TW201235784A - Coloring photosensitive resin composition - Google Patents

Coloring photosensitive resin composition Download PDF

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Publication number
TW201235784A
TW201235784A TW101103806A TW101103806A TW201235784A TW 201235784 A TW201235784 A TW 201235784A TW 101103806 A TW101103806 A TW 101103806A TW 101103806 A TW101103806 A TW 101103806A TW 201235784 A TW201235784 A TW 201235784A
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Taiwan
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group
resin composition
photosensitive resin
solvent
acid
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TW101103806A
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Chinese (zh)
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TWI578105B (en
Inventor
Kimiyuki Shirouchi
Yoshinori Koyama
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Sumitomo Chemical Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/201Filters in the form of arrays
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Disclosed is a coloring photosensitive resin composition, containing a colorant, resin, a polymerizable compound, a polymerization initiator and a solvent, where the colorant contains dyes and pigments, the solvent contains dipropylene glycol monomethyl ether acetate; decompression drying is performed after the coloring photosensitive resin composition of the present invention is applied on a substrate, so as to reduce formation of crater defects on the dried coating film as manufactured.

Description

201235784 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種著色感光性樹脂組合物。 【先前技術】 著色感光性樹脂組合物係於液晶顯示面板、電致發光面 板、電漿顯示面板等顯示裝置中所使用之彩色濾光片之製 造中使用。 於曰本專利公開日本專利特開2010_32999號公報中,已 知含有咄P星染料及顏料作為著色劑,且含有丙二醇單甲醚 乙酸酯及4-羥基-4-甲基-2-戊酮作為溶劑之著色感光性樹 脂組合物。 【發明内容】 若將著色感光性樹脂組合物塗佈於基板上後,進行減壓 乾燥而製作乾燥後塗膜,則有時產生火山口(crater)狀之缺 陷。本發明之目的在於’提供一種火山口狀缺陷之產生較 少的著色感光性樹脂組合物。 [解決問題之技術手段] 本發明係提供以下[1]〜[5]者。 [1 ] 一種著色感光性樹脂組合物,其含有著色劑、樹脂、 聚合性化合物、聚合起始劑及溶劑, 者色劑係含有卩山p星染料(xanthenedye)及顏料者, 溶劑係含有二丙二醇單甲醚乙酸酯(dipr〇pylene glyc〇1 monomethylether acetate)者。 [2]如上述[1 ]之著色感光性樹脂組合物,其中二丙二醇單 161707.doc 201235784 甲越乙酸酯於溶劑中之含量為〇.丨質量%以上3〇質量%以 下。 [3] 如上述[1]或[2]之著色感光性樹脂組合物,其中溶劑 係進而含有乳酸乙酯者。 [4] 如上述[3]之著色感光性樹脂組合物,其中溶劑係進而 含有丙二醇單曱醚及/或丙二醇單甲醚乙酸酯者。 [5] 如上述Π]至[4]中任一項之著色感光性樹脂組合物, 其中樹脂為驗可溶性樹脂。 [6] 如上述[1]至[5]中任一項之著色感光性樹脂組合物, 其中聚合性化合物為(甲基)丙烯酸酯。 [7] —種彩色濾光片,其藉由如上述⑴至[6]中任一項之 者色感光性樹脂組合物形成。 [8] -種顯示裝置’其含有如上述[7]之彩色濾光片。 即便將本發明之著色感光性樹脂組合物塗佈於基板上並 進行減壓乾燥而乾燥後製作塗膜,火山口狀缺陷之產生亦 較少。 【實施方式】 本發明之著色感光性樹脂組合物含有著色劑⑷、樹脂 ⑻、聚合性化合物(〇、聚合起始劑⑼及溶劑⑻,著色 劑⑷係含有顏料及_染料者,溶劑係含有二丙二醇單 甲醚乙酸酯者。 本發明之著色感光性樹脂 有顏料及咕P星染料β 組合物所使用之著色劑(Α)含 作為顏料 可列舉有機顏料及無機顏 料,可列舉於色指 161707.doc 201235784 數(染色家學會(The Society of Dyers and Colourists)出版) 中分類為顏料之化合物。其中’較佳為有機顏料。 作為有機顏料,具體而言,例如可列舉:C I.(c〇l〇ur Index,色指數)顏料黃 1、3、12、13、14、15、16、17、 2〇、24、31、53、83、86、93、94、1〇9、110、117、 125 、 128 、 137 、 138 、 139 、 147 、 148 、 150 、 153 、 154 、 166、173、194、214等黃色顏料; C·1.顏料橙 13、31、36、38、40、42、43、51、55、59 61、64、65、71、73等橙色顏料; C-Ι.顏料紅 9、97、105、122、123、144、149、166 ⑽、175 、 176 、 177 、 180 、 192 、 209 、 215 、 216 、 224 、 242、254 ' 255、264、265等紅色顏料; C.I.顏料藍 15、15: 3、15: 4、15: 6、6〇、8〇等藍色顏 料’ c.i.顏料紫】、19、23、29、32、36、38等紫色顏料; C-Ι.顏料綠7、36、58等綠色顏料; CJ.顏料棕23、25等棕色顏料;及 C.I.顏料黑1、7等黑色顏料。 # 其中,較佳為c.i.顏料藍15、15 : 3、15 : 4、15 : 6、 60、80等藍色顏料,αι顏料紫i、19、23、29、32、^、 等紫色顏料,更佳為含有選自[•顏料紫23、c工.顏料 藍15 : 3及c·1.顏料藍15 : 6所組成群之至少-種之顏料, 進而較佳為含有C.1.顏料藍15 : 6之顏料。藉由將該等顏料 ^山嗤染料組合’可獲得耐熱性及色性能優異之彩色遽光 片。該等顏料可單獨使用亦可混合使用2種以上。 16l707.doc 201235784 上述顏料亦可根據需要而實施松脂處理、使用導入有酸 性基或鹼性基之顏料衍生物或顏料分散劑等之表面處理、 藉由高分子化合物等對顏料表面之接枝處理、利用硫酸微 粒化法等之微粒化處理、或利用用以除去雜質之有機溶劑 或水等之清洗處理、離子性雜質利用離子交換法等之除去 處理等。X ’較佳為顏料之粒徑均勻。藉由含有顏料分散 劑而進行分散處理,可獲得顏料於溶液中呈均勻地分散之 狀態之顏料分散液。 作為上述顏料分散劑,可使用市售之界面活性劑,例如 可列舉:聚矽氧系、氟系、酯系、陽離子系、陰離子系、 非離子系、兩性物、聚酯系、聚胺系、丙烯酸系等界面活 性劑等。作為上述界面活性劑,除聚氧乙烯烷基醚類、聚 氧乙烯烧基苯_、聚乙二醇二s旨類、山梨糖醇肝脂肪酸 酯類、脂肪酸改性聚酯類、三級胺改性聚胺酯類、聚乙烯 亞胺類等之外’可按商品名列舉:κρ(信職學卫業股份 有限公司製造)' Fl〇wlen(共榮社化學股份有限公司製 造)、S〇lsperse (Zeneca股份有限公司製造)、efka⑴ 公司製造)、Ajisper(味之素精密技術(Ajin〇m〇t〇201235784 6. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition. [Prior Art] The colored photosensitive resin composition is used for the production of a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. In Japanese Patent Laid-Open Publication No. 2010-32999, it is known to contain a ruthenium P star dye and a pigment as a colorant, and to contain propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone. A colored photosensitive resin composition as a solvent. SUMMARY OF THE INVENTION When a colored photosensitive resin composition is applied onto a substrate and then dried under reduced pressure to form a dried coating film, a crater-like defect may occur. SUMMARY OF THE INVENTION An object of the present invention is to provide a colored photosensitive resin composition which produces less crater-like defects. [Technical means for solving the problem] The present invention provides the following [1] to [5]. [1] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein the colorant contains xanthenedye and a pigment, and the solvent contains two Dipp〇pylene glyc〇1 monomethylether acetate. [2] The colored photosensitive resin composition according to the above [1], wherein the content of dipropylene glycol mono 161707.doc 201235784 formazan acetate in the solvent is 〇.丨% by mass or more and 3% by mass or less. [3] The colored photosensitive resin composition according to the above [1] or [2] wherein the solvent further contains ethyl lactate. [4] The colored photosensitive resin composition according to the above [3], wherein the solvent further contains propylene glycol monoterpene ether and/or propylene glycol monomethyl ether acetate. [5] The colored photosensitive resin composition according to any one of the above [4], wherein the resin is a soluble resin. [6] The colored photosensitive resin composition according to any one of [1] to [5] wherein the polymerizable compound is (meth) acrylate. [7] A color filter formed by the color photosensitive resin composition according to any one of the above (1) to [6]. [8] A display device which contains the color filter as described in [7] above. Even if the colored photosensitive resin composition of the present invention is applied onto a substrate and dried under reduced pressure and dried to prepare a coating film, the occurrence of crater-like defects is less. [Embodiment] The colored photosensitive resin composition of the present invention contains a colorant (4), a resin (8), a polymerizable compound (rhodium, a polymerization initiator (9), and a solvent (8), and the colorant (4) contains a pigment and a dye, and the solvent contains Diethylene glycol monomethyl ether acetate. The coloring photosensitive resin of the present invention is a pigment and a bismuth dye. The coloring agent (Α) used in the composition of the pigment is exemplified as an organic pigment and an inorganic pigment. Refers to the compound classified as a pigment in 161707.doc 201235784 (published by The Society of Dyers and Colourists), wherein 'preferably an organic pigment. As the organic pigment, specifically, for example, C I. (c〇l〇ur Index, color index) Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 2, 24, 31, 53, 83, 86, 93, 94, 1〇9, Yellow pigments such as 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; C·1. Pigment orange 13, 31, 36, 38, 40 , 42, 43, 51, 55, 59 61, 64, 65, 71, 73, etc. Pigment; C-Ι. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166 (10), 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254 '255, 264 , 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 6 〇, 8 〇 and other blue pigments 'ci pigment purple】, 19, 23, 29, 32, 36, 38, etc. Purple pigment; C-Ι. Pigment green 7,36,58 and other green pigments; CJ. Pigment brown 23,25 and other brown pigments; and CI pigment black 1,7 and other black pigments. # Among them, preferably ci pigment blue 15 , 15 : 3, 15 : 4, 15 : 6, 60, 80 and other blue pigments, α i pigment purple i, 19, 23, 29, 32, ^, and other purple pigments, more preferably containing selected from [• pigment purple 23, c work. Pigment blue 15: 3 and c · 1. Pigment blue 15: 6 of the group of at least a kind of pigment, and further preferably contains C.1. Pigment blue 15: 6 pigment. These pigments and hawthorn dye combinations can be used to obtain color calenders having excellent heat resistance and color properties. These pigments can be used singly or in combination of two or more. 16l707.doc 201235784 The above pigments can also be carried out as needed. a surface treatment such as a fat treatment, a pigment derivative or a pigment dispersant introduced with an acidic group or a basic group, a graft treatment of a pigment surface by a polymer compound or the like, a micronization treatment by a sulfuric acid micronization method, or the like, Alternatively, the cleaning treatment using an organic solvent or water for removing impurities, the ionic impurities, the removal treatment by an ion exchange method or the like may be employed. X ' is preferably such that the particle diameter of the pigment is uniform. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained. As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polyfluorene-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester, and polyamine. , surfactants such as acrylics, etc. As the above surfactant, in addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl benzene, polyethylene glycol s, sorbitol liver fatty acid esters, fatty acid modified polyesters, tertiary amines Others, such as modified polyurethanes, polyethyleneimine, etc., can be listed by brand name: κρ (manufactured by Shinji Shogi Co., Ltd.) Fl〇wlen (manufactured by Kyoeisha Chemical Co., Ltd.), S〇lsperse (made by Zeneca Co., Ltd.), manufactured by efka (1), Ajisper (Ajinomoto Precision Technology (Ajin〇m〇t〇)

Techno)股份有限公司製造)、msperbyk(畢克化學⑺Techno) Co., Ltd.), msperbyk (BYK Chemical (7)

Chemie)公司製造)等。該等可分別單獨使用亦可組合使用 2種以上。 於使用顏料分散劑之情形時,其使用量相對於顏料1〇〇 質量份,較佳為100質量份以下,更佳為5〜5〇質量份。若 顏料分散劑之使用量為上述範圍,則有可獲得均勻之分散 161707.doc 201235784 狀態之顏料分散液之傾向。 口山口星染料係含有具有叫骨架之化合物之染料。 作為—星染料,例如可列舉:CI.酸性Mm ";94 "89' U右丹明 6G)、2、3、4、S η Τ 紅 ,C.1·鹼性紅10(若丹明Β)、 ”’^.驗性紫1。、11、25,0.1.^…,。.^“ 2太7直C.1.反應性紅36(孟加拉玫魂紅…項基若丹明G,日 ^利特開测·32"9號公報所記載之㈣染料及日本專 利第料92760號所記載之咄嗤染料等。 今 其中,作為•星染料,較佳為含有式⑴所表示 物(以下有時稱作「化合物⑴」)之染料。化合物⑴亦W 其互變異構物。於使用化合物⑴之情形時,相對於•星染 枓之總量,化合物⑴之含量較佳為5〇質量%以上,更 :〇質量%以上,進而較佳為90質量%以上。尤其較佳為: 實質上僅使用化合物(1)作為ρ山蠼染料。Chemie) manufactured by the company). These may be used alone or in combination of two or more. In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 to 5 parts by mass, per part by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a uniform dispersion of the pigment dispersion in the state of 161707.doc 201235784. The Yamaguchi star dye contains a dye having a compound called a skeleton. As the star dye, for example, CI. Acid Mm "; 94 "89' U-Rhodan 6G), 2, 3, 4, S η Τ Red, C.1·Basic Red 10 (Rudan)明Β), ”'^.Experimental Violet 1., 11, 25, 0.1.^...,..^” 2 To 7 Straight C.1. Reactive Red 36 (Bangladesh Rose Soul... Item Ji Ruo Danming G, ^ 特 开 · 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 a dye (hereinafter sometimes referred to as "compound (1)"). Compound (1) is also a tautomer thereof. In the case of using compound (1), the content of compound (1) is preferably relative to the total amount of star dye 5 % by mass or more, more preferably: 〇 by mass or more, further preferably 90% by mass or more, and particularly preferably: substantially only the compound (1) is used as the ρ-Hawthorn dye.

a® (1) a(Xe) [式⑴中,Ri〜R4分別獨立地表示氫原子、碳數㈣之】價 飽和烴基或碳數6〜Η)。價料族煙基,該芳香族煙基所 含有之氫原子可被_素原子、_R8、_〇H、_〇R8、、 -S03H、-SCVM+、-C〇2H、.c〇2-M+、_c〇2R8、_sr38、 -SOW、·δ〇3ι^_δ〇2ΝιΛΐ0取代。上述飽和煙基所含有 16l707.doc 201235784 之氫原子可被碳數6〜10之芳香族烴基或函素原子取代該 芳香族烴基所含有之氫原子可被碳數丨〜3之烷氧基取代, 上述飽和烴基所含有之可被七_、{小或氺…,取 代。R1及R2亦可一同形成含有氮原子之環,r3&r4亦可一 同形成含有氮原子之環。 -C02H、-CO: R 表示-OH、-S03-、-S03H、-S03.M+、 M+、-C02R8、_s〇3R8或-so2nr9r10 〇 m表示〇 5之整數。於爪為2以上之情形時,複數個r5相 同或相互不同。 R及R7分別獨立地表示氫原子或碳數1〜6之烷基。 M+表示+N(RU)4、Na+或 K+ » X表示鹵素原子。 a表示0或1之整數。 R表示碳數1〜20之1價飽和烴基,該飽和烴基所含有之 氫原子可被鹵素原子取代。 R11分別獨立地表示氫原子、碳數丨〜2〇之i價飽和烴基或 碳數7〜10之芳烷基。 R及R1G分別獨立地表示氫原子、或碳數丨〜⑽之丨價飽和 烴基,該飽和烴基所含有之氫原子可被羥基或齒素原子取 代’該飽和脂肪族烴基所含有之_CIl2·可被_〇_、_c〇_、 -NH-或-NR8-取代,R9及Ri〇可相互鍵結而形成含有氮原子 之3〜10員環之雜環]。 作為R〜R中之碳數6〜丨〇之1價芳香族烴基’例如可列 舉:苯基、曱苯甲醯基、二甲苯基'菜基、丙苯基及丁苯 161707.doc 201235784 基等。 R1〜R 4中之碳數6〜10之1價芳香族烴基較佳為具有選自 由-so3、_s〇3h、_s〇3.m+& _s〇2Nr9r1。所组成群之至少 1 種作為取代基,更佳為具有選自由_sc^.M+& ♦nry。 所組成群之至少1種作為取代基。作為此情形時之_S03· Μ,較佳為_S〇3-+N(Rll)4。若Rl〜R4為該等基,則可由含 有《物(1)之本發明之著色感光性樹脂組合物形成異物之 產生較少且而ί熱性優異之彩色濾光片。 、 作為R1及R2-同形成之環、與RW—同形成之環,例 如可列舉以下者。 ^ Ρ -Ο X) X}A® (1) a (Xe) [In the formula (1), Ri to R4 each independently represent a hydrogen atom, a carbon number (tetra), a valence saturated hydrocarbon group or a carbon number of 6 to Η). The aldehyde group of the valence group, the hydrogen atom contained in the aromatic smog group can be _ 素 atoms, _R8, _〇H, _〇R8, -S03H, -SCVM+, -C〇2H, .c〇2-M+ , _c〇2R8, _sr38, -SOW, ·δ〇3ι^_δ〇2ΝιΛΐ0 replaced. The saturated atomic group containing 16l707.doc 201235784 may be replaced by an aromatic hydrocarbon group or a functional atom having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having a carbon number of 丨3. The above saturated hydrocarbon group may be substituted by VII, {small or 氺.... R1 and R2 may together form a ring containing a nitrogen atom, and r3&r4 may also form a ring containing a nitrogen atom. -C02H, -CO: R represents -OH, -S03-, -S03H, -S03.M+, M+, -C02R8, _s〇3R8 or -so2nr9r10 〇 m represents an integer of 〇 5. In the case where the claw is 2 or more, the plurality of r5s are the same or different from each other. R and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M+ represents +N(RU)4, Na+ or K+»X represents a halogen atom. a represents an integer of 0 or 1. R represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom. R11 each independently represents a hydrogen atom, an i-valent saturated hydrocarbon group having a carbon number of 丨2 or 2, or an aralkyl group having a carbon number of 7 to 10. R and R1G each independently represent a hydrogen atom or a valence saturated hydrocarbon group having a carbon number of (~(10), and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a hydroxyl group or a dentate atom. _CIl2 contained in the saturated aliphatic hydrocarbon group It may be substituted by _〇_, _c〇_, -NH- or -NR8-, and R9 and Ri〇 may be bonded to each other to form a heterocyclic ring of a 3 to 10 member ring containing a nitrogen atom]. Examples of the monovalent aromatic hydrocarbon group having a carbon number of 6 to 中 in R to R include, for example, a phenyl group, an anthranilyl group, a xylyl group, a propylphenyl group, and a butylbenzene 161707.doc 201235784 Wait. The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R1 to R 4 is preferably selected from the group consisting of -so3, _s〇3h, _s〇3.m+&_s〇2Nr9r1. At least one of the constituent groups is preferably a substituent selected from the group consisting of _sc^.M+& ♦nry. At least one of the constituent groups is a substituent. In this case, _S03·Μ is preferably _S〇3-+N(Rll)4. When R1 to R4 are these groups, a color filter which is less likely to be formed into a foreign color of the coloring photosensitive resin composition of the present invention containing the object (1) and which is excellent in heat can be used. Examples of the ring formed by R1 and R2- and the ring formed by the same as RW may be exemplified by the following. ^ Ρ -Ο X) X}

