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TW200931178A - Colored photosensitive resin composition - Google Patents

Colored photosensitive resin composition Download PDF

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Publication number
TW200931178A
TW200931178A TW097150117A TW97150117A TW200931178A TW 200931178 A TW200931178 A TW 200931178A TW 097150117 A TW097150117 A TW 097150117A TW 97150117 A TW97150117 A TW 97150117A TW 200931178 A TW200931178 A TW 200931178A
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TW
Taiwan
Prior art keywords
compound
monomer
resin composition
colored photosensitive
photosensitive resin
Prior art date
Application number
TW097150117A
Other languages
Chinese (zh)
Other versions
TWI439808B (en
Inventor
Masaru Shida
Mitsuru Kondo
Dai Shiota
Tetsuya Kato
Original Assignee
Tokyo Ohka Kogyo Co Ltd
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Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of TW200931178A publication Critical patent/TW200931178A/en
Application granted granted Critical
Publication of TWI439808B publication Critical patent/TWI439808B/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/492—Photosoluble emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

The present invention provides a colored photosensitive resin composition having improved ink repellency and a good developing property. The colored photosensitive resin composition comprises a photopolymerizable compound (A), an ink-repellent compound (B), a photopolymerization initiator (C) and a colorant (D), wherein the ink-repellent compound (B) is a copolymer formed by copolymerizing a monomer (B1) containing at least a vinyl unsaturated group and expressed by the following formula (b1) and a fluorinated monomer (B2) copolymerizable with the monomer (B1), wherein R1b is ylide with 1-5 carbons, and n is an integer greater than 1.

Description

200931178 九、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成物，尤其係關 於一種在形成彩色濾光片之黑色矩陣時適合使用之著色感 光性樹脂組成物。 【先前技術】 φ 液晶顯示器等顯示體係形成為以下結構：在相互對向 而形成有成對電極的2片基板間夾入液晶層。並且，在一 片基板之内側形成具有包括紅色（R)、綠色（G)、藍色（B) 等各色之像素區域的彩色濾光片。該彩色濾光片通常為了 提高對比度及防止漏光等，而形成配置成矩陣狀之黑色矩 陣，以劃分R、G、B各色之像素區域。 通常’彩色濾光片係利用光微影法製造。該光微影法 首先在基板上塗佈黑色感光性樹脂組成物後，進行曝光、 顯影而形成黑色矩陣。繼而，對每種R、G、B各色感光性 〇 樹脂組成物反覆進行塗佈、曝光、顯影，藉此在規定位置 上形成各色圖案而製造彩色濾光片。 又’近年來為提高彩色濾光片之生產性，正在研究利 用喷墨方式來製造彩色濾光片之方法。於該喷墨方式中， 首先’利用光微影法形成黑色矩陣。繼而，將R、G、B各 色之墨汁自喷墨嘴喷出至由黑色矩陣劃分之各區域中，利 用熱或光使所蓄積之墨汁硬化，藉此而製造彩色濾光片。 [專利文獻1]國際公開第2004/042474號小冊子 5 200931178 【發明内容】 [發明所欲解決之問題] 然而，於該噴墨方式中，為防止鄰接之像素區域間之 墨汁發生混色等，而要求用於形成黑色矩陣之著色感光性 樹脂組成物具有對墨汁溶劑之抗溶劑性，即所謂之斥墨性。 如上所述之具有斥墨性之著色感光性樹脂組成物，例 如於專利文獻1中揭示有含有斥墨劑之負型感光性樹脂組 成物，該斥墨劑係由具有以下單元之聚合物所形成，即， 具有氫原子中之至少1個經氟原子取代的碳數為20以下之 烷基（其中，上述烷基包括具有醚性氧原子者）的單元、 以及具有乙烯性不飽和基之單元。該負型感光性樹脂組成 物由斥墨劑之氟烷基而獲得斥墨性。又，斥墨劑含有具有 乙烯性不飽和基之單元，因此可利用光照射而硬化，且斥 墨性得到維持。 然而，於使用專利文獻1所記載之負型感光性樹脂組 成物來形成黑色矩陣之情形時，存在亦會排斥顯影液而難 以獲得線寬之均勻性的問題。又，有在像素區域殘留顯影 後之殘渣，並在喷出R、G、B各色之墨汁時會在像素區域 内排斥墨汁的顧慮。 本發明係鑒於以上課題而完成者，目的在於提供一種 具有高斥墨性，且顯影性亦良好之著色感光性樹脂組成物。 [解決問題之手段] 本發明者等人為解決上述課題而反覆進行努力研究。 結果發現，可藉由使著色感光性樹脂組成物中含有特定之 6 (Μ)BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition suitable for use in forming a black matrix of a color filter. [Prior Art] A display system such as a φ liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates in which a pair of electrodes are formed to face each other. Further, a color filter having pixel regions of respective colors such as red (R), green (G), and blue (B) is formed inside the substrate. In order to improve contrast and prevent light leakage, the color filter is usually formed in a matrix of black matrices to divide pixel regions of R, G, and B colors. Usually, the color filter is manufactured by photolithography. This photolithography method firstly applies a black photosensitive resin composition on a substrate, and then exposes and develops to form a black matrix. Then, each of the R, G, and B photosensitive resin compositions is repeatedly coated, exposed, and developed to form a color filter at a predetermined position to form a color filter. Further, in recent years, in order to improve the productivity of color filters, a method of manufacturing a color filter by an ink jet method has been studied. In the ink jet method, first, a black matrix is formed by photolithography. Then, inks of respective colors of R, G, and B are ejected from the ink ejecting nozzles to respective regions divided by the black matrix, and the accumulated ink is hardened by heat or light, thereby producing a color filter. [Patent Document 1] International Publication No. 2004/042474 Booklet 5 200931178 [Disclosure] [Problems to be Solved by the Invention] However, in the inkjet method, in order to prevent color mixing of ink between adjacent pixel regions, The colored photosensitive resin composition for forming a black matrix is required to have solvent resistance to an ink solvent, that is, so-called ink repellency. The colored photosensitive resin composition having ink repellency as described above, for example, Patent Document 1 discloses a negative photosensitive resin composition containing an ink repellent, which is composed of a polymer having the following units. Forming, that is, a unit having at least one hydrogen atom substituted with a fluorine atom and having an alkyl group having 20 or less carbon atoms (wherein the above alkyl group includes an etheric oxygen atom), and having an ethylenically unsaturated group unit. This negative photosensitive resin composition is obtained by the fluoroalkyl group of the ink repellent to obtain ink repellency. Further, since the ink repellent contains a unit having an ethylenically unsaturated group, it can be cured by light irradiation, and the ink repellency is maintained. However, when a negative-type photosensitive resin composition described in Patent Document 1 is used to form a black matrix, there is a problem that the developer is repelled and it is difficult to obtain uniformity of line width. Further, there is a concern that residue after development is left in the pixel region, and ink is repelled in the pixel region when ink of each of R, G, and B colors is ejected. The present invention has been made in view of the above problems, and an object of the invention is to provide a coloring photosensitive resin composition which has high ink repellency and is excellent in developability. [Means for Solving the Problems] The inventors of the present invention have repeatedly made efforts to solve the above problems. As a result, it has been found that a specific 6 (Μ) can be contained in the colored photosensitive resin composition.

200931178 斥墨性化合物而解決上述課題，從而完成本發明。具 言，本發明提供如下者。 本發明之著色感光性樹脂組成物係含有光聚合性 物（A )、斥墨性化合物（B)、光聚合起始劑（C)以 色劑（D)者，其特徵在於：上述斥墨性化合物（B) 少使具有乙烯性不飽和基及由下述式（bl)所表示之 的單體（B1)、與可與該單體（B1)共聚合之氟系單體i 進行共聚合而成的共聚物。 [化學式1] + Rlb-〇\ (式（bl)中，Rlb表示碳數為 1〜5之亞 (alkylene)，η表示1以上之整數。） [功效] 根據本發明，可提供一種具有高斥墨性、且顯影 良好之著色感光性樹脂組成物。該著色感光性樹脂組 例如適合在形成彩色濾光片之黑色矩陣時使用。 【實施方式】 以下，對本發明之實施形態加以說明。本說明書 謂「（曱基）丙烯酸」，係表示丙烯酸及曱基丙烯酸中之 或兩者。同樣，所謂「（曱基）丙烯酸酯」，係表示丙烯 及曱基丙烯酸酯中之一者或兩者。 體而 化合 及著 係至 結構 Β2 ) 炫《基 性亦 成物 中所 一者 酸酯 7200931178 An ink repellent compound solves the above problems, thereby completing the present invention. In other words, the present invention provides the following. The colored photosensitive resin composition of the present invention contains a photopolymerizable material (A), an ink repellent compound (B), and a photopolymerization initiator (C) colorant (D), which is characterized in that the above-mentioned ink repellent The compound (B) is less likely to have an ethylenically unsaturated group and a monomer (B1) represented by the following formula (b1), and a fluorine-based monomer i copolymerizable with the monomer (B1). A copolymer obtained by polymerization. [Chemical Formula 1] + Rlb-〇\ (In the formula (b1), Rlb represents an alkylene having a carbon number of 1 to 5, and η represents an integer of 1 or more.) [Efficacy] According to the present invention, it is possible to provide a high A coloring photosensitive resin composition which is excellent in ink repellent property and which is developed well. The colored photosensitive resin group is suitably used, for example, when forming a black matrix of a color filter. [Embodiment] Hereinafter, embodiments of the present invention will be described. The present specification means "(fluorenyl)acrylic acid" and means either or both of acrylic acid and methacrylic acid. Similarly, "(mercapto) acrylate" means one or both of propylene and methacrylate. Body and combination to structure Β2) Hyun "one of the basic properties of the acid ester 7

200931178 [著色感光性樹脂組成物] 本發明之著色感光性樹脂組成物含有光聚合性 (A )、斥墨性化合物（B )、光聚合起始劑（C )以 劑（D )。以下對各成分加以說明。 [光聚合性化合物（A )] 光聚合性化合物（A )係受到紫外線等光之照 合、硬化之物質。光聚合性化合物（A)較好的是 烯性不飽和基之樹脂或者單艎，更好的是將該等 合。藉由將具有乙烯性不飽和基之樹脂與具有乙烯 和基之單體進行組合，可提高硬化性，容易形成圖 者，本說明書中，在具有乙烯性不飽和基之化合物 重量平均分子量為10 〇〇以上者稱為「具有乙烯性不 之樹脂」，將重量平均分子量小於1000者稱為「具 性不飽和基之單體」。 <具有乙烯性不飽和基之樹脂》 作為具有乙烯性不飽和基之樹脂，可列舉：Γ 烯酸、反丁烯二酸、順丁烯二酸、反丁烯二酸單甲 丁烯二酸單乙酯、（曱基）丙烯酸2 -羥乙酯、乙二醇 (甲基）丙烯酸酯、乙二醇單乙醚（甲基）丙烯酸酯、 丙烯酸甘油酯、（曱基）丙烯醯胺、丙烯腈、曱基丙烯 基）丙烯酸甲酯、（曱基）丙烯酸乙酯、（曱基）丙烯酸姜 (甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸苄酯、乙二i 基）丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二（ 烯酸酯、四乙二醇二（甲基）丙烯酸酯、丁二醇二甲 化合物 及著色 射而聚 具有乙 進行組 性不飽 案。再 中，將 飽和基 有乙烯 P基）丙 酯、反 單甲醚 (曱基） 腈、（甲 -丁酯、 淳二（甲 f基）丙 基丙烯 8 200931178 酸酯、丙二醇二（曱基）丙烯酸酯、三羥甲基丙烷三（曱基） 丙烯酸酯、四羥甲基丙烷四（曱基）丙烯酸酯、季戊四醇三 (甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四 酵五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、1>6· 己二醇二（甲基）丙烯酸酯、咔哚環氧二丙烯酸酯（cardo Ο ❹ epoxy diacrylate)等進行聚合而獲得之寡聚物·類；使（甲基） 丙烯酸與將多元酵類與一元酸或多元酸進行縮合而獲得之 聚酯預聚物進行反應而獲得之聚酯（曱基）丙烯酸酯、使多 元醇與具有2個異氰酸酯基之化合物反應後再與（甲基）丙 烯酸進行反應而獲得之聚（甲基）丙烯酸胺基甲酸酯；使$ 酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹月旨、 苯酚或者甲酚酚醛清漆型環氧樹脂、可溶酚醛型環氧樹月旨 (resol epoxy resin)、三苯酚甲烷型環氧樹脂、聚羧酸聚縮 水甘油輯、多元醇聚縮水甘油酯、脂肪族或者脂環式環 樹脂、胺環氧樹脂、二羥基苯型環氧樹脂等環氧樹脂與 基）丙烯酸反應而獲得之環氧'甲 衣礼（甲基）丙烯酸酯樹脂等。 外’可使用使多元酸酐與環田曾、 此 六及氧（曱基）丙烯酸酯樹脂反 獲得之樹脂。 應而 又，具有乙烯性不飽和 使環氧化合物（A1)與含 (A2 )的反應物，進一步與多元 基之樹脂可較好地使用 乙稀性不飽和基之羧酸 樹脂。 酸酐（A3 )反應而 •藉由 化合物 獲得之 〈環氧化合物（A1 ) > 作為環氧化合物（A1),可列$ 縮水甘油越型 縮 9200931178 [Coloring photosensitive resin composition] The colored photosensitive resin composition of the present invention contains photopolymerizable (A), ink repellent compound (B), and photopolymerization initiator (C) as agent (D). Each component will be described below. [Photopolymerizable Compound (A)] The photopolymerizable compound (A) is a substance which is irradiated and hardened by light such as ultraviolet rays. The photopolymerizable compound (A) is preferably an ethylenically unsaturated group-containing resin or a monoterpene, and more preferably the same. By combining a resin having an ethylenically unsaturated group with a monomer having an ethylene group and a group, the hardenability can be improved and the image is easily formed. In the present specification, the weight average molecular weight of the compound having an ethylenically unsaturated group is 10 The above is referred to as "a resin having an ethylenic property", and a person having a weight average molecular weight of less than 1,000 is referred to as a "monounsaturated monomer". <Resin having an ethylenically unsaturated group. Examples of the resin having an ethylenically unsaturated group include a decenoic acid, a fumaric acid, a maleic acid, and a fumaric acid monomethylbutene. Acid monoethyl ester, 2-hydroxyethyl (meth)acrylate, ethylene glycol (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glyceryl acrylate, (mercapto) acrylamide, Acrylonitrile, mercaptopropenyl)methyl acrylate, ethyl (meth) acrylate, 2-ethylhexyl acrylate (meth) acrylate, benzyl (meth) acrylate, ethylenediyl Acrylate, diethylene glycol diacrylate, triethylene glycol di(methacrylate), tetraethylene glycol di(meth)acrylate, butanediol dimethyl compound and colored shots In addition, the saturated group will have ethylene P-based propyl ester, anti-monomethyl ether (mercapto) nitrile, (methyl-butyl ester, bismuth (methylf-) propyl propylene 8 200931178 acid ester, propylene glycol II (fluorenyl) acrylate, trimethylolpropane tris(decyl) acrylate, tetramethylol Alkane (mercapto) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1 &gt ;6· hexanediol di(meth)acrylate, oxime epoxy diacrylate (cardo Ο ❹ epoxy diacrylate) and other oligomers obtained by polymerization; (meth)acrylic acid and multi-fermented a polyester (mercapto) acrylate obtained by reacting a polyester prepolymer obtained by condensation with a monobasic acid or a polybasic acid, reacting a polyol with a compound having two isocyanate groups, and reacting with (meth) Poly(meth)acrylic acid urethane obtained by the reaction of acrylic acid; making phenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac Varnish type epoxy resin, resol epoxy resin, trisphenol methane epoxy resin, polycarboxylic acid polyglycidyl series, polyglycol polyglycidyl ester, aliphatic or alicyclic Ring resin, amine ring An epoxy 'methyl acrylate resin obtained by reacting an epoxy resin such as an oxygen resin or a dihydroxybenzene type epoxy resin with an acrylic acid. A resin obtained by reversing a polybasic acid anhydride with a ring-shaped, hexa- and oxo-(meth) acrylate resin can be used. Further, the ethylenically unsaturated carboxylic acid resin having an ethylenically unsaturated group can be preferably used as the resin of the epoxy compound (A1) and the (A2)-containing reactant, and further with the polybasic group. The anhydride (A3) is reacted and • the epoxy compound (A1) > obtained as a compound can be listed as the epoxy compound (A1), and the glycidol can be classified.

