TWI376569B - - Google Patents
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- TWI376569B TWI376569B TW096142535A TW96142535A TWI376569B TW I376569 B TWI376569 B TW I376569B TW 096142535 A TW096142535 A TW 096142535A TW 96142535 A TW96142535 A TW 96142535A TW I376569 B TWI376569 B TW I376569B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- 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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
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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
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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
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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
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
1376569 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 一種適合於形成彩色濾光片之黑色矩陣時使用之著色感光 性樹脂組成物。 【先前技術】 液晶顯示器等顯示體，係形成為如下結構：於形成有 相互對向而成對之電極的兩塊基板之間，夾持液晶層。並 且’於其中一塊基板之内側，形成具有包含紅色（R )、綠 色（G)、藍色（B)等各色之像素區域的彩色濾光片。該彩 色遽光片上’通常為提高對比度或防止漏光等，而形成被 配置成矩陣狀之黑色矩陣，以區劃r、G、b各色之像素區 域。 通常’彩色濾光片係利用微影術而製造。於該微影術 中，首先於基板上塗佈黑色感光性樹脂組成物，其後進行 曝光、顯影，形成黑色矩陣。繼而，將每種r、g'b各色 之感光性樹脂組成物，反覆進行塗佈、曝光、顯影，藉此 而於規定位置上形成各色圖案，以製造彩色濾光片。 又，近年來為提高彩色濾光片之生產力，研究有以噴墨 方式製造彩色濾光片之方法。於該喷墨方式中，首先利用 微影術形成黑色矩陣。繼而，將R、G、U色之墨水自喷 墨嘴喷出至由黑色矩陣所區劃之各區域，以熱或光使積蓄 之墨水硬化，藉此製造彩色濾光片。 5 然而’於該喷墨方式中，為防止鄰接之像素區域間產生 墨水混色等’要求用以形成黑色矩陣之感光性樹脂組成 物，具有對水或二？苯等墨水溶劑之斥溶劑性亦即斥墨 性。 作為如上述之具有斥墨性之感光性樹脂組成物，例如於 下述專利文獻1中揭示有含有斥墨劑之負型感光性樹脂組 成物，該斥墨劑包含具有如下聚合單元之聚合物：具有氣 原子中之至少i個被取代為氟原子之碳數為2〇以下之烧基 (其中，上述烷基包含具有醚性氧者）的聚合單元、具有 乙埽性雙鍵之聚合單元。該負型感光性樹脂組成物係由斥 墨劑之氟烷基而獲得斥墨性。又，-因_.斥皇，包含.真有乙烯 性雙鍵之聚合單元，故可藉由光照射而硬化，且維持斥墨 性。 [專利文獻1]國際公開第2004/042474號小冊子 【發明内容】 [發明所欲解決之問題] 然而’該專利文獻1中所揭示之負型感光性樹脂組成 物，雖可維持斥墨性’但斥墨性本身並不充分，故期待進 一步提高斥墨性。 本發明係鑒於以上問題而開發者，其目的在於提供一種 斥墨性進一步提高之著色感光性樹脂組成物。 [解決問題之技術手段] 1376569 本發明者等人為解決上述問題而反覆進行積極研究結 果發現：藉由使用至少使氟系單體與含有環氧基之丙稀酸 系單體進打共聚合而獲得之共聚物，可獲得高斥墨性從 而完成本發明。 更具體而言，本發明之目的在於提供一種著色感光性樹 脂組成物，其係含有光聚合性化合物（Α)、斥墨性化合物 (Β)、光聚合起始劑（C)和著色劑（D)之著色感光性樹 脂組成物，其特徵在於：上述斥墨性化合物（Β)係至少使 3有環氧基之丙稀酸系單體（bl)、和可與該含有環氧基之 丙烯酸系單體（bl)共聚合之氟系單體（b2)，進行共聚合 而獲得之共聚物》 ….[Technical Field] The present invention relates to a colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition which is suitable for use in forming a black matrix of a color filter. [Prior Art] A display body such as a liquid crystal display is formed by sandwiching a liquid crystal layer between two substrates on which electrodes opposed to each other are formed. Further, a color filter having pixel regions of respective colors of red (R), green (G), and blue (B) is formed on the inner side of one of the substrates. On the color grading sheet, a black matrix arranged in a matrix is formed to generally improve contrast or prevent light leakage, thereby arranging pixel regions of respective colors of r, G, and b. Usually 'color filters are manufactured using lithography. In this lithography, a black photosensitive resin composition is first coated on a substrate, and then exposed and developed to form a black matrix. Then, the photosensitive resin composition