:.1. Pigment Red 254, (:.1) .Pigment Red 25 5, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; C·!·Pigment Violet 1, C_I·Pigment Violet 19, CI Pigment Violet 23, CI YanΟ Violet 29, C_I·Pigment Violet 32, CI·Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI·Pigment Blue 15: 6, CI·Pigment Blue 60, CI Pigment Blue 80; C.I_Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58; C.I_Pigment Brown 23, CI·Pigment Brown 25; CI Pigment Black i, c·〗. Pigment Black 7. In the present invention, the organic pigment can also be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the above inorganic pigment may, for example, be titanium oxide, barium sulfate, carbonic acid 200949437 calcium, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine blue, indigo, Chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. These colorants may also be used by modifying the surface of the particles using a polymer as needed. For example, a polymer described in JP-A-8-25987 6 or a commercially available polymer or oligomer for dispersing various pigments can be used. The method of coating the polymer on the surface of the carbon black is disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei 9-7 1 73 No., No. Hei 9-9 5-6, No. 9-124969, and the like. These coloring agents can be used alone or in combination of two or more. When the radiation sensitive composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and heat resistance, the colorant (A) is a coloring agent having high color developability and high heat resistance, particularly A coloring agent having high heat decomposition resistance is preferred, and an organic coloring agent is particularly preferred, and an organic pigment is particularly preferred. On the other hand, when the radiation sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light blocking properties, the coloring agent (A) is preferably an organic pigment or carbon black. The content of the coloring agent of the radiation sensitive composition of the present invention is such that even when it is 30% by weight or more based on the total solid content of the radiation sensitive composition, it can form an appropriate smooth shape and residual film ratio or adhesion. Excellent pixel. Further, in the present invention, the content of the coloring agent is preferably 7 7% by weight or less, and particularly preferably 60% by weight or less, from the viewpoint of ensuring the developing property, in the total solid content of the radiation sensitive composition. Here, the solid content is a component other than the solvent 200949437 described later. The coloring agent of the present invention can be used together with a dispersing agent and a dispersing aid as needed. As the dispersant, for example, a suitable dispersant such as a cationic system, an anionic system, a nonionic surfactant or an amphoteric acid can be used, and a polymer dispersant is preferred. Specific examples thereof include an alkyl amide salt or a phosphate salt of a modified acrylic copolymer, an acrylic copolymer, a polyurethane, a polyester, or a polymer copolymer, and an cation-free comb type. Branch polymers, etc. Here, the cationic comb-type graft polymer means a molecule of a dry polymer having a plurality of basic groups (cationic functional groups) and grafting a branched polymer of 2 or more molecules. The polymer of the structure, for example, the dry polymer portion may be a polyamidene, and the branched polymer may be a polymer composed of a ring-opening polymer of ε-caprolactone. Among these dispersants, a modified acrylic copolymer, a polyurethane, and a cationic comb-type graft polymer are preferred. Such dispersants can be obtained commercially, for example, modified acrylic conjugated polymers include Disperbyk-2000, D isperbyk - 2 0 0 1 BYK-LPN6919, BYK-LPN 21116 (above BYK-Chemie (BYK)) ,), the polyurethane can be exemplified by Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, D ispe rb y k-1 7 0, D isperbyk -1 8 2 (above BYK-Chemie) (BYK) company, SOLSPERSE765 00 (manufactured by LUBRIZOL Co., Ltd.), and cationic comb type graft polymer, SOLSPERSE 24000 (manufactured by LUBRIZOL Co., Ltd.), AJISPER PB821, AJISPER PB 822 (Aj inomoto - Fine-Techno) (share) system, etc. -10-200949437 These dispersants may be used alone or in combination of two or more. The content of the dispersant is preferably 100 parts by weight or less with respect to 100 parts by weight of the (A) coloring agent, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight. Preferably, it is particularly preferably 10 to 50 parts by weight. The dispersing aid may, for example, be a blue pigment derivative or a yellow pigment derivative, and specific examples thereof include a copper phthalocyanine derivative. - (B) Alkali-soluble resin - All of the (B) alkali-soluble resin in the radiation-sensitive composition of the present invention is soluble in the alkaline developing solution used in the development process for forming the colored layer. In particular, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, those having a polymer having a carboxyl group are preferred, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomer" and other copolymerizable ethylenically unsaturated monomers. A copolymer of a monomer (hereinafter referred to as "copolymerizable unsaturated monomer") (hereinafter referred to as "carboxyl group-containing copolymer") is particularly preferable. Further, in the present specification, (meth)acrylic acid is used. It means methacrylic acid or acrylic acid. The carboxyl group-containing unsaturated monomer may, for example, be an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, 0:-chloroacrylic acid or cinnamic acid; maleic acid, cis Butenoic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid unsaturated dicarboxylic acid or anhydride thereof; such as succinic acid-[2-(A 1--11-200949437 [(meth)acryloyl hydrazide of a divalent or higher polycarboxylic acid of a propylene methoxyethyl ester, a [2-(methyl) propylene methoxyethyl] phthalate An oxyalkyl] ester; such as ω-carboxypolycaprolactone-(meth) acrylate having a carboxy group at both ends And a (meth) acrylate of a polymer of a hydroxyl group. In the present invention, the carboxyl group-containing unsaturated monomer is (meth)acrylic acid, succinic acid-[2-(methyl)acryloxyethyl ester] Ω-carboxypolycaprolactone-(meth)acrylate, etc., preferably (meth)acrylic acid. The carboxyl group-containing unsaturated monomers may be used singly or in combination. The copolymerizable unsaturated monomer may, for example, be fluorene-phenyl maleimide, fluorene o-hydroxyphenyl maleimide, hydrazine-m-hydroxyphenyl-butylene Amine, Ν-p-hydroxyphenyl maleimide, Ν-benzyl maleimide, Ν-cyclohexyl maleimide, Ν-amber quinone imine-3- Maleimide benzoate, hydrazine-succinimide-4-butyleneimine butyrate, hydrazine-succinimide-6-m-butyleneimine酸酯, Ν-amber quinone imino-3-butyl succinimide propionate oxime ester, Ν-(acridinyl) maleimide hydrazine - position-substituted maleic acid Amine; such as styrene, hydrazine: -methylstyrene, o-vinyl , m-vinyl toluene, p-vinyl toluene, p-chlorostyrene, o-methoxy styrene, m-methoxy phenyl b, p-methoxy phenyl b, o-ethylene phenol, m-ethyl phenol, ethylene Phenol, p-hydroxy-α-methylstyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl epoxy propyl ether, An aromatic vinyl compound of m-vinylbenzylepoxypropyl ether, p-vinylbenzylepoxypropyl ether; -12- 200949437 such as hydrazine, 1-methyl hydrazine; such as (meth) acrylate Ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Second butyl acrylate, tert-butyl (meth) acrylate, 2-methyl hexanoic acid (methyl) propylene, 2-methyl acrylate (methyl) acrylate, (meth) acrylate 2 -hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyrate (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, (methyl) ) 2-methoxyethyl acrylate, 2-phenoxyethyl (meth) acrylate, methoxy diglycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, A Oxypropanediol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, isodecyl (meth) acrylate, tricyclo [5.2.1.0''6] decane-8-yl (methyl Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ring of p-cumylphenol An oxyethylene modified (meth) acrylate unsaturated carboxylic acid ester; an unsaturated carboxylic acid glycidyl ester such as glycidyl (meth) acrylate; such as vinyl acetate, vinyl propionate, butyric acid a vinyl carboxylate or a vinyl carboxylate of vinyl benzoate; such as vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether a non-saturated ether; such as (meth)acrylonitrile, α-chloroacrylonitrile, vinyl cyanide vinyl cyanide compound; -13- 200949437 such as (meth) acrylamide, α-chloropropene oxime An amine, an unsaturated decyl amine of N-2-hydroxyethyl (meth) acrylamide; an aliphatic conjugated diene such as 1,3-butadiene, isoprene or chloroprene; A macromonomer having a (meth) acrylonitrile group at the terminal of the polymer molecular chain of styrene, poly(methyl) methacrylate, poly(meth) acrylate, or polyoxyalkylene. 0 These copolymerizable unsaturated monomers may be used alone or in combination of two or more. In the present invention, the copolymerizable unsaturated single system contains a maleimide group selected from the N-position, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and one at the end of the polymer molecular chain. It is preferred that at least one of the group consisting of (meth)acryloyl group-based macromonomers is selected to contain N-phenyl maleimide, N-cyclohexyl-n-butylene Amine, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl methacrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, 2-hydroxyethyl (meth)acrylate, allyl acrylate, benzyl (meth)acrylate, mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, p-cumene At least one of the group consisting of ethylene oxide-modified (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer of phenol is more preferably selected from the group consisting of ruthenium -Phenyl-p-butyleneimine, Ν_cyclohexyl cis-butane diimide, benzene, susceptibility, <2-methylbenzene Base) methyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, mono(meth) acrylate, and isopropyl Phenylbenzene-14-200949437 At least one of the groups consisting of oxirane-modified (meth) acrylates is particularly preferred. In the present invention, for example, an acrylic acid-soluble resin obtained by copolymerizing a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and 2-(meth)acryloyloxy group B By reacting an unsaturated isocyanate compound such as a isocyanate, a polymerizable unsaturated bond can be introduced into a side chain of the acrylic acid-soluble resin. The copolymerization ratio of π in the carboxyl group-containing copolymer and the carboxyl group-containing unsaturated monomer is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the copolymerization ratio is too small, the solubility of the radiation-sensitive composition obtained in the alkaline developing solution tends to be low. On the other hand, when too much, the solubility of the alkaline developing solution becomes too large. When the image is developed using an alkaline developing solution, there is a tendency that the pixel is easily detached from the substrate or the surface of the pixel is easily roughened. The weight average molecular weight (hereinafter, also referred to as "Mw") converted to polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin of the present invention is usually 1 , 000~ 45,000 > preferably 3,000~20,000. When the Mw is too small, the residual film ratio of the obtained film may be lowered, or the pattern shape, heat resistance, and the like may be impaired, and electrical characteristics may be deteriorated. On the other hand, when Mw is too large, the resolution is lowered. Or the shape of the pattern is impaired, and the tendency to dry foreign matter is likely to occur when coated by the slit nozzle method. Further, the alkali-soluble resin of the present invention is measured by a gel permeation chromatograph (GPC, elution solvent: tetrahydrofuran). The amount converted to polystyrene -15- 200949437 The average molecular weight (hereinafter referred to as "Μη") is usually 1, 〇〇〇 ~ 45,000, preferably 3,000 ~ 20,000. Further, the ratio (Mw/?) of Mw to Μη in the alkali-soluble resin of the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 4.0. The alkali-soluble resin of the present invention can be produced by a known method, for example, by the method disclosed in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, International Publication No. 07/029871, and the like. Control its structure or Mw, Mw / Μη. In the present invention, the alkali-soluble resin may be used alone or in combination of two or more. In the present invention, the content of the (base) alkali-soluble resin is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the (Α) coloring agent. When the content of the alkali-soluble resin is too small, for example, the developing property is lowered, or there is a possibility that residue or surface contamination occurs on the substrate of the unexposed portion or on the light shielding layer. In contrast, when there is too much, there is a possibility that it is difficult to achieve the target color density of the film because the relative toner concentration is lowered. 〇-(C) polyfunctional monomer - The polyfunctional single system of the present invention is composed of a monomer having two or more polymerizable unsaturated bonds, and is 1 相对 relative to the (Β) alkali soluble resin. The compound contains 100 to 300 parts by weight of a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule (hereinafter, there will be a "polyfunctional monomer having a caprolactone structure"). Case), preferably containing 100 to 250 parts by weight. When the content of the caprolactone-modified polyfunctional monomer is less than 100 parts by weight, the desired effect may be impaired. On the other hand, when it is more than 300 parts by weight, the adhesion to the substrate may be lowered. -16- 200949437 A polyfunctional single system containing a caprolactone structure, for example, by tris-methylethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, A polyol such as pentaerythritol, dipentaerythritol, tripentenol, glycerin, diglycerin or trimethylol melamine is obtained by esterification with (meth)acrylic acid and ε-caprolactone. A polyfunctional (meth) acrylate having an ε-caprolactone structure can be mentioned. Among them, a multi-functional monomer having an e-caprolactone structure represented by the following formula (1) is preferred from the viewpoint of forming a suitable smooth-shaped pixel even at a low exposure amount.