200931178 水甘油酯型、縮水甘油胺型、脂環型、雙酚A 型、雙酚S型、聯苯型、萘型、苐型、苯酚酚 鄰甲酚型環氧樹脂等。其中，較好的是聯苯型 聯苯型環氧樹脂係於主鏈上具有1個以上的由 所表示之聯苯骨架，並且具有1個以上之環氧 為環氧化合物（A1)，較好的是具有2個以上之 該環氧化合物（A1)可單獨使用或者將2種以 用。 [化學式2] 型、雙酚F 醛清漆型、 環氧樹脂。 下述式（al ) 基。又，作 環氧基者。 上組合而使200931178 Water glyceride type, glycidylamine type, alicyclic type, bisphenol A type, bisphenol S type, biphenyl type, naphthalene type, hydrazine type, phenol phenol o-cresol type epoxy resin. Among them, a biphenyl type biphenyl type epoxy resin preferably has one or more biphenyl skeletons represented by a main chain, and one or more epoxy groups are epoxy compounds (A1). Preferably, the epoxy compound (A1) having two or more of them may be used singly or in combination of two or more. [Chemical Formula 2] type, bisphenol F aldehyde varnish type, epoxy resin. The following formula (al) is used. Also, as an epoxy group. Combine

式（al )中，多個Rla分別獨立表示氫原 1〜12之烷基、齒原子、或可具有取代基之苯基 〜4之整數。 於聯苯型環氧樹脂中，較好的是使用由下 所表示之環氧樹脂，尤其好的是使用由下述式 示之環氧樹脂。藉由使用式（a3)之環氧樹脂 好地平衡了靈敏度及溶解性，並且像素邊緣（ 晰（sharp)性、密著性優異之著色感光性樹脂 [化學式3] 子、碳數為 ；_，m表示 1 述式（a2) (a3 )所表 ，可獲得良 e d g e )之清 組成物。 10 200931178In the formula (al), a plurality of Rla each independently represent an alkyl group of a hydrogen atom of 1 to 12, a tooth atom, or an integer of phenyl group 4 which may have a substituent. In the biphenyl type epoxy resin, it is preferred to use an epoxy resin represented by the following, and it is particularly preferable to use an epoxy resin represented by the following formula. By using the epoxy resin of the formula (a3), the sensitivity and the solubility are well balanced, and the coloring photosensitive resin (chemical formula 3) having a sharp edge and a good adhesion is used, and the carbon number is _ , m represents a clear composition of the formula (a2) (a3), which can be obtained. 10 200931178

式（a2 )、（ a3 )中，多個R2a分別獨立表示氫原子、 碳數為1〜12之烷基、鹵原子、或可具有取代基之苯基，p 〇 表示1〜4之整數。q為平均值，表示0〜10之數，較好的 是小於1。 又，於聯苯型環氧樹脂中，亦較好的是使用由下述式 (a4)所表示之環氧樹脂。藉由使用式（a4)之環氧樹脂， 可獲得良好地平衡了靈敏度及溶解性，並且像素邊緣之清 晰性、密著性優異之著色感光性樹脂組成物。 [化學式4]In the formulae (a2) and (a3), a plurality of R2a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent, and p 〇 represents an integer of 1 to 4. q is an average value indicating a number of 0 to 10, preferably less than 1. Further, in the biphenyl type epoxy resin, it is also preferred to use an epoxy resin represented by the following formula (a4). By using the epoxy resin of the formula (a4), it is possible to obtain a colored photosensitive resin composition which is excellent in balance between sensitivity and solubility, and which is excellent in clarity and adhesion of the pixel edge. [Chemical Formula 4]

式（a4 )中，多個R3a分別獨立表示氫原子、碳數為 1〜12之烷基、鹵原子、或可具有取代基之苯基。r為平均 值，表示0〜10之數，較好的是小於1。 〈含乙烯性不飽和基之羧酸化合物（A2)〉 11 200931178 的鍵 好雙 較性 ,&quot; 2)乙 A性 (應 物反 合等 化基 酸稀 缓丙 之基 基曱 和或 飽基 不烯 性丙 稀有 乙含 含 中 為子 作分 在 是 之單羧酸化合物。作為此種含乙烯性不飽和基之羧酸化合 物，可列舉：丙烯酸、甲基丙烯酸、yS -苯乙烯基丙烯酸、 /3-糠基丙烯酸、α -氰基肉桂酸、肉桂酸等。該含乙烯性 不飽和基之羧酸化合物（Α2)可單獨使用或者將2種以上 組合而使用。 ❹ ❹ 作為使環氧化合物（Α1)與含乙烯性不飽和基之羧酸 化合物（Α2 )反應之方法，可使用公知之方法。例如可列 舉以下方法：以三乙胺、苄基乙胺等三級胺；氣化十二烷 基三曱基銨、氣化四曱基銨、氣化四乙基銨、氣化苄基三 乙基銨等四級銨鹽；吡啶，三苯基膦等為觸媒，在有機溶 劑中，於50 °C〜150 °C之反應溫度，使環氧化合物（Α1) 與含乙烯性不飽和基之羧酸化合物（A2)反應數小時〜數 十小時。 環氧化合物（A1)與含乙烯性不飽和基之羧酸化合物 (A2)的反應中之使用量比率，以環氧化合物（A1)之環 氧當量與含乙烯性不飽和基之羧酸化合物（A2)的羧酸當 量之比計，通常為 1:0.5〜1:2，較好的是 1:0.8〜1: 1.25，更好的是1: 1。藉由設為上述範圍，而有提高交聯 效率之傾向，故較好。 〈多元酸酐（A3 )〉 多元酸酐（A3)係具有2個以上羧基之羧酸的酸酐， 且包括具有至少 2個苯環之化合物。作為此種多元酸酐 12 200931178 (A3 )，例如可列舉：如下述式（a5 )所表示的具有聯苯 骨架之酸酐、如下述式（a6)所表示的2個苯環經由有機 基而鍵結之酸酐。 [化學式5]In the formula (a4), a plurality of R3a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. r is an average value and represents a number of 0 to 10, preferably less than 1. <Carboxylic acid-containing unsaturated group-containing carboxylic acid compound (A2)> 11 200931178 The bond is good and double, &quot; 2) B-A (the compound is reversed, the acid is diluted, and the base is saturated or saturated) The ethylenic propylene-containing propylene has a monocarboxylic acid compound containing a succinic group. Examples of the carboxylic acid compound containing an ethylenically unsaturated group include acrylic acid, methacrylic acid, and yS-styryl. Acrylic acid, /3-mercaptoacrylic acid, α-cyano cinnamic acid, cinnamic acid, etc. The carboxylic acid compound (Α2) containing an ethylenically unsaturated group may be used singly or in combination of two or more kinds. A method of reacting the epoxy compound (Α1) with a carboxylic acid compound (Α2) containing an ethylenically unsaturated group can be carried out by a known method, and examples thereof include a tertiary amine such as triethylamine or benzylethylamine; Gasification of tetra-ammonium salts such as dodecyltrimethylammonium, vaporized tetradecylammonium, vaporized tetraethylammonium, vaporized benzyltriethylammonium; pyridine, triphenylphosphine, etc. as catalyst, Epoxy compound (Α) in an organic solvent at a reaction temperature of 50 ° C to 150 ° C 1) The reaction with the ethylenically unsaturated group-containing carboxylic acid compound (A2) for several hours to several tens of hours. The use amount of the epoxy compound (A1) in the reaction with the ethylenically unsaturated group-containing carboxylic acid compound (A2) The ratio is usually 1:0.5 to 1:2, preferably 1 in terms of the ratio of the epoxy equivalent of the epoxy compound (A1) to the carboxylic acid equivalent of the ethylenically unsaturated group-containing carboxylic acid compound (A2). : 0.8 to 1: 1.25, more preferably 1:1. It is preferably in the above range, and has a tendency to improve the crosslinking efficiency. <Polyureic acid anhydride (A3)> The polybasic acid anhydride (A3) has 2 An acid anhydride of a carboxylic acid having a carboxyl group or more, and a compound having at least two benzene rings. As such a polybasic acid anhydride 12 200931178 (A3 ), for example, an acid anhydride having a biphenyl skeleton represented by the following formula (a5) An acid anhydride which is bonded to the two benzene rings represented by the following formula (a6) via an organic group. [Chemical Formula 5]

〇5)〇5)

—O-R^-O 06) 式（a6)中，R4a表示碳數為1〜10的可具有取代基 之亞烷基》 藉由使用上述具有2個以上羧基之羧酸的酸酐，可在 光聚合性化合物（A)中導入至少2個苯環。 又，多元酸酐（A3)除了上述具有至少2個苯環之酸 酐以外，可包括其他多元酸酐。作為其他多元酸酐，例如 可列舉：順丁烯二酸酐、丁二酸酐、亞曱基丁二酸酐、鄰 苯二曱酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、曱 基六氫鄰苯二曱酸酐、甲基四氫鄰苯二甲酸酐、偏苯三曱 酸酐、均苯四曱酸酐、二苯甲酮四甲酸二酐、3 -甲基六氫 鄰苯二曱酸酐、4 -曱基六氫鄰苯二曱酸酐、3 -乙基六氫鄰 苯二甲酸酐、4 -乙基六氫鄰苯二甲酸酐、四氫鄰苯二甲酸 酐、3 -甲基四氫鄰苯二曱酸酐、4 -曱基四氫鄰苯二甲酸酐、 13 200931178 3-乙基四氩鄰笨二甲酸酐、4_乙基四氫鄰苯二甲酸酐。該 等多70酸軒可單獨使用或者將2種以上組合而使用。 作為使環氧化合物（Α1)與含乙稀性不餘和基之幾酸 化合物（Α2)反應後，進一步與多元酸酐（A3)反應之方 法’可使用公知之方法。又，使用量比率，以環氧化合物 (Α1)與含乙烯性不飽和基之羧酸化合物（Α2)的反應物 中之ΟΗ基之莫耳數、與多元酸酐（A3)之酸酐基的當量 ❹ 比計’通常為1: 1〜1: 0.1’較好的是1: 0.8〜1: 0.2。 藉由設為上述範圍’而有對顯影液之溶解性變得適度之傾 向，故較好。 藉由使環氧化合物（Α1)與含乙烯性不飽和基之羧酸 化合物（Α2)的反應物進一步與多元酸酐（A3)反應而獲 得之樹腊的酸價，以樹脂固體成分計，較好的是1〇 mgKOH/g 〜15〇 mgKOH/g，更好的是 70 mgKOH/g 〜110 mgKOH/g。藉由將樹脂之酸償設為1〇 mgKOH/g以上，可 獲得對顯影液之充分溶解性，又，藉由設為15〇 mgKOH/g 0 以下’可獲得充分之硬化性，並且可使表面性良好。 又’樹脂之重量平均分子量較好的是1〇〇〇〜4〇〇〇〇， 更好的是2〇〇〇〜30000。藉由將重量平均分子量設為1000 以上’可提高对熱性 '膜強度，又，藉由設為40000以下， 可獲得對顯影液之充分溶解性》 又’作為具有乙烯性不飽和基之樹脂，可較好地使用 在分子内具有咔哚結構之樹脂。具有咔哚結構之樹脂的耐 熱性及耐化學藥品性高，因此可藉由用於光聚合性化合物 14 200931178 (A)而提高著色感光性樹脂組成物之耐熱性及耐化學藥 品性。例如，可較好地使用由下述式（a7 )所表示之樹脂。 [化學式6]—OR^—O 06) In the formula (a6), R 4a represents a substitutable alkylene group having a carbon number of 1 to 10, and photopolymerization can be carried out by using an acid anhydride of a carboxylic acid having two or more carboxyl groups as described above. At least two benzene rings are introduced into the compound (A). Further, the polybasic acid anhydride (A3) may include other polybasic acid anhydrides in addition to the above-mentioned acid anhydride having at least two benzene rings. Examples of the other polybasic acid anhydride include maleic anhydride, succinic anhydride, decylene succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and sulfhydryl groups. Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride , 4-mercaptohexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetra Hydrogen phthalic anhydride, 4-mercaptotetrahydrophthalic anhydride, 13 200931178 3-ethyltetrafluoro-o-dicarboxylic acid anhydride, 4-ethyltetrahydrophthalic anhydride. These 70 acid acids may be used singly or in combination of two or more. A known method can be used as a method of reacting the epoxy compound (Α1) with the ethyl acid compound (Α2) having an ethyl group and further reacting with the polybasic acid anhydride (A3). Further, the amount ratio used is the molar number of the mercapto group in the reaction product of the epoxy compound (Α1) and the ethylenically unsaturated group-containing carboxylic acid compound (Α2), and the equivalent amount of the acid anhydride group of the polybasic acid anhydride (A3). ❹ The ratio is usually 1:1~1: 0.1' is preferably 1: 0.8~1: 0.2. It is preferred to have a tendency to moderately dissolve the solubility of the developer by setting it as the above range. The acid value of the wax obtained by further reacting the reactant of the epoxy compound (Α1) with the carboxylic acid compound containing an ethylenically unsaturated group (Α2) with the polybasic acid anhydride (A3), based on the solid content of the resin Preferably, it is 1 〇 mgKOH/g to 15 〇 mgKOH/g, more preferably 70 mgKOH/g to 110 mg KOH/g. When the acid recovery of the resin is 1 〇 mgKOH/g or more, sufficient solubility in the developer can be obtained, and sufficient hardenability can be obtained by setting it to 15 〇 mgKOH/g 0 or less, and Good surface properties. Further, the weight average molecular weight of the resin is preferably from 1 to 4, more preferably from 2 to 300,000. By setting the weight average molecular weight to 1000 or more, the thermal strength of the film can be increased, and by setting it to 40,000 or less, sufficient solubility in the developer can be obtained, and the resin having an ethylenically unsaturated group can be obtained. A resin having a fluorene structure in a molecule can be preferably used. Since the resin having a ruthenium structure has high heat resistance and chemical resistance, it can be used for the photopolymerizable compound 14 200931178 (A) to improve the heat resistance and chemical resistance of the colored photosensitive resin composition. For example, a resin represented by the following formula (a7) can be preferably used. [Chemical Formula 6]

COOH H00C-Y-C0-0 (a7)COOH H00C-Y-C0-0 (a7)

II

X-0- CO-Z-CO-O-l-X-0- CO-Y-COOH COOH 式（a7)中，X係由下述式（a8)所表示之基。X-0-CO-Z-CO-O-l-X-0-CO-Y-COOH COOH In the formula (a7), X is a group represented by the following formula (a8).