乍為R R中之碳數丨〜之1價飽和烴基,可列舉甲 基 '乙基、丙基、異丙基、丁基、異丁基、戊基、異戊 基、新戊基、己基、庚基、辛基、2_乙基己基、壬基、癸 基、十二烧基、十六烷基、二十烷基等碳數1〜20之烷基, 環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等 碳數3〜20之脂環式飽和烴基。 作為-OR8 ’例如可列舉:曱氧基、乙氧基、丙氧基、丁 氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基 及二十烷氧基等。 161707.doc 201235784 作為-co2r,例如可列舉··甲氧基幾基、乙氧基数基' 丙氧基叛基、第三丁氧基Μ基、己氧基叛基及二十烧氧基 羰基等。 作為-SR8 ’例如可列舉:甲基硫基、乙基硫基、丁基硫 基、己基硫基、癸基硫基及二十烷基硫基等。 作為-S〇2R8,例如可列舉:甲基磺醯基、乙基磺醯基、 丁基績酿基、己基續酿基、癸基磺醯基及二十烷基磺醯基 等。 作為-SC^R8,例如可列舉:曱氧基磺醯基、乙氧基磺醯 基、丙氧基磺醯基'第三丁氧基磺醯基、己氧基磺酼基及 二十烷氧基磺醯基等。 作為-S〇2NR9Rl(),例如可列舉:胺磺醯基; N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、 N-異丙基胺磺醯基、ν· 丁基胺磺醯基、N_異丁基胺磺醯 基' N-第二丁基胺磺醯基' N_第三丁基胺磺醯基、N_戊基 胺磺醯基、N-(l-乙基丙基)胺磺醯基、二曱基丙基) 胺磺醯基、N-(l,2-二甲基丙基)胺磺醯基、N_(2,2_二曱基 丙基)胺磺醯基、N-(l-甲基丁基)胺磺醯基、n_(2-曱基丁 基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、Ν·環戊基胺磺醯 基、Ν-己基胺磺醯基、N-(l,3-二甲基丁基)胺磺醯基' Ν_ (3,3-二曱基丁基)胺績醯基、Ν-庚基胺項醯基' ν·(ι_曱基 己基)胺磺醯基、N-(l,4-二曱基戊基)胺磺醯基、Ν_辛基胺 續醯基、Ν-(2-乙基己基)胺罐醯基、N-(l,5 -二甲基)己基胺 磺醯基、>^-(1,1,2,2-四甲基丁基)胺磺醯基等1^_1取代之胺 161707.doc -10- 201235784 績醢基;及 N,N-—曱基胺磺醯基、N,N_乙基甲基胺磺醯基、n,n_二 基胺κ酿基、n,N-丙基甲基胺績醢基、n,N-異丙基曱基 胺磺醯基、N,N'第三丁基曱基胺磺醯基、N,N-丁基乙基胺 n 土 N’N-雙(1-甲基丙基)胺石黃醯基、n,N-庚基甲基胺 磺醯基等N,N-2取代之胺磺醯基等。 表示R及R之碳數1〜20之1價飽和烴基中,該飽和 烴基所含有之氫原子可被_〇H或鹵素原子取代,該飽和烴 基所含有之-CH2-可被_〇_、_c〇_、_NH•或_nr8_取代。 R及R可相互鍵結而形成含有氮原子之3〜1〇員環之雜 環。作為該雜環’例如可列舉以下者。乍 is a monovalent saturated hydrocarbon group of 碳 之 RR in RR, and examples thereof include methyl 'ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecyl, eicosyl, etc., alkyl having 1 to 20 carbon atoms, cyclopropyl, cyclopentyl, An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group. Examples of -OR8' include a decyloxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and Alkoxy group and the like. 161707.doc 201235784 Examples of -co2r include, for example, a methoxy group, an ethoxy group, a propoxy group, a third butoxy group, a hexyloxy group, and a hexyloxycarbonyl group. Wait. Examples of -SR8' include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group, and an eicosylthio group. Examples of -S〇2R8 include a methylsulfonyl group, an ethylsulfonyl group, a butyl group, a hexyl sulfonyl group, a decylsulfonyl group, and an eicosylsulfonyl group. Examples of -SC^R8 include a decyloxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosane. Oxysulfonyl and the like. As -S〇2NR9Rl(), for example, an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine Sulfonyl, ν·butylamine sulfonyl, N-isobutylamine sulfonyl 'N-t-butylamine sulfonyl' N-t-butylamine sulfonyl, N-pentylamine Sulfonyl, N-(l-ethylpropyl)amine sulfonyl, dimethyl propyl) sulfonyl, N-(l,2-dimethylpropyl)amine sulfonyl, N_( 2,2_Dimercaptopropyl)aminesulfonyl, N-(l-methylbutyl)aminesulfonyl, n-(2-mercaptobutyl)aminesulfonyl, N-(3-A Alkyl butyl) sulfonyl sulfonyl, fluorene cyclopentylamine sulfonyl sulfonyl, fluorenyl-hexylamine sulfonyl sulfhydryl, N-(l,3-dimethylbutyl)amine sulfonyl hydrazine Ν (3,3 - Dimercaptobutyl)amine fluorenyl, hydrazine-heptylamine fluorenyl' ν·(ι_曱ylhexyl)amine sulfonyl, N-(l,4-didecylpentyl)amine sulfonate Sulfhydryl, Ν-octylamine hydrazino, Ν-(2-ethylhexyl)amine sulfhydryl, N-(l,5-dimethyl)hexylamine sulfonyl, >^-(1, 1,2,2-tetramethylbutylamine sulfonyl group, etc. 1^_1 substituted amine 161707.doc -10- 201235784 醢基基; and N , N--decylamine sulfonyl, N,N-ethylmethylamine sulfonyl, n,n-diylamine κ, n,N-propylmethylamine, n, N-isopropyl decylamine sulfonyl, N, N't-butyl decyl sulfonyl sulfonyl, N, N-butyl ethylamine n soil N'N-bis (1-methyl propyl) An amine sulfonyl group substituted with an N, N-2 or the like such as an amine fluorenyl group or an n,N-heptylmethylamine sulfonyl group. In the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R and R, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by _〇H or a halogen atom, and the -CH2- contained in the saturated hydrocarbon group may be _〇_, _c〇_, _NH• or _nr8_ replaced. R and R may be bonded to each other to form a heterocyclic ring containing a 3 to 1 member ring of a nitrogen atom. As the heterocyclic ring, for example, the following may be mentioned.

/ Θ - O JO R5 較佳為-co2H、-co2r8、-so3-、-so3 M+、-so3H 或 S02NHR9,更佳為 S03-、-SO/M+、-so3h或 S02NHR9。 m較佳為l〜4,更佳為l或2。 作為R6及R7中之碳數1〜6之烷基,可列舉上述所舉之烷 基t之碳數1〜6者。 作為R11中之碳數7〜10之芳烷基,可列舉苄基、苯基乙 基、苯基丁基等。 M+為+N(Rn)4、Na+或 K+,較佳為+N(Rn)4 〇 作為+N(Rn)4 ’較佳為4個R1^,至少2個為碳數5〜2〇之 1價飽和烴基。又,4個R11之合計碳數較佳為20〜80,更佳 為20〜60。於化合物(1)中存在之情形時,若R11為 I6l707.doc -11 - 201235784 之著色感光性樹脂 該等基’料由含有化合物⑴之本發明 組合物形成異物較少之彩色濾光片。 化合物(1)較佳為式(2)所表 「化合物⑺」卜料叫㈣,(以下有時稱作 者。化人物mu &甘”較佳為含有化合物(2) 二乂 ()亦可為其互變異構物。於使用化合物⑺之 時,叫染料中之化合物⑺之含量較佳為50質量%以 上’更佳為70質量%以上’進而較佳為90質量%以上。尤 其較佳為,僅使用化合物(2)作為咄哇染料。/ Θ - O JO R5 is preferably -co2H, -co2r8, -so3-, -so3 M+, -so3H or S02NHR9, more preferably S03-, -SO/M+, -so3h or S02NHR9. m is preferably from 1 to 4, more preferably 1 or 2. Examples of the alkyl group having 1 to 6 carbon atoms in R6 and R7 include the above-mentioned alkyl group t having 1 to 6 carbon atoms. Examples of the aralkyl group having 7 to 10 carbon atoms in R11 include a benzyl group, a phenylethyl group, and a phenylbutyl group. M+ is +N(Rn)4, Na+ or K+, preferably +N(Rn)4 〇 as +N(Rn)4' is preferably 4 R1^, at least 2 are carbon number 5~2〇 A monovalent saturated hydrocarbon group. Further, the total carbon number of the four R11 is preferably from 20 to 80, more preferably from 20 to 60. In the case where the compound (1) is present, if R11 is a color-sensitive photosensitive resin of I6l707.doc -11 - 201235784, the base material of the present invention contains a color filter having less foreign matter from the composition of the present invention containing the compound (1). The compound (1) is preferably a compound (7) represented by the formula (2), which is called (four), and is sometimes referred to as the author. The character mu & Gan is preferably contained in the compound (2). When the compound (7) is used, the content of the compound (7) in the dye is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. For this, only compound (2) was used as the yaw dye.

[式(2)中’ R2i〜R24分別獨立地表示氫原+、_r26或碳數 6〜1〇之1價芳香族烴基,該芳香族烴基所含有之氫原子可 被-so3·、-so3 Ma+、-so3H、-so3R26或-S〇2NHR26取代。 乂3表示鹵素原子。 al表示〇或1之整數。 ml表示〇〜5之整數。於mi為2以上之整數之情形時,複 數個R25相同或相互不同。[In the formula (2), R 2i to R24 each independently represent a hydrogen atom +, _r26 or a monovalent aromatic hydrocarbon group having 6 to 1 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -so3·, -so3 Ma+, -so3H, -so3R26 or -S〇2NHR26 are substituted.乂3 represents a halogen atom. Al represents an integer of 〇 or 1. Ml represents an integer of 〇~5. In the case where mi is an integer of 2 or more, plural R25s are the same or different from each other.

Ma+表示+N(R27)4、Na+或 K+。 R25表示-S03·、-SO/Ma+、-so3h或 S02NHR26。 R26表示碳數1〜20之1價飽和烴基。 R27分別獨立地表示碳數1〜20之1價飽和烴基或苄基]。 161707.doc -12- 201235784 可列舉與 作為R21〜R24中之碳數6〜10之1價芳香族煙基 作為R1〜R4中之芳香族烴基而列舉者相同之基。 其中,作為R21〜R24之組合’較佳為尺2〗及汉23為氮原子, 且R22及R24為碳數^⑺之丨價芳香族烴基,該芳香族烴基所 含有之氫原子係可被-S〇3·、-SCVM+、-S〇3H、·8〇3Κ26或 -so2nhr26取代者。更佳為,R2i&R23為氫原子,且r22及 R24為碳數6〜10之1價芳香族烴基,該芳香族烴基所含有之 氫原子係可被-SCVM+或·SOzNHR26取代者。若尺2〗〜^為 該等基’則可由含有化合物⑺之本發明之著色感光性樹脂 組合物形成耐熱性優異之彩色濾光片。 作為R26及R27中之碳數1〜“之丨價飽和烴基,可列舉與 作為R8〜R11中之飽和烴基所列舉者相同之基。 於R21〜R24為-R26之情形時,較佳為劣26分別獨立為氫原 子、甲基或乙基。 作為-S〇3R26及-SOAhr26中之R26,較佳為碳數3〜2〇之 支鏈狀烷基,更佳為碳數6〜12之支鏈狀烷基,進而較佳為 2_乙基己基。若R26為該等基,則含有化合物(2)之著色感 光性樹脂組合物可形成異物之產生較少之彩色濾光片。Ma+ represents +N(R27)4, Na+ or K+. R25 represents -S03·, -SO/Ma+, -so3h or S02NHR26. R26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R27 each independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. 161707.doc -12-201235784 A monovalent aromatic nicotinyl group having 6 to 10 carbon atoms in R21 to R24 is the same as those exemplified as the aromatic hydrocarbon group in R1 to R4. Wherein, the combination of R21 to R24 is preferably a ruler 2 and the group 23 is a nitrogen atom, and R22 and R24 are an valence-valent aromatic hydrocarbon group having a carbon number of (7), and the hydrogen atom contained in the aromatic hydrocarbon group can be -S〇3·, -SCVM+, -S〇3H, ·8〇3Κ26 or -so2nhr26 are substituted. More preferably, R2i & R23 is a hydrogen atom, and r22 and R24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SCVM+ or SOZNHR26. When the ruler 2 is a base, the colored photosensitive resin composition of the present invention containing the compound (7) can be used to form a color filter excellent in heat resistance. Examples of the carbon number 1 to "the valence-saturated hydrocarbon group in R26 and R27 include the same groups as those of the saturated hydrocarbon group in R8 to R11. When R21 to R24 are -R26, it is preferably inferior. 26 is independently a hydrogen atom, a methyl group or an ethyl group. R26 of -S〇3R26 and -SOAhr26 is preferably a branched alkyl group having a carbon number of 3 to 2 Å, more preferably a carbon number of 6 to 12. The branched alkyl group is more preferably a 2-ethylhexyl group. When R26 is such a group, the colored photosensitive resin composition containing the compound (2) can form a color filter having less foreign matter generation.

Ma+為 +N(R27)4、Na+或 K+,較佳為 +N(R27)4。 作為+N(R27)4 ’較佳為中至少2個為碳數卜“之! 價飽和烴基。又,4個r27之合計碳數較佳為20〜80,更佳 為20〜60。於化合物(2)中存在+N(R27)4之情形時,可由含 R為該等基之化合物(2)之本發明的著色感光性樹脂組 合物形成異物之產生較少之彩色濾光片。 I6I707.doc • Π· 201235784 作為化合物(1广例如 仆人铷了歹j舉式(M)〜式(1-30)所表示之 化ό物。再者,於下述Ma+ is +N(R27)4, Na+ or K+, preferably +N(R27)4. Preferably, at least two of the carbon atoms of +N(R27)4' are a valence saturated hydrocarbon group. Further, the total carbon number of the four r27 is preferably from 20 to 80, more preferably from 20 to 60. In the case where +N(R27)4 is present in the compound (2), the colored photosensitive resin composition of the present invention containing the compound (2) having R as the group can form a color filter having less generation of foreign matter. I6I707.doc • Π· 201235784 As a compound (1, for example, a servant 铷 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举

Ka表不奴數1〜20之1價飽和 基’較佳為表示碳數6〜12之主並 <又鏈狀烷基,進而較佳為表 示2_乙基己基。於該等中,較佳為C.L酸性紅289之績醯胺 化物、C.I.酸性紅289之四級錢鹽、c J酸性紫1〇2之續酿胺 化物或C_I.酸性紫102之四級銨鹽。作為此種化合物,例如 可列舉式U·1)〜式(1-8)、式(1-U)或式2)所表示之化合 物等。The Ka-representing number 1 to 20 monovalent saturated group' preferably represents a carbon number of 6 to 12 and is further a chain alkyl group, and more preferably represents a 2-ethylhexyl group. Among these, it is preferably a CL acid red 289 bismuth amide, a CI acid red 289 quaternary salt, a C J acid violet 〇2 continuation aminide or a C_I. acid violet 102 quaternary ammonium salt. Examples of such a compound include a compound represented by the formula U·1) to the formula (1-8), the formula (1-U) or the formula 2).

(1-7) (1-8) 161707.doc • 14- 201235784(1-7) (1-8) 161707.doc • 14- 201235784

(1-10)(1-10)

(1-9) HO3S(1-9) HO3S

Θ S〇3 (1-11)Θ S〇3 (1-11)

^so! A^so! A

(1-14)(1-14)

(1-15)(1-15)

C12H25 (1-16)C12H25 (1-16)

(卜 17) 161707.doc •15· 201235784(Bu 17) 161707.doc •15· 201235784

(1-22) (1-21)(1-22) (1-21)

Λ (1-23)Λ (1-23)

ΗΗ

161707.doc -16- 201235784161707.doc -16- 201235784

染料,較佳為含有式(3)所表示之化合物 (以下有時稱作「化合物(3)」)者。化八 昱爐撕 ^ 化5物(3)亦可為其互變 異構物。於使用化合物(3)之 ^ f P山嗟染料中之化合物 (3)之含量較佳為50質量%以上 尺住為7 0質量%以上,進 而較佳為90質量。/。以上。 ?31 浐The dye preferably contains a compound represented by the formula (3) (hereinafter sometimes referred to as "compound (3)"). The 5 (3) can also be a tautomeric isomer. The content of the compound (3) in the ^ f P hawmin dye of the compound (3) is preferably 50% by mass or more, and the amount of the scale is 70% by mass or more, and more preferably 90% by mass. /. the above. ?31 浐

JyS〇3e (3) [式(3)中’ R及R才目互獨立地表示碳數^,之烷基。π 及R34相互獨立地表示碳數丨〜4之烷基、碳數丨沁之燒美炉 基或碳數丨〜4之烷基磺醯基。及r33亦可一同形成含 原子之環,R32及R34亦可一同形成含有氮原子之環。 P及q相互獨立地表示〇〜5之整數,於?為2以上之情形 時,複數個R33可相同亦可不同,於9為2以上之情形時, 複數個R34可相同亦可不同;I。 I6J707.doc -17- 201235784 作為表示R31及R32之碳數0之烷基,可列舉:甲基、 乙基、丙基、丁基、異丙基、異丁基、第二丁基、第三丁 基 '己基'2-乙基己基、壬基、癸基等。作為表示R33及 R34之碳數1〜4之烷基,可列舉該等之中碳數為至4為止之 基。 作為表示R33及R34之碳數1〜4之烷基硫基,可列舉:曱 基硫基 '乙基硫基、丙基硫基、丁基硫基及異丙基硫基 等。 作為表示R及R之碳數1〜4之烧基續醯基,可列舉曱 基績醯基、乙基績酿基、丙基續醯基、丁基績酿基及異丙 基磺醯基等。 較佳為R”及R32相互獨立為甲基、乙基、丙基或異丙 基。R33及R34較佳為碳數卜4之烧基,更佳為甲基。 較佳為p及q相互獨立為〇〜2之整數,更佳為丨或二。 作為化合物⑺’例如分別可列舉:式(“Μ)〜式(ι·43)所 表:之化σ物。其中’就對有機溶劑之溶解性優異之觀點 而吕’較佳為式(1·31)〜式(1_4G)所表示之化合物。JyS〇3e (3) [In the formula (3), R and R each independently represent an alkyl group having a carbon number of ^. π and R34 independently of each other represent an alkyl group having a carbon number of 44, a calcined base of carbon number, or an alkylsulfonyl group having a carbon number of 丨4. And r33 may also form a ring containing an atom, and R32 and R34 may together form a ring containing a nitrogen atom. P and q independently represent the integers of 〇~5, as in ? In the case of 2 or more, a plurality of R33s may be the same or different. When 9 is 2 or more, a plurality of R34s may be the same or different; I6J707.doc -17- 201235784 As the alkyl group having a carbon number of 0 and R32, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third group are exemplified. Butyl 'hexyl' 2-ethylhexyl, decyl, decyl and the like. Examples of the alkyl group having 1 to 4 carbon atoms of R33 and R34 include those having a carbon number of up to 4. Examples of the alkylthio group having 1 to 4 carbon atoms of R33 and R34 include a mercaptothio group 'ethylthio group, a propylthio group, a butylthio group and an isopropylthio group. Examples of the alkyl group having a carbon number of 1 to 4 of R and R include a fluorenyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl sulfonyl group. Preferably, R" and R32 are independently methyl, ethyl, propyl or isopropyl. R33 and R34 are preferably a carbon number of 4, more preferably a methyl group. Preferably, p and q are mutually Independently, it is an integer of 〇~2, and more preferably 丨 or 2. As the compound (7)', for example, the formula ("Μ"~ ((113)) is represented by the formula: In view of the fact that the solubility in the organic solvent is excellent, L' is preferably a compound represented by the formula (1·31) to the formula (1_4G).