CH20——R CH2〇——RCH20——R CH2〇——R

I II I

R—T-〇CH2—-c—ch2——o——ch2—c—ch2o-RR-T-〇CH2—c—ch2——o——ch2—c—ch2o-R

I I (1)I I (1)

CH20——R CH20-R (式中’ 6個R係全部爲下述式（2)所示之基，或是6個R q 之中1〜5個係下述式（2)所示之基，剩餘係下述通式（3)所 示之基）CH20——R CH20-R (wherein all six R systems are groups represented by the following formula (2), or 1 to 5 of 6 R q are represented by the following formula (2) Base, the remainder is a group represented by the following formula (3)

CH2CH2CH2CH2CH2〇-)—C Ο R1 C=CH； (2) (式中’ Rl係表示氫原子或甲基，m係表示1或2的數目 「*」係表示懸掛鍵） -17- (3) 200949437 0 R1CH2CH2CH2CH2CH2〇-)-C Ο R1 C=CH; (2) (wherein R1 represents a hydrogen atom or a methyl group, and m represents a number of 1 or 2 "*" means a dangling bond) -17- (3) 200949437 0 R1

1 l_CH *C " 1 "C "〇»»2 (式中，R1係表示氫原子或甲基，「*」係表示懸掛鍵） 上述式（1)所示化合物之中，式（2)所示之基係以2個以 上者爲佳’以3個以上者爲更佳，以6個者爲特佳。 此種含己內酯結構的多官能性單體係例如日本化藥 (股）所市售之KAYARAD DPCA系列，可舉出DPCA-20(在 〇 上述式（1)〜（3)，m=l，式（2)所示之基的數目=2，R1係全 部爲氫原子之化合物）、DPCA-30(同式，m=l，式（2)所示之 基的數目=3，R1係全部爲氫原子之化合物）、DPCA-60(同 式，m=l，式（2)所示之基的數目=6，R1係全部爲氫原子之 化合物）、DPCA-120(同式，m = 2，式（2)所示之基的數目=6， R1係全部爲氫原子之化合物）等。 在本發明，含己內酯結構的多官能性單體可單獨或混 合使用2種以上。1 l_CH *C " 1 "C "〇»»2 (wherein R1 represents a hydrogen atom or a methyl group, and "*" represents a dangling bond) Among the compounds represented by the above formula (1), 2) The base system shown is preferably two or more. It is more preferable to use three or more, and it is particularly preferable to use six. Such a polyfunctional single system containing a caprolactone structure, for example, a KAYARAD DPCA series commercially available from Nippon Kayaku Co., Ltd., may be exemplified by DPCA-20 (in the above formula (1) to (3), m= l, the number of groups represented by formula (2) = 2, R1 is a compound in which all hydrogen atoms are), DPCA-30 (the same formula, m = 1, the number of groups represented by formula (2) = 3, R1 a compound which is all a hydrogen atom), DPCA-60 (the same formula, m = 1, the number of groups represented by the formula (2) = 6, a compound in which all of the R1 is a hydrogen atom), DPCA-120 (the same formula, m = 2, the number of groups represented by the formula (2) = 6, R1 is a compound in which all hydrogen atoms), and the like. In the present invention, the polyfunctional monomer having a caprolactone structure may be used alone or in combination of two or more.