[化學式7][Chemical Formula 7]

又，式（a7)中，Y係自順丁烯二酸酐、丁二酸酐、 亞曱基丁二酸酐、鄰苯二曱酸酐、四氫鄰苯二曱酸酐、六 氫鄰苯二甲酸酐、曱基内亞曱基四氫鄰苯二甲酸酐、氣橋 酸酐、曱基四氫鄰苯二甲酸酐、戊二酸酐等二羧酸酐中除 去羧酸酐基（-C0-0-C0-)而得之殘基。 又，式（a7)尹，Z係自均苯四甲酸酐、二苯甲酮四 曱酸二酐、聯苯四曱酸二酐、聯苯醚四曱酸二酐等四羧酸 二酐中除去2個羧酸酐基而得之殘基。 又，式（a7)中，s為0〜20之整數。 《具有乙烯性不飽和基之單體》 15 200931178 具有乙烯性不飽和基之單體中，有單官能單體以及多 官能單體。Further, in the formula (a7), Y is derived from maleic anhydride, succinic anhydride, decylene succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, The carboxylic acid anhydride group (-C0-0-C0-) is removed from a dicarboxylic anhydride such as mercaptoinyltetrahydrophthalic anhydride, gas anhydride, decyltetrahydrophthalic anhydride or glutaric anhydride. Remaining residue. Further, the formula (a7) Yin, Z is derived from tetracarboxylic dianhydride such as pyromellitic anhydride, benzophenone tetraphthalic acid dianhydride, biphenyl tetraphthalic acid dianhydride, and diphenyl ether tetradecanoic acid dianhydride. Residues obtained by removing two carboxylic anhydride groups. Further, in the formula (a7), s is an integer of 0 to 20. "Monomer having an ethylenically unsaturated group" 15 200931178 Among the monomers having an ethylenically unsaturated group, there are a monofunctional monomer and a polyfunctional monomer.

作為單官能單體，可列舉：（曱基）丙烯醯胺、羥甲基（曱 基）丙烯醯胺、曱氧基甲基（甲基）丙烯醯胺、乙氧基曱基（曱 基）丙烯醯胺、丙氧基甲基（甲基）丙烯醯胺、丁氧基甲氧基 曱基（曱基）丙烯醯胺、N-羥曱基（甲基）丙烯醯胺、N-羥基 甲基（甲基）丙烯醯胺、（曱基）丙烯酸、反丁烯二酸、順丁 烯二酸、順丁烯二酸酐、亞甲基丁二酸、亞曱基丁二酸酐、 甲基順丁烯二酸、甲基順丁烯二酸酐、丁烯酸、2 -丙烯醯 胺-2 -甲基丙磺酸、第三丁基丙烯醯胺磺酸、（曱基）丙烯酸 甲酯、（曱基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（曱基）丙烯 酸2-乙基己酯、（甲基）丙烯酸環己酯、（曱基）丙烯酸2 -羥 乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸2-羥丁酯、（曱 基）丙烯酸2-苯氧基-2-羥丙酯、鄰苯二曱酸2-(曱基）丙烯 醢氧基-2-羥丙酯、單（甲基）丙烯酸甘油酯、（曱基）丙烯酸 四氫糠酯、（曱基）丙烯酸二曱胺酯、（曱基）丙烯酸縮水甘 油酯、（曱基）丙烯酸2,2,2-三氟乙酯、（曱基）丙烯酸2,2,3,3-四氟丙酯、鄰苯二曱酸衍生物之（甲基）丙烯酸半酯等。該 等單官能單體可單獨使用或者將2種以上組合而使用。 另一方面，作為多官能單體，可列舉：乙二醇二（曱基） 丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基） 丙烯酸酯、丙二醇二（甲基）丙烯酸酯、聚丙二醇二（曱基） 丙烯酸酯、丁二醇二（曱基）丙烯酸酯、新戊二醇二（曱基） 丙烯酸酯、1,6 -己二醇二（甲基）丙烯酸酯、三羥甲基丙烷三 16 200931178Examples of the monofunctional monomer include (fluorenyl) acrylamide, hydroxymethyl (mercapto) acrylamide, decyloxymethyl (meth) acrylamide, and ethoxy fluorenyl (fluorenyl). Acrylamide, propoxymethyl (meth) acrylamide, butoxy methoxy fluorenyl (decyl) acrylamide, N-hydroxydecyl (meth) acrylamide, N-hydroxyl (meth)acrylamide, (mercapto)acrylic acid, fumaric acid, maleic acid, maleic anhydride, methylene succinic acid, sulfhydryl succinic anhydride, methyl cis Butenedioic acid, methyl maleic anhydride, crotonic acid, 2-propenylamine-2-methylpropanesulfonic acid, tert-butylacrylamide, methyl (meth)acrylate, Mercapto) ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(indenyl) propylene oxime Base 2-hydroxypropyl ester, single (meth)acrylic acid glyceride, (mercapto)acrylic acid tetrahydrofurfuryl ester, (mercapto)acrylic acid diamylamine ester, (mercapto)acrylic acid glycidyl ester, (mercapto)acrylic acid 2,2,2-trifluoro Ethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid half ester of phthalic acid derivative, and the like. These monofunctional monomers may be used singly or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(indenyl)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth) acrylate, polypropylene glycol bis(indenyl) acrylate, butanediol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate, 1,6-hexanediol di(A) Base) acrylate, trimethylolpropane three 16 200931178

(甲基）丙烯酸酯、二（甲基）丙烯酸甘油酯、季戊四醇三丙 烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、 二季戊四醇六丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季 戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、 二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（曱基）丙烯 酸酯、2,2-雙（4-(甲基）丙烯醢氧基二乙氧基苯基）丙烷、2,2-雙（4-(曱基）丙烯醯氧基聚乙氧基苯基）丙烷、（甲基）丙烯酸 2 -羥基- 3- (甲基）丙烯醯氧基丙酯、乙二醇二縮水甘油醚二 (曱基）丙烯酸酯、二乙二醇二縮水甘油醚二（曱基）丙烯酸 酯、鄰苯二甲酸二縮水甘油酯二（甲基）丙烯酸酯、三丙烯 酸甘油酯、甘油聚縮水甘油醚聚（曱基）丙烯酸酯、（曱基） 丙烯酸胺基曱酸酯（即，曱笨二異氰酸酯）、三曱基六亞曱 基二異氰酸酯及六亞曱基二異氰酸酯等與（曱基）丙烯酸2-. 羥乙酯的反應物、亞甲基雙（曱基）丙烯醯胺、（曱基）丙烯 醯胺亞曱醚、多元醇與N-羥甲基（甲基）丙烯醯胺之縮合物 等多官能單體、或三丙烯基縮甲醛等。該等多官能單體可 單獨使用或者將2種以上組合而使用。 相對於著色感光性樹脂組成物之固體成分，該具有乙 烯性不飽和基之單體的含量較好的是3〜40質量％，更好 的是5〜20質量％之範圍。藉由設為上述範圍，而有容易 取得靈敏度、顚影性、解析性之平衡的傾向，故較好。 相對於著色感.光性樹脂組成物之固體成分，光聚合性 化合物（A)之含量較好的是3〜40質量％，更好的是5〜 20質量％之範圍。藉由設為上述範圍，而有容易取得靈敏 17 200931178 度、顯影性、解析性之平衡的傾向，故較好。 [斥墨性化合物（B )] 斥墨性化合物（B)係至少使具有乙烯性不飽和基及 特定結構之單體（B1)、與可與該單體（B1)共聚合之氟 系單體（B2)進行共聚合而成的共聚物。藉由使用此種斥 墨性化合物（B )，可獲得具有高斥墨性、且顯影性亦良好 之著色感光性樹脂組成物。 〈單體（B1 )〉 單體（B1)係具有乙烯性不飽和基及由下述式（bl) 所表示之結構的單趙。 [化學式8] (b1) 該單體（B1)更好的是具有乙烯性不飽和基及由下述 式（b2 )所表示之結構的單體。 〇 [化學式9] R1fe-0-^- R2b (b2) 式（bl)、（b2)中，Rlb表示碳數為1〜5之亞烷基， 可為直鏈狀亦可為支鏈狀。其中，較好的是碳數為1〜3 之亞烷基，最好的是亞乙基。R2b表示氫原子、羥基、或 者可具有取代基的碳數為1〜20之烷基，可為直鏈狀亦可 18 200931178 為支鏈狀。其中，較好的是碳數為1〜4之烷基，最好的是 曱基。作為上述取代基，可列舉：羧基、羥基、碳數為1 〜5之烷氧基等。η表示1以上之整數，較好的是1〜60 之整數，更好的是1〜30之整數。 作為此種單體（Β1)，可列舉由下述式（b3)所表示 之化合物等。該等單體（B1)可單獨使用或者將2種以上 組合而使用。 ❹ ❹ [化學式10] R3b (Μ) CH2= C - C - 0-( R1 - Ο ^ R2b Ο 2b(meth) acrylate, glyceryl di(meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth) acrylate, pentaerythritol III ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, 2,2-bis(4-(methyl) propylene oxime Diethoxyphenyl)propane, 2,2-bis(4-(indolyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acrylate Propylene methoxypropyl ester, ethylene glycol diglycidyl ether bis(indenyl) acrylate, diethylene glycol diglycidyl ether bis(indenyl) acrylate, diglycidyl phthalate di(methyl) Acrylate, glyceryl triacrylate, glycerol polyglycidyl ether poly(indenyl) acrylate, (mercapto) acrylic acid amide (ie, stilbene diisocyanate), tridecyl hexamethylene diisocyanate And Liu Yaji Reaction of cyanate ester and the like with 2-hydroxyethyl (meth) acrylate, methylene bis(indenyl) acrylamide, (mercapto) acrylamide decyl ether, polyol and N-hydroxyl A polyfunctional monomer such as a condensate of a (meth)acrylamide or a tripropenyl formal or the like. These polyfunctional monomers may be used singly or in combination of two or more. The content of the monomer having an ethylenically unsaturated group is preferably from 3 to 40% by mass, more preferably from 5 to 20% by mass, based on the solid content of the colored photosensitive resin composition. By setting it as the said range, it is easy to acquire the balance of sensitivity, the glazing property, and the analytical property, and it is preferable. The content of the photopolymerizable compound (A) is preferably from 3 to 40% by mass, more preferably from 5 to 20% by mass, based on the solid content of the photosensitive resin composition. By setting it as the said range, it is easy to acquire the balance of the sensitive 17 200931178 degree, developability, and analytical property, and it is preferable. [Ink Repellent Compound (B)] The ink repellent compound (B) is a monomer having at least an ethylenically unsaturated group and a specific structure (B1) and a fluorine compound copolymerizable with the monomer (B1). The copolymer obtained by copolymerization of the body (B2). By using such an ink repellent compound (B), a colored photosensitive resin composition having high ink repellency and good developability can be obtained. <Monomer (B1)> The monomer (B1) is a single-electrode having an ethylenically unsaturated group and a structure represented by the following formula (bl). (b1) The monomer (B1) is more preferably a monomer having an ethylenically unsaturated group and a structure represented by the following formula (b2). R1fe-0-^- R2b (b2) In the formulae (b1) and (b2), Rlb represents an alkylene group having 1 to 5 carbon atoms, and may be linear or branched. Among them, an alkylene group having 1 to 3 carbon atoms is preferred, and an ethylene group is most preferred. R2b represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may be linear or 18. Among them, preferred is an alkyl group having 1 to 4 carbon atoms, and most preferably an anthracenyl group. Examples of the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms. η represents an integer of 1 or more, preferably an integer of 1 to 60, more preferably an integer of 1 to 30. Examples of such a monomer (Β1) include a compound represented by the following formula (b3). These monomers (B1) may be used singly or in combination of two or more. ❹ ❹ [Chemical Formula 10] R3b (Μ) CH2= C - C - 0-( R1 - Ο ^ R2b Ο 2b