of each of r and g'b colors is repeatedly applied, exposed, and developed to form a color pattern at a predetermined position to produce 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 this ink jet method, a black matrix is first formed by lithography. Then, inks of R, G, and U colors are ejected from the ink ejecting nozzles to respective regions partitioned by the black matrix, and the accumulated ink is hardened by heat or light, thereby producing a color filter. 5 However, in the ink jet method, in order to prevent ink color mixing or the like between adjacent pixel regions, a photosensitive resin composition for forming a black matrix is required, which is water or two? The solvent property of an ink such as benzene is also ink repellency. As a photosensitive resin composition having an ink repellency as described above, for example, Patent Document 1 below discloses a negative photosensitive resin composition containing an ink repellent containing a polymer having the following polymerization unit. a polymerized unit having at least one of the gas atoms substituted with a fluorine atom and having a carbon number of 2 Å or less (wherein the above alkyl group contains an etheric oxygen), and a polymerized unit having an ethylidene double bond . This negative photosensitive resin composition is obtained by the fluoroalkyl group of the ink repellent to obtain ink repellency. Further, since _. 斥 ,, contains a polymer unit having a true ethyl double bond, it can be hardened by light irradiation and maintains ink repellency. [Patent Document 1] International Publication No. 2004/042474 [Claim of the Invention] [Problems to be Solved by the Invention] However, the negative photosensitive resin composition disclosed in Patent Document 1 can maintain ink repellency. However, the ink repellency itself is not sufficient, and it is expected to further improve the ink repellency. The present invention has been made in view of the above problems, and an object of the invention is to provide a colored photosensitive resin composition having further improved ink repellency. [Technical means for solving the problem] 1376569 The inventors of the present invention have repeatedly conducted active research to solve the above problems, and found that at least a fluorine-based monomer is copolymerized with an epoxy group-containing monomer having an epoxy group. The obtained copolymer can obtain high ink repellency to complete the present invention. More specifically, it is an object of the present invention to provide a colored photosensitive resin composition containing a photopolymerizable compound (Α), an ink repellent compound (Β), a photopolymerization initiator (C), and a colorant ( The colored photosensitive resin composition of D), wherein the ink repellent compound (Β) is an acrylic acid-based monomer (bl) having at least 3 epoxy groups, and the epoxy group-containing monomer a fluorine-based monomer (b2) copolymerized with an acrylic monomer (bl), a copolymer obtained by copolymerization.