Q w 在本發明，就提高殘膜率而言，與含己內酯結構的多 官能性單體同時，以並用其他的多官能性單體爲佳，以與 未具有己內酯結構而具有2個以上的聚合性不飽鍵之化合 物並用爲特佳。 其他的多官能性單體可舉出例如 乙二醇、丙二醇等的伸烷基二醇的二（甲基）丙烯酸酯 類； 聚乙二醇、聚丙二醇等的聚伸烷基二醇的二（甲基）丙 -18- 200949437 烯酸酯類； 甘油、三羥甲基丙烷、新戊四醇、二新戊四醇 以上的多元醇的聚（甲基）丙烯酸酯類或該等的二竣 物； 聚酯、環氧樹脂、胺基甲酸酯樹脂、醇酸樹脂 脂、螺烷樹脂等的低聚（甲基）丙烯酸酯類； 兩末端羥基聚-1,3-丁二烯、兩末端羥基聚異戊 0 兩末端羥基聚己內酯等的兩末端羥基化聚合物的= 丙烯酸酯類； 參[2-(甲基）丙烯醯氧基乙基]磷酸酯、或異三聚 氧乙烷改性三丙烯酸酯等。 該等其他的多官能性單體之中，以三元以上的 的聚（甲基）丙烯酸酯類或該等的二羧酸改性物，具 以三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基 酯、新戊四醇三丙烯酸酯、新戊四醇三甲基丙烯酸 Ο 戊四醇四丙烯酸酯、新戊四醇四甲基丙烯酸酯、二 醇五丙烯酸酯、二新戊四醇五甲基丙烯酸酯、二新 六丙烯酸酯、二新戊四醇六甲基丙烯酸酯、新戊二 烯酸酯與琥珀酸的單酯化物、新戊二醇五丙烯酸酯 酸的單酯化物、二新戊四醇五丙烯酸酯與琥珀酸的 物、二新戊四醇五甲基丙烯酸酯與琥珀酸的單酯 佳，因爲著色層的強度高、著色層的表面平滑性優 未曝光部的基板上及遮蔽層上不容易產生表面污染 等，以三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯 等三元 酸改性 、砂樹 二烯、 (甲基） 氰酸環 多元醇 體上， 丙烯酸 酯、新 新戊四 戊四醇 醇三丙 與琥珀 單酯化 化物爲 良且在 、殘膜 酸酯、 -19- 200949437 二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯、新戊二 醇三丙烯酸酯與琥珀酸的單酯化物及二新戊四醇五丙烯酸 酯與琥珀酸的單酯化物爲特佳。 前述其他的多官能性單體係可單獨或混合2種以上而 使用。 在本發明之（C)多官能性單體的含量係相對於（B)鹼可 溶性聚合物100重量份，以100〜400重量份爲佳，以1〇〇 〜3 00重量份爲更佳。合計含量太少時，會有損害本發明 Ο 的希望效果之可能性，另一方面，太多時會有例如鹸顯像 性低落、或在未曝光部的基板上或遮蔽層上容易產生表面 污染、殘膜等之傾向。 又，（C)多官能性單體中的含己內酯結構的多官能性單 體之含有比率，以25〜100重量％爲佳，以50〜75重量％ 爲更佳。藉由以此種比率使用含己內酯結構的多官能性單 體，即便低曝光量亦能夠形成適當的順錐狀的像素。 又，在本發明，亦能夠將多官能性單體的一部分取代 Q 成爲具有1個聚合性不飽鍵之單官能性單體。 該單官能性單體除了可舉出例如琥珀酸一 [2-(甲基）丙 烯醯氧基乙基]酯、酞酸一 [2-(甲基）丙烯醯氧基乙基]酯之 二元以上的多元羧酸的一[(甲基）丙烯醯氧基烷基]酯、ω-羧基聚己內酯一（甲基）丙烯酸酯之在兩末端具有羧基及羥 基之聚合物的一（甲基）丙烯酸酯、Ν-(甲基）丙烯醯基味啉、 Ν-乙烯基吡咯啶酮、Ν-乙烯基-ε-己內醯胺等以外，市售品 可舉出Μ-5600(商品名、東亞合成（股）製）等。 該等單官能性單體可單獨或混合使用2種以上。單官 能性單體的含有比率係相對於多官能性單體及單官能性單 -20- 200949437 體的合計，通常爲90重量％以下，以50重量％以下爲佳。 單官能性單體的含有比率太多時，所得到著色層的強度或 表面平滑性會有不充分的可能性。 -(D)光聚合引發劑- 在本發明之光聚合引發劑係藉由可見光線、紫外線、 遠紫外線、電子射線、X射線等放射線之曝光，前述（C)多 官能性單體及依照情況而使用的單官能性單體會開始聚合 π 而產生活性種之化合物。 ❹ 此種光聚合引發劑可舉出例如噻噸酮系化合物、乙醯 苯系化合物、二咪唑系化合物、三畊系化合物、0-醯肟系 化合物、鑰鹽系化合物、苯偶姻系化合物、二苯基酮系化 合物、二酮系化合物、多核苯醌系化合物、咕噸酮系化 合物、重氮系化合物、醯亞胺基磺酸鹽系化合物等。 在本發明，光聚合引發劑可單獨或混合使用2種以 上，在本發明之光聚合引發劑以含有選自由噻噸酮系化合 〇物、乙醯苯系化合物、二咪唑系化合物、三哄系化合物及 〇-醯肟系化合物所組成群組之至少1種爲佳。 在本發明之較佳光聚合引發劑之中，噻噸酮系化合物 的具體例可舉出噻噸酮、2·氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2，4-二氯噻噸酮、2，4-二 甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。 又，前述乙醯苯系化合物的具體例可舉出 2-甲基 甲硫基）苯基]-2-味啉丙烷-1-酮、2·苄基-2-二甲胺基 -1-(4-味啉苯基）丁烷-1-酮、2-(4-甲苄基）-2-(二甲胺 -21- 200949437 基）-1-(4 -味琳苯基）丁院-1-酮等。 又，前述二咪唑系化合物的具體例可舉出2，2’·雙（2-氯苯基）-4,4，，5,5，-四苯基-1,2，-二咪唑、2,2’-雙（2,4-二氯苯 基）-4,4，，5,5，-四苯基-1，2，-二咪唑、2,2’-雙（2,4,6-三氯苯 基）-4,4’，5,5’-四苯基-1，2’-二咪唑等。 又，光聚合引發劑係使用二咪唑系化合物時’就能夠 改良敏感度而言，以並用氫給予體爲佳。在此所謂「氫給 ^ 予體」係指能夠對因曝光而從二咪唑化合物產生的自由基 〇 給予氫原子之化合物。氫給予體可舉出例如2-氫硫基苯并 噻唑、2-氫硫基苯并噚唑等的硫醇系氫給予體、4，4’·雙（二 甲胺基）二苯基酮、4,4’-雙（二乙胺基）二苯基酮等的胺系氫 給予體。在本發明，氫給予體可單獨或混合使用2種以上’ 就能夠更改良敏感度而言，以組合使用1種以上的硫醇系 氫給予體與1種以上的胺系氫給予體爲佳。 又，前述的三阱系化合物之具體例，可舉出2,4,6-參（三 Ο 氯甲基）-s-三畊、2-甲基-4,6-雙（三氯甲基）-s-畊、2-[2-(5-甲基呋喃-2 -基）乙烯基]·4,6 -雙（三氯甲基）-s -三畊、 2-[2-(呋喃-2 -基）乙烯基]-4,6-雙（三氯甲基）-3-三畊、 2-[2-(4-二乙胺基-2 -甲基苯基）乙烯基]-4,6·雙（三氯甲 基）-s-三畊、2-[2-(3,4-二甲氧基苯基）乙烯基]-4,6-雙（三氯 甲基）-s-三哄、2-(4-甲氧基苯基）-4,6-雙（三氯甲基）-s-三 畊、2-(4-乙氧基苯乙烯基）-4,6-雙（三氯甲基）-s-三畊、2-(4-正丁氧基苯基）-4,6-雙（三氯甲基）-s-三畊等具有鹵甲基之 三阱系化合物。 -22- 200949437 又’ 0-醯肟系化合物的具體例可舉出i — (苯硫基）苯 基]· 1，2-辛院二酮- 2-(0-苯甲酿聘）、1_[9_乙基- 6-(2 -甲基苯 甲醯基）-9H -咔唑-3-基]•乙酮- l-(〇 -乙醯肟）、^卜乙基 -6-(2 -甲基-4-四氫呋喃基甲氧基苯甲酿基）_9H_咔哩_3_ 基]-乙酮- l- (〇 -乙醒時）、1-[9 -乙基- 6-{2 -甲基- 4-(2,2 -二甲 基-1，3 -二氧雜戊環基）甲氧基苯甲醯基}-911-味唑-3-基]-乙 酮-1-(0-乙醯肟）等。 在本發明’使用乙醯苯系化合物等的二咪唑系化合物 以外的光自由基產生劑時，亦可並用敏化劑。此種敏化劑 可舉出例如4,4’-雙（二甲胺基）二苯基酮、4,4’-雙（二乙胺基） 二苯基酮、4-二乙胺基乙醯苯、4-二甲胺基丙醯苯、4-二甲 胺基苯甲酸乙酯、4-二甲胺基苯甲酸2-乙酸己酯、2,5-雙（4· 二乙胺基亞苄基）環己酮、7 -二乙胺基- 3- (4 -二乙胺基苯甲 醯基）香豆素、4-(二乙胺基）查耳酮等。 在本發明，光聚合引發劑的含量係相對於（C)多官能性 〇 單體100重量份，通常爲0.01〜120重量份，以1〜100重 量份爲佳。光聚合引發劑的含量太少時，會有藉由曝光之 硬化變爲不充分、或難以得到著色層圖案依照規定配成的 彩色濾光片之可能性，另一方面，所形成的著色層會有容 易從基板脫落之傾向。 -添加劑- 本發明的感放射線性組成物係含有上述（A)〜（D)成 分，但是亦可按照必要進而含有其他的添加劑。 在此，其他的添加劑可舉出例如玻璃、氧化鋁等的塡 -23- 200949437 料；聚乙烯醇、聚（丙烯酸氟烷基酯）類等的高分子化合物； 非離子系界面活性劑、陽離子系界面活性劑、陰離子系界 面活性劑等的界面活性劑；乙烯基三甲氧基矽院、乙烯基 三乙氧基矽烷、乙烯基參（2-甲氧基乙氧基）矽烷、N-(2-胺 乙基）-3-胺丙基甲基二甲氧基矽烷、N-(2-胺乙基）-3-胺丙基 三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-環氧丙氧基丙 基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、 0 2-(3,4-環氧基環己基）乙基三甲氧基矽烷、3-氯丙基甲基二 甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基 丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等的黏附 促進劑；2,2-硫代雙（4-甲基-6-第三丁基苯酚）、2,6-二-第 三丁基苯酚等的抗氧化劑；2-(3-第三丁基-5-甲基-2-羥苯 基）-5-氯苯并三唑、烷氧基二苯基酮類等的紫外線吸收劑； 聚丙烯酸鈉等的抗凝聚劑；丙二酸、己二酸、伊康酸、檸 康酸、反丁烯二酸、中康酸等的鹼溶解性改良劑等。 〇 -溶劑- 本發明的著色層形成用感放射線性組成物係以前述（A) 〜（D)成分作爲必要成分，並按照必要含有前述添加劑成 分，通常係調配溶劑來調製成爲液狀組成物。 前述溶劑只要是能夠溶解或分散（A)〜（D)成分或添加 劑成分，且不會與該等成分反應並具有適當的揮發性者 時，可適當地選擇而使用。 此種溶劑可舉出例如 乙二醇一甲基醚、乙二醇一乙基醚、乙二醇一正丙基 -24- 200949437 醚、乙二醇一正丁基醚、二甘醇一甲基醚、二甘醇一乙基 醚、二甘醇一正丙基醚、二甘醇一正丁基醚、三甘醇一甲 基醚、三甘醇一乙基醚、丙二醇一甲基醚、丙二醇一乙基 醚、丙二醇一正丙基醚、丙二醇一正丁基醚、二伸丙二醇 一甲基醚、二伸丙二醇一乙基醚、二伸丙二醇一正丙基醚、 二伸丙二醇一正丁基醚、三伸丙二醇一甲基醚、三伸丙二 醇一乙基醚等的（聚）伸烷基二醇一烷基醚類； ^ 乙二醇一甲基醚乙酸酯、乙二醇一乙基醚乙酸酯、二 甘醇一甲基醚乙酸酯、二甘醇一乙基醚乙酸酯、丙二醇一 甲基醚乙酸酯、丙二醇一乙基醚乙酸酯、3-甲氧基丁基乙 酸酯、3-甲基-3-甲氧基丁基乙酸酯等的（聚）伸烷基二醇一 烷基醚乙酸酯類； 二甘醇二甲基醚、二甘醇甲基乙基醚、二甘醇二乙基 醚、四氫呋喃等其他的醚類： 甲基乙基酮、環己酮、2-庚酮、3-庚酮等的酮類； 〇 乳酸甲酯、乳酸乙酯等的乳酸烷酯類； 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 氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯' 3_甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙 酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸 異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙 酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙 酯、乙醯乙酸甲酯、乙醢乙酸乙酯、2-側氧基丁酸乙酯等 -25- 200949437 其他的酯類； 甲苯、二甲苯等的芳香族烴類； N，N-二甲基甲醯胺、N，N-二甲基乙醯胺、N甲基吡咯 啶酮等的醯胺或內醯胺類等。 該等溶劑之中’從溶解性、轅料分散性、塗布性等的 觀點，以丙二醇一甲基醚、乙二醇〜甲基醚乙酸酯、丙二 醇一甲基醚乙酸酯、丙二醇一乙基醚乙酸酯、3_甲氧基丁 Q 基乙酸酯、二甘醇二甲基醚、二甘醇甲基乙基醚、環己酮、 2-庚酮、3-庚酮、乳酸乙酯、3-甲氧基丙酸乙酯、3_乙氧基 丙酸甲酯、3 -乙氧基丙酸乙醋、3 -甲基-3-甲氧基丁基丙酸 酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、 丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮 酸乙酯等爲佳。 前述溶劑可單獨或混合使用2種以上。 又，亦可與前述溶劑同時並用苄基乙基醚、二-正己基 〇 醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬 醇、苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯 二酸二乙酯、r-丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙二 醇一苯基醚乙酸酯等高沸點溶劑。 該等高沸點溶劑可單獨或混合使用2種以上。 溶劑的含量沒有特別限定，從所得到的感放射線性組 成物的塗布性、安定性等觀點’該組成物除去溶劑後之各 成分的合計濃度係通常爲5〜50重量％，以成爲10〜40重 量％的量爲佳。 -26- 200949437 在本發明’感放射線性組成物能夠藉由適當的方法來 調製’例如能夠藉由（A)〜（D)成分與溶劑或添加劑一同混 合來調製，以將顏料在溶劑中且分散劑及按照必要而添加 之分散助劑的存在下，且按照情況與（B)成分的一部分一同 使用例如珠磨機、輥磨機等，邊粉碎邊混合、分散來製成 顔料分散液，並對其添加（B)〜（D)成分及按照必要進而追 加的溶劑或添加劑且混合來調製爲佳。 @ -彩色濾光片的形成方法- 接著，說明使用本發明的感放射線性組成物來形成本 發明的彩色濾光片之方法。 形成彩色濾光片之方法，通常至少包含下述（1)〜（4) 的製程。 (1) 在基板上形成本發明的感放射線性組成物的塗膜之製 程。 (2) 對前述塗膜的至少一部分曝光之製程。 〇 (3)將曝光後的塗膜進行顯像之製程。 (4)將顯像後的塗膜後烘烤之製程。 以下，依照順序說明該等製程。 (1)製程 首先，在基板的表面，按照必要以區隔形成像素部分 的方式形成遮光層（黑色矩陣），並在該基板上，例如將含 有紅色的（A)著色劑之本發明的感放射線性組成物通常製 成液狀組成物而塗布後，藉由預烘烤並蒸發除去溶劑來形 成塗膜 -27- 200949437 在該製程所使用的基板除外可舉出例如玻 碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、 聚醚楓以外，可舉出環狀烯烴的開環聚合物或 等。 又，該等基板亦可按照需要預先使用矽烷 行藥品處理、電漿處理、離子噴鍍、濺鍍、氣 真空蒸鍍等適當的前處理。 將液狀組成物塗布在基板時，能採用旋轉 延塗布法、輥塗布法、使用狹縫模頭塗布器之 當的塗布法，以使用旋轉塗布法、使用狹縫模 塗布法等佳。 預烘烤的條件通常爲70〜110 °C、2〜4分妾 依本發明的感放射線性組成物，即便省略預烘 能夠形成像素及黑色矩陣。 塗布厚度係溶劑除去後的膜厚度通常爲 Ο 米，以1·〇〜6.0微米爲佳，以1·〇〜4·0微米爲 (2)製程 隨後，將所形成的塗膜之至少一部分曝光 塗膜的一部分曝光通常係透過具有規定圖案 光。 曝光所使用的放射線例如可使用可見光線 遠紫外線、電子射線、X射線，以波長爲190 -範圍之放射線爲佳。 放射線的曝光量通常爲10〜1 0,000J/m2。 璃、政、聚 聚醯亞胺、 其氫添加物 偶合劑等施 相反應法、 塗布法、流 塗布法等適 頭塗布器之 壅左右。又， 烤製程，亦 1.0〜10微 特佳。 。此時，將 的光罩來曝 、紫外線、 / 450奈米的 依照本發明 -28- 200949437 的感放射線性組成物，即便800J/m2以下的曝光量，進而 600 J/m2以下的曝光量，亦能夠形成適當的順錐狀且殘膜率 及黏附性都優良的像素。又，從使用照度高的光源時的控 制性之觀點，曝光量的下限以20(U/m2以上爲佳。 (3)製程 隨後，使用顯像液、較佳是鹼性顯像液，溶解除去塗 膜之未曝光部。 U 前述鹼性顯像液例如以碳酸鈉、氫氧化鈉、氫氧化鉀、 氫氧化四甲銨、膽鹼、1,8-二氮雜雙環-[5.4.0]-7-十一烯、 1，5-二氮雜雙環-[4.3.0]-5-壬烯等的水溶液爲佳。 前述鹼性顯像液亦可適量添加例如甲醇、乙醇等的水 溶性有機溶劑及界面活性劑等。 顯像處理法可以應用噴淋顯像法、噴霧顯像法、浸漬 (dip)顯像法、浸置（puddle)式顯像法等。 顯像條件係在常溫10〜300秒左右爲佳。 Ο -(4)製程- 隨後，藉由將顯像後的塗膜後烘烤，能夠得到由感放 射線性組成物的硬化物所構成之紅色像素圖案係以規定配 列配置而成的基板。 後烘烤的條件以在 180〜230 °C、20〜40分鐘左右爲 佳。 如此進行所形成的像素之厚度通常爲0.5〜5.0微米， 以1.0〜3.0微米爲佳。 又，藉由使用含有綠色的（A)著色劑之綠色感放射線性 -29- 200949437 組成物，並重複前述（1)〜（4)製程，在同一基板上形成綠色 的像素圖案，進而使用含有藍色的（A)著色劑之藍色感放射 線性組成物，並重複前述（1)〜（4)製程，在同一基板上形成 藍色的像素圖案，能夠在基板上形成以規定配列配置紅 色、綠色及藍色的三原色而成之像素陣列。惟，各顏色的 像素圖案形成順序能夠任意地選擇。 使用含有黑色的（A)著色劑之綠色感放射線性組成 q 物，並藉由進行前述（1)〜（4)製程，能夠形成黑色矩陣。 彩色濾光片 本發明的彩色濾光片係具有由本發明的感放射線性組 成物並如上述進行所形成的像素及/或黑色矩陣者。 彩色液晶顯示元件 本發明的彩色液晶顯示元件係具備本發明的彩色濾光 片者。 在如上述進行所形成的彩色濾光片上，按照必要形成 Ο 保護膜後，藉由濺鍍形成透明導電膜。透明導電膜可舉出 由氧化銦·氧化錫所構成的ITO膜、由氧化銦-氧化鋅所構 成的IZO膜等。因爲使用本發明的感放射線性組成物所形 成的像素圖案之剖面形狀爲順錐狀，所以透明電極不會斷 線。又，因爲錐角亦未太平緩，所以像素的邊緣亦不會產 生膜厚變薄的部分。因此，能夠製造電特性及色度特性都 優良之高品質的彩色液晶顯示元件。 又，本發明的彩色液晶顯示元件之一個形態係使用本 發明的著色層形成用感放射線性組成物，在薄膜電晶體基 -30- 200949437 板陣列上，藉由如前述進行來形成像素及/或黑色矩陣，能 夠製造具有特別優良特性之彩色液晶顯示元件。 [實施例] 以下，舉出實施例來更具體地說明本發明的實施形 態。但是本發明未限定於下述的實施例。 顏料分散液的調製。 調製例1 Q 使用20重量份C_I.顔料紅254/C.I.顏料紅177/C.I.顏 料黃1 50 = 20/70/1 0(重量比）混合物作爲（A)著色劑，5重量 份（換算成固體成分）〇丨3?61^71^20 0 1(8丫〖-(：116 11^6以？311公 司製作爲分散劑，以固體成分濃度成爲25%的方式使用丙 二醇一甲基醚乙酸酯作爲溶劑，並使用珠粒分散機處理， 來調製顏料分散液（R1)。 調製例2 使用20重量份C.I.顏料紅254作爲（A)著色劑，5重量 Ο 份（換算成固體成分）Disperbyk-2001 (BYK-ChemieJapan 公 司製作爲分散劑，以固體成分濃度成爲25 %的方式使用丙 二醇一甲基醚乙酸酯作爲溶劑，並使用珠粒分散機處理， 來調製顏料分散液（R2)。 調製例3 使用20重量份C.I.顏料紅254/C.I·顏料紅242/C.I.顏 料黃1 3 9 = 3 0/60/ 1 0(重量比）混合物作爲（A)著色劑，5重量 份（換算成固體成分）DisPerbyk-2001(BYK-Chemie Japan 公 司製作爲分散劑’以固體成分濃度成爲25%的方式使用丙 -31- 200949437 二醇一甲基醚乙酸酯作爲溶劑，並使用珠粒分散機處理， 來調製顏料分散液（R3)。 調製例4 使用20重量份C_I_顏料綠36/C.I.顏料黃150 = 5〇/5〇(重 量比）混合物作爲（A)著色劑，5重量份（換算成固體成 分）Disperbyk-2001(BYK-Chemie Japan 公司製作爲分散 劑，以固體成分濃度成爲25 %的方式使用丙二醇一甲基酸 0 乙酸酯作爲溶劑，並使用珠粒分散機處理，來調製顏料分 散液（G1)。 調製例5 使用20重量份C.I.顏料綠58/C.I.顏料黃1 50 = 60/40(重 量比）混合物作爲（A)著色劑，5重量份（換算成固體成 分）Disperbyk-2001(BYK-Chemie Japan 公司製作爲分散 劑，以固體成分濃度成爲25 %的方式使用丙二醇一甲基酸 乙酸酯作爲溶劑’並使用珠粒分散機處理，來調製顔料分 〇散液（G2)。 調製例6 使用20重量份C.I.顏料綠36/C.I.顏料黃1 5 0 = 60/40(重 量比）混合物作爲（A)著色劑，5重量份（換算成固體成 分）Disperbyk-2001(BYK-Chemie Japan 公司製作爲分散 劑，以固體成分濃度成爲25%的方式使用丙二醇一甲基酸 乙酸酯作爲溶劑，並使用珠粒分散機處理，來調製顏料分 散液（G3)。 調製例7 -32- 200949437 使用20重量份C.I·顔料藍15: 6作爲（A)著色劑，5 重量份（換算成固體成分）Disperbyk-200 1 (BYK-Chemie Japan公司製作爲分散劑，以固體成分濃度成爲2 5 %的方式 使用丙二醇一甲基醚乙酸酯作爲溶劑，並使用珠粒分散機 處理，來調製顏料分散液（B1)。 調製例8 使用 20 重量份 C.I.顏料藍 15:6/C.I.顏料紫 q 23 = 80/20(重量比）混合物作爲（A)著色劑，5重量份（換算成 固體成分）Disperbyk-200 1 (BYK-Chemie Japan 公司製作爲 分散劑，以固體成分濃度成爲25%的方式使用丙二醇一甲 基醚乙酸酯作爲溶劑，並使用珠粒分散機處理，來調製顏 料分散液（B2)。 調製例9 使用 20 重量份 C.I.顏料藍 15 : 6/C.I.顏料紫 23 = 60/40(重量比）混合物作爲（A)著色劑，5重量份（換算成 Ο 固體成分）Disperbyk-200 1 (BYK-Chemie Japan 公司製作爲 分散劑，以固體成分濃度成爲25%的方式使用丙二醇一甲 基醚乙酸酯作爲溶劑，並使用珠粒分散機處理，來調製顏 料分散液（B3)。 鹼可溶性樹脂的合成 合成例1 在具備有冷卻管、攪拌器之燒瓶添加3重量份2,2’-偶 氮雙異丁腈、200重量份丙二醇一甲基醚乙酸酯，接著， 添加15重量份甲基丙烯酸、35重量份甲基丙烯酸苄酯、 -33- 200949437 19重量份N-苯基順丁烯二醯亞胺、ι〇重量份甘油甲基丙 嫌酸醋、11重量份苯乙烯、1〇重量份ω -羧基聚己內酯一 丙烯酸醋及5重量份2,4-二苯基-4-甲基-1-戊烯（鏈轉移 劑）’並氮氣取代。隨後，藉由慢慢地攪拌並使反應溶液的 溫度上升至80°C，且在該溫度保持3小時來進行聚合，來 得到共聚物溶液。所得到的樹脂係Mw=ll，000, Mn = 5,000、 固體成分濃度=33· 0%。將該共聚物作爲「鹼可溶性樹脂 〇 (B-D」。 合成例2 在具備有冷卻管、攪拌器之燒瓶添加153重量份丙二 醇一甲基醚乙酸酯、15重量份甲基丙烯酸、35重量份甲基 丙烯酸苄酯、11重量份N-苯基順丁烯二醯亞胺、20重量 份2-丙烯醯氧基乙基琥珀酸、19重量份苯乙烯及5重量份 2，4_二苯基-4-甲基-1-戊烯（鏈轉移劑），接著，添加將3重 量份2,2’-偶氮雙異丁腈溶解於47重量份丙二醇一甲基醚 〇乙酸酯而成的溶液並氮氣取代。隨後，慢慢地攪拌並使反 應溶液的溫度上升至80°c，且在該溫度保持4小時來進行 聚合後，添加將0.5重量份2,2’-偶氮雙異丁腈溶解於9.5 重量份丙二醇一甲基醚乙酸酯而成的溶液，接著藉由將反 應溶液的溫度上升至100°C，且在該溫度保持1小時而進 一步聚合，來得到共聚物溶液。所得到的樹脂係 Mw=l〇,〇〇〇，Mn = 6,00 0、固體成分濃度= 30.0%。將該共聚 物作爲「鹼可溶性樹脂（B-2)」。 合成例3 -34- 200949437 在具備有冷卻管、攪拌器之燒瓶添加5重量份2，2，-偶 氮雙異丁腈、200重量份丙二醇一甲基醚乙酸酯，接著， 添加15重量份甲基丙烯酸、35重量份甲基丙烯酸苄酯、 25重量份N -苯基順丁烯二醯亞胺、1〇重量份甘油甲基丙 烯酸酯、15重量份苯乙烯及7.5重量份2,4-二苯基-4-甲基 -1-戊烯（鏈轉移劑），並氮氣取代。隨後，藉由慢慢地攪拌 並使反應溶液的溫度上升至80 °C，且在該溫度保持3小時 φ 來進行聚合’來得到共聚物溶液。所得到的樹脂係 Mw = 7,000，Mn = 3,500、固體成分濃度=32.0%。將該共聚物 作爲「鹸可溶性樹脂（B-3)」。 實施例1 將100重量份顏料分散液（R1)、1〇重量份鹼可溶性樹 脂（A-1)作爲（B)鹼可溶性樹脂、15重量份日本化藥公司製 KAYARAD DPCA-60(式（1)中，m=l，式（2)所示之基的數目 =6之化合物）/二新戊四醇六丙烯酸酯= 50/50(重量比）混合 〇 物作爲（C)多官能性單體、5重量份2-苄基-2-二甲胺基 -1-(4-味啉苯基）丁烷-1-酮（CIBA SPECIALTY CHEMICALS 公司製、商品名IRGACURE3 69)作爲（D)光聚合引發劑及以 固體成分濃度成爲25重量％的方式混合丙二醇一甲基醚乙 酸酯作爲溶劑，來調製液狀組成物（S-1)。 對液狀組成物（S-1)依照下述的順序進行評價。評價結 果係如表2所示。 敏感度的評價 在玻璃基板的表面上，使用旋轉塗布器塗布液狀組成 -35- 200949437 物（s-l)後，使用90 °c的熱板進行預烘烤4分鐘，來形成膜 厚度1.3微米的塗膜。接著，將該基板冷卻至室溫後，對 基板上的塗膜，使用高壓水銀燈並透過光罩，以400J/m2 的曝光量進行曝光。隨後，在基板上的塗膜，藉由將23 °C 的0.04重量％氫氧化鉀水溶液以lkgf/cm2的顯像壓力（噴嘴 徑1毫米）吐出60秒，來進行噴淋顯像後，進而在220°C進 行後烘烤30分鐘，來形成200x200微米的點圖案。 0 將在前述圖案形成所得到基板上的點圖案，藉由使用 掃描型電子顯微鏡觀察來測定膜厚度，並算出殘膜率（後烘 烤後的膜厚度xlO 0/1.3)。殘膜率高的程度可說是敏感度良 好。 黏附性評價 在玻璃基板的表面上，使用旋轉塗布器塗布液狀組成 物（s-l)後，使用90 °c的熱板進行預烘烤4分鐘，來形成膜 厚度1·3微米的塗膜。接著，將該基板冷卻至室溫後，對 © 基板上的塗膜，使用高壓水銀燈並透過光罩，以400J/m2 的曝光量進行曝光。隨後，在基板上的塗膜，藉由將2 3 °C 的0·04重量％氫氧化鉀水溶液以lkgf/cm2的顯像壓力（噴嘴 徑1毫米）吐出60秒，來進行噴淋顯像後，進而在220°C進 行後烘烤30分鐘。 接著，依照JIS K5400規格，將硬化膜橫切成爲1〇〇 個棋盤格狀來進行黏附性評價。而且，棋盤格未產生剝離 時評價爲〇，棋盤格之中1〜10個剝離時評價爲△，棋盤 格剝離多於10個時爲X。 -36- .200949437 剖面形狀及顯像耐性的評價 在玻璃基板的表面上，使用旋轉塗布器塗布液狀組成 物（S-1)後，使用90°C的熱板進行預烘烤4分鐘，來形成膜 厚度1.3微米的塗膜。接著，將該基板冷卻至室溫後，對 基板上的塗膜，使用高壓水銀燈並透過光罩，以400J/m2In the present invention, in order to increase the residual film ratio, it is preferable to use a polyfunctional monomer together with a caprolactone structure in combination with other polyfunctional monomers, and to have a caprolactone structure. It is particularly preferable to use two or more compounds having a polymerizable unsaturated bond. Examples of the other polyfunctional monomer include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. (methyl)-C-18-200949437 enoate; poly(meth) acrylate of glycerol, trimethylolpropane, neopentyl alcohol, dipentaerythritol or higher polyol or the like Anthraquinone; oligomeric (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, spiro resin, etc.; two-terminal hydroxy poly-1,3-butadiene, Two-terminal hydroxylated polymer of both ends of hydroxy polyisoprene 0 and two terminal hydroxylated caprolactates = acrylates; gin[2-(methyl) propylene oxyethyl] phosphate, or heterotrimerization Oxyethane modified triacrylate or the like. Among these other polyfunctional monomers, trivalent or higher poly(meth)acrylates or these dicarboxylic acid modified products have trimethylolpropane triacrylate and trishydroxyl Methyl propane trimethyl ester, neopentyl alcohol triacrylate, neopentyl alcohol trimethyl methacrylate pentaerythritol tetraacrylate, neopentyl alcohol tetramethacrylate, diol pentaacrylate, two new Pentaerythritol pentamethyl acrylate, dihexa hexaacrylate, dipentaerythritol hexamethacrylate, monopentate of pivalate and succinic acid, neopentyl glycol pentaacrylate The esterified product, dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol penta methacrylate and monoester of succinic acid are preferred because of the high strength of the colored layer and the excellent surface smoothness of the colored layer. On the substrate of the exposed portion and on the shielding layer, surface contamination or the like is less likely to occur, and tribasic acid such as trimethylolpropane triacrylate or pentaerythritol triacryl is modified, sand dendrimer, or (meth) cyanate. On the ring polyol, acrylate, neopentylpentaerythritol tripropyl Amber monoesterified compound is good and in, residual film ester, -19-200949437 dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, neopentyl glycol triacrylate and monoester of succinic acid The monoester of the compound and dipentaerythritol pentaacrylate and succinic acid is particularly preferred. The above other polyfunctional single system may be used singly or in combination of two or more. The content of the (C) polyfunctional monomer in the present invention is preferably 100 to 400 parts by weight, more preferably 1 to 300 parts by weight, per 100 parts by weight of the (B) alkali-soluble polymer. When the total content is too small, there is a possibility of impairing the desired effect of the crucible of the present invention. On the other hand, if there is too much, for example, the developing property is lowered, or the surface is easily formed on the substrate of the unexposed portion or the shielding layer. The tendency of pollution, residual film, etc. Further, the content ratio of the polyfunctional monomer having a caprolactone structure in the (C) polyfunctional monomer is preferably 25 to 100% by weight, more preferably 50 to 75% by weight. By using a polyfunctional monomer having a caprolactone structure at such a ratio, an appropriate smooth tapered pixel can be formed even at a low exposure amount. Further, in the present invention, a part of the polyfunctional monomer may be substituted with Q to form a monofunctional monomer having one polymerizable unsaturated bond. The monofunctional monomer may, for example, be bisuccinic acid mono [2-(methyl) propylene oxiranyl ethyl ester] or citric acid mono [2-(methyl) propylene methoxyethyl ester] One [(meth) propylene decyloxyalkyl] ester of a polyvalent carboxylic acid or more, and one of a polymer having a carboxyl group and a hydroxyl group at both ends of the ω-carboxypolycaprolactone mono(meth) acrylate ( Other than methyl acrylate, fluorene-(meth) propylene sulfenyl porphyrin, hydrazine-vinyl pyrrolidone, hydrazine-vinyl-ε-caprolactam, etc., commercially available products are Μ-5600 ( Trade name, East Asian synthetic (share) system, etc. These monofunctional monomers may be used alone or in combination of two or more. The content ratio of the monofunctional monomer is usually 90% by weight or less, and preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional mono-20-200949437. When the content ratio of the monofunctional monomer is too large, the strength or surface smoothness of the obtained colored layer may be insufficient. - (D) Photopolymerization Initiator - The photopolymerization initiator of the present invention is exposed to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc., the above (C) polyfunctional monomer and, as the case may be The monofunctional monomer used will begin to polymerize π to produce a compound of the active species.此种 such a photopolymerization initiator may, for example, be a thioxanthone compound, an acetophenone compound, a diimidazole compound, a tri-grain compound, a 0-fluorene compound, a key salt compound, or a benzoin compound. A diphenyl ketone compound, a diketone compound, a polynuclear benzoquinone compound, a xanthone compound, a diazo compound, or a quinone sulfonate compound. In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator of the present invention contains a compound selected from the group consisting of a thioxanthone compound, an acetophenone compound, a diimidazole compound, and a triterpenoid. At least one of the group consisting of a compound and an anthraquinone-based compound is preferred. Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2·chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like. Further, specific examples of the acetaminophen compound include 2-methylmethylthio)phenyl]-2-morpholinepropan-1-one and 2·benzyl-2-dimethylamino-1- (4-glyphosylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamine-21-200949437-based)-1-(4--linylphenyl) -1-ketone and the like. Further, specific examples of the diimidazole-based compound include 2,2'·bis(2-chlorophenyl)-4,4,5,5,-tetraphenyl-1,2,-diimidazole, 2 , 2'-bis(2,4-dichlorophenyl)-4,4,5,5,-tetraphenyl-1,2,-diimidazole, 2,2'-bis (2,4,6 -Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like. Further, when the photopolymerization initiator is a diimidazole-based compound, it is preferable to use a hydrogen donor in combination in order to improve the sensitivity. Here, "hydrogen donor compound" means a compound capable of imparting a hydrogen atom to a radical 〇 generated from a diimidazole compound by exposure. Examples of the hydrogen donor include a thiol-based hydrogen donor such as 2-hydrothiobenzothiazole or 2-hydrothiobenzoxazole, and 4,4′·bis(dimethylamino)diphenyl ketone. An amine-based hydrogen donor such as 4,4'-bis(diethylamino)diphenyl ketone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. In order to change the good sensitivity, it is preferred to use one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogen donors in combination. . Further, specific examples of the above-described triple well-based compound include 2,4,6-paraxyl (trimethylchloromethyl)-s-three tillage and 2-methyl-4,6-bis(trichloromethyl). )-s-cultivation, 2-[2-(5-methylfuran-2-yl)vinyl]·4,6-bis(trichloromethyl)-s-three tillage, 2-[2-(furan) -2 -yl)vinyl]-4,6-bis(trichloromethyl)-3-trin, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]- 4,6·bis(trichloromethyl)-s-three tillage, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)- S-triterpene, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three tillage, 2-(4-ethoxystyryl)-4,6 - bis(trichloromethyl)-s-three tillage, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three tillage, etc. Well compound. -22- 200949437 Further, specific examples of the '0-lanthanide compound include i-(phenylthio)phenyl]· 1,2-octyldione- 2-(0-phenyl ketone), 1_ [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-l-(〇-acetamidine), ^iethyl-6-(2 - Methyl-4-tetrahydrofuranylmethoxybenzoyl)_9H_咔哩_3_yl]-ethanone- l- (〇-乙醒), 1-[9-ethyl-6-{2 - Methyl 4-(2,2-dimethyl-1,3-dioxapentyl)methoxybenzylidene}-911-isoxazole-3-yl]-ethanone-1-( 0- 醯肟) and so on. In the case of using a photoradical generator other than a diimidazole compound such as an acetophenone compound, a sensitizer may be used in combination. Such a sensitizer may, for example, be 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, or 4-diethylamino group B. Toluene, 4-dimethylaminopropionylbenzene, ethyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2-hexyl acetate, 2,5-bis(4·diethylamino) Benzylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like. In the present invention, the content of the photopolymerization initiator is usually 0.01 to 120 parts by weight, based on 100 parts by weight of the (C) polyfunctional fluorene monomer, and preferably 1 to 100 parts by weight. When the content of the photopolymerization initiator is too small, there is a possibility that the curing by the exposure becomes insufficient, or it is difficult to obtain a color filter in which the colored layer pattern is formed according to the specification, and on the other hand, the colored layer is formed. There is a tendency to easily fall off from the substrate. - Additive - The radiation sensitive composition of the present invention contains the above components (A) to (D), but may further contain other additives as necessary. Here, examples of other additives include 塡-23-200949437 materials such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); nonionic surfactants and cations; It is a surfactant such as a surfactant or an anionic surfactant; vinyl trimethoxy fluorene, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-( 2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 0 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxy Adhesion promoters such as decane and the like; antioxidants such as 2,2-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol; 2-(3) -T-butyl-5-methyl-2-hydroxyphenyl ) an ultraviolet absorber such as 5-chlorobenzotriazole or alkoxydiphenyl ketone; an anti-agglomerating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, and anti An alkali solubility improver such as butenedioic acid or mesaconic acid. 