R 式 之含義 相 單元的 之範圍 性樹脂 好。 〈 作 且可與 可列舉 (Β2) (b3 )中，R3b表示氫原子或者曱基。R11 與上述式（bl)、（b2)相同。 對於斥墨性化合物（B)，由單體（B1)衍生而來之 含量較好的是1〜40質量％，更好的是5〜15質量％ 。藉由設為上述範圍，而有顯影性以及與著色感光 組成物中其他成分之互溶性變得良好之傾向，故較 氟系單體（B2)&gt; 為氟系單體（B2)，較好的是具有乙烯性不飽和基、 單體（B1)共聚合之單體。作為此種氟系單體（B2)， 由下述式（b4)所表示之化合物等。該等氟系單體 可單獨使用或者將2種以上組合而使用。 19 200931178 [化學式11] cx1x2 = cx3-f cx4x5^ c〇4r Rf (b4&gt; 式（b4 )中，X1及X2分別獨立表示氫原子或者氟原 子，X3表示氫原子、氟原子、曱基、或者全氟曱基，X4 及X5表示氫原子、氟原子、或者全氟甲基，Rf表示碳數 Q 為1〜40之含氟烷基或者碳數為2〜100之具有醚鍵之含氟 烷基，a表示0〜3之整數，b及c分別獨立表示0或1。 相對於斥墨性化合物（B )，由氟系單體（B2 )衍生而 來之單元的含量較好的是30〜80質量％，更好的是40〜60 質量％之範圍。藉由設為上述範圍，而有斥墨性以及與著 色感光性樹脂組成物中其他成分之互溶性變得良好之傾 向，故較好。 又，於氟系單體（B2)中，較好的是具有由-(CF2)tF (t=l〜10)所表示之基的單體。t更好的是1〜8，進而 © 好的是2〜6。藉由具有上述基，而有斥墨性以及與著色感 光性樹脂組成物中其他成分之互溶性變得良好之傾向，故 較好。 〈單體（B3 )〉 斥墨性化合物（B)較好的是進一步使具有乙烯性不 飽和基及環氧基之單體（B3)進行共聚合而成的共聚物。 藉由使單體（B3)進行共聚合，可進一步提高斥墨性。 作為單體（B3)，可列舉：（甲基）丙烯酸縮水甘油酯、 20 200931178 由下述式（b5)〜（b7)所表示之脂環式環氧化合物、使（曱 基）丙烯酸之羧基與二官能以上之環氧化合物的環氧基進 行反應而獲得之單體、使侧鏈上具有羥基或羧基之丙烯酸 系單體之羥基或者羧基與二官能以上之環氧化合物之環氧 基進行反應而獲得的單體等。其中，較好的是（曱基）丙烯 酸縮水甘油酯。該等單體（B3)可單獨使用或者將2種以 上組合而使用。 [化學式12] ❹The meaning of the formula R The range of the phase unit is good. In the case of (Β2) (b3), R3b represents a hydrogen atom or a sulfhydryl group. R11 is the same as the above formulas (b1) and (b2). The content of the ink repellent compound (B) derived from the monomer (B1) is preferably from 1 to 40% by mass, more preferably from 5 to 15% by mass. When it is in the above range, the developability and the mutual solubility with other components in the colored photosensitive composition tend to be good, so that the fluorine-based monomer (B2) is a fluorine-based monomer (B2). Preferred is a monomer having an ethylenically unsaturated group and a monomer (B1) copolymerized. The fluorine-based monomer (B2) is a compound represented by the following formula (b4). These fluorine-based monomers may be used singly or in combination of two or more. 19 200931178 [Chemical Formula 11] cx1x2 = cx3-f cx4x5^ c〇4r Rf (b4) In the formula (b4), X1 and X2 each independently represent a hydrogen atom or a fluorine atom, and X3 represents a hydrogen atom, a fluorine atom, a fluorenyl group, or Perfluorodecyl, X4 and X5 represent a hydrogen atom, a fluorine atom or a perfluoromethyl group, and Rf represents a fluorine-containing alkyl group having a carbon number of Q of 1 to 40 or a fluorine-containing alkane having an ether bond of 2 to 100 carbon atoms. A, a represents an integer of 0 to 3, and b and c each independently represent 0 or 1. The content of the unit derived from the fluorine-based monomer (B2) is preferably 30 with respect to the ink-repellent compound (B). It is a range of 40 to 60% by mass, more preferably 40 to 60% by mass, and the ink repellency and the mutual solubility with other components in the colored photosensitive resin composition tend to be good. Further, in the fluorine-based monomer (B2), a monomer having a group represented by -(CF2)tF (t = 1 to 10) is preferred. t is more preferably 1 to 8, Further, it is preferably 2 to 6. By having the above-mentioned group, the ink repellency and the mutual solubility with other components in the colored photosensitive resin composition tend to be good, so that <Monomer (B3)> The ink repellent compound (B) is preferably a copolymer obtained by copolymerizing a monomer (B3) having an ethylenically unsaturated group and an epoxy group. The monomer (B3) is copolymerized to further improve the ink repellency. Examples of the monomer (B3) include glycidyl (meth)acrylate and 20 200931178 represented by the following formulas (b5) to (b7). An alicyclic epoxy compound, a monomer obtained by reacting a carboxyl group of (meth)acrylic acid with an epoxy group of a difunctional or higher epoxy compound, and an acrylic monomer having a hydroxyl group or a carboxyl group in a side chain. a monomer obtained by reacting a hydroxyl group or a carboxyl group with an epoxy group of a difunctional or higher epoxy compound, etc. Among them, a glycidyl (meth) acrylate is preferred. The monomers (B3) may be used singly or Two or more types are used in combination. [Chemical Formula 12] ❹

❹ 式（b6 )、（ b7 )中，R4b表示氫原子或者曱基，u表示 1〜10之整數，v及w分別獨立表示1〜3之整數。 相對於斥墨性化合物（B)，由單體（B3)衍生而來之 單元的含量較好的是1〜40質量％，更好的是5〜15質量％ 之範圍。藉由設為上述範圍，而有斥墨性提高之傾向，故 較好。 〈單體（B4)〉 21 200931178 斥墨性化合物（B)較好的是進一步使具有乙烯性不 飽和基及羧基之單體（B4)進行共聚合而成的共聚物。藉 由使單體（B4)進行共聚合，可調整斥墨性化合物（B) 之酸價，可提高顯影性》 作為單體（B4 )，可列舉：由下述式（b8 )所表示之 化合物、順丁烯二酸、亞甲基丁二酸、曱基順丁烯二酸、 丁烯酸等。其中，較好的是（甲基）丙烯酸，尤其好的是曱 基丙烯酸。該等單體（B4)可單獨使用或者將2種以上組 合而使用。 [化學式13] R5b CH2=C (b8)In the formulae (b6) and (b7), R4b represents a hydrogen atom or a fluorenyl group, and u represents an integer of 1 to 10, and v and w each independently represent an integer of 1 to 3. The content of the unit derived from the monomer (B3) is preferably from 1 to 40% by mass, more preferably from 5 to 15% by mass, based on the ink repellent compound (B). By setting it as the said range, it is a tendency for the ink repellency to improve, and it is preferable. <Monomer (B4)> 21 200931178 The ink repellent compound (B) is preferably a copolymer obtained by further copolymerizing a monomer (B4) having an ethylenically unsaturated group and a carboxyl group. By copolymerizing the monomer (B4), the acid value of the ink repellent compound (B) can be adjusted, and the developability can be improved. As the monomer (B4), it is represented by the following formula (b8). A compound, maleic acid, methylene succinic acid, mercapto maleic acid, crotonic acid or the like. Among them, preferred is (meth)acrylic acid, and particularly preferred is mercaptoacrylic acid. These monomers (B4) may be used singly or in combination of two or more. [Chemical Formula 13] R5b CH2=C (b8)

II

COOH 式（b8)中，R5b表示氫原子或者碳數為1〜5之烷基。 相對於斥墨性化合物（B)，由單體（B4)衍生而來之 單元的含量較好的是0.1〜30質量％，更好的是1〜20質 量％之範圍。藉由設為上述範圍，而有顯影性變得適度之 傾向，故較好。 〈其他單體〉 斥墨性化合物（B)可視需要而與其他單體進行共聚 合。作為此種其他單體，可列舉上述具有乙烯性不飽和基 之單體。其中，較好的是丙烯酸系單體。相對於斥墨性化 合物（B)，由其他單體衍生而來之單元的含量較好的是0 22 200931178 〜20質量％。 作為使單體（B1)、氟系單體（B2)、單體（B3)、單 體（B4)、及視需要之其他單體進行反應而獲得共聚物之 方法，可使用公知之方法。 斥墨性化合物（B)之重量平均分子量較好的是2〇〇〇 〜50000，更好的是5000〜20000»藉由將重量平均分子量 設為2000以上，可提高耐熱性、膜強度。又，藉由將重量 平均分子量設為50000以下，可提高顯影性，同時可抑制 凝膠化而提高保存穩定性》 又，斥墨性化合物（B)之含量較好的是光聚合性化 合物（A)與斥墨性化合物（B)之質量比為 99.9: 0.1〜 70: 30。藉由設為上述範圍，而有容易取得靈敏度、顯影 性、解析性、斥墨性之平衡的傾向，故較好。 [光聚合起始劑（C)] 作為光聚合起始劑（C)，可列舉：1-羥基環己基苯基 酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥乙氧基） 苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基笨基）-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基）-2-羥基-2-甲 基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙（4-二曱胺基苯基）酮、2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉基丙 燒-1-嗣（2-methyl-l-[4-(methylthio)phenyl]-2-morpholino propane-1-one)、2 -节基-2-二甲胺基-1-(4-嗎说基苯基）-丁 烷-1-酮、乙賙-1-[9·乙基-6-(2-曱基苯甲醢基）-9H-咔唑基 -3-基]-1-(鄰乙醯肟）、2,4,6-三曱基苯曱醯基二苯基氧化 23 200931178 膦、4-苯曱醯基-4、甲基二甲硫醚、4-二甲胺基苯曱酸、4-二曱胺基苯曱酸曱酯、4-二曱胺基苯曱酸乙酯、4-二曱胺 基苯甲酸丁酯、4-二曱胺基-2-乙基己基苯甲酸、4-二甲胺 基-2-異戊基苯曱酸、苄基-冷-曱氧基乙基縮醛、苄基二曱 基縮酮、1-苯基-1,2 -丙二酮- 2-(鄰乙氧基羰基）肟、鄰苯曱 醯基苯甲酸甲酯、2,4 -二乙基噻噸酮、2 -氯噻噸酮、2，4-二曱基噻噸酮、1-氣-4-丙氧基噻噸酮、噻噸、2 -氣噻噸、 2,4-二乙基噻噸、2-甲基噻噸、2-異丙基噻噸、2-乙基蒽醌、 八曱基蒽醌、1，2 -苯幷蒽醌、2,3 -二苯基蒽醌、偶氮雙異丁 腈、過氧化苯甲醢、過氧化異丙苯、2 -疏基苯幷咪唑、2-疏基苯幷°惡嗤（2-mercaptobenzoxazole)、2-疏基苯幷售唾、 2-(鄰氣苯基）-4,5-二（間曱氧基苯基）-咪唑基二聚物、二苯 甲酮、2-氣二苯甲酮、p，p’-雙二曱胺基二苯甲酮、4,4、雙 二乙胺基二苯曱酮、4，4'-二氣二苯甲酮、3,3-二曱基-4 -曱 氧基二苯甲酮、苯偶醯、安息香、安息香曱醚、安息香乙 醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息 香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二曱基苯乙酮、 對二f胺基苯丙酮、二氣苯乙酮、三氣苯乙酮、對第三丁 基苯乙酮、對二曱胺基苯乙酮、對第三丁基三氣苯乙酮、 對第三丁基二氣苯乙酮、α,α-二氯-4 -苯氧基苯乙酮、噻 噸酮、2 -甲基噻噸酮、2 -異丙基噻噸酮、二苯幷環庚酮、 4-二曱胺基苯甲酸戊酯、9-苯基吖啶、1，7-雙-(9-吖啶基） 庚烷、1，5-雙-(9-吖啶基）戊烷、1，3-雙-(9-吖啶基）丙烷、對 甲氧基三嗪（卩-11161；110\&gt;^1^&amp;71116)、2,4,6-三（三氣曱基）-均三 24 200931178 嗪、2-甲基-4,6-雙（三氣甲基）·均三嗪、2_[2-(5_甲基呋喃_2_ 基）乙烯基]-4,6-雙（三氣甲基）·均三嗪、2_[2_(呋喃_2_基）乙 烯基]-4,6-雙（三氣甲基）-均三嗪、2_[2_(4_二乙胺基_2_甲基 苯基）乙烯基]-4,6-雙（三氣曱基）·均三嗪、2_[2_(3,4_二甲氧 基苯基）乙烯基]-4,6-雙（三氣甲基）_均三嗪、2_(4_曱氧基苯 基）·4,6-雙（三氣甲基）均三嗪、2 (4乙氧基苯乙烯基）4,6_ 雙（三氣甲基）-均三嗪、2-(訌正丁氧基苯基）-4,6-雙（三氣甲 ❹COOH In the formula (b8), R5b represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The content of the unit derived from the monomer (B4) is preferably from 0.1 to 30% by mass, more preferably from 1 to 20% by mass, based on the ink repellent compound (B). When the above range is employed, the developability tends to be moderate, which is preferable. <Other monomers> The ink repellent compound (B) may be copolymerized with other monomers as needed. As such another monomer, the above monomer having an ethylenically unsaturated group can be mentioned. Among them, an acrylic monomer is preferred. The content of the unit derived from the other monomer is preferably 0 22 200931178 to 20% by mass based on the ink repellent compound (B). A known method can be used as a method of obtaining a copolymer by reacting a monomer (B1), a fluorine-based monomer (B2), a monomer (B3), a monomer (B4), and other monomers as necessary. The weight average molecular weight of the ink repellent compound (B) is preferably from 2 Å to 50,000, more preferably from 5,000 to 20,000 Å. By setting the weight average molecular weight to 2,000 or more, heat resistance and film strength can be improved. In addition, by setting the weight average molecular weight to 50,000 or less, the developability can be improved, and the gelation can be suppressed to improve the storage stability. Further, the content of the ink repellent compound (B) is preferably a photopolymerizable compound ( A) The mass ratio of the ink repellent compound (B) is 99.9: 0.1 to 70:30. By setting it as the said range, it is easy to acquire the balance of sensitivity, developability, resolution, and ink repellent, and it is preferable. [Photopolymerization initiator (C)] Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. , 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxyl -2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2 -diphenylethane-1-one, bis(4-didecylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan 2-methyl-l-[4-(methylthio)phenyl]-2-morpholino propane-1-one), 2-mercapto-2-dimethylamino-1-(4-) Phenyl)-butan-1-one, acetamidine-1-[9.ethyl-6-(2-mercaptobenzylidene)-9H-carbazolyl-3-yl]-1-(o- Ethylene oxime), 2,4,6-trimercaptobenzoyldiphenyl oxide 23 200931178 Phosphine, 4-phenylhydrazin-4, methyl dimethyl sulfide, 4-dimethylaminophenyl hydrazine Acid, decyl 4-diguanyl benzoate, ethyl 4-diguanyl benzoate, butyl 4-diguanyl benzoate, 4-diguanylamino-2-ethylhexyl benzene Formic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-cold- Alkoxyethyl acetal, benzyl dimercapto ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimercaptothioxanthone, 1-aluminum-4-propoxythioxanthone, thioxanthene, 2-air thioxanthene , 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, octadecylhydrazine, 1,2-benzoquinone, 2, 3-diphenyl hydrazine, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, 2-phenylbenzoimidazole, 2-mercaptobenzoxazole, 2-benzyl benzoquinone sold saliva, 2-(o-phenyl)-4,5-di(m-decyloxyphenyl)-imidazolyl dimer, benzophenone, 2-benzophenone , p,p'-bis-diamine benzophenone, 4,4, bisdiethylaminodibenzophenone, 4,4'-dibenzobenzophenone, 3,3-didecyl- 4-methoxybenzophenone, benzoin, benzoin, benzoin ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2- Diethoxyacetophenone p-Dimercaptoacetophenone, p-di-aminopropiophenone, diacetophenone, tri-o-acetophenone, p-tert-butylacetophenone, p-diguanylacetophenone, p-third Trioxane acetophenone, p-tert-butyl diacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropyl Thiophenone, diphenylguanidinone, amyl 4-diguanylbenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) heptane, 1,5- Bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine (卩-11161; 110\&gt;^1^&amp;71116), 2,4,6-tris(trimethylsulfonyl)-all three 24 200931178 azine, 2-methyl-4,6-bis(trismethyl)·s-triazine, 2_[2-(5-methyl) Furan-2-yl)vinyl]-4,6-bis(trismethyl)·s-triazine, 2_[2_(furan-2-yl)vinyl]-4,6-bis(trimethyl) - s-triazine, 2_[2_(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trimethyl sulfhydryl)·s-triazine, 2_[2_(3,4 _Dimethoxyphenyl)vinyl]-4,6-bis(trismethyl)-s-triazine, 2-(4-methoxyphenyl)·4,6-bis (three Gas methyl) s-triazine, 2 (4 ethoxystyryl) 4,6_bis(trimethylmethyl)-s-triazine, 2-(indolyloxyphenyl)-4,6-double (three gas hyperthyroidism