161707.doc 201235784161707.doc 201235784

16l707.doc •19- 201235784 作為咄嗟染料,可使用市售之咄 Λ ΒΠ·八士 杀料(例如’中外化 成股份有限公司製造之「Ch丨 〇/η 呂 Amino1 Fast Pink R- 6G」莖田岡化學工業股份有限公司製造之「Rh—in 又’亦可將市售之㈣染料作為起始原料,並 參考曰本專利特開2〇1〇_32999號公報而進行合成。 著色劑⑷亦可含有與帽料不同之染料。作為該等 =,例如可列舉:偶氮染料、金屬錯鹽偶氮染料、葱酿 …三苯甲炫染料、花青染料、萘酿染料、酿亞胺染 料、甲川染料、方酸染料及酞菁染料。 著色劑㈧可根據所期望之彩色滤光片之顏色而選擇。 亦可將複數種上述染料及顏料加以組合使用。 著色劑⑷中"山,星染料之含量相對於著色劑㈧之總 量,較佳為1〜80質量%,更佳為3〜5〇質量%,進而較佳為 3〜35質量%。顏料之含量相對於著色劑(a)較佳為2〇〜99質 量0/。,更佳為50〜97質量。/。,進而較佳為65〜97質量%。若 心星染料及顏料之含量為上述範圍内,則可獲得耐熱性及 色性能優異之彩色濾光片。 著色劑(A)之含量相對於本發明之著色感光性樹脂組合 物中之固形物成分,較佳為5〜60質量%,更佳為8〜55質量 %,進而較佳為10〜50質量%。若著色劑(A)之含量為上述 之範圍内,則製成彩色濾光片時之色濃度充分,且可使組 合物中含有必需量之樹脂,故而有可形成機械強度充分之 圖案之傾向,故而較佳。此處,所謂固形物成分係指,自 本發明之著色感光性樹脂組合物之總量中除去溶劑而獲得 I61707.doc -20- 201235784 201235784 之量。固形物成分之總 如可藉由液相層析法或 測定。 量及相對於其之各成分之含量,例 氣相層析法等公知之分析方法進行 本發明之著色感光性樹脂組合物含有樹脂 脂⑻’並無㈣限定,較佳為驗可溶性樹脂。# 作為樹〗Θ(Β) ’例如可列舉以下之樹脂[Κ1ΗΚ4]等。 [Κ1]具有蛟數2〜4之環狀趟結構與乙烯性不飽和鍵之單 體⑷(以下有時稱作「⑷」)、與選自由不飽和缓酸及不飽 和叛酸針所組成群之至少1種(b)(以下有時稱作「⑻」)之 共聚物》 [K2](a)、⑻及可與(a)共聚合之單體⑷(但與⑷及⑻ 不同)(以下有時稱作「(c)」)之共聚物。 [K3](b)與(c)之共聚物。 [K4]使(b)與(c)之共聚物與(a)進行反應而獲得之樹脂。 [K5]使(a)與(c)之共聚物與(b)進行反應而獲得之樹脂。 [K6]使(a)與(c)之共聚物與(b)進行反應,進而與鲮酸酐 進行反應而獲得之樹脂》 (a)係例如,具有碳數2〜4之環狀醚結構(例如,選自由環 氧乙烷環、氧雜環丁烧環及四氫呋喃環所組成群之至少i 種)及乙烯性不飽和鍵之聚合性化合物。較佳為(a)係具有 碳數2〜4之環狀醚及(曱基)丙烯酿氧基之單體。 再者’於本說明書中,所謂「(曱基)丙烯酸」係表示選 自由丙烯酸及曱基丙稀酸所組成群之至少1種。「(甲基)丙 烯醯基」及「(甲基)丙烯酸酯」等記法亦有相同意義。 161707.doc 201235784 作為(a),例如可列舉:具有環氧乙烷基及乙烯性不飽和 鍵之單體(al)(以下有時稱作r(al)」)、具有氧雜環丁基及 乙稀性不飽和鍵之單體(a2)(以下有時稱作「(a2)」)、具有 四氫吱喃基及乙烯性不飽和鍵之單體以下有時稱作 「⑷)」)等。 關於(al) ’例如可列舉:具有使直鏈狀或支鏈狀脂肪族 不飽和煙環氧化而成之結構及乙烯性不飽和鍵之單體(al- 1)(以下有時稱作r (a 1 ·】)」),及具有使脂環式不飽和烴環 氧化而成之結構及乙烯性不飽和鍵之單體(al_2)(以下有時 稱作「(al-2)」)。 作為(al-Ι) ’可列舉:(甲基)丙烯酸縮水甘油酯、(曱基) 丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸p_乙基縮水甘油 酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙 烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、心甲 基-鄰乙烯基苄基縮水甘油醚、α·甲基_間乙烯基苄基縮水 甘油醚α-甲基-對乙稀基苄基縮水甘油醚、2,3-雙(縮水 甘油氧基甲基)苯乙烯、2,4·雙(縮水甘油氧基甲基)苯乙 稀2’5-雙(縮水甘油氧基甲基)苯乙烯、2,6_雙(縮水甘油 氧基甲基)苯乙稀、2,3,4-三(縮水甘油氧基甲基)苯乙稀、 2’3’5·三(縮水甘油氧基甲基)苯乙稀、2,3,6_三(縮水甘油氧 基曱基)笨乙稀、3,4,5·三(縮水甘油氧基甲基)苯乙稀、 2,4,6-二(縮水甘油氧基甲基)苯乙烯等。 作為(al-2),可列舉:乙彿基環己稀一氧化物、^-環 氧-4-乙烯基環己烷(例如CelI〇xide 2〇〇〇 ,大賽璐化學工= 161707.doc •22· 201235784 股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基曱酯(例 如CyClomer A400,大賽璐化學工業股份有限公司製造)、 (甲基)丙稀酸M-環氧環己基曱酯(例如Cyci〇mer M1〇〇, 大赛璐化學工業股份有限公司製造)、式⑴所表示之化合 物及式(II)所表示之化合物等。16l707.doc •19- 201235784 As an anthraquinone dye, commercially available 咄Λ·························································································· The "Rh-in" manufactured by Chemical Industry Co., Ltd. can also be used as a starting material in the commercially available (4) dyes, and can be synthesized by referring to the Japanese Patent Publication No. 2〇1〇_32999. The coloring agent (4) can also be used. Containing a dye different from the cap material. As such =, for example, an azo dye, a metal mis-salt azo dye, a scallion, a benzotriene dye, a cyanine dye, a naphthalene dye, a brewing imine dye, Amethyst dye, squaric acid dye and phthalocyanine dye. Colorant (8) can be selected according to the color of the desired color filter. A plurality of the above dyes and pigments can also be used in combination. Colorant (4) "Mountain, Star The content of the dye is preferably from 1 to 80% by mass, more preferably from 3 to 5% by mass, still more preferably from 3 to 35% by mass, based on the total amount of the coloring agent (VIII). The content of the pigment is relative to the coloring agent (a) ) preferably 2〇~99 mass 0/., It is preferably 50 to 97% by mass, and more preferably 65 to 97% by mass. If the content of the heart dye and the pigment is within the above range, a color filter excellent in heat resistance and color performance can be obtained. The content of the (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition of the present invention. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the necessary amount of the resin can be contained in the composition, so that the tendency to form a pattern having sufficient mechanical strength is obtained. Preferably, the solid content means that the solvent is removed from the total amount of the colored photosensitive resin composition of the present invention to obtain an amount of I61707.doc -20-201235784 201235784. The colored photosensitive resin composition of the present invention may contain a resin resin (8) by the liquid chromatography or the amount of each component, and a known analytical method such as gas chromatography. (4) Limited, preferably Soluble resin. # As a tree Θ (Β), for example, the following resins [Κ1ΗΚ4] and the like are exemplified. [Κ1] A monomer having a cyclic oxime structure of 2 to 4 and an ethylenically unsaturated bond (4) (hereinafter) At the time, it is called "(4)"), and at least one type (b) (hereinafter sometimes referred to as "(8)") which is selected from the group consisting of unsaturated acid-lowering acid and unsaturated acid-reducing needles [K2] (a And (8) and a copolymer which can be copolymerized with (a) a monomer (4) (other than (4) and (8)) (hereinafter sometimes referred to as "(c)"). [K3] (b) and (c) Copolymer [K4] A resin obtained by reacting the copolymer of (b) and (c) with (a). [K5] A resin obtained by reacting the copolymer of (a) and (c) with (b). [K6] A resin obtained by reacting the copolymer of (a) and (c) with (b) and further reacting with phthalic anhydride, (a) is, for example, a cyclic ether structure having a carbon number of 2 to 4 ( For example, a polymerizable compound selected from the group consisting of at least one of an oxirane ring, an oxetan ring and a tetrahydrofuran ring, and an ethylenically unsaturated bond. Preferably, (a) is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (fluorenyl) acryloxy group. In the present specification, the term "(fluorenyl)acrylic acid" means at least one selected from the group consisting of acrylic acid and mercaptoacrylic acid. The notation such as "(meth) propyl thiol" and "(meth) acrylate" has the same meaning. 161707.doc 201235784 (a), for example, a monomer (al) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as r(al)"), having an oxetanyl group And a monomer having an ethylenically unsaturated bond (a2) (hereinafter sometimes referred to as "(a2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond may be referred to as "(4))" )Wait. (al) ', for example, a monomer (al-1) having a structure in which a linear or branched aliphatic unsaturated smoke is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as r) (a 1 ·]))), and a monomer (al_2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(al-2)") . Examples of (al-Ι)' include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, p-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cardiomethyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl benzyl ether Glycidyl ether α-methyl-p-ethylene benzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4·bis(glycidoxymethyl)benzene Dilute 2'5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)benzene Ethylene, 2'3'5·tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxycarbonyl), stupid ethylene, 3,4,5·3 (shrinkage) Glyceroxymethyl) styrene, 2,4,6-di(glycidoxymethyl)styrene, and the like. As (al-2), there may be mentioned: acetylcyclohexanone monooxide, ^-epoxy-4-vinylcyclohexane (for example, CelI〇xide 2〇〇〇, Daicel Chemicals = 161707.doc •22·201235784 (manufactured by Co., Ltd.), 3,4-epoxycyclohexyl decyl (meth)acrylate (for example, CyClomer A400, manufactured by Daicel Chemical Industry Co., Ltd.), M-ring (meth) acrylate Oxycyclohexyl decyl ester (for example, Cyci〇mer M1〇〇, manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (1), a compound represented by the formula (II), and the like.

(1) (II) [式(I)及式(II)中’ Rf>相互獨立地表示氫原子、或碳數 1〜4之烷基,該烷基所含有之氫原子可被羥基取代。 X1及X2相互獨立地表示單鍵、_Re…*_Re_〇_、*_Re_s_、 *-Re-NH-。(1) (II) [In the formula (I) and the formula (II), Rf> independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X1 and X2 independently represent a single bond, _Re...*_Re_〇_, *_Re_s_, *-Re-NH-.

Re表示碳數1〜6之燒二基。 *表示與Ο之鍵結鍵]。 作為碳數1〜4之院基,可列舉f基、乙基 '正丙基、異 丙基、正丁基、第二丁基、第三丁基等。 作為氫原子被經基取代而成之院基,可列舉:經甲基、 1·經乙基、2-經乙基、卜經丙基、2_經丙基、3_經丙基、卜 羥基-1-甲基乙基、2•經基.甲基乙基、丁基、2_經丁 基、3-羥丁基、4-羥丁基等。 作為Ra及Rb’較佳為可列舉,氫原子、甲基、經甲基、 1-羥乙基、2-羥乙基,更佳為可列舉氫原子、甲基。 作為院二基,可列舉:亞甲基、伸乙基、丙院丄2•二 16J707.doc •23· 201235784 基 烷-1,4-二基、戊烷-1,5 基、丙烷_1,3- 二基等。 作為X1Υ 2 ‘、 ,較佳為可列舉,單鍵、亞甲基、伸乙基、 不與〇之鍵結鍵)基、*-CH2CH2-〇-基,更佳 為可列舉單鍵、*_CH2CH2_0基。 _尔為式(I)所表示之化合物,可列舉式卜式⑴⑸所表 丁之化。物等。較佳為可列舉式、式⑴3)、式(U)、 式(1 7)式(1_9)或式(Ml)〜式(115)所表示之化合物更 佳為可列舉式(I_n、式 ^人此 ()式(1-7)、式(!·9)或式(1_15)所表示之 化合物。Re represents a calcined diyl group having a carbon number of 1 to 6. * indicates the key with the key]. Examples of the hospital base having a carbon number of 1 to 4 include an f group, an ethyl 'n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Examples of the hospital group in which a hydrogen atom is substituted by a radical are exemplified by methyl, 1·ethyl, 2-ethyl, propyl, 2-propyl, 3-propyl, and Hydroxy-1-methylethyl, 2•transmethyl, methylethyl, butyl, 2-butyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. The Ra and Rb' are preferably a hydrogen atom, a methyl group, a methyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group. As the second base of the hospital, there are mentioned: methylene, exoethyl, propylamine 2•two 16J707.doc •23· 201235784 alkyl-1,4-diyl, pentane-1,5-base, propane_1 , 3-diyl, etc. X1Υ 2 ', preferably, a single bond, a methylene group, an ethylidene group, a bond group which does not bond with fluorene, and a *-CH2CH2-〇- group, more preferably a single bond, * _CH2CH2_0 base. The compound represented by the formula (I) is exemplified by the formula (1) (5). Things and so on. Preferably, the compound represented by the formula, the formula (1) 3), the formula (U), the formula (17), the formula (1-9) or the formula (M1) to the formula (115) is more preferably a formula (I_n, formula ^) The compound represented by the formula (1-7), the formula (!·9) or the formula (1-15).

I61707.doc -24- 201235784 作為式(II)所表示之化合物,可列舉式〜式(π_15)所 表不之化合物等。較佳為可列舉式、式(11_3)、式(π_ 5)、式(11-7)、式(ΙΙ-9)或式(Π-ll)〜式(π-15)所表示之化合 物°更佳為可列舉式(ΙΙ-1)、式(n-7)、式(ΙΙ-9)或式(ΙΙ-15) 所表示之化合物。 h2c:ch~ ?H3〇 H2C==c- H2C:CH—C一0 H2C=CH—C—〇—ch2 c-o-c2h, H2C=CH—C~0-C2H4-0 CH3 0 H2C=C一c—o CH3 0 H2C=C—c~o—ch2 CH3 0 H2C==C—C-〇-c2H4I61707.doc -24- 201235784 The compound represented by the formula (II) may, for example, be a compound represented by the formula (π_15). Preferably, it is a compound represented by the formula, the formula (11_3), the formula (π_5), the formula (11-7), the formula (ΙΙ-9) or the formula (Π-ll) to the formula (π-15). More preferably, it is a compound represented by the formula (ΙΙ-1), the formula (n-7), the formula (ΙΙ-9) or the formula (ΙΙ-15). H2c:ch~ ?H3〇H2C==c- H2C:CH—C—0 H2C=CH—C—〇—ch2 co-c2h, H2C=CH—C~0-C2H4-0 CH3 0 H2C=C-c —o CH3 0 H2C=C—c~o—ch2 CH3 0 H2C==C—C-〇-c2H4

o II Η2〇:ΟΗ"·0—O—C2H4—s i? -c 一 o-c2h4-oo II Η2〇:ΟΗ"·0—O—C2H4—s i? —c one o-c2h4-o

(Π-15) h2c=c (Π-2) Η2〇:ΟΗ一C~0—C2H4—N ch3〇 .,I 11 H;jC=0—C—O_C2H4—S CH30 I II h2c=c—c-o-c2h4- η20=Π-0 ch2oh 0 I 11 h2c=c-c—0 c2h4oh o —c-o(Π-15) h2c=c (Π-2) Η2〇:ΟΗC~0—C2H4—N ch3〇., I 11 H;jC=0—C—O_C2H4—S CH30 I II h2c=c—co -c2h4- η20=Π-0 ch2oh 0 I 11 h2c=cc—0 c2h4oh o —co