〇-solvent - The radiation sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components, and if necessary, the additive component is contained, and a solvent is usually prepared to prepare a liquid composition. . The solvent can be appropriately selected and used as long as it can dissolve or disperse the components (A) to (D) or the additive component, and does not react with these components and has appropriate volatility. Such a solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl-24-200949437 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, di-propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tri-propylene glycol monomethyl ether, tri-propylene glycol monoethyl ether; ^ ethylene glycol monomethyl ether acetate, ethylene Alcohol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3 (poly)alkylene glycol monoalkyl ether acetates such as -methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether Diethylene glycol Other ethers such as ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.: ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl lactate, lactate B Alkyl lactate such as ester; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3 · ethoxy propionate ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate ' 3 -methyl-3-methoxybutyl propionic acid Ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyric acid Ethyl ester, etc.-25- 200949437 Other esters; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidine A guanamine or an indoleamine or the like. Among these solvents, propylene glycol monomethyl ether, ethylene glycol to methyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are used from the viewpoints of solubility, pigment dispersibility, and coating properties. Ethyl ether acetate, 3-methoxybutyl Q-acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, Ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, N-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. . These solvents may be used alone or in combination of two or more. Further, benzyl ethyl ether, di-n-hexyl decyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, acetic acid may be used together with the solvent. High boiling point solvents such as benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate . These high-boiling point solvents may be used alone or in combination of two or more. The content of the solvent is not particularly limited, and the total concentration of each component after removing the solvent from the composition is usually 5 to 50% by weight from the viewpoint of applicability, stability, and the like of the obtained radiation-sensitive composition. An amount of 40% by weight is preferred. -26- 200949437 In the present invention, the 'radiation-sensitive composition can be prepared by an appropriate method' can be prepared, for example, by mixing the components (A) to (D) with a solvent or an additive to remove the pigment in a solvent. In the presence of a dispersing agent and a dispersing aid to be added as necessary, and using a part of the component (B), for example, a bead mill, a roll mill, or the like, and mixing and dispersing, and preparing a pigment dispersion liquid, It is preferred to add (B) to (D) components and, if necessary, additional solvents or additives, and mix them to prepare them. @ - Method of Forming Color Filter - Next, a method of forming the color filter of the present invention using the radiation sensitive composition of the present invention will be described. The method of forming a color filter usually includes at least the following processes (1) to (4). (1) A process for forming a coating film of the radiation sensitive composition of the present invention on a substrate. (2) A process of exposing at least a portion of the aforementioned coating film. 〇 (3) The process of developing the exposed coating film. (4) The process of post-baking after filming. Hereinafter, the processes will be described in order. (1) Process First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to form a pixel portion, and a feeling of the present invention containing, for example, a red (A) coloring agent is formed on the substrate. The radiation-linear composition is usually formed into a liquid composition and coated, and the solvent is removed by prebaking and evaporation to form a coating film. -27-200949437 Except for the substrate used in the process, for example, a glass carbonate or a polyester is exemplified. Examples of the aromatic polyamine, the polyamidimide, and the polyether maple include a ring-opening polymer of a cyclic olefin or the like. Further, these substrates may be subjected to an appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, or vacuum vapor deposition in advance using decane as needed. When the liquid composition is applied to a substrate, a spin coating method, a roll coating method, or a coating method using a slit die coater can be used, and a spin coating method or a slit die coating method can be used. The prebaking conditions are usually 70 to 110 ° C and 2 to 4 minutes. According to the radiation sensitive composition of the present invention, the pixel and the black matrix can be formed even if the prebaking is omitted. The thickness of the film after the solvent removal is usually Ο, preferably 1·〇~6.0 μm, and 1·〇~4·0 μm is (2), and then at least a part of the formed coating film is exposed. A portion of the exposure of the coating film is typically transmitted through a predetermined pattern of light. For the radiation used for the exposure, for example, visible light ultraviolet rays, electron rays, and X-rays can be used, and radiation having a wavelength of 190 - is preferable. The exposure amount of the radiation is usually 10 to 10,000 J/m2. Glass, etc., polyacrylamide, hydrogen additive coupling agent, etc., such as a phase reaction method, a coating method, a flow coating method, and the like. Also, the baking process is also 1.0 to 10 micro-excellent. . At this time, the photomask is exposed, ultraviolet light, /450 nm, and the radiation-sensitive composition according to the present invention -28-200949437, even if the exposure amount is 800 J/m 2 or less, and further, the exposure amount is 600 J/m 2 or less. It is also possible to form a pixel which is suitably tapered and has excellent residual film ratio and adhesion. Further, from the viewpoint of controllability when using a light source having a high illuminance, the lower limit of the exposure amount is preferably 20 (U/m2 or more. (3) The process is followed by dissolution using a developing solution, preferably an alkaline developing solution. The unexposed portion of the coating film is removed. U The above alkaline developing solution is, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0 An aqueous solution of 7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene is preferred. The alkaline developing solution may be added with a suitable amount of water such as methanol or ethanol. Organic solvents, surfactants, etc. Development methods can be applied by spray imaging, spray imaging, dip imaging, puddle imaging, etc. The normal temperature is preferably about 10 to 300 seconds. Ο - (4) Process - Subsequently, by baking the developed coating film, a red pixel pattern composed of a cured product of the radiation sensitive composition can be obtained. The substrate to be arranged is arranged in a row. The post-baking conditions are preferably about 180 to 230 ° C for about 20 to 40 minutes. The degree is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm. Further, by using a green-sensitive radiation-linear -29-200949437 composition containing a green (A) colorant, and repeating the above (1) to (4) a process of forming a green pixel pattern on the same substrate, and further using a blue radiation-sensitive linear composition containing a blue (A) colorant, and repeating the above processes (1) to (4) to form on the same substrate. In the blue pixel pattern, a pixel array in which three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the pixel pattern forming order of each color can be arbitrarily selected. The green sensation of the colorant is linearly composed of q, and a black matrix can be formed by performing the above processes (1) to (4). Color filter The color filter of the present invention has a radiation-sensitive linear composition of the present invention. The pixel and/or the black matrix formed as described above are formed as described above. Color liquid crystal display element The color liquid crystal display element of the present invention includes the color filter of the present invention. A transparent conductive film is formed by sputtering on the color filter formed in the row, and a transparent conductive film is formed by sputtering. The transparent conductive film is an ITO film composed of indium oxide and tin oxide, and is indium oxide-oxidized. An IZO film made of zinc or the like. Since the cross-sectional shape of the pixel pattern formed using the radiation sensitive composition of the present invention is a tapered shape, the transparent electrode is not broken. Moreover, since the taper angle is not too gentle, The edge of the pixel does not have a portion where the film thickness is reduced. Therefore, it is possible to manufacture a high-quality color liquid crystal display element having excellent electrical characteristics and chromaticity characteristics. Further, one aspect of the color liquid crystal display element of the present invention is used. The luminescent layer forming composition for coloring layer formation of the invention can form a color liquid crystal display element having particularly excellent characteristics by forming a pixel and/or a black matrix on the thin film transistor substrate-30-200949437 plate array as described above. . [Examples] Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples. Modulation of the pigment dispersion. Preparation Example 1 Q Using 20 parts by weight of C_I. Pigment Red 254/CI Pigment Red 177/CI Pigment Yellow 1 50 = 20/70/1 0 (by weight) mixture as (A) colorant, 5 parts by weight (converted to solid Ingredients) 〇丨3?61^71^20 0 1 (8丫〖-(:116 11^6 was made into a dispersant by 311 company, and propylene glycol monomethyl ether acetate was used in such a manner that the solid content concentration became 25%) The pigment was used as a solvent and treated with a bead disperser to prepare a pigment dispersion (R1). Preparation Example 2 20 parts by weight of CI Pigment Red 254 was used as (A) colorant, and 5 parts by weight (in terms of solid content) Disperbyk -2001 (BYK-Chemie Japan Co., Ltd. was prepared as a dispersant, and propylene glycol monomethyl ether acetate was used as a solvent in a solid content concentration of 25%, and a pigment dispersion liquid (R2) was prepared by treatment using a bead disperser. Preparation Example 3 Using 20 parts by weight of a mixture of CI Pigment Red 254/CI·Pigment Red 242/CI Pigment Yellow 1 3 9 = 3 0/60/10 (weight ratio) as (A) colorant, 5 parts by weight (converted into Solid component) DisPerbyk-2001 (produced by BYK-Chemie Japan as a dispersant) with a solid content The pigment dispersion (R3) was prepared by a method of 25% using C-31-200949437 diol monomethyl ether acetate as a solvent and using a bead disperser. Preparation Example 4 Using 20 parts by weight of C_I_pigment Green 36/CI Pigment Yellow 150 = 5〇/5〇 (by weight) mixture as (A) colorant, 5 parts by weight (in terms of solid content) Disperbyk-2001 (by BYK-Chemie Japan, a dispersant, solid The pigment dispersion (G1) was prepared by using a propylene glycol monomethyl acid 0 acetate as a solvent and a bead disperser to prepare a pigment dispersion (G1). Preparation Example 5 Using 20 parts by weight of CI Pigment Green 58/CI Pigment Yellow 1 50 = 60/40 (by weight) mixture as (A) colorant, 5 parts by weight (calculated as solid content) Disperbyk-2001 (produced by BYK-Chemie Japan as a dispersant, the solid concentration was 25%) The method of using propylene glycol monomethyl acetate as a solvent' and using a bead disperser to prepare a pigment splitting liquid (G2). Preparation Example 6 Using 20 parts by weight of CI Pigment Green 36/CI Pigment Yellow 1 5 0 = 60/40 (weight ratio) mix As a coloring agent (A), 5 parts by weight (in terms of solid content) Disperbyk-2001 (produced by BYK-Chemie Japan Co., Ltd. as a dispersing agent, and propylene glycol monomethyl acetate as a solvent so that the solid content concentration was 25%) And using a bead disperser to prepare a pigment dispersion (G3). Preparation Example 7 - 32 - 200949437 20 parts by weight of CI·Pigment Blue 15: 6 was used as (A) coloring agent, and 5 parts by weight (in terms of solid content) Disperbyk-200 1 (produced by BYK-Chemie Japan Co., Ltd. as a dispersing agent) The pigment dispersion liquid (B1) was prepared by using a propylene glycol monomethyl ether acetate as a solvent and using a bead disperser to prepare a solid content concentration of 25 %. Preparation Example 8 Using 20 parts by weight of CI Pigment Blue 15: 6/CI Pigment Violet q 23 = 80/20 (by weight) mixture as (A) colorant, 5 parts by weight (in terms of solid content) Disperbyk-200 1 (by BYK-Chemie Japan, a dispersant, solid content) The pigment dispersion (B2) was prepared by using a propylene glycol monomethyl ether acetate as a solvent and a bead disperser to prepare a concentration of 25%. Preparation Example 9 Using 20 parts by weight of CI Pigment Blue 15 : 6/CI Pigment Violet 23 = 60/40 (by weight) mixture as (A) colorant, 5 parts by weight (in terms of Ο solid content) Disperbyk-200 1 (produced by BYK-Chemie Japan as a dispersant, the solid concentration was 25 % way to use C Monomethyl ether acetate was used as a solvent and treated with a bead disperser to prepare a pigment dispersion (B3). Synthesis of an alkali-soluble resin Synthesis Example 1 3 parts by weight of a flask equipped with a cooling tube and a stirrer was added 2 2'-azobisisobutyronitrile, 200 parts by weight of propylene glycol monomethyl ether acetate, followed by addition of 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, -33-200949437 19 parts by weight of N -Phenylsynyleneimine, ι 重量 份 份 份 份 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 -diphenyl-4-methyl-1-pentene (chain transfer agent)' and nitrogen substitution. Subsequently, by slowly stirring and raising the temperature of the reaction solution to 80 ° C, and maintaining at this temperature 3 The copolymer solution was obtained in an hour to obtain a copolymer solution, and the obtained resin was Mw = ll, 000, Mn = 5,000, and solid content concentration = 33.0%. The copolymer was referred to as "alkali-soluble resin hydrazine (BD). Example 2 Adding 153 parts by weight of propylene glycol monomethyl ether acetate to a flask equipped with a cooling tube and a stirrer Ester, 15 parts by weight of methacrylic acid, 35 parts by weight of benzyl methacrylate, 11 parts by weight of N-phenyl maleimide, 20 parts by weight of 2-acryloxyethyl succinic acid, 19 parts by weight Styrene and 5 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (chain transfer agent), followed by addition of 3 parts by weight of 2,2'-azobisisobutyronitrile in 47 A solution of propylene glycol monomethyl ether oxime acetate was substituted with nitrogen. Subsequently, the mixture was slowly stirred and the temperature of the reaction solution was raised to 80 ° C, and after the polymerization was carried out for 4 hours at this temperature, 0.5 part by weight of 2,2'-azobisisobutyronitrile was dissolved in 9.5 by weight. A solution of propylene glycol monomethyl ether acetate was further polymerized by raising the temperature of the reaction solution to 100 ° C and maintaining the temperature for 1 hour to obtain a copolymer solution. The obtained resin was Mw = l, 〇〇〇, Mn = 6,00 0, and solid content concentration = 30.0%. This copolymer was referred to as "alkali-soluble resin (B-2)". Synthesis Example 3 - 34 - 200949437 5 parts by weight of 2,2,-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by addition of 15 weights a portion of methacrylic acid, 35 parts by weight of benzyl methacrylate, 25 parts by weight of N-phenyl maleimide, 1 part by weight of glycerol methacrylate, 15 parts by weight of styrene and 7.5 parts by weight of 2, 4-Diphenyl-4-methyl-1-pentene (chain transfer agent) and substituted with nitrogen. Subsequently, the copolymer solution was obtained by slowly stirring and raising the temperature of the reaction solution to 80 ° C, and maintaining the temperature at this temperature for 3 hours φ to obtain a copolymer solution. The obtained resin was Mw = 7,000, Mn = 3,500, and solid content concentration = 32.0%. This copolymer was referred to as "bismuth soluble resin (B-3)". Example 1 100 parts by weight of a pigment dispersion liquid (R1) and 1 part by weight of an alkali-soluble resin (A-1) were used as (B) an alkali-soluble resin, and 15 parts by weight of KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd. (Formula (1) In the formula, m = l, the number of groups represented by formula (2) = 6 compounds) / dipentaerythritol hexaacrylate = 50 / 50 (by weight) mixed with as a (C) polyfunctional single 5 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one (manufactured by CIBA SPECIALTY CHEMICALS, trade name IRGACURE 3 69) as (D) light The polymerization initiator and the propylene glycol monomethyl ether acetate were mixed as a solvent so that the solid content concentration was 25% by weight to prepare a liquid composition (S-1). The liquid composition (S-1) was evaluated in the following order. The evaluation results are shown in Table 2. Evaluation of Sensitivity On the surface of the glass substrate, a liquid composition of -35-200949437 (sl) was applied using a spin coater, and then prebaked for 4 minutes using a hot plate at 90 °C to form a film thickness of 1.3 μm. Coating film. Next, after the substrate was cooled to room temperature, the coating film on the substrate was exposed to light at a exposure amount of 400 J/m 2 using a high pressure mercury lamp and passing through a photomask. Subsequently, the coating film on the substrate was sprayed and developed by spraying a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C at a development pressure of lkgf/cm 2 (nozzle diameter: 1 mm) for 60 seconds. Post-baking was carried out at 220 ° C for 30 minutes to form a dot pattern of 200 x 200 microns. 0 The dot pattern on the obtained substrate was formed by the above pattern, and the film thickness was measured by observation with a scanning electron microscope, and the residual film ratio (film thickness after laking x10 / 1.3) was calculated. The degree of residual film rate is high enough to be sensitive. Adhesive evaluation The liquid composition (s-1) was applied onto the surface of a glass substrate by a spin coater, and then prebaked for 4 minutes using a hot plate at 90 °C to form a coating film having a film thickness of 1·3 μm. Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to a exposure amount of 400 J/m 2 using a high-pressure mercury lamp and passing through a photomask. Subsequently, the coating film on the substrate was sprayed by spraying a 0. 04% by weight aqueous potassium hydroxide solution at 23 ° C at a development pressure of lkgf/cm 2 (nozzle diameter of 1 mm) for 60 seconds. Thereafter, post-baking was further carried out at 220 ° C for 30 minutes. Next, in accordance with JIS K5400, the cured film was cross-cut into 1 checkerboard shape to evaluate the adhesion. Further, when the checkerboard was not peeled off, it was evaluated as 〇, and 1 to 10 peelings in the checkerboard were evaluated as Δ, and when the checkerboard peeled off more than 10, it was X. -36-.200949437 Evaluation of cross-sectional shape and development resistance On the surface of a glass substrate, the liquid composition (S-1) was applied using a spin coater, and then prebaked for 4 minutes using a hot plate at 90 °C. A coating film having a film thickness of 1.3 μm was formed. Next, after cooling the substrate to room temperature, a high pressure mercury lamp was used on the coating film on the substrate and passed through a photomask at 400 J/m2.