基）-均三嗪、2,4-雙-三氣甲基_6_(3_溴_4_甲氧基）苯基均三 嗪、2,4-雙-三氣甲基-6-(2-溴_4_甲氧基）苯基-均三嗪、2 4_ 雙-三氣甲基-6-(3-溴-4-曱氧基）苯乙烯基苯基-均三嗪、 2,4-雙-三氣甲基-6-(2-溴·4_甲氧基）苯乙烯基苯基均三嗪 等。其中，就靈敏度方面而言，尤其好的是使用肟系光聚 合起始劑。該等光聚合起始劑可單獨使用或者將2種以上 组合而使用。 相對於著色感光性樹脂組成物之固體成分’光聚合起 始劑（（：）之含量較好的是〇5〜3〇質量％，更好的是1〜 20質量％之範圍。藉由設為上述範圍，可獲得充分之耐砵 性、耐化學藥品性，又，可提高成膜，並且可 ： 化不良。 柙制先硬 [著色劑（D )] 作為著色劑（D )，可列舉碳黑或鈦黑等遮光劑。 亦可使用 Cu、Fe、Μη、Cr、c〇、 Ζη 又 _ 以、MgBase)-s-triazine, 2,4-bis-trismethylmethyl_6_(3_bromo-4-yloxy)phenyl s-triazine, 2,4-bis-tris-methyl-6-( 2-bromo-4-yloxyphenyl-s-triazine, 2 4 bis-tris-methylmethyl-6-(3-bromo-4-indolyl)styrylphenyl-s-triazine, 2 , 4-bis-tris-methyl-6-(2-bromo-4-yl)styrylphenyl s-triazine, and the like. Among them, in terms of sensitivity, it is particularly preferable to use a lanthanide photopolymerization initiator. These photopolymerization initiators may be used singly or in combination of two or more. The content of the solid component 'photopolymerization initiator ((:)) which is a solid component of the coloring photosensitive resin composition is preferably 5 to 3 % by mass, more preferably 1 to 20% by mass. In the above range, sufficient smear resistance and chemical resistance can be obtained, and film formation can be improved, and the film can be made poor. Tanning is first hard [coloring agent (D)] as a coloring agent (D), An opacifier such as carbon black or titanium black. It is also possible to use Cu, Fe, Μη, Cr, c〇, Ζη__, Mg

Ca、Sr、Ba' Pd、Ag、Cd、In、.Sn、以、Hg、以、b: Si及A1等各種金屬氧化物、複合氧化物、金屬 ^^化物 25 200931178 金屬硫酸鹽、或者金屬碳酸鹽等無機顏料。Various metal oxides, composite oxides, and metal oxides such as Ca, Sr, Ba' Pd, Ag, Cd, In, .Sn, I, Hg, and b: Si and A1 25 200931178 Metal sulfate or metal Inorganic pigments such as carbonates.

碳黑可使用槽黑、爐黑 '熱碳黑、燈黑等公知之碳黑， 尤其槽黑因遮光性優異而可較好地使用。又，亦可使用經 樹脂包覆之碳黑。具體可列舉：將碳黑以及與存在於碳黑 表面之羧基、羥基、羰基具有反應性之樹脂混合，於50°C 〜380 °C進行加熱而獲得的經樹脂包覆之碳黑；或者將乙烯 性單體分散於水-有機溶劑混合系或者水-界面活性劑混合 系中，於聚合起始劑之存在下進行自由基聚合或者自由基 共聚合而獲得的經樹脂包覆之碳黑等。與未經樹脂包覆之 碳黑相比，該經樹脂包覆之碳黑的導電性低，因此在用作 液晶顯示器等之彩色濾光片時，可形成漏電少、可靠性高 之低耗電顯示器》 作為著色劑，可在上述無機顏料中添加有機顏料來作 為輔助顏料。有機顏料藉由適當選擇添加呈現無機顏料之 補色的有機顏料而獲得如下效果。例如，碳黑呈現略帶紅 色之黑色。因此，藉由在碳黑中添加呈現紅色之補色即藍 色的有機顏料來作為輔助顏料，可消除碳黑之紅色，從而 整體上呈現出更好之黑色。相對於無機顏料與有機顏料之 合計，有機顏料之使用量較好的是10〜80質量％之範圍， 更好的是20〜60質量％之範圍，尤其好的是為20〜40質 量％之範圍。 作為上述無機顏料及有機顏料，可使用利用分散劑以 適當濃度分散顏料而得之溶液。例如，作為無機顏料，可 列舉：御國色素公司製造之碳分散液CF Black (含有濃度 26 之碳分激 司製造之 ’作為有 顏料分散 司製造之 ’作為分 _樹脂系As the carbon black, a known carbon black such as black in the tank or black in the furnace, such as hot black or black, can be used. In particular, the black is excellent in light-shielding property and can be preferably used. Further, a carbon black coated with a resin can also be used. Specific examples thereof include a carbon black and a resin-coated carbon black obtained by mixing carbon black and a resin reactive with a carboxyl group, a hydroxyl group, or a carbonyl group present on the surface of the carbon black, and heating at 50 ° C to 380 ° C; The resin-coated carbon black obtained by performing radical polymerization or radical copolymerization in the presence of a polymerization initiator in a water-organic solvent mixed system or a water-surfactant mixed system . Compared with the carbon black which is not coated with the resin, the resin-coated carbon black has low conductivity, and therefore, when used as a color filter such as a liquid crystal display, it can form low leakage and high reliability. Electric Display As an coloring agent, an organic pigment may be added to the above inorganic pigment as an auxiliary pigment. The organic pigment obtains the following effects by appropriately selecting and adding an organic pigment which exhibits a complementary color of the inorganic pigment. For example, carbon black presents a slightly reddish black. Therefore, by adding an organic pigment which exhibits a red complementary color, that is, blue, to the carbon black as an auxiliary pigment, the red color of the carbon black can be eliminated, thereby exhibiting a better black overall. The amount of the organic pigment to be used is preferably in the range of 10 to 80% by mass, more preferably in the range of 20 to 60% by mass, particularly preferably 20 to 40% by mass, based on the total of the inorganic pigment and the organic pigment. range. As the inorganic pigment and the organic pigment, a solution obtained by dispersing a pigment at a suitable concentration with a dispersing agent can be used. For example, as the inorganic pigment, a carbon dispersion CF Black (manufactured by Carbon Selenium Co., Ltd. having a concentration of 26) is manufactured as a pigment dispersion company as a sub-resin system.

200931178 為2 0 %之碳）、御國色素公司裳造： 24%之高電阻碳）、御國色素公 Black (含20%之黑鈦顏料）。又 列舉：御國色素公司製造之藍色 有20%之藍色顏料）、御國色素公 (含有10%之紫色顏料）等。又 使用：聚乙烯亞胺系、胺基甲酸 系高分子分散劑。 -π孓固 含量較好的是10〜70質量〇/0。Μ丄 释由將4 以下’可抑制光硬化不良，又， 精由將. 以上’可獲得充分之遮光性。 ，在以 明之著色感光性樹脂組成物來成祺為黑 之濃度較好的是調整成每1以边膜 Density ’光學密度）值成為1 5以上。 OD值為1.5以上，則用於液晶顯示器之 得充分之對比度》 [溶劑] 本發明之著色感光性樹脂組成物較好 釋之溶劑》作為該溶劑，例如可列舉：乙 二醇單乙醚、乙二醇單正丙醚、乙二醇單 醇單曱醚、二乙二醇單乙醚、二乙二醇單 醇單正丁醚、三乙二醇單甲醚、三乙二醇 單甲謎、丙二醇單乙醚、丙二醇單正丙醚 液 CF Black(含 鈦黑分散液CF 機顏料，例如可 液 CF Blue (含 紫色顏料分散液 散劑，較好的是 、丙烯酸系樹脂 成分，著色劑之 t設為70質量％ 量設為1 〇質量％ 述方式使用本發 矩陣時，著色劑 之 OD ( Optical 每1从m膜厚之 色矩陣時，可獲 的是含有用以稀 二醇單甲鍵、乙 正丁鍵、二乙二 正丙鍵、二乙二 單乙鰱、丙二醇 、丙二醇單正丁 27200931178 is 20% carbon), Yuguo pigment company: 24% high resistance carbon), Yuguo pigment Gong Black (including 20% black titanium pigment). Also listed are: 20% blue pigment produced by Royal Chinese Pigment Co., Ltd., and Royal Chinese pigment (containing 10% purple pigment). Further, a polyethyleneimine-based or aminocarboxylic acid-based polymer dispersant is used. The -π tamping content is preferably 10 to 70 mass 〇 / 0. Μ丄 由 将 将 4 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 可 ’ 可 ’ ’ ’ ’ ’ ’ ’ ’ The concentration of the photosensitive resin composition which is colored in the bright color is preferably adjusted to a value of 15 or more per side of the film Density ’ optical density. When the OD value is 1.5 or more, the contrast ratio for the liquid crystal display is sufficient. [Solvent] The solvent of the colored photosensitive resin composition of the present invention is preferably released. As the solvent, for example, ethylene glycol monoethyl ether or B is exemplified. Glycol mono-n-propyl ether, ethylene glycol monool monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl mystery, Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether liquid CF Black (containing titanium black dispersion CF machine pigment, such as liquid CF Blue (containing purple pigment dispersion liquid powder, preferably, acrylic resin component, colorant t setting) The amount of 70% by mass is set to 1 〇% by mass. When the present matrix is used, the OD of the colorant (when the color matrix of the film thickness per m is obtained, it is obtained by using a single molecule bond for the dilute diol, Ethylene n-butyl bond, di-di-n-di-propyl bond, diethylenediacetone, propylene glycol, propylene glycol mono-n-butyl 27