式(1)所表示之化合物及式(II)所表示之化合物可分別單 獨使用。又,該等可按任意比率混合。於進行混合之情形 時,其混合比率以莫耳比計,式(1):式(11)較佳為5:95〜 95:5,更佳為 10:90〜90:10,尤佳為 20:80〜80:20。 16l707.doc -25· 201235784 作為具有氧雜環丁基及乙烯性不飽和鍵之單體(a2),更 佳為具有氧雜豸丁基及(甲基)丙烯醯氧基之單體。作 ⑽可列舉:3_甲基_3•曱基丙烯醯氧基曱基氧雜環丁烷: 3-曱基-3-丙烯酼氧基甲基氧雜環丁烷、弘乙 : 醯氧基甲基氧雜環丁烧、3·乙基_3_丙稀醯氧基甲基氧雜環 丁烷、3-甲基·3_曱基丙烯醯氧基乙基氧雜環丁烷、弘甲 基-3-丙烯醯氧基乙基氧雜環丁烷、3_乙基|曱基丙烯醯 氧基乙基氧雜環丁炫、3·乙基_3·丙烯醯氧基乙基氧雜環丁 烷等。 ’衣 作為具有四氫呋喃基及乙烯性不飽和鍵之單體(a3),更 佳為具有四氫呋喃基及(曱基)丙烯醯氧基之單體。 作為(a3),具體而言,可列舉:丙烯酸四氫糠酯(例如 Viscoat V# 150,大阪有機化學工業股份有限公司製造)、 曱基丙烯酸四氫糠酯等。 作為(a) ’就可使所獲得之彩色濾光片之耐熱性、耐化學 品性等可靠性更高之觀點而言,較佳為(al)。進而,就著 色感光性樹脂組合物之保存穩定性優異之觀點而言,更佳 為(a 1 - 2 )。 作為(b),具體而言’例如可列舉:丙烯酸、甲基丙稀 酸、丁稀酸、鄰乙烤基苯甲酸、間乙稀基苯曱酸、對乙稀 基苯甲酸等不飽和一元羧酸類; 順丁烯二酸、反丁烯二酸、檸康酸、中康酸、衣康酸' 3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氣 鄰苯二曱酸、1,2,3,6-四氫鄰苯二曱酸、二曱基四氫鄰苯 161707.doc -26- 201235784 二曱酸、1,4-環己烯二曱酸等不飽和二叛酸類; 5-降祜烯-2,3-二曱酸曱酯、5_羧基雙環[2 21]庚_2·烯、 5,6-二羧基雙環[2.2.1]庚_2_烯、5-羧基-5-曱基雙環[2.2.1] 庚-2-烯、5-羧基-5-乙基雙環[221]庚_2_烯、5_羧基_6_曱 基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2·2.1]庚-2-烯等 含有緩基之雙環不飽和化合物類; 順丁烯二酸酐、擰康酸酐、衣康酸酐、3-乙烯基鄰苯二 曱酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6_四氩鄰苯二甲酸 針、1,2,3,6-四氫鄰苯二曱酸酐、二曱基四氫鄰苯二甲酸 酐、5,6-二羧基雙環[2.2.1]庚_2-烯酸酐等不飽和二羧酸類 酸酐; 丁二酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二曱酸單 [2-(曱基)丙烯醯氧基乙基]酯等2價以上之多元羧酸之不飽 和單[(甲基)丙烯醯氧基烷基]酯類;及 如丙烯酸α-(羥甲基)酯般,於同一分子中含有羥基及羧 基之不飽和丙烯酸酯類等。 忒等之中,就共聚合反應性之觀點或所獲得之樹脂對鹼 )·生水/合液之溶解性之觀點而言,較佳為丙烯酸、甲基丙烯 酸、順丁烯二酸酐等。 作為(c),例如可列舉:(曱基)丙烯酸曱酉旨、(曱基)丙烯 酼乙鼬、(甲基)丙烯酸正丁酯、(曱基)丙烯酸第二丁酯、 (甲基)丙稀酸第三丁醋、(甲基)丙稀酸2-乙基己醋、(甲基) 丙稀酸十二燒基S|、(曱基)丙烯酸月桂S旨、(曱基)丙豨酸 硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲 16l707.doc •27· 201235784 基)丙烯酸2-曱基環己酯、(甲基)丙烯酸三環[5·21 〇2 6]癸 烷-8-基酯(於該技術領域中,作為慣用名而稱為(曱基)丙 烯酸雙環戊酯)、(曱基)丙烯酸雙環戊氧基乙酯、(曱基)丙 稀酸二環[5.2.1 ·02’6]癸烯-8-基酯(於該技術領域中,作為慣 用名而稱為(曱基)丙烯酸雙環戊烯基酯)、(甲基)丙稀酸異 莅酯、(曱基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲 基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(曱基)丙烯酸萘 酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類; (曱基)丙烯酸2-羥乙酯、(曱基)丙烯酸2_羥丙酯等含有羥 基之(甲基)丙烯酸酯類; 順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙酯 等二羧酸二酯; 雙環[2.2.1]庚-2-烯、5-曱基雙環[2 2庚·2_烯、5•乙基 雙環[2.2.1]庚-2-烯、5-羥基雙環[2.21]庚_2_烯、5_羥甲基 雙環[2.2.1]庚-2-烯、5-(2’-經乙基)雙環[2 2」]庚_2_烯、% 甲氧基雙環[2.2.1]庚-2-烯' 5_乙氧基雙環[22丨]庚·2_烯、 5,6-二羥基雙環烯、5,6•二(羥曱基)雙環[22 庚-2-烯、5,6-二(2’-羥乙基)雙環[221]庚_2_烯、5,6•二甲 氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.21]庚_2· 烯、5-羥基-5·甲基雙環烯、5_羥基_5_乙基雙 環[2.2.1]庚-2-稀、5-經甲基_5_甲基雙環[221]庚_2_烯、5_ 第一丁氧基羰基雙環[2.2.1]庚_2-烯、5-環己氧基羰基雙環 [2.2·1]庚·2_烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙 (第三丁氧基羰基)雙環[2.2·!]庚·2_烯、5,6_雙(環己氧基羰 161707.doc •28· 201235784 基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類; N-苯基順丁烯二醯亞胺、N_環己基順丁烯二醯亞胺、N 节基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二酿亞 胺苯曱酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸 酉曰 N-丁 一醒亞胺基-6-順丁烯二酿亞胺己酸醋、N-丁二 醯亞胺基-3-順丁烯二醯亞胺丙酸酯、Ν_(9·吖啶基)順丁烯 二酿亞胺等二羰基醯亞胺衍生物類; 苯乙烯、α·甲基苯乙烯、間甲基苯乙烯、對甲基苯乙 烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯 腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙 酸乙烯酯、1,3-丁二烯、異戊二烯及2,3_二甲基_丨,3-丁二 烯等。 ’ 〇亥等之中,就共聚合反應性及耐熱性之觀點而言,較佳 為苯乙烯、乙烯基甲苯、比苯基順丁烯二醯亞胺、Μ·環己 基順丁稀二醯亞胺、Ν•节基順丁晞二醯亞胺、雙環[2.2.1] 庚-2-稀等。 於樹知[κι]中,各來源之結構單元於構成樹脂[κ丨]之總 結構單元中之比率,較佳為以下之範圍。 來自(a)之結構單元’ 5〇〜98莫耳%(更佳為⑼〜⑽莫耳⑹ 來自(b)之結構單元,2〜5G莫耳%(更佳為丨㈣莫耳。 若樹脂[K1]之結構單元之比率為上述範圍内,則有著色 感光|±樹月曰組合物之保存穩定性、顯影性及彩色滤光片之 耐溶劑性變得良好之傾向。 樹脂[Κ1 ]係例如可念_ # 士占,Γ 』參考文獻「高分子合成之實驗法」 16l707.doc -29· 201235784 (大津隆行著’發行所股份有限公司,化學同人,第1版第 1次印刷,1972年3月1日發行)所記載之方法及該文獻所記 載之引用文獻而製造β 具體而言,可列舉:將(a)及(15)之特定量、聚合起始劑 及溶劑等投入反應容器中,例如利用氮氣置換氧氣,而形 成脫氧環境,一面攪拌一面加熱及保溫之方法。再者,此 處所使用之聚合起始劑及溶劑等並無特別限定,可使用任 一種通常於該領域中所使用者。作為聚合起始劑,例如可 列舉:偶氮化合物(2,2,-偶氮二異丁腈、2,2,·偶氮雙(2,4_二 甲基戊腈)等)或有機過氧化物(過氧化苯曱醯等作為溶 劑,只要是能溶解各單體者便可,可使用下述之溶劑等作 為本發明之著色感光性樹脂組合物之溶劑(E)。 再者,㈣得之共聚物可直接使用反應後之溶液,亦可 使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以 固體(粉體)之形態而提取者。尤丨是,於該聚合時,使用 /本發明之著色感光性樹脂組合物所含有之溶劑作為溶劑, 從而可直接使用反應後之溶液製備本發明之著色感光性樹 脂組合物’故而可使本發明之著色感光性樹脂組合物 造步驟變簡單。 於樹脂[K2]中,各來源之結構單元於構成樹脂⑽之總 結構單元中之比率,較佳為以下範圍。 “ 來自(a)之結構單元,2〜95莫耳%(更佳為5〜8〇莫耳 來自(b)之結構單元’ 4〜45莫耳%(更佳為丨q〜Μ莫耳叫 來自(c)之結構單元,丨~65莫耳%(更佳為5〜6〇莫耳%) 161707.doc 30· 201235784 若樹脂[κ取結構單元之比率為上述範㈣,則有著色 感光性樹脂組合物之保存穩定性、顯影性,及彩色濾光片 之耐溶劑性、耐熱性及機械強度變得良好之傾向。 樹脂[Κ2]例如可以與作為樹脂則之製造方法而記载者 同樣之方式製造。 具體而言,可列舉將⑷、(b)及⑷之特定量、聚合起始 劑及溶劑投人反應容器巾’例如,㈣氮氣置換氧氣而形 j脫氧環境’從而一面攪拌一面加熱及保溫之方法。所獲 付之共聚物可直接使用反應後之溶液,亦可使用經漠縮或 稀釋之冷液’亦可使用藉由再沈殿等方法以固體(粉體)之 形態提取者。 於樹脂㈣中,各來源之結構單元於構成樹脂_之總 結構單元中之比率,較佳為以下範圍。 0)2〜50莫耳%,更佳為5〜4〇莫耳% (c)5 0〜98莫耳% ’更佳為6〇〜95莫耳% 樹脂[K3]例如可以與作為樹脂[Kl]之製造方法而記載者 同樣之方式製造。 樹脂[Κ4]可藉由以下方式而得到:獲得沙)與(〇之共聚 物,並使(a)所具有之碳數2〜4之環狀醚與(b)所具有之羧基 或羧酸酐進行加成。 首先,以與作為[K1]之製造方法而記載者同樣之方式製 造⑻與⑷之共聚物。於此情形時,纟來源之結構單元於 構成(b)與(c)之共聚物之總結構單元中之比率,較佳為以 下範圍。 161707.doc 31 201235784 (b)5〜50莫耳❶/〇、更佳為10〜45莫耳% (C)50〜95莫耳°/β、更佳為55〜90莫耳% 其-人’使上述共聚物中來自(b)之結構單元所含有之緩 基及/或敌酸酐之-部分與⑷所具有之碳數2〜4之環狀鍵進 行反應。 产可於製造(b)與(e)之共聚物後,繼而將燒瓶内環境自氮 氣置換為空氣,將⑷、羧基與環狀醚之反應觸媒投入燒瓶 内,例如於6〇〜130。(:下反應卜1〇小時,藉此獲得樹脂 [K4]。作為上述反應觸媒,例如可列舉三(二甲胺基甲基) 苯紛等。上述反應觸媒之使用量相對於⑷〜⑷之合計量土較 =為0顧〜5質量%。作為上述聚合抑制劑例如可列舉對 苯一酚等。上述聚合抑制劑之使用量相對於(a)〜(c)之合計 量較佳為0._〜5質量%β裝人方法、反應溫度及時料反 應條件可考慮製造設備或聚合❹之❹㈣而適當調 整。再者,與聚合條件相同,可考慮製造設備或聚合引起 之發熱量等而適當調整裝入方法或反應溫度。 此情料之⑷之使用量相對於(b)1〇〇莫耳,較佳為5〜8〇 莫耳,更佳為H)〜75莫耳,尤佳為15〜7〇莫耳。藉由設為該 範圍’則有I色感光性樹脂組合物之保存穩定性、顯影性 及感光度’及彩色遽光片之耐溶劑性 '耐熱性及機械強度 之平衡變得良好之傾向。 關於樹脂[K5],作為第一階段,以與上述樹脂[κυ之製 造方法同樣之方式獲得(a)與(c)之共聚物。與上述相同, 所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃 161707.doc -32- 201235784 縮或稀釋之溶液’亦可使用藉由再沈澱等方法以固體(粉 體)之形態提取者。 車交佳為,來自⑷及⑷之結構單元之比率相對於構成上 述共聚物之總結構單7C之合計莫耳數’分別為以下之範 圍。 來自(a)之結構單元’ 5〜95莫耳%(更佳為1〇〜9〇莫耳%) 來自(c)之結構單元,5〜95莫耳%(更佳為1〇〜9〇莫耳%) 進而,可於與樹脂[K4]之製造方法相同之條件下,使(a) 與(c)之共聚物所具有之來自(a)之環狀醚與(b)所具有之羧 酸或羧酸酐進行反應,藉此獲得樹脂[艮5]。 與上述共聚物進行反應之(b)之使用量相對於(a)l〇〇莫 耳,較佳為5〜80莫耳。就環狀醚之反應性較高且不易殘留 未反應之(a)之觀點而言,作為樹脂[K5]中所使用之 較佳為(al),進而較佳為(al-1)。 樹脂[K6]係於樹脂[K5]中進而❹酸肝進行反應而形成 之樹脂。使藉由環狀_缓酸或缓酸軒之反應而產生之經 基與羧酸酐進行反應。 作為叛酸if ’可列舉順丁稀二酸軒、檸康酸針、衣康酸 肝。-乙稀基鄰苯二甲酸野、4_乙婦基鄰苯二甲酸酐、 M,5,6-四氫鄰苯二甲酸酐、以,3,6_四氫鄰苯二、 二甲基四氫鄰苯二甲酸軒、5’6_二竣基雙環[2 2·】]庚 酸酐等。 作為樹脂(B) ’具體 環己基甲酯/(甲基)丙 而言可列舉:(甲基)丙烯酸3,4•環氧 烯酸共聚物、丙烯酸3,4-環氧三環 16f707.doc •33· 201235784 [5.2.1.02 6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1];(甲基) 丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚 物、(曱基)丙烯酸縮水甘油酯/苯乙烯/(曱基)丙稀酸共聚 物、丙烯酸3,4-環氡三環[5.2.1.02.6]癸酯/(曱基)丙烯酸/N_ 環己基順丁稀二酿亞胺共聚物、丙烯酸3,4-環氧三環 [5.2.1.02 6]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、3_曱基_ 3-(甲基)丙烯酸醯氡基甲基氧雜環丁烷/(曱基)丙烯酸/苯乙 烯共聚物等樹脂[K2];(甲基)丙稀酸苄酯/(甲基)丙稀酸共 聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3];使(曱基) 丙烯酸苄酯/(甲基)丙烯酸共聚物與(曱基)丙烯酸縮水甘油 酯進行加成而形成之樹脂,使(甲基)丙烯酸三環癸酯/苯乙 烯/(甲基)丙烯酸共聚物與(甲基)丙烯酸縮水甘油酯進行加 成而形成之樹脂,使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸 苄酯/(甲基)丙烯酸共聚物與(甲基)丙烯酸縮水甘油酯進行 加成而形成之樹脂等樹脂[Κ4];使(甲基)丙烯酸雙環戊 酯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸進行 反應而形成之樹脂,使(甲基)丙烯酸雙環戊酯/苯乙烯甲 基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸進行反應而 形成之樹脂等樹脂[Κ5];使(甲基)丙烯酸雙環戊酯/(甲基) 丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸進行反應而形 成之樹脂進而與四氫鄰苯二甲酸酐進行反應而形成之樹脂 等樹脂[Κ6]等。其中,較佳為樹脂[Κ1]及樹脂[κ2],更佳 為樹脂[Κ1],進而較佳為丙烯酸3,4_環氧三環[5.2 1 Μ’癸 酯/(甲基)丙烯酸共聚物。若樹脂(Β)係含有來自(a)之結構 I61707.doc -34 - 201235784 單元者,則可進-步提高所獲得之彩色滤光片之耐熱性、 耐化學品性等可靠性。 樹脂(B)以聚苯乙烯換算計之重量平均分子量較佳為 3,000〜100,刪’更佳為5,〇〇〇〜50,〇〇〇,進而較佳為5〇〇〇〜 35,〇〇〇,特佳為6,_,,刚,尤佳為7,_〜28,_。若分 子量為上述範圍’則有塗膜硬度提高,且殘膜率亦較高, 未曝光部對顯影液之溶解性良好而使解像度提高之傾向。 樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均 分子量(Μη)]較佳為L1〜6,更佳為〗2 + 樹月曰(B)之酸值較佳為5〇〜15G mg K〇H/g,更佳為〜⑴ mg-K〇H/g’進而較佳為7〇〜135mg_K〇H/g。此處,酸值係 作為中和!代樹脂所需要之氣氧化卸之量㈣而測定之 值’例如可藉由㈣氫氧化料溶液進行敎而求得。 樹脂(B)之含量相對於本發明之著色感光性樹脂組合物 之固形物成分,較佳為7〜65質量%,更佳為】3〜6〇質量%, 進而較佳為17〜55質量%。若樹脂⑻之含量為上述範圍, 則有可形成著色圖案’且解像度及殘膜率提高之傾向。 本發明之者色感光性樹脂組合物含有聚合性化合物 :二聚合性化合物(C)係可藉由自聚合起始劑⑼產生之活 性自由基及酸等而聚合之化合物,例如可列 —合物等,一— 性二::聚合性化合物(C),較佳為具有3個以上乙浠 於生不飽和鍵者。作為此種聚合性化合物,例如可列舉··季 I61707.doc -35- 201235784 戊四醇四(甲基)丙烯酸酯' 二季戊四醇五(甲基)丙烯酸 酉旨、二季戊四醇六(曱基)丙稀酸酯、三季戊四醇八(甲基) 丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十 (甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、異氰尿 酸三(2-(甲基)丙烯醯氧基乙基)g旨、乙二醇改性季戊四醇 四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙稀 酸酯、丙二醇改性季戊四醇四(曱基)丙烯酸酯、丙二醇改 性二季戊四醇六(曱基)丙烯酸酯、己内酯改性季戊四醇四 (甲基)丙烯酸酯及己内酯改性二季戊四醇六(甲基)丙烯酸 醋等。其中,較佳為可列舉二季戊四醇五(甲基)丙稀酸 酯、二季戊四醇六(曱基)丙烯酸酯等。聚合性化合物可單 獨使用’亦可組合使用2種以上。 聚合性化合物(C)之重量平均分子量較佳為ι5〇以上且 2,900以下,更佳為250^,500以下。 聚合性化合物(C)之含量相對於本發明之著色感光性樹 脂組合物之固形物成分,較佳為7〜65質量%,更佳為 13〜60質量% ’進而較佳為17〜55質量%。若上述聚合性化 合物(C)之含量為上述範圍内,則有使硬化充分進行,顯 影中之殘膜率提高,著色圖案中不易產生底切而使密接性 變得良好之傾向,故而較佳。 本發明之著色感光性樹脂組合物含有聚合起始劑(D)。 作為上述聚合起始劑(D),只要是可藉由光或熱之作用 而產生活性自由基、酸等而使聚合開始之化合物,則並無 特別限定’可使用公知之聚合起始劑。 16l707.doc •36- 201235784 作為聚合起始劑(D) ’較佳為藉由光之作用而產生活性 自由基者,更佳為烷基笨酮化合物、三畊化合物、醯基氧 化膦化合物、肟化合物及聯咪唑化合物,進而較佳為肟化 合物。 上述烷基苯酮化合物係具有式(d2)所表示之部分結構或 式(d3)所表示之部分結構之化合物。於該等部分結構中, 苯環可具有取代基。The compound represented by the formula (1) and the compound represented by the formula (II) can be used singly. Also, these can be mixed in any ratio. In the case of mixing, the mixing ratio is in molar ratio, and the formula (1): formula (11) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20:80~80:20. 16l707.doc -25· 201235784 The monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond is more preferably a monomer having a xanthene butyl group and a (meth) acryloxy group. (10) can be exemplified by: 3-methyl- 3 - mercapto propylene fluorenyloxy oxetane: 3-mercapto-3-propenyloxymethyl oxetane, Hong B: oxime Methyloxetane, 3·ethyl_3_acryloxymethyloxetane, 3-methyl·3_mercaptopropenyloxyethyloxetane,甲基Methyl-3-propenyloxyethyloxetane, 3-ethyl-mercaptopropenyloxyethyloxetane,3·ethyl_3·acryloxyethyl Oxetane and the like. The monomer (a3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (fluorenyl)acryloxy group. Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V# 150, manufactured by Osaka Organic Chemical Co., Ltd.), and tetrahydrofurfuryl methacrylate. (a) ' is preferably (al) from the viewpoint of higher reliability such as heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of excellent storage stability of the colored photosensitive resin composition, (a 1 - 2 ) is more preferable. Specific examples of (b) include, for example, acrylic acid, methacrylic acid, butyric acid, o-bromobenzoic acid, m-phenylbenzoic acid, and ethylidenebenzoic acid. Carboxylic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid '3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5 ,6-tetraqiphthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimercaptotetrahydroortylene 161707.doc -26- 201235784 dicapric acid, 1,4-ring Unsaturated ditoxaic acid such as hexene dicapric acid; 5-decalin-2,3-didecanoate, 5-carboxybicyclo[2 21]hept-2-ene, 5,6-dicarboxybicyclo[ 2.2.1] hept-2-ene, 5-carboxy-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[221]hept-2-ene, 5_ a bicyclic unsaturated compound containing a buffer group such as a carboxyl group of 6-fluorenylbicyclo[2.2.1]hept-2-ene or 5-carboxy-6-ethylbicyclo[2·2.1]hept-2-ene; Adipic anhydride, tococanic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic acid needle, 1, 2,3,6-tetrahydroortylene An unsaturated dicarboxylic acid anhydride such as an acid anhydride, dimercaptotetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]heptan-2-ene anhydride; succinic acid mono [2-(methyl)] Unsaturated mono[(methyl) propylene oxime of a polyvalent carboxylic acid having two or more valences such as propylene methoxyethyl ester and phthalic acid mono [2-(indenyl) propylene oxyethyl] ester; An alkyl group] ester; and an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule as the α-(hydroxymethyl)acrylate. Among the above, from the viewpoint of the copolymerization reactivity or the solubility of the obtained resin to the alkali/liquid/liquid mixture, acrylic acid, methacrylic acid, maleic anhydride or the like is preferable. Examples of (c) include (fluorenyl)acrylic acid, (fluorenyl)acrylonitrile, n-butyl (meth)acrylate, and dibutyl (meth)acrylate, (methyl). Acetic acid third butyl vinegar, (methyl) acrylic acid 2-ethylhexyl vinegar, (methyl) acrylic acid dodecapine S|, (mercapto) acrylic acid Laurel S, (mercapto) C Stearyl phthalate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-nonylcyclohexyl acrylate, (meth)acrylic acid Cyclo [5·21 〇 2 6] decane-8-yl ester (referred to in the art as a customary name (diyl) dicyclopentanyl acrylate), (fluorenyl) biscyclopentyloxyethyl acrylate (indenyl) acrylic acid bicyclo [5.2.1 · 02'6] decene-8-yl ester (referred to in the technical field as (fluorenyl) dicyclopentenyl acrylate) , (meth) isopropyl isopropionate, (amyl) adamantyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylates such as naphthyl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; bicyclo [2.2.1] hept-2-ene, 5 - indenylbicyclo[2 2 heptyl-2-ene, 5•ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.21]hept-2-ene, 5-hydroxymethylbicyclo[2.2 .1]hept-2-ene, 5-(2'-ethyl)bicyclo[2 2"]hept-2-ene, % methoxybicyclo[2.2.1]hept-2-ene' 5_B Oxybicyclo[22丨]hept-2-ene, 5,6-dihydroxybicycloalken, 5,6•bis(hydroxyindenyl)bicyclo[22 hept-2-ene, 5,6-di(2'- Hydroxyethyl)bicyclo[221]hept-2-ene, 5,6•dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.21]hept-2· Alkene, 5-hydroxy-5.methylbicycloalkenene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-diene, 5-methyl-5-methylbicyclo[221]hept_2 _ene, 5_ first butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2·1]hept-2-ene 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2·!]hept-2-ene, 5,6-bis (cyclic Hexyloxycarbonyl 161707.doc •28·201235784 base) bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenyl maleimide, N-cyclohexylpentene Dimethyleneimine, N-n-butylsuccinimide, N-butylenedimino-3-butylbutenylene benzoate, N-butanediamine-4- Maleic acid imide butyl phthalate N-butyl ketone imine-6-m-butylene hexanoic acid hexanoic acid vinegar, N-butyl diimide imino-3-butylene Dicarbonyl quinone imine derivatives such as amine propionate, Ν_(9. acridinyl) maleimide, styrene, α-methyl styrene, m-methyl styrene, p-methyl benzene Ethylene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene and 2,3-dimethyl-oxime, 3-butadiene, and the like. In the viewpoint of copolymerization reactivity and heat resistance, it is preferably styrene, vinyl toluene, phenyl butyl succinimide, Μ·cyclohexyl cis-butane dioxime. Imine, Ν•节基顺丁晞晞iimine, bicyclo [2.2.1] hept-2-thene, etc. In Yu Shuzhi [κι], the ratio of the structural unit of each source to the total structural unit constituting the resin [κ丨] is preferably in the following range. From the structural unit of (a) '5〇~98 mol% (more preferably (9) ~ (10) Moer (6) from the structural unit of (b), 2~5G mol% (more preferably 丨(四)莫耳. If resin When the ratio of the structural unit of [K1] is within the above range, the storage stability, the developability, and the solvent resistance of the color filter of the colored photosensitive resin are preferably good. Resin [Κ1] For example, you can read _ #士占,Γ 参考 "Research method for polymer synthesis" 16l707.doc -29· 201235784 (Otsu Takayuki, 'issuing company, chemical co-owner, first edition, first print, In the method described in the above-mentioned publication, the method described in the above-mentioned document, and the reference to the literature, the production of β, specifically, the specific amount of (a) and (15), a polymerization initiator, a solvent, etc. In the reaction vessel, for example, a method of heating and holding the oxygen in a deoxidizing atmosphere by a nitrogen gas is formed by stirring, and the polymerization initiator, the solvent, and the like used herein are not particularly limited, and any of them may be used. User in the field. As a polymerization initiator For example, an azo compound (2,2,-azobisisobutyronitrile, 2,2, azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoate) As the solvent, ruthenium or the like can be used as the solvent (E) of the colored photosensitive resin composition of the present invention, as long as it can dissolve each monomer. Further, the copolymer obtained in (4) can be directly used. As the solution after the reaction, a concentrated or diluted solution may be used, or a method of extracting in the form of a solid (powder) by reprecipitation or the like may be used. In particular, at the time of the polymerization, the present invention is used. The solvent contained in the colored photosensitive resin composition is used as a solvent, and the colored photosensitive resin composition of the present invention can be directly used as the solution after the reaction. Thus, the coloring photosensitive resin composition of the present invention can be easily formed. In the resin [K2], the ratio of the structural unit of each source to the total structural unit constituting the resin (10) is preferably in the following range. " Structural unit derived from (a), 2 to 95 mol% (more preferably 5) ~8〇莫耳from the structural unit of (b) ' 4 45% by mole (more preferably 丨q~Μ莫耳called the structural unit from (c), 丨~65mol% (more preferably 5~6〇%) 161707.doc 30· 201235784 If resin [ When the ratio of the κ structural unit is the above-mentioned criterion (4), the storage stability and developability of the colored photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the color filter tend to be good. Κ2] can be produced, for example, in the same manner as described for the production method of the resin. Specifically, a specific amount of (4), (b), and (4), a polymerization initiator, and a solvent are introduced into the reaction container towel. For example, (4) a method in which nitrogen is replaced with oxygen and the shape of the oxygen is deoxidized, thereby heating and keeping warm while stirring. The obtained copolymer may be directly used as a solution after the reaction, or may be a cold liquid which is diluted or diluted, or may be extracted as a solid (powder) by a method such as re-sinking. In the resin (4), the ratio of the structural unit of each source to the total structural unit constituting the resin is preferably in the following range. 0) 2 to 50 mol%, more preferably 5 to 4 〇 mol% (c) 5 0 to 98 mol% 'better than 6 〇 to 95 mol% Resin [K3] can be used as a resin, for example [ The manufacturing method of Kl] is produced in the same manner as described. The resin [Κ4] can be obtained by obtaining a copolymer of sand and (〇), and (a) having a cyclic ether having 2 to 4 carbon atoms and (b) having a carboxyl group or a carboxylic anhydride; First, the copolymer of (8) and (4) is produced in the same manner as described in the production method of [K1]. In this case, the structural unit derived from cerium is copolymerized in the structures (b) and (c). The ratio in the total structural unit of the substance is preferably in the following range. 161707.doc 31 201235784 (b) 5 to 50 moles/〇, more preferably 10 to 45 moles (C) 50 to 95 moles /β, more preferably 55 to 90 mol%, which is - a human 'the part of the copolymer derived from the structural unit derived from (b) and/or the portion of the hydrocarbon anhydride and the carbon number of (4) The ring bond of 4 is reacted. After the copolymer of (b) and (e) is produced, the environment in the flask is replaced with air from nitrogen, and the reaction catalyst of (4), carboxyl group and cyclic ether is put into the flask. For example, it is 6 〇 to 130. (: The reaction is carried out for 1 hour, whereby the resin [K4] is obtained. As the above reaction catalyst, for example, tris(dimethylamino) can be cited. The amount of the above-mentioned reaction catalyst is 0 to 5% by mass based on the total amount of the catalysts of (4) to (4). Examples of the polymerization inhibitor include p-phenylene phenol and the like. The amount of use relative to the total amount of (a) to (c) is preferably 0. _ to 5 mass%. The method of loading, the reaction temperature, and the reaction conditions of the material can be appropriately adjusted in consideration of the manufacturing equipment or the polymerization enthalpy (4). In the same manner as the polymerization conditions, the charging method or the reaction temperature may be appropriately adjusted in consideration of the heat generated by the production equipment or the polymerization, etc. The amount of use of (4) is preferably (b) 1 mol, preferably 5 to 8 〇 Mo Er, more preferably H) 〜 75 摩尔, and particularly preferably 15 to 7 〇 Mo. By setting it as the range, there is storage stability and developability of the I color photosensitive resin composition. And the sensitivity of the sensitivity and the heat resistance and the mechanical strength of the color-sensitive film are improved. The resin [K5] is the first stage in the same manner as the above-mentioned method of producing the resin [κυ]. A copolymer of (a) and (c) is obtained. The same as above, obtained The polymer may be directly used as a solution after the reaction, or a solution diluted or diluted by 161707.doc -32-201235784 may be used. It may also be extracted as a solid (powder) by reprecipitation or the like. Preferably, the ratio of the structural units from (4) and (4) to the total number of moles of the total structure of the above-mentioned copolymers 7C is the following range. The structural unit derived from (a) is 5 to 95% by mole ( More preferably, it is 1〇~9〇mol%). The structural unit derived from (c), 5 to 95% by mole (more preferably 1〇~9〇% by mole) Further, it can be manufactured with resin [K4] Under the same conditions, the copolymer of (a) and (c) has a cyclic ether derived from (a) and (b) a carboxylic acid or a carboxylic anhydride, thereby obtaining a resin [艮5] ]. The amount of (b) used for the reaction with the above copolymer is preferably from 5 to 80 moles per mol of (a). In view of the fact that the cyclic ether is highly reactive and does not easily remain unreacted (a), it is preferably (al), more preferably (al-1), used as the resin [K5]. The resin [K6] is a resin formed by reacting a citrate liver with a resin [K5]. The reaction group produced by the reaction of a cyclic acid or a slow acid acid is reacted with a carboxylic acid anhydride. As the acid-reducing if ’, there may be mentioned cis-butyl succinate, citraconic acid, and itaconic acid. -ethylene phthalic acid, 4_ethyl phthalic phthalic anhydride, M, 5,6-tetrahydrophthalic anhydride, 3,6-tetrahydrophthalic acid, dimethyl Tetrahydrophthalic acid, 5'6-dimercaptobicyclo[2 2 ·]]heptanoic anhydride, and the like. As the resin (B) 'specific cyclohexyl methyl ester / (methyl) C, (meth)acrylic acid 3,4•epoxy enoic acid copolymer, acrylic 3,4-epoxy tricyclic 16f707.doc •33· 201235784 [5.2.1.02 6]Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; (meth) glycidyl acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer , (fluorenyl) glycidyl acrylate / styrene / (mercapto) acrylic copolymer, 3,4-cyclopyrene tricyclo[3.2.1.02.6] oxime ester / (fluorenyl) acrylic acid / N_ ring Hexyl cis-butyl diimide copolymer, 3,4-epoxytricyclo[5.2.1.02 6]decyl acrylate / (meth) acrylate / vinyl toluene copolymer, 3 曱 _ 3- (A Resin such as fluorenylmethyl oxetane/(mercapto)acrylic acid/styrene copolymer [K2]; benzyl (meth) acrylate/(meth) acrylate copolymer, a resin such as a styrene/(meth)acrylic copolymer [K3]; a resin obtained by adding a (benzyl) methacrylate/(meth)acrylic copolymer and a glycidyl (mercapto)acrylate to form a resin. (Methacrylate A resin formed by addition of a tricyclodecyl ester/styrene/(meth)acrylic acid copolymer and glycidyl (meth)acrylate to give tricyclode(meth)acrylate/benzyl (meth)acrylate a resin such as a resin formed by addition of a /(meth)acrylic acid copolymer and glycidyl (meth)acrylate [Κ4]; copolymerization of dicyclopentanyl (meth)acrylate/glycidyl (meth)acrylate a resin formed by reacting a substance with (meth)acrylic acid, and a resin such as a resin obtained by reacting a copolymer of dicyclopentyl (meth)acrylate/glycidylmethyl methacrylate with (meth)acrylic acid [Κ5]; a resin formed by reacting a copolymer of dicyclopentyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride Resin such as resin [Κ6]. Among them, a resin [Κ1] and a resin [κ2] are preferable, and a resin [Κ1] is more preferable, and a 3,4-epoxytricyclo[5.2 1 Μ' oxime/(meth)acrylic acid copolymer is further preferred. Things. If the resin (Β) contains the structure of the structure I61707.doc -34 - 201235784 from (a), the reliability of the heat resistance and chemical resistance of the obtained color filter can be further improved. The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100, more preferably 5, 〇〇〇 50, 〇〇〇, and further preferably 5 〇〇〇 to 35, 〇 Hey, especially good for 6, _,, just, especially good for 7, _~28, _. When the molecular weight is in the above range, the coating film hardness is improved, and the residual film ratio is also high, and the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] of the resin (B) is preferably L1 to 6, more preferably 〖2 + the acid value of the tree (B) is preferably 5 〇 15G mg K〇H/g is more preferably ~(1) mg-K〇H/g' and further preferably 7〇~135mg_K〇H/g. Here, the acid value is neutralized! The value measured by the amount of gas oxidative removal required for the resin (4) can be determined, for example, by enthalpy of the (iv) hydroxide solution. The content of the resin (B) is preferably 7 to 65 mass%, more preferably 3 to 6 mass%, still more preferably 17 to 55 mass, based on the solid content of the colored photosensitive resin composition of the present invention. %. When the content of the resin (8) is in the above range, the colored pattern ’ can be formed, and the resolution and the residual film ratio tend to be improved. The color photosensitive resin composition of the present invention contains a polymerizable compound: the dimerizable compound (C) is a compound which can be polymerized by an active radical derived from a polymerization initiator (9), an acid or the like, for example, can be classified. And the like, the first two: the polymerizable compound (C), preferably having three or more ethyl hydrazides in the unsaturated bond. Examples of such a polymerizable compound include, for example, Quarter I61707.doc -35 - 201235784 Pentaerythritol Tetramethyl (meth)acrylate Dipentaerythritol Penta(methyl)acrylate, Dipentaerythritol Hexa(propyl)propyl Dilute ester, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, isocyanuric acid three (2 -(Methyl)acryloxyethyl)g, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(methyl) acrylate, propylene glycol modified pentaerythritol Tetrakis(yl) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, and caprolactone modified dipentaerythritol hexa(meth) acrylate vinegar . Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexakisyl acrylate, and the like are preferable. The polymerizable compound may be used singly or in combination of two or more. The weight average molecular weight of the polymerizable compound (C) is preferably io 5 Å or more and 2,900 or less, more preferably 250 Å or less. The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and further preferably 17 to 55 mass, based on the solid content of the coloring photosensitive resin composition of the present invention. %. When the content of the polymerizable compound (C) is within the above range, the curing is sufficiently performed, the residual film ratio during development is improved, and undercut is less likely to occur in the colored pattern, and the adhesion tends to be good. . The colored photosensitive resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used. 16l707.doc •36- 201235784 As the polymerization initiator (D) 'It is preferred to generate active radicals by the action of light, more preferably an alkyl ketone compound, a tri-nized compound, a fluorenyl phosphine oxide compound, The hydrazine compound and the biimidazole compound are further preferably an anthracene compound. The above alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