的曝光量進行曝光。隨後，在基板上的塗膜，藉由將23 °C 的0.04重量％氫氧化鉀水溶液以1.5kgf/cm2的顯像壓力（噴 I 嘴徑1毫米）吐出60秒，來進行噴淋顯像後，進而在220 ❹ °C進行後烘烤30分鐘，在基板形成90微米的條紋狀像素 圖案。 接著，使用光學顯微鏡觀察所得到的條紋狀像素圖 案，觀察圖案邊緣是否有缺損。 而且使用掃描型電子顯微鏡（SEM)觀察所得到像素圖 案，並測定第1圖所示之錐角。該錐角係80度以上時，透 明電極膜有斷線之可能性。另一方面，錐角爲20度以下 〇 時，像素圖案的傾斜部分變長，致使在像素的邊綠會產生 膜厚度變薄的部分。理想的錐角爲30〜70度。 實施例2〜1 2及比較例1〜1 1 除了液狀組成物的各成分之種及量係如表1所示以 外，與實施例1同樣地進行來調製液狀組成物（S-2)〜 (S-23)。 接著，除了各自使用液狀組成物（S-2)〜（S_23)代替液 狀組成物（S-1)以外，與實施例1同樣地進行評價。結果如 表2所示。 -37- 200949437The exposure is exposed. Subsequently, the coating film on the substrate was subjected to spray development by discharging a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C at a development pressure of 1.5 kgf/cm 2 (spraying a nozzle diameter of 1 mm) for 60 seconds. Thereafter, post-baking was carried out at 220 ❹ ° C for 30 minutes to form a 90 μm stripe-shaped pixel pattern on the substrate. Next, the obtained striped pixel pattern was observed using an optical microscope to observe whether or not the edge of the pattern was defective. Further, the obtained pixel pattern was observed using a scanning electron microscope (SEM), and the taper angle shown in Fig. 1 was measured. When the taper angle is 80 or more, the transparent electrode film may be broken. On the other hand, when the taper angle is 20 degrees or less, the inclined portion of the pixel pattern becomes long, so that a portion where the film thickness becomes thinner occurs at the side of the pixel. The ideal cone angle is 30 to 70 degrees. Example 2 to 1 2 and Comparative Examples 1 to 1 1 The liquid composition (S-2) was prepared in the same manner as in Example 1 except that the kinds and amounts of the respective components of the liquid composition were as shown in Table 1. ) ~ (S-23). Then, evaluation was carried out in the same manner as in Example 1 except that the liquid compositions (S-2) to (S_23) were used instead of the liquid composition (S-1). The results are shown in Table 2. -37- 200949437