200931178 醚、二丙二醇單曱醚、二丙二醇單乙醚、二丙二醇單 醚、二丙二醇單正丁醚、三丙二醇單曱醚、三丙二醇 醚等（聚）烷二醇單烷基醚類；乙二醇單甲醚乙酸酯、 醇單乙醚乙酸酯、二乙二醇單曱醚乙酸酯、二乙二醇 醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸 (聚）烷二醇單烷基醚乙酸酯類；二乙二醇二曱醚、二 醇曱基乙醚、二乙二醇二乙醚、四氫呋喃等其他醚類 基乙基酮、環己酮、2-庚酮、3-庚酮等酮類；2-羥基 甲酯、2 -羥基丙酸乙酯等乳酸烷基酯類；2 -羥基-2-曱 酸乙酯、3 -曱氧基丙酸甲酯、3 -甲氧基丙酸乙酯、3-基丙酸曱酯、3 -乙氧基丙酸乙酯、乙氧基乙酸乙酯、 乙酸乙酯、2 -羥基-3-曱基丁酸曱酯、乙酸3 -甲氧基丁 乙酸3-曱基-3-曱氧基丁酯、丙酸-3-甲基-3-甲氧基丁 乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、 異丁酯、曱酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁 酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲 丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸曱酯、乙醯乙 酯、2 -氧代丁酸乙酯等其他酯類；甲苯、二甲苯等芳 烴類；N-曱基吡咯烷酮、Ν,Ν-二曱基甲醯胺、N，N-二 乙醯胺等醯胺類等。該等溶劑可單獨使用或者將2種 組合而使用。 相對於著色感光性樹脂組成物之固體成分 1 00 份，溶劑之含量較好的是50〜500質量份。 [其他成分] 正丙 單乙 乙二 單乙 酯等 乙二 :甲 丙酸 基丙 乙氧 經基 酯、 8旨、 乙酸 酸乙 醋、 酸乙 香族 甲基 以上 質量 28 200931178 本發明之著色感光性樹脂組成物中，可与 添加劑。作為添加劑，可列舉：熱聚合抑制矣 界面活性劑、敏化劑、硬化促進劑、光交則 a散劑、分散助劑、填充劑、密著促進劑、击 外線吸收劑、抗凝聚劑等。 [著色感光性樹脂组成物之製備方法] 本發明之著色感光性樹脂組成物可藉由將 Q 全部以搜掉機進行混合而獲得》再者，為了使 合物變得均勻，可使用過濾器進行過濾。 [彩色濾光片之製造方法] 首先’使用輕塗機（r〇〗〗 c〇ater)、反向塗佈 coater)、到棒塗佈機（bar coater)等接觸轉印隹 或者旋轉器（spinner)(旋轉式塗佈裝置）、淋 裝機（curtain fl〇w coater)等非接觸型塗佈裝 明之著色感光性樹脂組成物塗佈於基板上。基 有透光性之基板。 〇 繼而，使所塗佈之著色感光性樹腊組成物 塗膜。乾燥方法並無特別限定，例如可使用以 任一種方法：（1 )利用加熱板（hot plate )於 °c、較好的是於9〇t〜1〇〇&lt;t之溫度乾燥6〇〜 法，（2)在室溫玫置數小時〜數日之方法，（3 熱器或紅外線加熱器中放置數十分鐘〜數小時 之方法。 繼而經·由負像光罩（negativemask)，對 需要而含有 、消泡劑、 、光敏劑、 氧化劑、紫 上述各成分 所獲得之混 機（reverse 丨塗佈裝置， 幕式平面塗 置，將本發 板係使用具 乾燥而形成 下方法中之 8〇〇C 〜120 120秒之方 )在溫風加 而除去溶劑 該塗膜照射 29 200931178 紫外線、準分子雷射光等活性能量線而進行部分曝光 照射之能量線量根據著色感光性樹鹿組成.物之組成而 不同，例如較好的是30〜2000 mJ/cm2左右。 繼而，利用顯影液對曝光後之膜進行顯影而形成 形狀之圖案。顯影方法並無特別限定，例如可使用浸清 喷霧法等。作為顯影液，可列舉：單乙醇胺、二乙醇 三乙醇胺等有機系顯影液，或者氫氧化鈉、氫氧化鉀 在 酸納、氨、四級敍鹽等之水溶液。 〇 繼而，於200 °C左右之溫度對顯影後之圖案進行 烤（post-bake )。此時，較好的是對所形成之圖案進 面曝光。藉由以上操作可形成具有規定圖案形狀之黑 陣。 繼而，將R、G、B各色墨汁自喷墨嘴喷出至由黑 陣所劃分之各區域内，利用熱或光使所蓄積之墨汁硬 藉此可製造彩色濾光片。 [實施例] Q 〈實施例1 &gt; 光聚合性化合物（A )係使用下述樹脂（A-1 )、 單體（A-3)二季戊四醇六丙烯酸酯。 [樹脂（A-1 )之合成] 樹脂（A-1)之合成方法如下所述。 一面以25 ml/分鐘之速度吹入空氣，一面於90°C。 °C對235 g雙酚苐型環氧樹脂（環氧當量為23 5 )、11 氣化四甲基銨、100 mg之2,6-二第三丁基-4 -甲基苯酌 。所 有所 所需 法、 胺、 、碳 後烘 行全 色矩 色矩 化》 以及 -100 0 mg 、及 30 200931178 72.0g丙烯酸進行加熱而使之溶解後，緩慢升溫至i20°C β 其間，測定酸價’連續加熱挽拌約1 2小時直至酸價小於 1.0 mgKOH/g為止。繼而冷卻至室溫，獲得無色透明立固 體狀之雙酚苐型環氧丙烯酸酯》 繼而，在307.0 g所獲得之上述雙酚第型環氧丙嫌酸 酯中加入350g丙二醇單甲醚乙酸酯（PGMEA )使之溶解 後，將80.5 g二苯曱酮四甲酸二酐及1 g溴化四乙基銨進 行混合，於Π 0 °C〜11 5 °C反應4小時。確認酸酐基消失後’ 混合38.0 g之1，2,3,6 -四氫鄰苯二曱酸酐，並於9(TC反應 6小時而獲得樹脂（A-1)。再者，酸酐基之消失係藉由紅 外（IR)光譜而確認。所獲得之樹脂（A-1)以凝膠滲透 層析法（gel permeation chromatograph，GPC )而測定之 重量平均分子量為5000，酸價為80 mgKOH/g。該樹脂 (A-1)係利用乙酸-3-甲氧基丁酯而調整成固體成分浪度 為5 5質量％。 斥墨性化合物（B )係使用下述化合物（B-1 ) ° [化合物（B-1 )之合成] 化合物（B-1)之合成方法如下所述β 將8 g甲基丙烯酸縮水甘油酯、100 g氣系單體 (CH2=C(CH3)COOCH2CH2(CF2)4F)、24g 甲基丙稀酸、32g 甲氧基二乙二醇甲基丙烯酸酯、7 g破轉移劑正十一燒基 硫醇、2 g之2,2，-偶氮雙（4 -甲氧基二甲基戍猜）溶解 於348g之乙酸3 -曱氧基丁酯中，於氮氣環境下、在4〇 C 一面攪拌一面使之聚合而獲得共聚物。所獲得之化合物 31 200931178 (B-l )以GPC測定之重量平均分子量為9000。再者，拔 化合物（B-1 )係利用乙酸-3-曱氧基丁酯而調整成固艘成 分濃度為3 0質量％。 光聚合起始劑（C )係使用化合物（C- 1 )(汽巴精化 (Ciba Specialty Chemicals)公司製造，IRGACURE OXE 02)。 著色劑（D)係使用著色劑（D-Ι)(御國色素公司製 造，CF Black :碳黑為25質量％，溶劑：乙酸-3-甲氧基丁 酯）。 將上述各成分與溶劑（乙酸3 -甲氧基丁酯：環己酮== 60 : 40 )以表1之比例進行調配，以攪拌機混合2小時後， .以5从m膜渡器（membrane filter)進行過渡，製備著色 感光性樹脂組成物。再者，表1中之數值表示質量份。 〈實施例2〜11、比較例1〜6〉 根據表1〜3所示之調配，以與實施例1相同之方式製 備著色感光性樹脂組成物。再者，表1〜3中之數值表示質 量份。表1〜3所記載之各成分之合成方法如下所述。 [樹脂（A-2)之合成] 將 400 g 之 Epikote YX4000H (日本環氣樹脂（Japan EpoxyResins)公司製造，環氧當量為I92)、4g三苯基膦、 153 g丙烯酸、600 g乙醭-3-甲氧基丁酯加以混合，於90 。(：〜100°C使之反應。然後，添加40 g四氫鄰苯二甲酸酐、 及3 60 g聯苯四甲酸二酐來作為多元酸酐，進一步使之反 應，藉此獲得具有聯苯骨架之樹脂（A-2 )。該樹脂（A-2 ) 32 200931178 以 GPC測定之重量平均分子量為7000，酸償為9〇 mgKOH/g »再者’該樹脂（A-2 )係利用乙酸-3-甲氧基丁 酯而調整成固體成分濃度為50質量％。 [化合物（B-2 )之合成] 將 8 g甲基丙烯酸縮水甘油酯、1〇〇 g氧系單敢 (CH2 = C(CH3)COOCH2CH2(CF2)4F)、32 g 甲基丙歸酸、 g甲氧基二乙二醇甲基丙烯酸酯、7g鏈轉移劑正十二燒基 硫酵' 2 g之2,2·-偶氮雙（4-甲氧基-2,4-二甲基戊腈）溶解 於348 g乙酸-3-甲氧基丁酯中，於氮氣環境下、在4〇β(： _ 面攪拌一面使之聚合而獲得共聚物。所獲得之化合物 以GPC測定之重量平均分子量為9000。再者，該化合物 (B-2 )係利用乙酸-3 -甲氧基丁酯而調整成固體成分濃度 為3 0質量％。 [化合物（B-3 )之合成] 將40 g甲基丙烯酸縮水甘油酯、72 g氟系單艘 (CH2 = C(CH3)COOCH2CH2(CF2)4F)、24 g 曱基丙稀酸、32 g曱氧基二乙二醇曱基丙烯酸酯、7g鏈轉移劑正十二燒基 硫酵、2 g之2,2匕偶氮雙（4-曱氧基-2,4-二甲基戊腈）溶解 於348g乙酸-3 -甲氧基丁酯中，於氮氣環境下、在4(TC_ 面攪拌一面使之聚合而獲得共聚物。所獲得之化合物（Β·3：) 以GPC測定之重量平均分子量為9000。再者，該化合物 (B-3 )係利用乙酸-3-甲氧基丁酯而調整成固體成分漢度 為3 0質量％。 [化合物（B-4)之合成] 33 200931178 將 8 g甲基丙烯睃縮水甘油酯' 100 g (CH2 = C(CH3)COOCH2CH2(CF2)4F)、24 g 甲基丙 g甲氧基聚乙二醇# 400甲基丙烯酸酯（產品名： M-90G，新中村化學工業公司製造）、7 g鏈轉移 烷基硫酵、2 g之2,2·-偶氮雙（4-甲氧基-2,4-二 溶解於348g乙酸-3·曱氧基丁酯中，於氮氣環境 °C 一面攪拌一面使之聚合而獲得共聚物》所獲得 (B-4 )以GPC測定之重量平均分子量為9400。 化合物（B-4 )係利用乙酸-3 -甲氧基丁酯而調整 分濃度為3 0質量％。 [化合物（B-5 )之合成] 將 8 g甲基丙烯酸縮水甘油酯、100 g (CH2 = C(CH3)COOCH2CH2(CF2)4F)、24 g 甲基两 g曱氧基聚乙二醇#1000曱基丙烯酸酯（產品名 M-23 0G，新中村化學工業公司製造）、7g鏈轉移 烷基硫醇、2 g之2,2'-偶氮雙（4-曱氧基-2,4_二 〇 溶解於348 g乙酸-3·甲氧基丁酯中，於氮氣環境 °C 一面攪拌一面使之聚合而獲得共聚物》所獲得 (B-5 )以GPC測定之重量平均分子量為99〇〇。 化合物（B-5 )係利用乙酸-3-曱氧基丁酯而調整 分濃度為3 0質量％。 [化合物（B-6 )之合成] 將 8 g曱基丙烯酸縮水甘油酯、1〇〇 g (CH2 = C(CH3)COOCH2CH2(CF2)6F)、24 g 甲基丙 氟系單體 烯酸、32 NK Ester 劑正十二 甲基戊腈） 下、在40 之化合物 再者，該 成固體成 氟系單體 I烯酸、32 :NK Ester 劑正十二 甲基戊腈） 下、在40 •之化合物 再者，該 成固體成 氟系單體 |烯酸異冰 34200931178 (poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol monoterpene ether, dipropylene glycol monoethyl ether, dipropylene glycol monoether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monoterpene ether, tripropylene glycol ether; Alcohol monomethyl ether acetate, alcohol monoethyl ether acetate, diethylene glycol monoterpene ether acetate, diethylene glycol ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (poly) Alkylene glycol monoalkyl ether acetates; diethylene glycol dioxime ether, diol decyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether ethyl ketones, cyclohexanone, 2-heptanone a ketone such as 3-heptanone; an alkyl lactate such as 2-hydroxymethyl ester or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-furoate or methyl 3-methoxyoxypropionate; Ethyl 3-methoxypropionate, decyl 3-propylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl acetate, bismuth 2-hydroxy-3-mercaptobutyrate Ester, 3-methoxy-3-butoxy-3-butoxy-3-acetate, ethyl-3-methyl-3-methoxybutyl propionate, n-propyl acetate, isopropyl acetate , n-butyl acetate, isobutyl ester, hydrazine Isoamyl acetate, isoamyl acetate, n-butyl propionate, butyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate pyruvate, n-propyl pyruvate , other esters such as acetonitrile acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-decyl pyrrolidone, hydrazine, hydrazine-dimercaptocarboxamide, Amidoxime such as N,N-diethylamine. These solvents may be used singly or in combination of two or more. The content of the solvent is preferably from 50 to 500 parts by mass based on 100 parts by weight of the solid component of the colored photosensitive resin composition. [Other Ingredients] Ethylene, such as propylene, ethyl ethanediethyl ester, etc.: diethyl propionate, propyl ethoxylate, hexaacetate, acetic acid, ethyl acetate, acid, ethyl urethane, above mass 28 200931178 In the photosensitive resin composition, an additive can be used. Examples of the additive include a thermal polymerization inhibitor 矣 surfactant, a sensitizer, a hardening accelerator, a photo-dispersing agent, a dispersing aid, a filler, an adhesion promoter, an external absorbent, and an anti-agglomerating agent. [Method for Producing Colored Photosensitive Resin Composition] The colored photosensitive resin composition of the present invention can be obtained by mixing all Qs with a search machine. Further, in order to make the composition uniform, a filter can be used. Filter. [Manufacturing method of color filter] First, use a light coater (r〇〗 〖c〇ater), a reverse coater), a bar coater, etc., such as a contact transfer 隹 or a rotator ( A non-contact type coating of a colored photosensitive resin composition such as a spinner (a rotary coating apparatus) or a curtain coater is applied onto a substrate. A substrate with a light transmissive base.继 Next, the coated colored photosensitive wax composition is coated. The drying method is not particularly limited, and for example, any one of the methods may be used: (1) drying with a hot plate at ° c, preferably at a temperature of 9 〇 t 〜 1 〇〇 &lt; t 〜 Method, (2) at room temperature for several hours to several days, (3 or less than a few hours in a three-heater or infrared heater. Then by negative mirror, negative A mixing machine obtained by containing the above components, a defoaming agent, a photosensitizer, an oxidizing agent, and a purple component (reverse 丨 coating device, a curtain type flat coating, and the present hair plate is used in a drying method to form a lower method) 8〇〇C ~ 120 120 seconds) in the warm air to remove the solvent, the coating film irradiation 29 200931178 ultraviolet, excimer laser light and other active energy lines for partial exposure irradiation energy line amount according to coloring photosensitive tree deer composition. The composition of the material is preferably, for example, about 30 to 2000 mJ/cm 2 . Then, the film after exposure is developed by a developing solution to form a pattern of a shape. The development method is not particularly limited, and for example, a dip spray can be used. Fog method, etc. Examples of the developer include an organic developer such as monoethanolamine or diethanoltriethanolamine, or an aqueous solution of sodium hydroxide or potassium hydroxide in sodium hydride, ammonia, or a quaternary salt. Then, at about 200 ° C. The temperature is post-bake on the developed pattern. At this time, it is preferred to expose the formed pattern to the surface. By the above operation, a black matrix having a predetermined pattern shape can be formed. The inks of the respective colors G and B are ejected from the ink ejecting nozzle into the respective regions divided by the black matrix, and the accumulated ink is hardened by heat or light to thereby produce a color filter. [Embodiment] Q <Example 1 &gt; The photopolymerizable compound (A) is the following resin (A-1) or monomer (A-3) dipentaerythritol hexaacrylate. [Synthesis of Resin (A-1)] Resin (A-1) The synthesis method is as follows: Air is blown at a rate of 25 ml/min on one side at 90 ° C. 235 g of bisphenol quinone type epoxy resin (epoxy equivalent of 23 5 ), 11 gasification of four Base ammonium, 100 mg of 2,6-di-t-butyl-4-methylbenzene, all required methods, amines, carbon After performing full-color moment coloring and -100 0 mg, and 30 200931178 72.0g of acrylic acid, heating and dissolving it, slowly raising the temperature to i20 ° C β, and measuring the acid value 'continuous heating to stir for about 12 hours until The acid value is less than 1.0 mgKOH/g, and then cooled to room temperature to obtain a bisphenol oxime type epoxy acrylate having a colorless transparent solid state. Then, the above bisphenol type epoxy propylene acrylate obtained at 307.0 g is obtained. After adding 350 g of propylene glycol monomethyl ether acetate (PGMEA) to dissolve it, 80.5 g of dibenzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed at Π 0 °C to 11 5 °. C reacted for 4 hours. After confirming that the acid anhydride group disappeared, '38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the resin (A-1) was obtained at 9 (TC reaction for 6 hours. Further, the disappearance of the acid anhydride group) It was confirmed by infrared (IR) spectroscopy. The obtained resin (A-1) was measured by gel permeation chromatograph (GPC) to have a weight average molecular weight of 5,000 and an acid value of 80 mgKOH/g. The resin (A-1) was adjusted to have a solid content of 55 mass% using 3-methoxybutyl acetate. The ink repellent compound (B) was the compound (B-1) below. [Synthesis of Compound (B-1)] The synthesis method of Compound (B-1) is as follows: β will be 8 g of glycidyl methacrylate, 100 g of gaseous monomer (CH2=C(CH3)COOCH2CH2(CF2) 4F), 24g methacrylic acid, 32g methoxydiethylene glycol methacrylate, 7 g of the transfer agent n-decyl mercaptan, 2 g of 2,2,-azo double (4 - Methoxy dimethyl hydrazine was dissolved in 348 g of 3-methoxy butyl acetate, and polymerized under stirring in a nitrogen atmosphere at 4 ° C to obtain a copolymer. The obtained compound 31 200931178 (Bl) The weight average molecular weight measured by GPC was 9000. Further, the compound (B-1) was adjusted to have a solid concentration of 30% by mass using -3-butyloxybutyl acetate. The starting agent (C) is a compound (C-1) (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE 02). The coloring agent (D) is a coloring agent (D-Ι) (Yuguo Pigment Co., Ltd.) Manufactured, CF Black: carbon black: 25% by mass, solvent: 3-methoxybutyl acetate). The above components and solvent (3-methoxybutyl acetate: cyclohexanone == 60: 40) The mixture was blended in the ratio of Table 1, and after mixing for 2 hours with a stirrer, a coloring photosensitive resin composition was prepared by transitioning from 5 to a membrane filter. Further, the numerical values in Table 1 represent parts by mass. <Examples 2 to 11 and Comparative Examples 1 to 6> According to the blending shown in Tables 1 to 3, a colored photosensitive resin composition was prepared in the same manner as in Example 1. Further, the numerical values in Tables 1 to 3 were shown. The mass fraction is as follows. The synthesis method of each component described in Tables 1 to 3 is as follows. [Synthesis of Resin (A-2)] 400 g Epikote YX4000H (manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent I92), 4 g of triphenylphosphine, 153 g of acrylic acid, and 600 g of acetamidine-3-methoxybutyl ester were mixed at 90 °C. (:~100 ° C to react. Then, 40 g of tetrahydrophthalic anhydride and 3 60 g of biphenyltetracarboxylic dianhydride are added as a polybasic acid anhydride, and further reacted, thereby obtaining a biphenyl skeleton Resin (A-2). The resin (A-2) 32 200931178 The weight average molecular weight measured by GPC is 7000, and the acidity is 9 〇 mg KOH/g. » The resin (A-2) is made of acetic acid. 3-methoxybutyl ester was adjusted to have a solid concentration of 50% by mass. [Synthesis of Compound (B-2)] 8 g of glycidyl methacrylate and 1 〇〇g of oxygen alone (CH2 = C (CH3)COOCH2CH2(CF2)4F), 32 g methacrylic acid, g methoxydiethylene glycol methacrylate, 7 g chain transfer agent n-dodecyl thiol ' 2 g of 2, 2 · -Azobis(4-methoxy-2,4-dimethylvaleronitrile) was dissolved in 348 g of 3-methoxybutyl acetate, and stirred under a nitrogen atmosphere at 4 〇β (: _ surface) The copolymer was obtained by polymerization, and the obtained compound had a weight average molecular weight measured by GPC of 9000. Further, the compound (B-2) was adjusted to a solid concentration by using 3-methoxybutyl acetate. For 3 0 % Synthesis [Synthesis of Compound (B-3)] 40 g of glycidyl methacrylate, 72 g of fluorine-based single vessel (CH2 = C(CH3)COOCH2CH2(CF2)4F), 24 g of mercaptopropionic acid , 32 g of decyloxydiethylene glycol methacrylate, 7 g of chain transfer agent, n-dodecyl thiol, 2 g of 2,2 匕 azobis(4-decyloxy-2,4-dimethyl The valeronitrile was dissolved in 348 g of 3-methoxybutyl acetate and polymerized under stirring in a nitrogen atmosphere at 4 (TC_ surface) to obtain a copolymer. The obtained compound (Β·3:) was GPC. The weight average molecular weight measured was 9000. Further, the compound (B-3) was adjusted to have a solid content of 30% by mass using 3-methoxybutyl acetate. [Compound (B-4) Synthesis] 33 200931178 8 g of methacryloyl hydral glycidyl ester '100 g (CH2 = C(CH3)COOCH2CH2(CF2)4F), 24 g of methyl propyl methoxypolyethylene glycol #400 methacrylate (product name: M-90G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 7 g chain transfer alkyl sulphate, 2 g of 2,2·-azobis (4-methoxy-2,4-di dissolved in 348g of acetic acid-3·decyloxybutyl ester, stirred in a nitrogen atmosphere °C (B-4) obtained by polymerization to obtain a copolymer, the weight average molecular weight measured by GPC is 9400. The compound (B-4) is adjusted to have a concentration of 3 0 by using 3-methoxybutyl acetate. quality%. [Synthesis of Compound (B-5)] 8 g of glycidyl methacrylate, 100 g (CH2 = C(CH3)COOCH2CH2(CF2)4F), 24 g of methyl di-glyoxypolyethylene glycol# 1000 mercapto acrylate (product name M-23 0G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 7 g chain transfer alkyl mercaptan, 2 g 2,2'-azobis(4-decyloxy-2,4 _ Dioxins were dissolved in 348 g of acetic acid-3·methoxybutyl ester, and stirred under a nitrogen atmosphere at ° C while stirring to obtain a copolymer. (B-5 ) The weight average molecular weight determined by GPC was 99. The compound (B-5) is adjusted to have a concentration of 30% by mass using 3-methoxybutyl acetate. [Synthesis of Compound (B-6)] 8 g of glycidyl methacrylate, 1〇〇g (CH2 = C(CH3)COOCH2CH2(CF2)6F), 24 g methyl propyl fluoride monomeric acid, 32 NK Ester agent n-dodecyl valeronitrile), compound at 40 , the solid into a fluorine-based monomer I enoic acid, 32: NK Ester agent n-dodecyl valeronitrile), in 40 • compound, the solid into a fluorine-based monomer |