4為具有式(d2)所表示之部分結構之化合物,例如可列 舉’ 2-曱基-2-嗎啉基-丨气扣甲基硫基苯基)丙烷_丨_酮、2_二 甲胺基-1-(4-嗎啉基苯基)·2_苄基丁烷_丨·酮、及2_(二曱胺 基)-2-[(4-曱基苯基)曱基]嗎啉基)苯基]丁燒小嗣 等。亦可使用Irgacure(註冊商標)369、907及3?9(以上為 BASF公司製造)等市售品。 作為具有式(d3)所表示之部分結構之化合物,例如可列 舉· 2-羥基-2-曱基-1-笨基丙烷·丨_酮、2_羥基_2_曱基-丨-^· (2-羥乙氧基)苯基]丙烷_丨_酮、丨_羥基環己基苯基酮、2-羥 基-2-曱基-1-(4-異丙烯基苯基)丙烷·丨_酮之低聚物、胃二 乙氡基苯乙酮及苯偶酿二曱基縮酮等。 就感光度之觀點而言,作為烷基苯酮化合物,較佳為具 有式(d2)所表示之部分結構之化合物,更佳為2·曱基嗎 啉基-1-(4-甲基硫基苯基)丙烷_丨_酮及2_二曱胺基_丨嗎 I61707.doc •37· 201235784 啉基苯基)-2-节基丁烷-1-酮。 作為上述三畊化合物,可列舉:2,4-雙(三氣甲基)_6_(4· 曱氧基苯基)-1,3,5-三畊、2,4·雙(三氯曱基)-6-(4-曱氧基萘 基)-1,3,5-二11井、2,4-雙(三氣甲基)-6-向日蔡基_1,3,5-三 畊、2,4·雙(三氣甲基)-6-(4-甲氧基苯乙烯基)_i,3,5•三,井、 2,4-雙(三氣甲基)_6-[2-(5 -甲基呋喃-2-基)乙烯基]_ι,3,5·三 井' 2,4-雙(二氣曱基)_6-[2-(。夫。南-2-基)乙稀基]_ι,3,5·三 畊、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯 基]-1’3,5-三畊、2,4-雙(三氣甲基)-6-[2-(3,4-二甲氧基苯 基)乙烯基]-1,3,5-三畊等。 作為上述醯基氧化膦化合物,可列舉2,4,6_三甲基苯甲 酿基二苯基氧化膦等。亦可使用Irgacure(註冊商 標)819(BASF公司製造)等市售品。 上述將化合物係具有式(d 1)所表示之部分結構之化合 物。以下,*表示鍵結鍵。4 is a compound having a partial structure represented by the formula (d2), and, for example, '2-mercapto-2-morpholinyl-fluorene-methyl thiophenyl)propane oxime ketone, 2-dimethyl dimethyl ketone Amino-1-(4-morpholinylphenyl)-2-benzylbutane-indoleone and 2-(diamino)-2-[(4-indolylphenyl)indenyl] Polinyl) phenyl] butyl saponin and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 3-9 (manufactured by BASF Corporation) can also be used. Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-mercapto-1-indolyl propane ketone, 2-hydroxy-2-indolyl-indole-? (2-hydroxyethoxy)phenyl]propane oxime ketone, hydrazine-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-mercapto-1-(4-isopropenylphenyl)propane 丨Olefin oligomers, gastric diacetyl acetophenone and benzoic dinonyl ketals. From the viewpoint of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by the formula (d2) is preferred, and more preferably a quinolylmorpholin-1-(4-methylsulfide). Phenyl phenyl) propane _ 丨 ketone and 2 dioxin 丨 I I61707.doc • 37· 201235784 phenyl phenyl)-2-pyrylbutane-1-one. Examples of the above-mentioned three-till compound include 2,4-bis(trimethylmethyl)_6_(4·decyloxyphenyl)-1,3,5-three tillage, and 2,4·bis(trichloroindenyl). )-6-(4-decyloxynaphthyl)-1,3,5-di-11, 2,4-bis(trimethylmethyl)-6-to-caiji_1,3,5-three Tillage, 2,4·bis(trimethylmethyl)-6-(4-methoxystyryl)_i, 3,5•three, well, 2,4-bis(trimethyl)methyl-6-[ 2-(5-methylfuran-2-yl)vinyl]_ι,3,5·三井' 2,4-bis(dioxamethyl)_6-[2-(.f.nan-2-yl) Ethyl]_ι,3,5·three tillage, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1 '3,5-three tillage, 2,4-bis(trimethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three tillage, etc. . The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used. The above compound is a compound having a partial structure represented by the formula (d 1). Hereinafter, * indicates a keying key.