oQ u s 链 g 重量份 5/0.1/0.4/0.1 5/0.1/0.4/0.1 *—< s 5/0.1/0.4/0.1 5/1/1/0.5 4/1/1/1/0.5 4/1/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/0.1/0.4/0.1 5/1/1/0.5 4/1/1/1/0.5 4/1/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/1/1/0.5 1 Μ UBd P D-l/D-5 D-2/D-5 D-2/D-4/D-5/D-6 2/28 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D~2/D-4/D*5/D-6 D-1/D-4/D-5/D-6 D-1/D-3/D-4/D-5/D-6 v〇 § i § 1 Q ά D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D-l/D-5 1 D-l/D-5 D-l/D-5 D-2/D-5 D-2/D-4/D-5/D-6 D-1/D-4/D-5/D-6 D-1/D-3/D-4/D-5/D-6 D-l/D-2；D-4/D-5/D-6 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 链 s mm份 vr> ΧΓί m 7/23 7/23 2 \n OO vr> ο 2 〇 is o 0〇 5/14 〇 駿 Ρ 寸 a in C-2/C-3 C-l/C-3 C-l/C-3 C-l/C-5 C-l/C-6 寸 0 cn ώ C-l/C-3 C-l/C-3 CO ό 1 C-l/C-3 吁 Ο 寸 o 寸 ό C-2/C-3 C-l/C-3 寸 ύ cn ύ ύ C-l/C-3 CO ό »—* ό 链 g 1 ψ $ 魅 φ _ Μ 〇 o o 〇 o <N OJ vn cs r—< \o 卜 V 〇 寸 CS T-* VO 异 重置份 麵' PQ S <N ώ CO PQ cn PQ CO pq cn PQ (ώ PQ CO PQ PQ (N PQ PQ ώ ώ ώ CS PQ cn PC ώ c<t PQ cn pq "T PQ PQ ώ 8 s ·— g s 8 s B s r*H 8 8 s s «—4 s 4—4 8 1*· 8 S — 8 8 «-Η s 8 i-H 8 8 觀 S 2 CO oi 2 CO oi δ s cn 〇 CQ CN CQ cn PQ s 2 2 2 £ ο s c PQ CN PQ CO PQ . I i 3 GO CO C/3 S c0 CO oo OQ CPs c/b S-10 S-ll S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 S-23 1 τΉ 琴 m m cs 琴 m m m 1 辑 K i m m 1 m m v〇 辑 i m m 實施例8 ! ON 1 辑 實施例10 f—1 *—H i 镯 m CS i 辑 a 比_2 m 鎰 i ：H 1 Ό 愆 比較例7 比較例9 i i_H z： 1 -οοτ 200949437 在表1，各成分係如以下。 c-i:二新戊四醇六丙烯酸酯 C-2:新戊四醇四甲基丙烯酸酯 C-3:在上述式（1)〜（3)，m=l，式（2)所示之基的數目=6， R1係全部爲氫原子之化合物（商品名KAYARAD DPCA-60、 日本化藥公司製） C-4:在上述式（1)〜（3)，m = 2 ’式（2)所示之基的數目=6， R1係全部爲氫原子之化合物（商品名 KAYARAD DPCA-120 '日本化藥公司製） 〇 C-5:在上述式（1)〜（3)’ m=l’式（2)所示之基的數目=2， R1係全部爲氫原子之化合物（商品名KAYARAD DPCA-20、 曰本化藥公司製） C-6:在上述式（1)〜（3)，m=l’式（2)所示之基的數目=3， R1係全部爲氫原子之化合物（商品名KAYARAD DPCA-30、 曰本化藥公司製） D-1 : 2-苄基-2-二甲胺基·1-(4 -味啉苯基）丁烷-1-酮（商品名 IRGACURE 369、CIBA SPECIALTY CHEMICALS 公司製） 〇 D-2 : 2-甲基-l-[4-甲硫基）苯基]-2-味啉丙烷-1-酮（商品名 IRGACURE 907、CIBA SPECIALTY CHEMICALS 公司製） D-3: l-[9-乙基- 6-(2-甲基苯甲醯基）-9H-咔唑-3-基]-乙酮 -1-(0-乙醯肟）（商品名 IRGACURE OXE02 ' CIBA SPECIALTY CHEMICALS 公司製） D-4: 2,2’-雙（2-氯苯基）-4,5,4’，5’-四苯基-1，2’-二咪唑 D-5: 4,4’-雙（二乙胺基）二苯基酮 D-6 : 2-氫硫基苯并噻唑 -39- .200949437 [表2]oQ us chain g parts by weight 5/0.1/0.4/0.1 5/0.1/0.4/0.1 *—< s 5/0.1/0.4/0.1 5/1/1/0.5 4/1/1/1/0.5 4/ 1/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/0.1/0.4/0.1 5/1/1/0.5 4/1/1/1/ 0.5 4/1/1/1/0.5 5/1/1/0.5 5/1/1/0.5 5/1/1/0.5 1 Μ UBd P Dl/D-5 D-2/D-5 D-2 /D-4/D-5/D-6 2/28 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D~2/D -4/D*5/D-6 D-1/D-4/D-5/D-6 D-1/D-3/D-4/D-5/D-6 v〇§ i § 1 Q ά D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 Dl/D -5 1 Dl/D-5 Dl/D-5 D-2/D-5 D-2/D-4/D-5/D-6 D-1/D-4/D-5/D-6 D-1/D-3/D-4/D-5/D-6 Dl/D-2; D-4/D-5/D-6 D-2/D-4/D-5/D- 6 D-2/D-4/D-5/D-6 D-2/D-4/D-5/D-6 Chain s mm parts vr> ΧΓί m 7/23 7/23 2 \n OO vr&gt ; ο 2 〇is o 0〇5/14 〇骏Ρ inch in C-2/C-3 Cl/C-3 Cl/C-3 Cl/C-5 Cl/C-6 inch 0 cn ώ Cl/ C-3 Cl/C-3 CO ό 1 Cl/C-3 Ο 寸 inch ό C-2/C-3 Cl/C-3 inch ύ cn ύ ύ Cl/C-3 CO ό »—* ό Chain g 1 ψ $ 魅 φ _ Μ 〇 oo 〇 o <N OJ vn cs r—< \o 卜 V 〇 CS T-* VO Different reset face ' PQ S <N ώ CO PQ cn PQ CO pq cn P Q (ώ PQ CO PQ PQ (N PQ PQ ώ ώ ώ CS PQ cn PC ώ c<t PQ cn pq "T PQ PQ ώ 8 s ·- gs 8 s B sr*H 8 8 ss «–4 s 4 —4 8 1*· 8 S — 8 8 «-Η s 8 iH 8 8 View S 2 CO oi 2 CO oi δ s cn 〇 CQ CN CQ cn PQ s 2 2 2 £ ο sc PQ CN PQ CO PQ . I i 3 GO CO C/3 S c0 CO oo OQ CPs c/b S-10 S-ll S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 S-20 S -21 S-22 S-23 1 τΉ Qin mm cs Qin mmm 1 Series K imm 1 mmv〇imm Example 8 ! ON 1 Series Example 10 f—1 *—H i Bracelet m CS i Series a _2 m 镒i : H 1 Ό 愆 Comparative Example 7 Comparative Example 9 i i_H z: 1 - οοτ 200949437 In Table 1, each component is as follows. Ci: dipentaerythritol hexaacrylate C-2: pentaerythritol tetramethacrylate C-3: a group represented by the above formula (1) to (3), m = 1, formula (2) The number of the formula =6, R1 is a compound of all hydrogen atoms (trade name: KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.) C-4: in the above formula (1) to (3), m = 2 'form (2) The number of the groups shown is =6, and R1 is a compound in which all hydrogen atoms (trade name KAYARAD DPCA-120 'made by Nippon Kayaku Co., Ltd.) 〇C-5: in the above formula (1) to (3)' m=l The number of the groups represented by the formula (2) is 2, and the compound in which R1 is a hydrogen atom (trade name: KAYARAD DPCA-20, manufactured by Sakamoto Chemical Co., Ltd.) C-6: in the above formula (1) to (3) m=l' The number of groups represented by the formula (2) = 3, and the compound in which R1 is a hydrogen atom (trade name: KAYARAD DPCA-30, manufactured by Sakamoto Chemical Co., Ltd.) D-1 : 2-benzyl group 2-Dimethylamino·1-(4-carbolinephenyl)butan-1-one (trade name: IRGACURE 369, manufactured by CIBA SPECIALTY CHEMICALS) 〇D-2 : 2-methyl-l-[4 -Methylthio)phenyl]-2-morpholinepropan-1-one (trade name: IRGACURE 907, manufactured by CIBA SPECIALTY CHEMICALS) D-3 : l-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-(0-acetamidine) (trade name IRGACURE OXE02 ' CIBA SPECIALTY CHEMICALS CO., LTD.) D-4: 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-diimidazole D-5: 4 , 4'-bis(diethylamino)diphenyl ketone D-6 : 2-Hydroxythiobenzothiazole-39- .200949437 [Table 2]