[發明之效果] 根據本發明’可提供一種斥墨性進一步提高之著色感光 性樹脂組成物。該著色感光性樹脂組成物，適合於例如形 成彩色濾光片之黑色矩陣時使用。 【實施方式】 以下，就本發明之實施形態加以說明。於本說明書中， 所謂「（甲基）丙烯酸」，係表示丙烯酸及甲基丙烯酸中之一 或兩者。同樣地，所謂「（甲基）丙稀酸酯」，係表示丙稀酸 酯及甲基丙烯酸酯中之一或兩者。 [著色感光性樹脂組成物] 本發明之著色感光性樹脂組成物係含有光聚合性化合 1376569 物（A)、斥墨性化合物⑴、光聚合起始劑（c)和著色劑 (D)之物。以下，就各個成分加以說明。 [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射而聚合、 硬化之物質。作為光聚合性化合物（A)，以具有乙烯性°不 飽和基之樹脂或單體為佳，更佳為將該等加以組合。藉由 將具有乙烯性不飽和基之樹脂與具有乙烯性不飽和基之單 體加以組合，可提高硬化性，使圖案形成變得容易。再者， 本說明書中，將具有乙烯性不飽和基之化合物中，質量平 均分子量為1000以上者稱為-「具肴乙烯性不飽和基之樹 脂」’將質量平均分子量小於1000者稱為「具有乙稀性不 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：（甲基）丙稀 酸、反丁烯二酸、順丁烯二酸、反丁烯二酸單甲酯、反丁 烯二酸單乙酯、（甲基）丙烯酸-2-羥基乙酯、乙二醇單甲鍵 (甲基）丙稀酸醋、乙一醇早乙謎（甲基）丙烯酸g旨、（甲其） 丙烯酸甘油酯、（甲基）丙烯酿胺、丙烯腈、甲基丙稀猜、（甲 基）丙烯酸曱酯、（甲基）丙烯酸乙酯、（甲基）丙婦酸異丁 酯、（曱基）丙烯酸-2-乙基己酯、（甲基）丙烯酸节酿、乙_ 醇二（甲基）丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇_ (甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、丁- 1376569 曱基丙烯酸酯、丙二醇二（曱基）丙烯酸酯、三羥甲基丙烧 三（甲基）丙烯酸酯、四羥甲基丙烷四（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、 —季戊四醇五（甲基）丙稀酸醋、二季戊四醇六（曱基）丙婦 酸醋、1,6 -己二醇二（甲基）丙稀酸醋、叶啤環氧二丙婦酸 酯（cardoepoxy diacrylate)等聚合而成之低聚物類；使 (甲基）丙烯酸與將多元醇類與一元酸或多元酸進行縮合而 獲得之聚酯預聚物，進行反應而獲得的聚酯（甲基）丙稀酸 酿；使多元醇與具有2個異氰酸酯基之化合物進行反應 後’與（曱基）丙烯酸反應而獲得的聚胺酯（甲基）丙稀酸 酉曰’使雙酌· A型環氧樹脂、雙紛-p型環氧樹脂、雙紛$型 環氧樹脂、苯酚或甲酚酚醛清漆型環氧樹脂、可溶酚醛型 環氧樹脂、三酚基甲烷型環氧樹脂、多羧酸多縮水甘油酯、 多兀醇多縮水甘油酯、脂肪族或脂環族環氧樹脂、胺環氧 樹脂、二羥基苯型環氧樹脂等環氧樹脂，與（甲基）丙烯酸 進行反應而獲得之環氧（甲基）丙烯酸酯樹脂等。進而，可 使用使多元酸酐與環氧（甲基）丙烯酸酯樹脂進行反應而獲 得之樹脂。 又，作為具有乙烯性不飽和基之樹脂，可以使用使環氧 化σ物（al)與含有乙烯性不飽和基之羧酸化合物（&2) 之反應物’進而與多元酸酐（a3)反應而獲得之樹脂為佳。 〈環氧化合物（al) > 作為環氧化合物（al)，可列舉·縮水甘油_、縮水[Effects of the Invention] According to the present invention, a colored photosensitive resin composition having further improved ink repellency can be provided. The colored photosensitive resin composition is suitably used, for example, when forming a black matrix of a color filter. [Embodiment] Hereinafter, embodiments of the present invention will be described. In the present specification, "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means one or both of acrylate and methacrylate. [Coloring photosensitive resin composition] The colored photosensitive resin composition of the present invention contains a photopolymerizable compound 1376569 (A), an ink repellent compound (1), a photopolymerization initiator (c), and a colorant (D). Things. Hereinafter, each component will be described. [Photopolymerizable Compound (A)] The photopolymerizable compound (A) is a substance which is polymerized and hardened by irradiation with light such as ultraviolet rays. The photopolymerizable compound (A) is preferably a resin or a monomer having an ethylenically unsaturated group, and more preferably these are combined. By combining a resin having an ethylenically unsaturated group with a monomer having an ethylenically unsaturated group, the hardenability can be improved and pattern formation can be facilitated. In the present specification, among the compounds having an ethylenically unsaturated group, those having a mass average molecular weight of 1,000 or more are referred to as "resin having an ethylenically unsaturated group", and those having a mass average molecular weight of less than 1,000 are referred to as " A monomer having a