作為上述肟化合物,可列舉:N_苯曱醯氧基_丨_(4_笨基硫 基本基)丁院-1-酮-2-亞胺、N-苯曱醯氧基-1-(4-苯基硫基 苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯 基)-3-環戊基丙烷-1·酮_2-亞胺、N-乙醯氧基-i-[9-乙基-6-(2 -甲基苯曱酿基)·9Η-味。坐-3-基]乙院-1-亞胺、N -乙醯氧 基乙基·6-{2-甲基-4-(3,3-二曱基-2,4-二》»号環戊基甲 161707.doc • 38 · 201235784 氧基)苯甲醯基卜9H-咔唑-3-基]乙烷-1-亞胺、N-乙醞氧基. N[9-乙基-6-(2_甲基苯甲醯基)-9Η·咔唑-3-基]-3-環戊基丙 烷-1-亞胺、Ν-苯甲醯氧基4_[9_乙基_6_(2_甲基苯甲醯基)_ 9Η-咔唑基]_3_環戊基丙烷_丨_酮_2_亞胺等。亦可使用 IrgaCUre(註冊商標)〇ΧΕ01、〇ΧΕ02(以上為BASF公司製 造)、N-1919(ADEKA公司製造)等市售品。其中,於本發 明之著色感光性樹脂組合物係藍色著色感光性樹脂組合物 之情形時,由於所獲得之彩色濾光片之明度變高,故而較 佳為使用選自由N_苯甲酿氧基·⑷苯基硫基苯基)丁统小 酮亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷_丨_酮_ 2-亞胺及N_苯甲醯氧基_丨_(4_苯基硫基苯基•環戊基丙 院1鲷2 -亞胺所組成群之至少丨種作為上述厢化合物。 作為聯咪唑化合物,可列舉:2,2,_雙(2_氯苯基 ::4’,5,5’-四苯基聯咪唑、2,2ι·雙(2,3-二氣苯基)·4,4|,5,5,-四 苯基聯味。坐(例如’參照日本專利特開平6_75372號公報及 日本專利特開平6_75373號公報等)、2,2ι_雙(2_氣苯基)_ 4,4’,5,5|-四苯基聯咪唾、2,2,·雙(2_氣苯基)-4,4|,5,5,_四(院 氧基苯基)聯咪唑、2,21_雙(2_氯苯基)·4,4ι,5,5,_四(二烷氧 $苯基)聯味唑、2,2、雙(2_氯苯基)_4,4,,5,5ι_四(三烷氧基 苯土)聯米坐(例如’參照日本專利特公昭48_384()3號公報 及日本專利特開昭叫74204號公報等)、4,4,5,5,_位之苯基 藉由院氧m基取代之❹化合物(例如,參照日本專利特 開平7·Η)913號公報等)等。較佳為可列舉:以,.雙(2_氣苯 基)-MW.四苯基聯^、2,2、雙(2,3_二氯苯基)· 161707.doc -39- 201235784 、2,2'·雙(2,4-二氣笨基)_4,4,,5,5,_四 4,4',5,5'-四苯基聯咪唑 苯基聯咪。坐。 進::為聚合起始劑⑼,可列舉:安息香、安息香曱 二女息香乙驗1息香異丙域、安息香異頂等安息香 化。物’二苯甲_、鄰苯曱醯基苯甲酸甲S旨、4苯基二笨 甲酮苯甲酿基+甲基二苯硫謎、3,3,,4,4,_四(第:丁 基過氧化羰基)二笨甲酮、2,4,6•三甲基二笨甲酮等二苯曱 酮化。物,9’10-菲醌、2_乙基蒽醌、樟腦醌等醌化合物; 10-丁基_2-氣。丫相、苯偶醯、乙酿酸笨基甲醋、二茂飲 化0物等。較佳為將該等與下述聚合起始助劑(D1)(尤其 疋胺類)組合使用。 作為藉由光而產生酸之酸產生劑,例如可列舉:4_羥基 苯基二甲基㈣甲苯錢鹽、4_經基笨基二甲基鈒六氣録 4乙酿氧基苯基二曱基疏對甲苯續酸鹽、乙酿氧 基本基-甲基-苄基銃六氟銻酸鹽、三苯基銃對甲笨磺酸 鹽、三苯基銃六氟錄酸鹽、二苯基鎭對甲苯俩鹽、二苯 基錤六氟銻酸鹽等鑌鹽類,或硝基节基甲苯磺酸鹽類,及 安息香甲苯磺酸鹽類等。 聚合起始劑(D)之含量相對於樹脂(B)及聚合性化合物(c) 之合計量100質量份,較佳為0.^30質量份,更佳為卜“ 質量份。若光聚合起始劑之含量為上述範圍内,則感光度 提高而曝光時間縮短’從而提高生產性。 本發明之著色感光性樹脂組合物亦可進而含有聚合起始 助劑(D1)。聚合起始助劑(D1)係用於促進藉由聚合起始劑 161707.doc •40· 201235784 碣始聚合之聚合性化合物之聚合之化合物,或者係增感 劑,通常與聚合起始劑(D)組合使用。 作為聚合起始助劑_,可列舉胺化合物、烧氧基葱化 合物、9·氧硫咄喳化合物、羧酸化合物等。 作為胺化合物’可列舉’三乙醇胺、甲基二乙醇胺、三 =丙醇胺、4-二曱胺基苯甲酸甲酯、4·二甲胺基苯甲酸乙 酯、4_二甲胺基笨甲酸異戊酿、苯甲酸2-二曱胺基乙醋、 4-二甲胺基苯甲酸2_乙基己酿、邮·二甲基對甲苯胺、 4,4,_雙(二曱胺基)二苯甲酮(通稱米其勒_)、4,4·-雙(二乙 胺基)二苯甲明、4,4,·雙(乙基甲胺基)二苯甲酮等,其中較 佳為4’4-雙(二乙胺基)二苯甲酮。亦可使用eaB-F(保土谷 化學工業股份有限公司製造)等市售品。 作為烷氧基蒽化合物,可列舉:9,1〇_二甲氧基蒽、2_乙 土,10 -甲氧基蒽、9,10-二乙氧基葱、2•乙基·9,1〇_二乙 氧基蒽、9,1〇-二丁氧基蒽、2.乙基_9,1〇_二丁氧基葱等。 作為9-氧硫咄疃化合物,可列舉:2·異丙基冬氧硫咄 嗟、心異丙基冬氧硫ρ山,星、2,4_二乙基_9_氧硫心星、κ 二氯-9-氧硫咄,星、;[_氯_4_丙氧基_9_氧硫咄喵等。 , 作為幾酸化合物,可列舉:苯基硫基乙酸、甲基苯基硫 基乙酸、乙基苯基硫基乙酸、曱基乙基苯基硫基乙酸、二Examples of the above hydrazine compound include N-benzoquinoneoxy-hydrazine-(4-phenylthiol basic) butyl-1-keto-2-imine, N-benzoquinone-1-( 4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1 Ketone-2-imine, N-acetoxy-i-[9-ethyl-6-(2-methylphenylhydrazone)·9Η-flavor. -3-K]B--1-imine, N-acetoxyethyl·6-{2-methyl-4-(3,3-dimercapto-2,4-di) Cyclopentyl 161707.doc • 38 · 201235784 oxy)benzimidyl 9H-carbazol-3-yl]ethane-1-imine, N-ethoxycarbonyl. N[9-ethyl- 6-(2-methylbenzylidenyl)-9Η·oxazol-3-yl]-3-cyclopentylpropane-1-imine, Ν-benzylideneoxy 4_[9_ethyl_6_ (2-Methylbenzylidene)_9Η-carbazolyl]_3_cyclopentylpropane_丨-ketone-2-imine. Commercial products such as IrgaCUre (registered trademark) 〇ΧΕ01, 〇ΧΕ02 (manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used. In the case where the colored photosensitive resin composition of the present invention is a blue colored photosensitive resin composition, since the brightness of the obtained color filter becomes high, it is preferred to use a material selected from N-Benyl. Oxyl (4) phenylthiophenyl) butyl ketimine, N-benzylideneoxy-1-(4-phenylthiophenyl)octane oxime ketone 2-imine and N_benzhydryloxy_丨_(4_phenylthiophenyl•cyclopentylpropanol 1鲷2-imine group of at least one species of the above-mentioned car compound. As the biimidazole compound, a :2,2,_bis(2_chlorophenyl::4',5,5'-tetraphenylbiimidazole, 2,2ι·bis(2,3-diphenyl)-4,4|, 5,5,-tetraphenyl-based taste. Sitting (for example, see Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Application Laid-Open No. Hei No. Hei 6-75373, etc.), 2, 2ι_double (2_gasphenyl)_4,4 ',5,5|-Tetraphenyl hydrazine, 2,2,·bis(2- phenyl)-4,4|,5,5,_tetra(indolyloxyphenyl)biimidazole, 2 , 21_bis(2_chlorophenyl)·4,4ι,5,5,_tetrakis(dialkyloxy$phenyl)-linked oxazole, 2,2, bis(2-chlorophenyl)_4,4, ,5,5ι_tetrakis Benzene) 联米坐 (for example, 'refer to Japanese Patent Special Publication No. 48_384 () No. 3, Japanese Patent Laid-Open No. 74204, etc.), 4, 4, 5, 5, _ position of phenyl by the hospital oxygen The m-substituted ruthenium compound (for example, refer to Japanese Patent Laid-Open No. Hei. No. 913), etc., etc., preferably, bis(2-phenylphenyl)-MW.tetraphenylene is exemplified. , 2, 2, bis(2,3-dichlorophenyl)·161707.doc -39- 201235784, 2,2'·double (2,4-two gas base)_4,4,,5,5, _4,4',5,5'-tetraphenylbiimidazolium phenyl carbene. Sit.:: as a polymerization initiator (9), which can be enumerated: benzoin, benzoin, scent, scent, scent, scent Isoproterenol, benzoin, etc., benzoin, etc., 'diphenylene _, o-benzoylbenzoic acid, A, 4 phenyl dibenzophenone, benzoyl ketone, methyl diphenyl sulfide, 3, Dibenzophenones such as 3,4,4,_tetra (p.: butylperoxycarbonyl) dimercapto ketone, 2,4,6•trimethyldibenzophenone, 9'10-phenanthrene醌, 2_ethyl hydrazine, camphor quinone and other hydrazine compounds; 10-butyl 2 - gas. 丫 phase, benzoin oxime, ethoxylated acid, gluten vinegar, dioxin Preferably, these are used in combination with the following polymerization initiation assistant (D1) (especially guanamine). As the acid generator which generates an acid by light, for example, 4-hydroxyphenyl group is exemplified. Methyl (tetra) toluene salt, 4 _ phenyl dimethyl sulfonium hexahydrate, 4 ethoxylated phenyl diphenyl sulfonium p-toluate, ethoxylated benzyl-methyl-benzyl fluorene Fluoride, triphenylsulfonium sulfonate, triphenylsulfonium hexafluoroate, diphenylphosphonium toluene salt, diphenylphosphonium hexafluoroantimonate, etc., or Nitro-succinyl tosylate, and benzoin tosylate. The content of the polymerization initiator (D) is preferably 0.1 part by mass, more preferably 0 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (c). When the content of the initiator is within the above range, the sensitivity is improved and the exposure time is shortened to improve productivity. The colored photosensitive resin composition of the present invention may further contain a polymerization initiation aid (D1). The agent (D1) is a compound for promoting polymerization of a polymerizable compound which is polymerized by a polymerization initiator 161707.doc • 40· 201235784, or a sensitizer, usually used in combination with a polymerization initiator (D). Examples of the polymerization initiation aids include an amine compound, a oxy-onion compound, a oxonium sulfonium compound, and a carboxylic acid compound. Examples of the amine compound 'triethanolamine, methyldiethanolamine, and three= Propylamine, methyl 4-diaminoaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, isoamyl, 2-diamylamine acetoacetate, 4 -dimethylaminobenzoic acid 2-ethylhexyl, dimethylpara-toluidine, 4,4,_ (Diammonium) benzophenone (commonly known as Michele _), 4,4·-bis(diethylamino)diphenylmethylamine, 4,4,·bis(ethylmethylamino)diphenyl A ketone or the like is preferred, and 4'4-bis(diethylamino)benzophenone is preferred. Commercial products such as eaB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used. The compound may, for example, be 9,1 〇dimethoxy oxime, 2 ethane bromide, 10-methoxy oxime, 9,10-diethoxy onion, 2•ethyl·9,1〇_2B. Oxime, 9,1〇-dibutoxyanthracene, 2.ethyl_9,1〇-dibutoxy onion, etc. As the 9-oxosulfonium compound, 2: isopropyl winter Oxime, isopropyl oxalate, mountain, star, 2,4_diethyl_9_oxythioxin, κ dichloro-9-oxopurine, star,;[_氯_4_ Propyloxy-9-oxopurine, etc., as the acid compound, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, mercaptoethylphenylsulfide Acetic acid, two

甲基苯基硫基乙酸、甲氧基苯基硫基乙酸 '二甲氧基笨I 硫基乙酸、氯苯基硫基乙酸、二氯苯基硫基乙酸 '心 甘胺酸、苯氧基乙酸、萘硫基乙酸、沁萘基甘胺 ^Methylphenylthioacetic acid, methoxyphenylthioacetic acid 'dimethoxy stupyl I thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid 'cardiamine, phenoxyacetic acid , naphthylthioacetic acid, indole naphthylamine