臟組成物 敏感度 黏附性 錐角(度） 圖案缺損 實施例1 S-1 78% 〇 50 ΜΙΓ /4 >> 實施例2 S-2 81% 〇 65 ΛττΤ·. 撕 實施例3 S-3 84% 〇 55 ΑτΤ /»ν\ 實施例4 S-4 86% 〇 50 iftlt 實施例5 S-5 82% 〇 35 ΑττΤ. 热 實施例6 S-6 80% 〇 40 int 實施例7 S-7 77% 〇 50 那 實施例8 S-8 80% 〇 60 實施例9 S-9 84% 〇 65 <frrr 實施例10 S-10 85% 〇 55 M /\w 實施例11 S-11 82% 〇 60 /fm* 賊 實施仿m S-12 84% 〇 60 4ττΤ·. 热 比較例1 S-13 73% 〇 10 有 比較例2 S-14 77% 〇 25 有 比較例3 S-15 80% X 75 An* 無 比較例4 S-16 76% 〇 85 m 比較例5 S-17 81% 〇 100 4rrt. τΤΤΓ 比較例6 S-18 74% 〇 20 有 比較例7 S-19 70% 〇 10 Μ /1、Ν 比較例8 S-20 82% 〇 105 ίΚ / \ \> 比較例9 S-21 81% 〇 85 無 比較例10 S-22 72% 〇 20 Μ /%w 比較例11 S-23 83% 〇 105 Μ t \ w -40- 200949437 從表2，得知相對於100重量份鹼可溶性樹脂，使用 含有100〜3 00重量份在分子內具有己內酯結構及2個以上 的聚合性不飽鍵的化合物作爲多官能性單體之著色層形成 用感放射線性組成物時（實施例1〜12)，能夠形成理想的順 錐形狀且黏附性亦優良。 另一方面，使用未含有在分子內具有己內酯結構及2 個以上的聚合性不飽鍵的化合物作爲多官能性單體者（比 較例8及11)時，像素圖案成爲逆錐狀。又，得知在分子內 ^ 具有己內酯結構及2個以上的聚合性不飽鍵的化合物若相 對於1 00重量份鹼可溶性樹脂爲小於1 〇〇重量份時（比較例 !、2、4〜7、9及10)，無法形成理想的順錐狀，同時會有 產圖案缺損之情形，另一方面，大於300重量份時（比較例 3 )時，黏附性變差。 【圖式簡單說明】 第1圖係像素圖案的剖面形狀之模式圖。 Q 【主要元件符號說明】 無。 -41-Dirty composition sensitivity Adhesive cone angle (degrees) Pattern defect Example 1 S-1 78% 〇50 ΜΙΓ /4 >> Example 2 S-2 81% 〇65 ΛττΤ·. Tear Example 3 S- 3 84% 〇55 ΑτΤ /»ν\ Example 4 S-4 86% 〇50 iftlt Example 5 S-5 82% 〇35 ΑττΤ. Thermal Example 6 S-6 80% 〇40 int Example 7 S- 7 77% 〇50 Example 8 S-8 80% 〇60 Example 9 S-9 84% 〇65 <frrr Example 10 S-10 85% 〇55 M /\w Example 11 S-11 82 % 〇60 /fm* thief implementation imitation m S-12 84% 〇60 4ττΤ·. Thermal comparison example 1 S-13 73% 〇10 Comparative example 2 S-14 77% 〇25 Comparative example 3 S-15 80 % X 75 An* No Comparative Example 4 S-16 76% 〇85 m Comparative Example 5 S-17 81% 〇100 4rrt. τΤΤΓ Comparative Example 6 S-18 74% 〇20 Comparative Example 7 S-19 70% 〇 10 Μ /1, Ν Comparative Example 8 S-20 82% 〇105 ίΚ / \ \> Comparative Example 9 S-21 81% 〇85 No Comparative Example 10 S-22 72% 〇20 Μ /%w Comparative Example 11 S-23 83% 〇105 Μ t \ w -40- 200949437 From Table 2, it is known that the use of 100 to 30,000 weight is used relative to 100 parts by weight of the alkali-soluble resin. When a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in a molecule is used as a radiation sensitive composition for forming a color layer of a polyfunctional monomer (Examples 1 to 12), it is possible to form an ideal one. It has a tapered shape and excellent adhesion. On the other hand, when a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is not used as the polyfunctional monomer (Comparative Examples 8 and 11), the pixel pattern is reversely tapered. In addition, it is found that a compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is less than 1 part by weight based on 100 parts by weight of the alkali-soluble resin (Comparative Example!, 2) 4 to 7, 9 and 10), it is impossible to form an ideal straight tapered shape, and at the same time, a pattern defect may occur. On the other hand, when it is more than 300 parts by weight (Comparative Example 3), the adhesion is deteriorated. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a cross-sectional shape of a pixel pattern. Q [Main component symbol description] None. -41-