200931178 片醋、32 g曱氧基二乙二酵甲基丙烯酸酯、7 g鏈轉移 正十二燒基硫醇、2 g之2,2'-偶氮雙（4-曱氧基-2,4-二甲 戊腈）溶解於348 g乙酸-3-甲氧基丁酯中，於氮氣環境下 在40°C —面攪拌一面使之聚合而獲得共聚物。所獲得之 合物（B-6 )以GPC測定之重量平均分子量為8900。再者 該化合物（B-6 )係利用乙酸-3 -曱氧基丁酯而調整成固 成分濃度為3 0質量。/。。 [化合物（B-7 )之合成] 將 8 g甲基丙烯酸縮水甘油酯、100 g氟系單 (CH2 = C(CH3)COOCH2CH2(CF2)8F)、24g 甲基丙烯酸異 片酯、32 g甲氧基二乙二酵曱基丙烯酸酯、7 g鏈轉移 正十二烷基硫酵、2g之2,2'-偶氮雙（4-甲氧基-2,4-二甲 戊腈）溶解於348g乙酸·3 -甲氧基丁酯中，於氮氣環境下 在40 °C —面攪拌一面使之聚合而獲得共聚物。所獲得之 合物（B-7 )以GPC測定之重量平均分子量為9300。再者 該化合物（B-7)係利用乙酸-3-甲氧基丁酯而調整成固 成分濃度為3 0質量％。 [化合物（B-8)之合成] 將16 g甲基丙烯酸縮水甘油酯、100 g氟系單 (CH2 = C(CH3)COOCH2CH2(CF2)4F)、50 g 曱基丙烯酸、’ 鏈轉移劑正十二烷基硫醇、2g之2,2'-偶氮雙（4-曱氧 -2,4 -二曱基戊腈）溶解於384 g乙酸-3 -曱氧基丁酯中， 氮氣環境下、在40 °C —面攪拌一面使之聚合而獲得共 物。所獲得之化合物（B-8)以GPC測定之重量平均分 劑 基 、 化 t 體 體 冰 劑 基 化 » 體 體 7 g 基 於 聚 子 35200931178 Tablets vinegar, 32 g of decyloxydiethylene glycol methacrylate, 7 g of chain transfer n-dodecyl mercaptan, 2 g of 2,2'-azobis(4-decyloxy-2, 4-Dimethylvaleronitrile) was dissolved in 348 g of 3-methoxybutyl acetate, and polymerized by stirring at 40 ° C under a nitrogen atmosphere to obtain a copolymer. The weight average molecular weight of the obtained compound (B-6) as measured by GPC was 8,900. Further, the compound (B-6) was adjusted to have a solid concentration of 30% by massification using acetic acid-3-butoxybutyl ester. /. . [Synthesis of Compound (B-7)] 8 g of glycidyl methacrylate, 100 g of fluorine mono (CH2 = C(CH3)COOCH2CH2(CF2)8F), 24 g of isophthalate methacrylate, 32 g of A Ethoxydiethanol decyl acrylate, 7 g chain transfer n-dodecyl thiol, 2 g of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) The copolymer was obtained by polymerizing in 348 g of acetic acid·3-methoxybutyl ester under a nitrogen atmosphere at 40 ° C while stirring. The weight average molecular weight of the obtained compound (B-7) measured by GPC was 9,300. Further, the compound (B-7) was adjusted to have a solid concentration of 30% by mass using 3-methoxybutyl acetate. [Synthesis of Compound (B-8)] 16 g of glycidyl methacrylate, 100 g of fluorine mono (CH2 = C(CH3)COOCH2CH2(CF2)4F), 50 g of methacrylic acid, 'chain transfer agent Dodecyl mercaptan, 2 g of 2,2'-azobis(4-oxo-oxy-2,4-dimercapto valeronitrile) dissolved in 384 g of 3-butoxybutyl acetate, nitrogen atmosphere The mixture was polymerized by stirring at 40 ° C to obtain a complex. The obtained compound (B-8) is a weight-averaged fraction based on GPC, and the body is ice-based. The body is 7 g based on the poly 35.

200931178 量為 10000。再者，該化合物（B-8)係利用乙酸-3-曱 基丁酯而調整成固體成分濃度為30質量％。 [化合物（B-9 )之合成] 除了不使用甲基丙烯酸縮水甘油酯以外，以化合 (B-8)之合成中的相同方式合成化合物（B-9)。所獲得 化合物（B-9 )以GPC測定之重量平均分子量為10900 再者，該化合物（B-9)係利用乙酸-3-曱氧基丁酯而調 成固體成分濃度為3 0質量％。 〈評價〉 將上述實施例1〜11、比較例1〜6中所製備之著色 光性樹脂組成物塗佈於玻璃基板上後，於90°C乾燥2分 而獲得具有約2 /zm膜厚之感光層。繼而，經由負像光 以200 mJ/cm2之曝光量對該感光層選擇性照射紫外線， 用N-A3K (東京應化工業公司製造）：純水=1: 25之溶 作為顯影液，於25 °C喷霧顯影60秒，藉此形成圖案。 後，於22°C對所形成之圖案實施30分鐘的後烘烤，藉 形成線寬為20 之格子狀黑色矩陣圖案。再者，以 下方式來評價顯影前之感光層上之溶劑接觸角、顯影時 顯影液之排斥、圖案上之溶劑接觸角、像素區域内之溶 之排斥、互溶性。 (感光層上之溶劑接觸角） 對形成於玻璃基板上之感光層上的丙二醇單甲 (PM )及水之接觸角進行測定。結果示於表1〜3中。 (顯影液之排斥） 氧 物 之 〇 整 感 鐘 罩 使 液 然 此 如 之 劑 醚 36 200931178 將顯影時不排斥顯影液者記作〇，將排斥顯影液 作X。結果示於表1〜3中。 (圖案上之溶劑接觸角） 對形成於玻璃基板上之圖案上的丙二醇單甲醚（ 及水之接觸角進行測定。結果示於表1〜3中。 (像素區域内之溶劑之排斥） 於所形成之格子内（像素區域内）滴加丙二醇單 (PM )，將不排斥者記作〇，將排斥者記作X。結果示 1〜3中。 (互溶性） 於玻璃基板上進行塗佈，將於液溫15 °C不存在析 者記作〇，將於液溫15 °C雖存在析出物但於液溫25 °C 在析出物者記作△，將於液溫25 °C存在析出物者記Ί 結果示於表1〜3中。 者記 PM ) 甲醚 於表 出物 不存 F X ° 37 200931178 [表i] 實施例1 實施例2實施例3 實施例4實施例5 實施例6 (A) A-1 180 180 180 180 180 180 A-2 A-3 35 35 35 35 35 35 (B) B-1 10 20 B-2 10 20 B-3 10 20 B-4 B-5 B-6 B-7 B-8 B-9 (C) C-1 20 20 20 20 20 20 (D) D-1 780 780 780 780 780 780 溶劑 1160 1160 1160 1160 1160 1160 感光層上之 溶劑接觸角 PM 39。 43。 37。 41。 42。 48。 水 106° 108° 114° 118° 105° 107° 顯影液之由 斥 〇 〇 〇 〇 〇 〇 圖案上之溶 劑接觸角 PM 38。 42。 38。 42。 42。 48。 水 105° 110° 110° 117° 98。 92。 像素區域内之排斥 〇 〇 〇 〇 〇 〇 互溶性 〇 〇 Δ △ 〇 〇200931178 The quantity is 10000. Further, the compound (B-8) was adjusted to have a solid content concentration of 30% by mass using 3-mercaptobutyl acetate. [Synthesis of Compound (B-9)] Compound (B-9) was synthesized in the same manner as in the synthesis of compound (B-8), except that glycidyl methacrylate was not used. The weight average molecular weight of the obtained compound (B-9) measured by GPC was 10,900. Further, the compound (B-9) was adjusted to have a solid concentration of 30% by mass using 3-methoxybutyl acetate. <Evaluation> The colored light-sensitive resin compositions prepared in the above Examples 1 to 11 and Comparative Examples 1 to 6 were applied onto a glass substrate, and then dried at 90 ° C for 2 minutes to obtain a film thickness of about 2 /zm. Photosensitive layer. Then, the photosensitive layer was selectively irradiated with ultraviolet light at a exposure amount of 200 mJ/cm 2 via negative image light, and dissolved in N-A3K (manufactured by Tokyo Ohka Kogyo Co., Ltd.): pure water = 1:25 as a developing solution, at 25 The film was developed by spray development at °C for 60 seconds. Thereafter, the formed pattern was subjected to post-baking at 22 ° C for 30 minutes to form a lattice-like black matrix pattern having a line width of 20. Further, the solvent contact angle on the photosensitive layer before development, the repulsion of the developer at the time of development, the solvent contact angle on the pattern, the repulsion of the solvent in the pixel region, and the mutual solubility were evaluated in the following manner. (Solvent contact angle on the photosensitive layer) The contact angle of propylene glycol monomethyl (PM) and water on the photosensitive layer formed on the glass substrate was measured. The results are shown in Tables 1 to 3. (Rejection of developer) 氧 〇 〇 〇 钟 使 2009 2009 2009 2009 36 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 The results are shown in Tables 1 to 3. (Solvent contact angle on the pattern) The contact angle of propylene glycol monomethyl ether (and water) on the pattern formed on the glass substrate was measured. The results are shown in Tables 1 to 3. (Rejection of the solvent in the pixel region) Propylene glycol mono (PM) was added dropwise in the formed lattice (in the pixel region), and the non-rejected person was referred to as 〇, and the repulsion was designated as X. The results are shown in 1 to 3. (Mixed property) Coating on a glass substrate Cloth, will not be recorded at the liquid temperature of 15 °C, and will be recorded as 〇 at the liquid temperature of 15 °C, but at the liquid temperature of 25 °C, the precipitate will be recorded as △, and the liquid temperature will be 25 °C. The results are shown in Tables 1 to 3. The results are as follows: PM) Methyl ether is not present in the FX ° 37 200931178 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) A-1 180 180 180 180 180 180 A-2 A-3 35 35 35 35 35 35 (B) B-1 10 20 B-2 10 20 B-3 10 20 B-4 B- 5 B-6 B-7 B-8 B-9 (C) C-1 20 20 20 20 20 20 (D) D-1 780 780 780 780 780 780 Solvent 1160 1160 1160 1160 1160 1160 Photosensitive The contact angle of the solvent on the PM 39. 43. 37. 41. 42. 48. Water 106° 108° 114° 118° 105° 107° Developer solution 斥 〇 〇 〇 〇 〇 溶 Solvent contact angle on the pattern PM 38. 42. 38. 42. 42. 48. Water 105° 110° 110° 117° 98. 92. Repulsive in the pixel region 〇 〇 〇 〇 〇 互 mutual solubility 〇 Δ Δ △ 〇 〇