基乙酸等。 I I61707.doc 201235784 聚合起始㈣可單㈣用’亦可組合使用2種以上。 於使用聚合起始助劑(D1)之情形時,其使用量相對於樹 脂(B)及聚合性化合物(C)之合計 ° &quot;t量100質量份’較佳為 0.1〜30質量份,更佳為丨〜2〇質量份。 夏物右聚合起始助劑(D1) 之量為此範圍内,則有可進一舟以古^ ^ ^步以尚感光度形成圓案,使 圖案之生產性提高之傾向。 本發明之著色感光性樹脂組合物含有溶劑⑻。溶劑⑻ 係含有二丙二醇單甲醚乙酸酯者。 一丙一醇單甲醚乙酸酯之含量相對於溶劑(E)之總量, 較佳為0.1質;t%以上30質量%以下,更佳為嘈量。/。以上2〇 質量%以下,進而較佳為2質量%以上15質量%以下。 溶劑(E)亦可含有二丙二醇單曱醚乙酸酯以外之溶劑。 作為此種溶劑並無特別限定,可使用該領域中通常使用之 溶劑。例如可列舉:酯溶劑(於分子内含有&lt;〇〇_結構,而 不含有-〇·結構之溶劑)' 醚溶劑(於分子内含有結構, 而不含有-COO-結構之溶劑)、醚酯溶劑(於分子内含有_ COO-結構及_〇_結構之溶劑)、酮溶劑(於分子内含有 結構’而不含有_coo_結構之溶劑)、醇溶劑(於分子内含 有OH基’而不含有結構、-C〇·結構及_c〇〇_結構之溶 劑)、芳香族烴溶劑、醯胺溶劑及二甲基亞砜等。 作為醋溶劑’可列舉:乳酸曱酯、乳酸乙酯、乳酸丁 s曰' 2-經基異丁酸曱酯、乙酸乙酯、乙酸正丁酯、乙酸異 丁醋、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、 丁 k乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸 I61707.doc •42· 201235784 丙酯、乙醯乙酸甲酯.、乙醯乙酸乙酯、環己醇乙酸酯、γ_ 丁内酯等。 作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單乙醚、 乙二醇單丙醚、乙二醇單丁醚、二乙二醇單曱醚、二乙二 醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙 醚、丙二酵單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-曱氧基-3 -曱基丁醇 '四氫呋喃、四氫〇比喃、1,4-二嘮'坑、 二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇曱基乙醚、 二乙二醇二丙醚、二乙二酵二丁醚、苯曱醚、苯乙醚、甲 基苯甲喊等。 作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸 乙輯、曱氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙 醋'3-甲氧基丙酸曱酯、3·曱氧基丙酸乙酯、3_乙氧基丙 酸曱酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸曱酯、2-曱氧 基丙酸乙酯' 2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-曱基丙酸乙酯、乙酸3·甲氧基丁酯、乙酸3_曱基·3_曱氧基 丁 S曰、丙二醇單曱醚乙酸酯、丙二醇單乙醚乙酸酯、丙二 醇單丙趟乙酸ί旨、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙 、一乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯 等。 作為谷劑,可列舉4-經基-4-甲基-2-戊酮、丙酮、2-丁 _、2-庚酮、3_庚酮、4_庚酮、4_甲基·2_戊綱、環戊酮、 環己酮、異佛綱等。 161707.doc .43- 201235784 醇、己醇、 甲笨、均三甲 作為醇溶劑,可列舉曱醇、乙醇、丙醇 環己醇'乙二醇、丙二醇、甘油等。 作為芳香族烴溶劑,可列舉苯、甲笨、 苯等。 作為醯胺溶劑’可列舉N n_ τ丞r醯胺、ν,ν-二甲« 乙醯胺、Ν-甲基比洛炫酮等。 土 該等溶劑可單獨使用亦可組合使用2種以上。 上述:财,就塗佈性、乾燥性之觀點而言,較佳為於 ⑷準大氣壓(1 atm)下之沸點為12代以上⑽。〇以下之右 機/谷劑。其中,較佳為丙二醇單甲秘7於故 鮮皁f醚乙酸酯、乳酸乙酯、 乳酸丁醋、丙二醇單甲㈣、3-乙氧基丙酸乙醋、乙二醇單 曱峻、二乙二醇單甲㈣、二乙二醇單乙Μ、4_經基句 基-2-戊酮、Ν,Ν二甲基甲醯胺、n-甲基吡咯烷酮等,更 佳為丙二醇單甲_乙酸輯、丙二醇單甲_、乳酸乙醋、 乙氧基丙酸乙酯等。 較佳為溶劑(E)同時含有二丙二醇單甲醚乙酸酯與乳酸 乙酯。此情形時乳酸乙酯之含量相對於溶劑(E)之總量’ 較佳為5質量%以上90質量%以下,更佳為2〇質量%以上8〇 質量%以下’進而較佳為4〇質量%以上7〇質量%以下。 又’較佳為溶劑(E)係含有二丙二醇單曱醚乙酸酯之3種 以上之混合溶劑,更佳為4種以上之混合溶劑。 於溶劑(E)為含有二丙二醇單曱醚乙酸酯之3種以上之混 合溶劑之情形時’較佳為溶劑(E)係含有二丙二醇單曱醚 乙酸酯、乳酸乙酯、丙二醇單曱醚及/或丙二醇單曱醚乙 I61707.doc •44· 201235784 酸醋者,更佳為含有二丙二醇單乙酸醋、乳酸乙醋、 丙二醇單甲驗及丙二醇單甲麵乙酸輯者。進而,較佳為含 有該等,且二丙二醇單甲驗乙酸醋、乳酸乙醋、丙二醇單 甲驗及丙二醇單甲越乙酿人, G駸自日之合計含量相對於溶劑(E)之 總量為90質量%以上,更佳為95質量%以上。 於溶劑⑹含有丙二醇單Μ之情形時,其含量相對於 溶劑⑻之總量,較佳豹質量乂以上4〇質量%以下,更佳 為5質量%以上30質量%以下。 於溶劑(Ε)含有丙二醇單f喊乙酸酿之情形時,其含量 相對於溶劑⑻之總量,較佳為】質量%以上40質量%以 下,更佳為5質量。/。以上3〇質量%以下。 右溶劑(E)為上述溶劑,則減壓乾燥而製作之膜中火山 口狀缺陷之產生較少,並且亦可抑制不均之產生。 溶,⑻之含量相對於本發明之著色感光性樹脂組合物 之總篁,較佳為70〜95質量%,更佳為乃〜%質量%。換言 之本發明之著色感光性樹脂組合物之固形物成分較佳為 5:30質量% ’更佳為8〜25質量%。若溶劑⑻之含量為上述 範圍内,則塗佈時之平坦性變得良好,並且形成彩色渡光 片時色濃度充足,故而有顯示特性變得良好之傾向。 發月之著色感光性樹脂組合物,進而可含有界面活性 劑(G)。作為界面活性劑(G) ’可列舉:聚矽氧系界面活性 劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑 等°該等亦可於支鏈上具有聚合性基。 作為聚矽氧系界面活性劑,可列舉具有矽氧烷鍵之界面 161707.doc -45- 201235784 活性劑等。具體而言,可列舉:Toray Silicone(商品 名)DC3PA ' Toray Silicone SH7PA、Toray Silicone DC11PA、 Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone 8400(Toray Dow Corning股份有限公司製造)、KP321、 KP322 ' KP323、KP324、KP326、KP340、KP341(信越化 學工業股份有限公司製造)、TSF400、TSF401、TSF410、 TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、 TSF4460(Momentive Performance Materials Japan 公司製 造)等。 作為上述氟系界面活性劑,可列舉具有氟碳鏈之界面活 性劑等。具體而言,可列舉:Fluorad(註冊商標)FC430、 Fluorad FC431(住友3M股份有限公司製造)、MEGAFAC(註 冊商標)F142D、MEGAFAC F171、MEGAFAC F172、 MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、. MEGAFAC F554、MEGAFAC R30、MEGAFAC RS-718-K(DIC股份有限公司製造)、Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱综合材料電子化 成(Mitsubishi Materials Electronic Chemicals)股份有限公 司製造)、Surflon(註冊商標)S381 ' Surflon S382、Surflon SC101、Surflon SC105(旭硝子股份有限公司製造)、 E5844(大金精密化學研究所(Daikin Fine Chemical)股份有 限公司製造)等。 作為上述具有氟原子之聚矽氧系界面活性劑,可列舉具 I61707.doc -46- 201235784 有石夕氧烧鍵及氟碳鍵之界面活性劑等。具體而言,可列 舉:MEGAFAC(註冊商標)R08、MEGAFAC BL20、 MEGAFAC F475 ' MEGAFAC F477 ' MHGAFAC F443(DIC 股份有限公司製造)等。 該等界面活性劑可單獨使用’亦可組合使用2種以上。 界面活性劑(G)之含量相對於本發明之著色感光性樹脂 組合物之總量,較佳為0.001質量%以上〇2質量%以下,較 佳為0_002質量%以上(^丨質量。/。以下,更佳為〇〇1質量%以 上0.05質量%以下。若界面活性劑(F)之含量為上述範圍, 則可使塗膜之平坦性良好。 本發明之著色感《性樹脂組合物亦可根據需要而含有: 填充劑、其他高分子化合物、密接促進劑、抗氧化劑、紫 外線抑制劑、光穩定劑、鏈轉移劑等各種添加劑(以下有 時稱作「其他成分」)。 本發明之著色感光性樹脂組合物例如可藉由使著色劑 (A)、樹脂⑻、聚合性化合物(c)、聚合起始劑⑼、溶劑 ⑻’及根據需要而使用之聚合起始助劑(叫、界面活性劑 (G)及其他成分混合而製備。 較佳為預先將顏料與溶劑⑻之一部分或全部混合,並 使用珠磨機等使其分散直至顏料之平均粒徑為Μ㈣以下 二為之止一。二時’亦可根據需要調配上述顏料分散劑、樹 9 或全部。於所獲得之顏料分散液中 餘之成分等而使其成為特定之濃度’藉 感光性樹脂組合物。 取備目払者色 161707.doc •47- 201235784 ,為預先將P山P星染料溶解於溶劑(E)之一部分或全部 製備冷液。較佳為利用孔徑G.G1〜1 μιη左右之過滤器 過濾該溶液。 較佳為利用孔徑〇 〇1〜1〇叫左右之過濾器過濾如上所 述般現合而製備之著色感光性樹脂組合物。 作,使用本發明之著色感光性樹脂組合物形成彩色濾光 片之著色圖案之方法’例如可列舉微影法及使用喷墨設備 之方法等。微影法係藉由以下方式而形成圖案之方法:將 本發月之著色感光性樹脂組合物塗佈於基板或其他樹脂層 (例如先於基板上形成之其他著色咸光性樹脂組合物層 等)上,將溶劑等揮發成分除去/乾燥而形成乾燥後塗膜, 介隔光罩使該乾燥後塗膜曝光並進行顯影。於該微影法 中’亦可於曝光時不使用光罩,及/或不進行顯影而形成 著色塗膜並製作彩色濾光片。 所製作之彩色濾光片之膜厚並無特別限定,可根據所使 用之材料、用途等適當調整’例如為〇1〜3〇 μηι,較佳為 1〜20 μιη ’進而較佳為1〜6 。 將著色感光性樹脂組合物塗佈於基板上,藉由加熱乾燥 (預烤)及/或減壓乾燥而除去溶劑,獲得平滑之乾燥後塗 膜。 作為基板,可使用石英玻璃、硼矽玻璃、鋁矽破璃、表 面經二氧化矽塗覆之鹼石灰玻璃等玻璃板,或聚碳酸酿、 聚曱基丙烯酸甲酯、聚對苯二曱酸乙二酯等樹脂板,石夕, 於上述基板上形成有鋁、銀、銀/銅/纪合金薄膜等者。 161707.doc -48- 201235784 塗佈方法’可列舉:旋轉塗佈法、狹縫式塗佈法、 狹縫&amp;旋轉式塗佈法等。 加熱乾燥較佳為30〜】2〇t&gt;c,更佳為4〇〜1〇〇。〇。又,作為 加熱時間,較佳為10秒鐘〜60分鐘,更佳為30秒鐘〜3〇分 鐘。 較佳為,減壓乾燥於5〇〜15〇 ^之塵力下之 溫度範圍下進行。本發明之著色感光性樹脂組合物於此種 條件下進仃減壓乾燥之情形時,亦可產生火山。狀缺陷之 產生較少之效果。 乾燥後塗膜之膜厚並無特別限$,可才艮據所使用之材 料、用途等而適當調整。 乾燥後塗膜介隔用以形成目標圖案之光罩而曝光。此時 光罩上之圖案並無特別限定,可使用對應於目標用途者。 作為曝光所使用之光源,較佳為產生25〇〜45〇 nm之波長 之光者。例如,可對於未滿35〇 ηηΐ2光使用可截止此波段 之濾波器進行截止,亦可對於436 nm左右、4〇8 nm左右、 365 nm左右之光使用可提取該等波段之帶通濾波器選擇性 地進行提取。具體而言,可列舉:水銀燈、發光二極體、 金屬鹵化物燈、鹵素燈等。 由於可對曝光面整體均勻地照射平行光線,或準備地進 行光罩與形成有乾燥後塗膜之基板之位置對準,較佳為使 用光罩對準曝光機、步進式曝光機等裝置。 於曝光後,可藉由使其接觸顯影液而將未曝光部溶解並 除去(即顯影)’而獲得著色圖案。作為顯影液,例如較佳 I61707.doc -49- 201235784 二氳氧化鉀、碳酸氳鈉、氫氧化四甲 。物之水溶液。該等驗性化合物於水溶液中之=驗性化 〇.〇1〜10質量。/。’更佳為0 /農度較佳為 含有界面活㈣卜 W ’顯影液亦可 ‘杨方法可為料法、浸潰法、喷霧法等之任 而’可於顯影時將基板傾斜為任意角度。 較佳為於顯影後進行水洗。 後烘烤之溫度較佳 後烘烤時間較佳為 進而’亦可根據需要而進行後烘烤 為150〜250°c,更佳為160〜220°c。 1〜120分鐘’更佳為10〜60分鐘。 )根據本發明之著色感光性樹脂組合物,可製作缺陷尤其 少之彩色據光片。該彩色渡光片作為顯示裝置(例如,液 晶顯示裝置、有機EL(Eiectro luminescent,電致發光)裝置 及電子紙)或固體攝像元件所使用之彩色濾光片而使用。 實施例 以下,利用實施例更詳細地說明本發明之著色感光性樹 脂組合物》例中之「%」及「份」若無特別說明,則為質 量%及質量份。 合成例1 向具備冷卻管及攪拌裝置之燒瓶中,投入式(A〇_1}所表 示之化合物及式(A0-2)所表示之化合物的混合物(中外化成 製造)15份 '氣仿15〇份及N,N-二甲基曱醯胺8.9份,一面搜 拌並維持於20°C以下’一面滴加亞硫醯氣10.9份。於滴入 結束後升溫至50°C,於該溫度下維持並反應5小時,其後 161707.doc • 50· 201235784 冷卻至20°C ^對冷卻後之反應溶液,一面攪拌並維持於 20°C以下,一面滴加2-乙基己胺12.5份及三乙胺22.1份之 展合液。其後,於20 C下搜;拌並反應5小時。繼而於旋轉 蒸發器中將所獲得之反應混合物進行溶劑餾去後’添加少 量曱醇並激烈地攪拌。一面攪拌一面將該混合物添加於離 子交換水375份之混合液中,使結晶析出。濾出析出之結 曰曰,利用離子交換水充分清洗,於6〇它下減壓乾燥而獲得 染料Al(化合物(1_υ〜化合物(1_8)之混合物)u 3份。Acetic acid and the like. I I61707.doc 201235784 The polymerization start (4) can be used alone or in combination of two or more. In the case of using the polymerization initiation aid (D1), the amount of use thereof is preferably 0.1 to 30 parts by mass based on the total amount of the resin (B) and the polymerizable compound (C). More preferably 丨~2〇 parts by mass. In the range of the summer start polymerization aid (D1), it is possible to enter a boat to form a round shape with a sensitivity to improve the productivity of the pattern. The colored photosensitive resin composition of the present invention contains a solvent (8). The solvent (8) is one containing dipropylene glycol monomethyl ether acetate. The content of monopropanol monomethyl ether acetate is preferably 0.1 mass based on the total amount of the solvent (E); t% or more and 30% by mass or less, more preferably hydrazine. /. The above 2% by mass or less, more preferably 2% by mass or more and 15% by mass or less. The solvent (E) may also contain a solvent other than dipropylene glycol monoterpene ether acetate. The solvent is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing a &lt;〇〇_ structure in the molecule and not containing a -〇· structure)] an ether solvent (a solvent containing a structure in a molecule and not containing a -COO-structure), an ether Ester solvent (solvent containing _COO-structure and _〇_ structure in the molecule), ketone solvent (solvent containing structure 'in the molecule without _coo_ structure), alcohol solvent (containing OH group in the molecule) It does not contain a structure, a solvent of -C〇·structure and _c〇〇_ structure, an aromatic hydrocarbon solvent, a guanamine solvent, and dimethyl sulfoxide. Examples of the vinegar solvent include: decyl lactate, ethyl lactate, butyl sulphate 2-iso-p-isobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetonate, amyl formate, and acetic acid Amyl ester, butyl propionate, isopropyl butyrate, butyl k ethyl ester, butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvic acid I61707.doc • 42· 201235784 propyl ester, acetamidine acetate Ester, ethyl acetate, cyclohexanol acetate, γ-butyrolactone, and the like. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-decyloxy-3-mercaptobutyl Alcohol 'tetrahydrofuran, tetrahydrofuran, 1,4-diox' pit, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol decyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, phenyl ether, phenethyl ether, methylbenzene shunt and so on. Examples of the ether ester solvent include methyl methoxyacetate, methoxyacetic acid, butyl oxyacetate, methyl ethoxyacetate, and ethoxyacetic acid vinegar '3-methoxypropionic acid. Ester ester, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-methoxypropionate, 2-nonoxypropionic acid Ethyl propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-mercaptopropionate, 3·methoxybutyl acetate, 33-yl-3-methoxybutane acetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropylene acetic acid, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. As the granule, 4-carbyl-4-methyl-2-pentanone, acetone, 2-butyl-, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2_ Ethyl, cyclopentanone, cyclohexanone, isophora, etc. 161707.doc .43- 201235784 Alcohol, hexanol, methyl benzene, and mesitylene. Examples of the alcohol solvent include decyl alcohol, ethanol, propanol cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, methyl benzene, and benzene. Examples of the guanamine solvent 'N n τ 丞 醯 醯 amine, ν, ν-dimethyl ethaneamine, Ν-methyl pirenone, and the like. These solvents may be used alone or in combination of two or more. From the viewpoint of coatability and dryness, it is preferred that the boiling point at (4) quasi-atmospheric pressure (1 atm) is 12 passages or more (10). 〇The right machine/grain below. Among them, preferred is propylene glycol monomethyl saponin 7 in fresh soap f ether acetate, ethyl lactate, lactic acid butyl vinegar, propylene glycol monomethyl (tetra), 3-ethoxypropionic acid ethyl acetonate, ethylene glycol mono sulphur, Diethylene glycol monomethyl (tetra), diethylene glycol monoethyl hydrazine, 4_ylidyl-2-pentanone, hydrazine, hydrazine dimethylformamide, n-methylpyrrolidone, etc., more preferably propylene glycol A-acetic acid series, propylene glycol monomethyl _, lactic acid ethyl acetonate, ethyl ethoxy propionate and the like. Preferably, the solvent (E) contains dipropylene glycol monomethyl ether acetate and ethyl lactate. In this case, the content of the ethyl lactate relative to the total amount of the solvent (E) is preferably 5% by mass or more and 90% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and further preferably 4%. The mass% or more is 7 〇 mass% or less. Further, the solvent (E) is preferably a mixture of three or more kinds of dipropylene glycol monoterpene ether acetate, and more preferably a mixed solvent of four or more. When the solvent (E) is a mixed solvent of three or more kinds of dipropylene glycol monoterpene ether acetate, it is preferred that the solvent (E) contains dipropylene glycol monoterpene ether acetate, ethyl lactate, and propylene glycol. Ether ether and / or propylene glycol monoterpene ether E I61707.doc • 44 · 201235784 Acid vinegar, more preferably contains dipropylene glycol monoacetic acid vinegar, lactic acid ethyl acetate, propylene glycol single test and propylene glycol mono-acetic acid. Further, it is preferable to contain the above, and the dipropylene glycol monoacetic acid vinegar, the lactic acid vinegar, the propylene glycol monomethyst, and the propylene glycol monomethyl acetonitrile, the total content of the G 骎 from the total amount of the solvent (E) The amount is 90% by mass or more, and more preferably 95% by mass or more. In the case where the solvent (6) contains propylene glycol monoterpene, the content thereof is preferably 4% by mass or less, more preferably 5% by mass or more and 30% by mass or less based on the total amount of the solvent (8). In the case where the solvent (Ε) contains propylene glycol mono-f-acetic acid, the content thereof is preferably 7% by mass or more, more preferably 40% by mass or less, more preferably 5% by mass based on the total amount of the solvent (8). /. The above 3〇% by mass or less. When the right solvent (E) is the above solvent, the film produced by drying under reduced pressure is less likely to generate crater defects, and the occurrence of unevenness can be suppressed. The content of the solvent (8) is preferably 70 to 95% by mass, more preferably 5% by mass based on the total mass of the colored photosensitive resin composition of the present invention. In other words, the solid content component of the colored photosensitive resin composition of the present invention is preferably 5:30% by mass or more preferably 8 to 25% by mass. When the content of the solvent (8) is within the above range, the flatness at the time of coating becomes good, and the color density is sufficient when the color light-emitting sheet is formed, so that the display characteristics tend to be good. The colored photosensitive resin composition of the moon may further contain a surfactant (G). Examples of the surfactant (G) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group on the branch. . Examples of the polyoxymethylene surfactant include an interface having a decane bond, 161707.doc -45 - 201235784, and the like. Specifically, Toray Silicone (trade name) DC3PA 'Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone 8400 (Manufactured by Toray Dow Corning Co., Ltd.) ), KP321, KP322 'KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Manufacturing) and so on. The fluorine-based surfactant may, for example, be an interface active agent having a fluorocarbon chain. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554 MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) Surflon (registered trademark) S381 ' Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), and the like. Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a cerium oxide bond and a fluorocarbon bond in I61707.doc - 46 - 201235784. Specifically, it can be listed as MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475 'MEGAFAC F477' MHGAFAC F443 (manufactured by DIC Corporation). These surfactants may be used singly or in combination of two or more. The content of the surfactant (G) is preferably 0.001% by mass or more and 〇2% by mass or less based on the total amount of the colored photosensitive resin composition of the present invention, and is preferably 0-002% by mass or more. In the following, it is more preferably 1% by mass or more and 0.05% by mass or less. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved. The coloring property of the present invention is also Various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet inhibitor, a light stabilizer, and a chain transfer agent (hereinafter sometimes referred to as "other components") may be contained as needed. The coloring photosensitive resin composition can be used, for example, by using a coloring agent (A), a resin (8), a polymerizable compound (c), a polymerization initiator (9), a solvent (8)', and a polymerization initiator which is used as needed. The surfactant (G) and other components are prepared by mixing. It is preferred to previously mix the pigment with a part or all of the solvent (8) and disperse it using a bead mill or the like until the average particle diameter of the pigment is Μ(4) or less. In the case of the second time, the pigment dispersant, the tree 9 or all of the above may be blended as needed, and the remaining component of the obtained pigment dispersion liquid may be a specific concentration of the photosensitive resin composition. Prepare the color 161707.doc •47- 201235784, to prepare a cold liquid in part or all of the P mountain P star dye dissolved in the solvent (E) in advance. It is preferably a filter using a pore size of G.G1~1 μηη. The solution is filtered. It is preferred to filter the colored photosensitive resin composition prepared as described above by using a filter having a pore size of 〜1 to 1 around the squeaking. The coloring resin composition of the present invention is used to form the photosensitive resin composition. The method of coloring the color filter is exemplified by a lithography method and a method using an inkjet apparatus, etc. The lithography method is a method of forming a pattern by the following method: coloring the photosensitive resin composition of the present month Applying to a substrate or another resin layer (for example, a layer of another colored light-sensitive resin composition formed on the substrate), removing or drying a volatile component such as a solvent to form a dried coating film, and blocking the light. The dried coating film is exposed and developed. In the lithography method, a color filter film can be formed without using a photomask and/or development without developing, and a color filter can be produced. The film thickness of the filter is not particularly limited, and can be appropriately adjusted according to the material to be used, the use, etc., for example, 〇1 to 3〇μηι, preferably 1 to 20 μmη, and more preferably 1 to 6. The photosensitive resin composition is applied onto a substrate, and the solvent is removed by heat drying (pre-baking) and/or drying under reduced pressure to obtain a smooth dried coating film. As the substrate, quartz glass, borosilicate glass, or aluminum can be used. a glass plate such as a soda lime glass coated with cerium oxide on the surface, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate, on the substrate Aluminum, silver, silver/copper/kid alloy thin films are formed thereon. 161707.doc -48- 201235784 The coating method is exemplified by a spin coating method, a slit coating method, a slit &amp; spin coating method, and the like. The heat drying is preferably 30 to 2 〇 t &gt; c, more preferably 4 Å to 1 Torr. Hey. Further, as the heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 3 minutes. Preferably, the drying under reduced pressure is carried out under a temperature range of 5 Torr to 15 Torr. When the colored photosensitive resin composition of the present invention is subjected to drying under reduced pressure under such conditions, a volcano may be generated. Shape defects produce less effect. The film thickness of the coating film after drying is not particularly limited to $, and may be appropriately adjusted depending on the materials to be used, the use, and the like. After drying, the coating film is exposed through a reticle that forms a target pattern. At this time, the pattern on the photomask is not particularly limited, and those corresponding to the intended use can be used. As the light source used for the exposure, it is preferable to generate light having a wavelength of 25 〇 to 45 〇 nm. For example, a filter that can cut off this band can be used for the light of less than 35〇ηηΐ2, and a band pass filter that can extract the bands can be used for light of about 436 nm, about 4 〇 8 nm, and about 365 nm. The extraction is selectively performed. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. Since the entire exposed surface can be uniformly irradiated with parallel rays, or the position of the mask and the substrate on which the dried coating film is formed can be prepared, it is preferable to use a mask alignment exposure machine, a stepper, or the like. . After the exposure, the colored portion can be obtained by dissolving and removing (i.e., developing) the unexposed portion by bringing it into contact with the developing solution. As the developer, for example, I61707.doc -49 - 201235784 dipotassium hydride, sodium bismuth carbonate or tetramethyl hydroxide is preferred. An aqueous solution of the substance. The test compound is in an aqueous solution = normalized 〇.〇1~10 mass. /. 'More preferably 0 / agricultural degree is better to contain interface activity (four) Bu W 'developing solution can also be 'Yang method can be material method, impregnation method, spray method, etc.' can be tilted to the substrate during development Any angle. It is preferred to carry out water washing after development. The post-baking temperature is preferably post-bake time preferably </ RTI> and may be post-baked as needed to be 150 to 250 ° C, more preferably 160 to 220 ° C. 1 to 120 minutes' is better for 10 to 60 minutes. According to the colored photosensitive resin composition of the present invention, a color light-receiving sheet having particularly few defects can be produced. The color light-emitting sheet is used as a display device (for example, a liquid crystal display device, an organic EL (e.g., electroluminescent) device, and an electronic paper) or a color filter used for a solid-state image sensor. EXAMPLES Hereinafter, the "%" and "parts" in the examples of the coloring photosensitive resin composition of the present invention will be described in more detail by way of examples, and unless otherwise specified, the amounts are % by mass and parts by mass. Synthesis Example 1 Into a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A〇_1} and a compound represented by the formula (A0-2) (manufactured by a Chinese company) was introduced. 〇份 and 8.9 parts of N,N-dimethyl decylamine, while mixing and maintaining below 20 ° C, add 10.9 parts of sulfite gas. After the end of the dropwise addition, the temperature is raised to 50 ° C. The temperature was maintained and reacted for 5 hours, after which 161707.doc • 50·201235784 was cooled to 20 ° C. The cooled reaction solution was stirred and maintained at 20 ° C or lower, and 2-ethylhexylamine 12.5 was added dropwise. And 22.1 parts of triethylamine in the exhibition liquid. Thereafter, search at 20 C; mix and react for 5 hours. Then, the obtained reaction mixture is subjected to solvent distillation in a rotary evaporator, and then a small amount of sterol is added. The mixture was stirred vigorously, and the mixture was added to a mixed solution of 375 parts of ion-exchanged water to cause precipitation of crystals. The precipitated precipitate was filtered off, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 6 Torr. Obtaining dye Al (compound of compound (1_υ~ compound (1_8)) u 3 parts

16l707.doc •51- 20123578416l707.doc •51- 201235784

合成例2 於遮光條件下使式(1 χ)所表示之化合物2〇份與N_乙基_鄰 甲苯胺(和光純藥工業股份有限公司製造)2〇〇份混合,將所 獲得之溶液於11 0°c下攪拌6小時。將所獲得之反應液冷卻 至室溫後’添加於水800份、35%鹽酸50份之混合液中於 室溫下攪拌1小時後’使結晶析出。將析出之結晶抽氣過 濾取得殘渣後進行乾燥,獲得式(1_31)所表示之化合物24 份。產率為80%。Synthesis Example 2 The compound obtained by the formula (1 χ) was mixed with 2 parts of N-ethyl o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) under a light-shielding condition, and the obtained solution was mixed. Stir at 110 ° C for 6 hours. After the obtained reaction liquid was cooled to room temperature, the mixture was added to a mixture of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were suction-filtered to obtain a residue, which was then dried to obtain 24 parts of the compound represented by the formula (1_31). The yield was 80%.

精確質量:602.2 合成例3 除使用N-丙基-2,6-二曱基苯胺代替N-乙基-鄰甲笨胺以 外,以與合成例1相同之方式獲得式(1-39)所表示之化合 物0 I6l707.doc •52· 201235784Exact mass: 602.2 Synthesis Example 3 A formula (1-39) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimercaptoaniline was used instead of N-ethyl-o-methylamine. Represented as compound 0 I6l707.doc •52· 201235784

式(丨-39)所表示之化合物之鑑定 (質量分析)離子化模式=ESI+ : m/z=[M+H]+ 659.9 精確質量:658.9 合成例4 在具備回流冷卻器、滴液漏斗及攪拌機之燒瓶内以〇 〇2 L/分鐘流入氮氣而形成氮氣環境,放入乳酸乙酯3〇5質量 份,一面攪拌一面加熱至7(TC為止。繼而,使甲基丙烯酸 60質量份、 丙烯酸3,4-環氧三環[5·21 〇2.6]癸酯(使式(M) 所表示之化合物及式(II-1)所表示之化合物以莫耳比計 50 : 50之方式混合)240質量份及乳酸乙酯丨4〇質量份溶解 而製備溶液,使用滴液漏斗歷時4小時將該溶解液滴入保 溫為70°C之燒瓶内。Identification of the compound represented by the formula (丨-39) (mass analysis) ionization mode = ESI + : m / z = [M + H] + 659.9 Exact mass : 658.9 Synthesis Example 4 With a reflux cooler, a dropping funnel and In a flask of a stirrer, nitrogen gas was introduced at L2 L/min to form a nitrogen atmosphere, and 5 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 7 (TC) while stirring. Then, 60 parts by mass of methacrylic acid and acrylic acid were added. 3,4-epoxytricyclo[5·21 〇2.6] oxime ester (the compound represented by the formula (M) and the compound represented by the formula (II-1) are mixed in a molar ratio of 50:50) A solution was prepared by dissolving 240 parts by mass and 4 parts by mass of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

獲得重量平均分子量“…為9.〗xlO3, 分子量分佈為2.5,固 I6I707.doc -53· 201235784 形物成分33質量% ’溶液酸值34 mg-KOH/g之樹脂B1溶 液。根據上述固形物成分與溶液酸值進行計算,樹脂B丨之 固形物成分酸值為100 mg-KOH/g。樹脂B 1具有以下所示 結構單元。Obtaining a weight average molecular weight "...9" xlO3, molecular weight distribution of 2.5, solid I6I707.doc -53·201235784 Shape component 33% by mass 'Solvent B1 solution of acid value 34 mg-KOH/g. According to the above solid matter The composition and the acid value of the solution were calculated, and the acid value of the solid content of the resin B was 100 mg-KOH/g. The resin B 1 had the structural unit shown below.