Claims (1)

.200949437 七、申請專利範圍： 1. 一種著色層形成用感放射線性組成物，其特徵係含有（A) 著色劑、（B)鹼可溶性聚合物、（C)多官能性單體及（D)光 聚合引發劑之著色層形成用感放射線性組成物，其中相 對於100重量份（B)鹼可溶性聚合物，含有100〜300重量 份在分子內具有己內酯結構及2個以上的聚合性不飽鍵 之化合物作爲（C)多官能性單體。 2. 如申請專利範圍第1項之著色層形成用感放射線性組成 © 物，其中該在分子內具有己內酯結構及2個以上的聚合 性不飽鍵之化合物係下述式（1)所示之化合物， CH2O**11 R CHgO. R R OCH2 C CHa一O CHa一C CH20 R 1 I 0H2〇—_ R CH2O-R / \ (式中，6個R係全部爲下述式（2)所示之基、或6個R之 中1至5個爲下述式（2)所示之基，剩餘爲下述式（3)所示 〇 之基）.200949437 VII. Patent Application Range: 1. A radiation-sensitive linear composition for coloring layer formation, characterized by (A) colorant, (B) alkali-soluble polymer, (C) polyfunctional monomer and (D) a photosensitive composition for forming a coloring layer of a photopolymerization initiator, wherein 100 to 300 parts by weight of a polymer having a caprolactone structure and two or more polymerizations in a molecule is contained with respect to 100 parts by weight of the (B) alkali-soluble polymer. A compound that is not saturated with a bond is (C) a polyfunctional monomer. 2. The sensitizing radioactive composition for coloring layer formation according to the first aspect of the patent application, wherein the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is the following formula (1) The compound shown, CH2O**11 R CHgO. RR OCH2 C CHa-O CHa-C CH20 R 1 I 0H2〇—_ R CH2O-R / \ (wherein the six R systems are all of the following formula (2) The base shown or 1 to 5 of the 6 Rs is a group represented by the following formula (2), and the remainder is a group of the formula represented by the following formula (3)) CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 (2) (式中，R1係表示氫原子或甲基，m係表示1或2，「*」 係表示懸掛鍵）， Ο R1 * Π—- ♦ .C·· C . -42- 200949437 . (式中，R1係表示氫原子或甲基，「*」係表示懸掛鍵）。 3 .如申請專利範圍第2項之著色層形成用感放射線性組成 物，其中該在分子內具有己內酯結構及2個以上的聚合 性不飽鍵之化合物係上述式（1)中，6個R係全部爲上述 式（2)所示之基之化合物。 4.如申請專利範圍第1至3項中任一項之著色層形成用感 放射線性組成物，其中更含有未具有己內酯結構之具有2 個以上的聚合性不飽鍵之化合物作爲（C)多官能性單體。 Ο 5·如申請專利範圍第1至4項中任一項之著色層形成用感 放射線性組成物，其係用以使用800J/m2以下的曝光量來 形成著色層之組成物。 6_ —種彩色濾光片’其係具備使用如申請專利範圍第1至5 項中任一項之著色層形成用感放射線性組成物所形成的 著色層。 7.—種彩色液晶顯示元件’其係具備如申請專利範圍第6 Q 項之彩色濾光片。 8·—種彩色濾光片的製造方法’其係含有使用如申請專利 範圍第1至5項中任一項之著色層形成用感放射線性組 成物，且使用800J/m2以下的曝光量來形成著色層之製 程。 -43-(2) (wherein R1 represents a hydrogen atom or a methyl group, m represents 1 or 2, "*" represents a dangling bond), Ο R1 * Π-- ♦ .C·· C. -42- 200949437 . (wherein R1 represents a hydrogen atom or a methyl group, and "*" represents a dangling bond). 3. The sensitizing radioactive composition for forming a color layer according to the second aspect of the invention, wherein the compound having a caprolactone structure and two or more polymerizable unsaturated bonds in the molecule is in the above formula (1), All of the six R groups are compounds represented by the above formula (2). 4. The radiation sensitive composition for forming a color layer according to any one of claims 1 to 3, further comprising a compound having two or more polymerizable unsaturated bonds having no caprolactone structure; C) Polyfunctional monomer. The sensitizing radioactive composition for forming a color layer according to any one of claims 1 to 4, which is used for forming a composition of a coloring layer using an exposure amount of 800 J/m 2 or less. A color filter layer formed by using the radiation-sensitive composition for coloring layer formation according to any one of claims 1 to 5 of the invention is provided. 7. A color liquid crystal display element' having a color filter as in the sixth aspect of the patent application. A method for producing a color filter, which comprises using a radiation-sensitive composition for forming a color layer according to any one of claims 1 to 5, and using an exposure amount of 800 J/m 2 or less. The process of forming a color layer. -43-
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TWI584069B (en) * 2011-01-18 2017-05-21 Ｌｇ化學股份有限公司 Photosensitive resin composition and photosensitive material comprising the same

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KR20100108621A (en) 2010-10-07
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KR101250684B1 (en) 2013-04-03

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