❹ 38 200931178 [表2]❹ 38 200931178 [Table 2]

實施例7實施例8實施例9實施例10實施例11 (A) A-1 180 180 180 180 A-2 180 A-3 35 35 35 35 35 (B) B-1 20 B-2 10 20 B-3 20 20 B-4 10 B-5 10 B-6 10 B-7 10 B-8 B-9 (C) C-1 20 20 20 20 20 (D) D-1 780 780 . 780 780 780 溶劑 1160 1160 1160 1160 1160 感光層上之 溶劑接觸角 PM 48。 39。 38。 38。 38。 水 107° 106° 105° 105° 105° 顯影液之老 •斥 〇 〇 〇 〇 〇 圖案上之 溶射接觸角 PM 48。 38。 38。 39° 39。 水 92。 105〇 103° 104° 104° 像素區域内之排斥 〇 〇 〇 〇 〇 互溶性 〇 〇 〇 〇 〇 39Example 7 Example 8 Example 9 Example 10 Example 11 (A) A-1 180 180 180 180 A-2 180 A-3 35 35 35 35 35 (B) B-1 20 B-2 10 20 B -3 20 20 B-4 10 B-5 10 B-6 10 B-7 10 B-8 B-9 (C) C-1 20 20 20 20 20 (D) D-1 780 780 . 780 780 780 Solvent 1160 1160 1160 1160 1160 Solvent contact angle PM 48 on the photosensitive layer. 39. 38. 38. 38. Water 107° 106° 105° 105° 105° Older developer • Resin 〇 〇 〇 〇 溶 Solvent contact angle PM 48 on the pattern. 38. 38. 39° 39. Water 92. 〇 〇 ° 〇 互 互 互

比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 (A) A-1 182 172 163 154 163 A-2 180 A-3 35 35 35 35 35 35 ⑻ B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 10 20 30 B-9 10 20 30 (C) C-1 20 20 20 20 20 20 (D) D-1 780 780 780 780 780 780 溶制 1160 1160 1160 1160 1160 1160 感光層上之 溶劑接觸角 PM 38* 42。 43。 7〇 r 9。 水 123β 124β 124s 92· 102° 102° 顯影液之身 €斥 X X X 〇 〇 〇 囷案上之 溶劑接觸角 PM 38。 42· 43。 4· 4° 4〇 水 120° 122° 122β 88。 92。 93。 像素區域内之排斥 〇 X X X X X 互溶性 X X X X X X 200931178 [表3] ❹ 由表1〜3可知，於使用實施例1〜11之著色感光性 脂組成物之情形時，由於顯影前之感光層上的水之接觸 低，且顯影時不排斥顯影液，因此可形成均勻線寬之圖# 另一方面，由於圖案上之丙二醇單曱醚及水之接觸角高 因此認為可獲得充分之斥墨性。此外，於由黑色矩陣所 分之像素區域内，所滴加之丙二醇單曱醚未被排斥，因 認為可於該像素區域均勻蓄積R、G、B各色之墨汁。 相對於此，於使用比較例1〜6之著色感光性樹脂組 物之情形時，無法獲得充分之互溶性。又，由於顯影前 感光層上的水之接觸角高，且顯影時排斥顯影液，因此 法形成均勻線寬之圖案。進而，於由黑色矩陣所劃分之 樹 角Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) A-1 182 172 163 154 163 A-2 180 A-3 35 35 35 35 35 35 (8) B-1 B-2 B -3 B-4 B-5 B-6 B-7 B-8 10 20 30 B-9 10 20 30 (C) C-1 20 20 20 20 20 20 (D) D-1 780 780 780 780 780 780 Solvent 1160 1160 1160 1160 1160 1160 Solvent contact angle PM 38* 42 on the photosensitive layer. 43. 7〇 r 9. Water 123β 124β 124s 92· 102° 102° Developer's body € X X X X 〇 〇 溶剂 Solvent contact angle PM 38 on the file. 42· 43. 4· 4° 4〇 Water 120° 122° 122β 88. 92. 93. Repulsive 〇XXXXXX mutual solubility in the pixel region XXXXXX 200931178 [Table 3] ❹ It can be seen from Tables 1 to 3 that in the case of using the colored photosensitive fat composition of Examples 1 to 11, the water on the photosensitive layer before development Since the contact is low and the developer is not repelled during development, a uniform line width can be formed. On the other hand, since the contact angle of propylene glycol monoterpene ether and water on the pattern is high, it is considered that sufficient ink repellency can be obtained. Further, in the pixel region defined by the black matrix, the propylene glycol monoterpene ether added dropwise is not repelled, and it is considered that the inks of the respective colors of R, G, and B can be uniformly accumulated in the pixel region. On the other hand, in the case of using the colored photosensitive resin compositions of Comparative Examples 1 to 6, sufficient mutual solubility could not be obtained. Further, since the contact angle of water on the photosensitive layer before development is high and the developer is repelled during development, a uniform line width pattern is formed. Furthermore, in the corner of the tree divided by the black matrix

劃 此 成 之 無 像 40 200931178It’s not like this 40 200931178

素區域内，所滴加之丙二醇單甲醚被排斥。 【圖式簡單說明】 無 【主要元件符號說明】 無 41In the prime region, the propylene glycol monomethyl ether added was rejected. [Simple description of the diagram] None [Key component symbol description] None 41

Claims (1)

(b1) 200931178 十、申請專利範圍： 1. 一種著色感光性樹脂組成物，其係含有光聚合性化合 (A)、斥墨性化合物（B)、光聚合起始劑（C)以及著 劑（D )者；其特徵在於： 上述斥墨性化合物（B )係至少使具有乙烯性不飽 基及由下述式（bl)所表示之結構的單體（B1)、與可 該單體（B1)共聚合之氟系單體（B2)進行共聚合而成 共聚物； [化學式1] (式（bl)中，Rlb表示碳數為1〜5之亞烷基，η 示1以上之整數）。 2. 如申諳專利範圍第1項所述之著色感光性樹脂組 物，其中上述式（bl)中，η表示1〜60之整數。 3. 如申請專利範圍第1項所述之著色感光性樹脂組 物，其中上述單體（Β1)係具有由下述式（b2)所表示 結構的單體； [化學式2] R1fe-0-^- R2b (b2) 物 色 和· 與 的 表 成 成 之 42 200931178 (式（b2 )中，R2b表示氫原子、羥基、或 取代基之碳數為1〜20之烷基，Rlb、η之含義與上 相同）。 4. 如申請專利範圍第1項所述之著色感光性 物，其中上述斥墨性化合物（Β)中由上述單體 生而來之單元的含量為 1〜40質量％，由上述 (Β2)衍生而來之單元的含量為30〜80質量％ ‘ 5. 如申請專利範圍第1項所述之著色感光性 物，其中上述斥墨性化合物（Β)係進一步使具 不飽和基及環氧基之單體（Β3)進行共聚合而成白 6. 如申請專利範圍第 5項所述之著色感光性 物，其中上述斥墨性化合物（Β)中由上述單體 生而來之單元的含量為1〜40質量％。 7. 如申請專利範圍第1項所述之著色感光性 物，其中上述斥墨性化合物（Β)係進一步使具 不飽和基及羧基之單體（Β4)進行共聚合而成的 8. 如申請專利範圍第7項所述之著色感光性 物，其中上述斥墨性化合物（Β)中由上述單體 者可具有 述式（bl ) 樹脂組成 (Β 1 )衍 氟系單體 樹脂組成 有乙烯性 共聚物。 樹脂組成 (B3 )衍 樹脂組成 有乙烯性 共聚物。 樹脂組成 (B4)衍 43 200931178 生而來之單元的含量為0.1〜30質量％。 9.如申請專利範圍第 1項所述之著色感光性樹脂組成 物，其中上述斥墨性化合物（B)之重量平均分子量為2 0 00 〜5 0 0 0 0 〇 1 0.如申請專利範圍第1項所述之著色感光性樹脂組成 物，其中上述光聚合性化合物（A)與上述斥墨性化合物 (B)的含有質量比率為99.9: 0.1〜70: 30。 11.如申請專利範圍第1項所述之著色感光性樹脂組成 物，其中上述光聚合性化合物（A)包括使環氧化合物（A1) 與含乙烯性不飽和基之羧酸化合物（A2)的反應物，進一 步與多元酸酐（A3)進行反應而獲得之樹脂。(b1) 200931178 X. Patent application scope: 1. A colored photosensitive resin composition containing a photopolymerizable compound (A), an ink repellent compound (B), a photopolymerization initiator (C), and a coating agent (D), wherein the ink repellent compound (B) is a monomer (B1) having at least an ethylenic unsaturated group and a structure represented by the following formula (b1), and the monomer; (B1) The copolymerized fluorine-based monomer (B2) is copolymerized to form a copolymer; (In the formula (b1), Rlb represents an alkylene group having a carbon number of 1 to 5, and η represents 1 or more. Integer). 2. The colored photosensitive resin composition according to Item 1, wherein in the above formula (b1), η represents an integer of from 1 to 60. 3. The colored photosensitive resin composition according to claim 1, wherein the monomer (Β1) has a monomer having a structure represented by the following formula (b2); [Chemical Formula 2] R1fe-0- ^- R2b (b2) Color and · Form with the formula 42 200931178 (In the formula (b2), R2b represents a hydrogen atom, a hydroxyl group, or an alkyl group having a carbon number of 1 to 20, and the meaning of Rb, η Same as above). 4. The colored photosensitive material according to claim 1, wherein the content of the unit derived from the monomer in the ink repellent compound (Β) is 1 to 40% by mass, as described above (Β2) The content of the derivatized unit is 30 to 80% by mass. The colored ink of the above-mentioned ink repellent compound (Β) is further made to have an unsaturated group and an epoxy resin. The coloring photosensitive material according to the fifth aspect of the invention, wherein the monomer of the above ink repellent compound (Β) is derived from the monomer The content is 1 to 40% by mass. 7. The colored photosensitive material according to claim 1, wherein the ink repellent compound (Β) is obtained by further copolymerizing a monomer having an unsaturated group and a carboxyl group (Β4). The colored photosensitive material according to claim 7, wherein the above-mentioned ink repellent compound (Β) may have a composition of the above formula (bl), a resin composition (Β 1 ), a fluorine-containing monomer resin, and the like. Ethylene copolymer. Resin composition (B3) Derivatized resin composition Ethylene copolymer. Resin composition (B4) derivative 43 200931178 The content of the unit derived is 0.1 to 30% by mass. 9. The colored photosensitive resin composition according to claim 1, wherein the above-mentioned ink repellent compound (B) has a weight average molecular weight of 2 00 to 5 0 0 0 〇1 0. The colored photosensitive resin composition according to the above aspect, wherein the photopolymerizable compound (A) and the ink repellent compound (B) have a mass ratio of 99.9: 0.1 to 70:30. The colored photosensitive resin composition according to the above aspect of the invention, wherein the photopolymerizable compound (A) comprises an epoxy compound (A1) and a carboxylic acid compound (A2) containing an ethylenically unsaturated group. The reactant is a resin obtained by further reacting with a polybasic acid anhydride (A3). 12.如申請專利範圍第1項所述之著色感光性樹脂組成 物，其中上述著色劑（D)為遮光劑。 44 200931178 七、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： 無0 八、本案若有化學式時，請揭示最能顯示 發明特徵的化學式： 無。 412. The colored photosensitive resin composition according to claim 1, wherein the coloring agent (D) is an opacifier. 44 200931178 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: No. 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. 4
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