合成例4 向具備攪拌機、溫度計、回流冷卻管、滴液漏斗及氮氣 導入管之燒瓶中導入丙二醇單曱醚乙酸酯182 g,於將燒 瓶内環境由空氣變為氮氣後,升溫至100°C後,將於包含 甲基丙烯酸苄酯70.5 g(0.40莫耳)、甲基丙烯酸43〇 g(〇5 莫耳)、曱基丙稀酸雙環戊酯(日立化成股份有限公司製造 FA-513M)22.0 g(0.10莫耳)及丙二醇單曱醚乙酸酯136 g之 混合物中添加有2,2'-偶氮二異丁腈3.6 g之溶液滴入,進而 於100°C下持續攪拌。繼而,將燒瓶内環境由氮氣變為空 氣,將甲基丙烯酸縮水甘油酯35.5 g[0.25莫耳 '(相對於用 於本反應之曱基丙烯酸之羧基為50莫耳。/〇)]、三(二曱胺基) 曱基苯酚0.9 g及對苯二酚0.145 g投入燒瓶内,於U〇〇CT 持續反應,獲得固形物成分32%,固形物成分酸值為79 mgKOH/g 之樹脂 B2 溶液。藉由 GPC(gel permeation chromatography,凝勝滲透層析)測定之以聚笨乙烯換算之 161707.doc • 54· 201235784 重量平均分子量為30,000。 合成例所獲得之樹脂之重量平均分子量(Mw)及數量平 均分子量(Μη)之測定係使用GPC法並於以下條件下進行。 裝置:Κ2479(島津製作所股份有限公司製造)Synthesis Example 4 182 g of propylene glycol monoterpene ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature in the flask was changed from air to nitrogen, and then the temperature was raised to 100°. After C, it will contain 70.5 g (0.40 mol) of benzyl methacrylate, 43 g of methacrylic acid (〇5 mol), and dicyclopentanyl thioglycolate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) A mixture of 22.0 g (0.10 mol) and 136 g of propylene glycol monoterpene ether acetate was added dropwise with a solution of 3.6 g of 2,2'-azobisisobutyronitrile, and stirring was continued at 100 °C. Then, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate was 35.5 g [0.25 mol' (50 mols relative to the carboxyl group of the mercaptoacrylic acid used in the reaction). (diammonium) 0.9 g of nonylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at U〇〇CT to obtain a resin B2 having a solid content of 32% and a solid content of 79 mgKOH/g. Solution. Measured by GPC (gel permeation chromatography) in terms of polystyrene. 161707.doc • 54· 201235784 The weight average molecular weight is 30,000. The weight average molecular weight (Mw) and the number average molecular weight (??) of the resin obtained in the synthesis example were measured by the GPC method under the following conditions. Device: Κ2479 (made by Shimadzu Corporation)

- 管柱:SHIMADZU Shim-pack GPC-80M- Column: SHIMADZU Shim-pack GPC-80M

. 管柱溫度:40°C 溶劑:THF(Tetrahydrofuran,四氫0夫喃)Column temperature: 40 ° C Solvent: THF (Tetrahydrofuran, tetrahydrofuran)

流速:1 ·0 mL/min 偵測器:RI 校正用標準物質··TSKSTANDARDPOLYSTYRENEF-40、F-4、F-288、A-2500、A-500(Tosoh股份有限公司製 造) 將上述獲得之以聚苯乙烯換算之重量平均分子量及數量 平均分子量之比(Mw/Mn)作為分子量分佈。 實施例1〜12及比較例1 以成為表1及表2所示之組成之方式混合各成分而獲得著 色感光性樹脂組合物。 161707.doc -55- 201235784 表1 單位為(份) 實施例 比較例 1 2 3 4 5 6 1 著色劑(Α) (A-1V) 23 23 23 23 23 23 20 (Α-2) 7 7 7 7 7 7 3.5 丙烯酸系分散劑 9 9 9 9 9 9 5 樹脂(Β) (Β-1) 40 40 40 40 40 40 (以固形物成分換算) (Β-2) 50 聚合性化合物(C) (C-1) 60 60 60 60 60 60 50 聚合起始劑(D) (D-1) 10 10 10 10 10 10 15 (E-D 44 62 79 84 89 93 (Ε-2) 149 149 149 149 149 149 溶劑(Ε) (Ε-3) 560 542 524 520 515 511 (Ε-4) 131 131 131 131 131 131 244 (Ε-5) 289 表2 單位為(份) 實施例 7 8 9 10 11 12 著色劑(Α) (A-1),J 23 23 23 23 23 23 (A-3) 7 7 7 7 7 7 丙烯酸系分散劑 9 9 9 9 9 9 樹脂(Β) (以固形物成分換算) (B-1) 40 40 40 40 40 40 (B-2) 聚合性化合物(C) (C-1) 60 60 60 60 60 60 聚合起始劑(D) (D-1) 10 10 10 10 10 10 溶劑(Ε) (E-1) 44 62 79 84 89 93 (E-2) 149 149 149 149 149 149 (E-3) 560 542 524 520 515 511 (E-4) 131 131 131 131 131 131 界面活性劑(G) (G-1) 0.21 0.21 0.21 0.21 0.21 0.21 於表1及表2中,(A-1)υ係使丙烯酸系分散劑及全量之丙 二醇單曱醚乙酸酯混合,並預先使其分散而使用。其中, 比較例1中之(A-1)係使丙烯酸系分散劑及丙二醇單曱醚乙 酸酯137份混合,並預先分散而使用。 再者,於表1及表2中,各成分表示如下。 著色劑(A),(A-l) : C.I.顏料藍15 : 6(顏料) 161707.doc •56- 201235784 著色劑(A),(A-2).染料A1(p山p星染料) 著色劑(A),(A-3):式(1-39)所表示之化合物(咄嗤染料) 樹脂(B),(B-1):樹脂B1,於表中表示以固形物成分換 算之質量份。 樹脂(B) ’(B-2):樹脂B2,於表中表示以固形物成分換 算之質量份。 聚合性化合物(C) ’(C-1):二季戊四醇六丙烯酸酯 (KAYARAD DPHA,日本化藥股份有限公司製造) 聚合起始劑(D) ’(D-l) : N·苯曱醯氧基4-(4-苯基硫基苯 基)辛烷-1-酮-2-亞胺(Irgacure OXE 01,BASF JAPAN 公司 製造) 溶劑(E),(E-1):二丙二醇單曱醚乙酸醋 溶劑(E),(E-2):丙二醇單甲醚 溶劑(E),(E-3):乳酸乙酯 溶劑(E),(E-4):丙二醇單甲醚乙酸酯 溶劑(E) ’(E-5) : 4-羥基-4-曱基_2·戊酮 界面活性劑(G),(G-1):聚醚改性聚矽氧油(T〇rayFlow rate: 1 · 0 mL / min. Detector: RI calibration standard substance · TSKSTANDARDPOLYSTYRENEF-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) in terms of polystyrene is taken as the molecular weight distribution. Examples 1 to 12 and Comparative Example 1 The components were mixed so as to have the compositions shown in Tables 1 and 2 to obtain a colored photosensitive resin composition. 161707.doc -55- 201235784 Table 1 Units are (parts) Example Comparative Example 1 2 3 4 5 6 1 Colorant (Α) (A-1V) 23 23 23 23 23 23 20 (Α-2) 7 7 7 7 7 7 3.5 Acrylic dispersant 9 9 9 9 9 9 5 Resin (Β) (Β-1) 40 40 40 40 40 40 (in terms of solid content) (Β-2) 50 Polymerizable compound (C) ( C-1) 60 60 60 60 60 60 50 Polymerization initiator (D) (D-1) 10 10 10 10 10 10 15 (ED 44 62 79 84 89 93 (Ε-2) 149 149 149 149 149 149 Solvent (Ε) (Ε-3) 560 542 524 520 515 511 (Ε-4) 131 131 131 131 131 131 244 (Ε-5) 289 Table 2 Units are (parts) Example 7 8 9 10 11 12 Colorant ( Α) (A-1), J 23 23 23 23 23 23 (A-3) 7 7 7 7 7 7 Acrylic dispersant 9 9 9 9 9 9 Resin (Β) (in terms of solid content) (B- 1) 40 40 40 40 40 40 (B-2) Polymerizable compound (C) (C-1) 60 60 60 60 60 60 Polymerization initiator (D) (D-1) 10 10 10 10 10 10 Solvent ( Ε) (E-1) 44 62 79 84 89 93 (E-2) 149 149 149 149 149 149 (E-3) 560 542 524 520 515 511 (E-4) 131 131 131 131 131 131 Surfactant ( G) (G-1) 0. 21 0.21 0.21 0.21 0.21 0.21 In Tables 1 and 2, (A-1) fluorene was mixed with an acrylic dispersant and a total amount of propylene glycol monoterpene ether acetate, and dispersed and used in advance. In (1), the acrylic dispersing agent and 137 parts of propylene glycol monoterpene ether acetate were mixed and used previously, and the components are shown in Table 1 and Table 2 below. (A), (Al) : CI Pigment Blue 15 : 6 (Pigment) 161707.doc • 56- 201235784 Colorant (A), (A-2). Dye A1 (p-mountain dye) Colorant (A) (A-3): a compound represented by the formula (1-39) (anthraquinone dye) Resin (B), (B-1): Resin B1, which shows the parts by mass in terms of solid content. Resin (B) '(B-2): Resin B2, which shows the parts by mass of the solid content. Polymerizable compound (C) '(C-1): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D) '(Dl) : N·benzoquinone 4 -(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure OXE 01, manufactured by BASF JAPAN Co., Ltd.) Solvent (E), (E-1): Dipropylene glycol monoterpene ether acetate vinegar Solvent (E), (E-2): propylene glycol monomethyl ether solvent (E), (E-3): ethyl lactate solvent (E), (E-4): propylene glycol monomethyl ether acetate solvent (E) ) '(E-5) : 4-hydroxy-4-indolyl-2-pentanone surfactant (G), (G-1): polyether modified polysiloxane (T〇ray)

Silicone SH8400 . Toray Dow Corning股份有限公司製造) &lt;著色圖案之製作&gt; 利用旋轉塗佈法於2英吋見方之玻璃基板(Eagie 2〇〇〇, 康寧(Corning)公司製造)上塗佈著色感光性樹脂組合物 後,於100 C下預烤3分鐘而形成乾燥後塗膜。於放置冷卻 後,將形成有該乾燥後塗臈之基板與具有圖案(丨〇〇 線 與間隙圖案)之石英玻璃製光罩之間隔設為1〇〇 μπι,並使 161707.doc •57· 201235784 用曝光機(TME-150RSK ’ TOPCON股份有限公司製造)於大 氣環境下以150 mJ/cm2之曝光量(365 nm基準)進行光照 射。於光照射後’於23°C下使上述塗膜於含有非離子系界 面活性劑0.12〇/。及氩氧化鉀0.04%之水系顯影液中浸潰顯影 80秒鐘,進行水洗後,於烘箱中且於22〇〇c下進行2〇分鐘 後烘烤而獲得著色圖案。於放置冷卻後,使用膜厚測定裝 置(DEKTAK3,曰本真空技術股份有限公司製造)測定所獲 得之著色圖案之膜厚為2.2 μηι。 &lt;色度評價&gt; 針對所獲得之著色圖案,使用測色機(〇Sp_Sp_2〇〇,奥 林巴斯股份有限公司製造)測定分光,使用C光源之特性函 數測定CIE之XYZ表色系中之xy色度座標(Βχ,By)及三刺 激值Y。Y值越大表示明度越高。將結果表示於表3及表 4 〇 &lt;缺陷評價&gt; 利用旋轉塗佈法於3英吋見方之破璃基板(Eagle 2〇〇〇, 康寧公司製造)上塗佈著色感光性樹脂組合物,並於減壓 乾燥機(VCD MICROTEK股份有限公司製造)中乾燥至減壓 度到達0_5 torr為止。繼而,於無塵供箱中,於下預 烤3分鐘而於基板上形成乾燥後塗膜。利用表面形狀光學 顯微鏡(倍率250倍’ VF-75 10 ’基恩斯(KEYENCE)股份有 限公司製造)觀察該乾燥後塗膜’數出除了距離基板端部1 cm之範圍以外之基板整體上存在的如火山口般之形狀之缺 陷個數。將結果表示於表3及表4。 I61707.doc •58· 201235784 &lt;耐熱性評價&gt; 除於曝光時未使用光罩以外,以與製作圖案相同之方法 製作著色塗膜。於烘箱中,於23〇t下加熱該著色塗膜2小 時’以與上述相同之方式測定色度及三刺激值γ。根據加 熱前後之色度及三刺激值Y計算色差AEab氺。色差^Eab *越小’則表示加熱前後之顏色變化越小,而耐熱性越良 好°將求得之色差AEab *之值表示於表3及表4之「耐熱 性」攔中。 表3Silicone SH8400 . manufactured by Toray Dow Corning Co., Ltd. &lt;Production of coloring pattern&gt; Coating coloring on a 2 inch square glass substrate (Eagie 2®, manufactured by Corning) by spin coating After the photosensitive resin composition, it was prebaked at 100 C for 3 minutes to form a dried coating film. After being left to cool, the interval between the substrate on which the dried coating is formed and the quartz glass mask having the pattern (twisted line and gap pattern) is set to 1 μm, and 161707.doc • 57· 201235784 Light exposure was carried out in an atmospheric environment at an exposure amount of 150 mJ/cm 2 (365 nm basis) using an exposure machine (TME-150RSK 'TOPCON Co., Ltd.). The coating film was allowed to contain 0.12 Å/min of a nonionic surfactant at 23 ° C after light irradiation. The solution was immersed and developed in an aqueous developing solution of 0.04% of potassium aroxide for 80 seconds, washed with water, and then baked in an oven at 22 ° C for 2 minutes to obtain a colored pattern. After the film was allowed to stand for cooling, the film thickness of the obtained color pattern was measured to be 2.2 μηι using a film thickness measuring device (DEKTAK3, manufactured by 曰本 Vacuum Technology Co., Ltd.). &lt;Chroma evaluation&gt; The color separation pattern obtained was measured by a color measuring machine (〇Sp_Sp_2〇〇, manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source was used to measure the XYZ color system of CIE. The xy chromaticity coordinates (Βχ, By) and the tristimulus value Y. A larger Y value indicates a higher brightness. The results are shown in Tables 3 and 4 〇 &lt;Defect Evaluation&gt; The colored photosensitive resin composition was applied onto a 3 inch square glass substrate (Eagle 2®, manufactured by Corning Incorporated) by a spin coating method. It was dried in a vacuum dryer (manufactured by VCD MICROTEK Co., Ltd.) until the degree of decompression reached 0_5 torr. Then, in a dust-free supply box, the coating film after drying was formed on the substrate by prebaking for 3 minutes. The surface shape optical microscope (magnification 250 times 'VF-75 10 ' manufactured by KEYENCE Co., Ltd.) was observed to observe that the dried coating film was counted as the whole of the substrate except for a range of 1 cm from the end of the substrate. The number of defects in the shape of a crater. The results are shown in Tables 3 and 4. I61707.doc •58·201235784 &lt;Heat resistance evaluation&gt; A colored coating film was produced in the same manner as in the patterning except that the mask was not used at the time of exposure. The coloring film and the tristimulus value γ were measured in the same manner as above by heating the colored coating film for 2 hours in an oven at 23 Torr. The color difference AEab氺 is calculated from the chromaticity before and after the heating and the tristimulus value Y. The smaller the color difference ^Eab*, the smaller the color change before and after heating, and the better the heat resistance. The value of the obtained color difference AEab* is shown in the "heat resistance" of Tables 3 and 4. table 3

Bx 實施例I 0.150 實施例2 實施例3 0.150 實施例4 0.150 實施例5 0.150 實施例6 0.150 比較例1 0.150 0 150 By 0.087 0.087 0.087 0.087 0.087 0.087 0 087 Y 9.9 9.9 9.9 9.9 9.9 9.9 9 〇 缺陷(個) 8 7 5 5 4 2 55 耐熱性 3.2 3.1 3.3 3.3 3,1 3.2 •j j 3.3 表4Bx Example I 0.150 Example 2 Example 3 0.150 Example 4 0.150 Example 5 0.150 Example 6 0.150 Comparative Example 1 0.150 0 150 By 0.087 0.087 0.087 0.087 0.087 0.087 0 087 Y 9.9 9.9 9.9 9.9 9.9 9.9 9 〇 Defects ( 8) 5 7 5 4 2 55 Heat resistance 3.2 3.1 3.3 3.3 3,1 3.2 •jj 3.3 Table 4

實施例13〜18 除了使用式(1-31)所表示之化合物代替染料A1以外,分 別以與實施例丨〜6相同之方式獲得著色感光性樹脂組合 物。進行與上述相同之操作而獲得缺陷較少之乾燥後塗 161707.doc •59· 201235784 膜進⑥冑得明度或耐熱性優異之著色圖案。 根據上述結果可知,藉由實施例卜12之著色感光性樹脂 組合物’可於不降低所獲得之彩色滤光片之明度或财熱性 之情況下,獲得缺陷較少之乾燥後塗膜。 如此,藉由自本發明之著色感光性樹脂組合物形成乾燥 後塗膜,並將自該乾燥後塗膜獲得之著色圖案製成彩色濾 光片’而可良率較高地製造顯示裝置。 產業上之可利用性 本發明之著色感光性樹脂組合物在塗佈於基板上後,進 行減壓乾燥,在所製作之乾燥後塗膜上火山口狀缺陷之產 生較少。 I61707.doc 60-(Examples 13 to 18) A coloring photosensitive resin composition was obtained in the same manner as in Example 丨6 except that the compound represented by the formula (1-31) was used instead of the dye A1. The same operation as above was carried out to obtain a dry after-coating with less defects. 161707.doc •59·201235784 The film was dyed with a color pattern excellent in brightness or heat resistance. According to the above results, it is understood that the colored photosensitive resin composition of Example 12 can obtain a post-drying coating film having few defects without lowering the brightness or the heat of the obtained color filter. By forming the dried coating film from the colored photosensitive resin composition of the present invention and forming the colored pattern obtained from the dried coating film into a color filter ', a display device can be manufactured with high yield. Industrial Applicability The colored photosensitive resin composition of the present invention is dried under reduced pressure after being applied onto a substrate, and the occurrence of crater-like defects on the coating film after drying is small. I61707.doc 60-

Claims (1)

201235784 七、申請專利範圍: 1_ 一種著色感光性樹脂組合物,其含有著色劑、樹脂、聚 合性化合物、聚合起始劑及溶劑, 著色劑係含有咄嗤染料及顏料者, 溶劑係含有二丙二醇單甲醚乙酸酯者。 2.如請求項1之著色感光性樹脂組合物,其中二丙二醇單 甲趟乙酸®旨於溶劑中之含量為0.1質量%以上30質量%以 下。 -.如β求項1或2之著色感光性樹脂組合物,其中溶劑係進 而含有乳酸乙酯者。 4_如睛求項3之著色感光性樹脂組合物,其中溶劑係進而 含有丙二醇單曱醚及/或丙二醇單甲醚乙酸酯者。 5. 如清求項1之著色感光性樹脂組合物,其中樹脂為鹼可 溶性樹脂。 6. 如請求項1之著色感光性樹脂組合物,其中聚合性化合 物為(曱基)丙烯酸酯。 7. 一種彩色渡光片,其係由如請求項1之著色感光性樹脂 組合物形成。 8. —種顯不裝置,其含有如請求項7之彩色濾光片。 161707.doc 201235784 四、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無) 161707.doc201235784 VII. Patent application scope: 1_ A colored photosensitive resin composition containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator and a solvent, the coloring agent containing an anthraquinone dye and a pigment, and the solvent containing dipropylene glycol Monomethyl ether acetate. 2. The colored photosensitive resin composition according to claim 1, wherein the content of the dipropylene glycol monomethylhydrazine acetic acid® in the solvent is 0.1% by mass or more and 30% by mass or less. A colored photosensitive resin composition according to the item 1 or 2, wherein the solvent is added to contain ethyl lactate. The coloring photosensitive resin composition of Claim 3, wherein the solvent further contains propylene glycol monoterpene ether and/or propylene glycol monomethyl ether acetate. 5. The colored photosensitive resin composition according to item 1, wherein the resin is an alkali-soluble resin. 6. The colored photosensitive resin composition of claim 1, wherein the polymerizable compound is (mercapto) acrylate. A color light-passing sheet formed of the colored photosensitive resin composition of claim 1. 8. A display device comprising a color filter as claimed in claim 7. 161707.doc 201235784 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 161707.doc
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