ethylenically unsaturated group." <<Resin having ethylenically unsaturated group>> Examples of the resin having an ethylenically unsaturated group include (meth)acrylic acid, fumaric acid, maleic acid, and fumaric acid monomethyl Ester, monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl (meth) acrylate vinegar, ethyl ketone , (meth) glyceryl acrylate, (meth) acrylamide, acrylonitrile, methyl propyl methacrylate, methacrylate (meth) acrylate, ethyl (meth) acrylate, (methyl) propylene glycolate Butyl ester, 2-ethylhexyl (meth) acrylate, (meth) acrylate, ethyl bis (meth) acrylate, diethylene glycol di acrylate, triethylene glycol _ (A Acrylate, tetraethylene glycol di(meth)acrylate, butyl-1376569 decyl acrylate, propylene glycol bis(indenyl) acrylate, trimethylolpropane tris(meth)acrylate, tetrahydroxyl Methylpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid , pentaerythritol penta (meth) acrylate vinegar, dipentaerythritol hexa(indenyl) propylene vinegar, 1,6-hexanediol di(methyl) acrylate vinegar, leaf beer epoxy dipropylene glycol An oligomer obtained by polymerizing a cardoepoxy diacrylate or the like; a polyester obtained by reacting a (meth)acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid (Methyl)acrylic acid brewing; the polyurethane (methyl) acrylate bismuth obtained by reacting a polyol with a compound having two isocyanate groups and reacting with (mercapto)acrylic acid Type epoxy resin, double-p-type epoxy resin, double-type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, trisphenol methane type epoxy resin, Epoxy resins such as polycarboxylic acid polyglycidyl ester, polyglycidyl polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, and (meth)acrylic acid An epoxy (meth) acrylate resin obtained by the reaction or the like. Further, a resin obtained by reacting a polybasic acid anhydride with an epoxy (meth) acrylate resin can be used. Further, as the resin having an ethylenically unsaturated group, a reaction product of the epoxidized σ substance (al) and the carboxylic acid compound (&2) containing an ethylenically unsaturated group can be further reacted with the polybasic acid anhydride (a3). The resin obtained is preferred. <Epoxy compound (al) > As the epoxy compound (al), glycidol _, shrinkage
CS 9 1376569 甘油酯型、縮水甘油胺型、脂環型、雙酚A型、雙酚F型、 又酚S型' 聯苯型、萘型、苐型、苯酚酚醛清漆型、鄰甲 酚型環氧樹脂等。#中，以聯苯型環氧樹脂為佳。聯苯型 環氧樹脂於主鏈上具有1個以上由下式⑴所表示之聯苯 骨架’且具有1個以上之環氧基。又，作為環氧化合物 U1)’以具有2個以上環氧基者為佳。該環氧化合物（ai) 可單獨或者组合2種以上使用。 [化1]CS 9 1376569 Glyceryl ester type, glycidylamine type, alicyclic type, bisphenol A type, bisphenol F type, phenolic type S biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol type Epoxy resin, etc. #中, Biphenyl type epoxy resin is preferred. The biphenyl type epoxy resin has one or more biphenyl skeletons represented by the following formula (1) in the main chain and has one or more epoxy groups. Further, as the epoxy compound U1)', it is preferred to have two or more epoxy groups. These epoxy compounds (ai) may be used alone or in combination of two or more. [Chemical 1]
(1) (式（1)中，複數個R1分別獨立表示氫原子、碳數為i 〜12之烷基、鹵素原子或可具有取代基之苯基，丨表示^ 〜4之整數。） 聯苯型環氧樹脂中，以使用由下式⑴所表示之環氧 樹脂為佳，特佳為使用由下式（3)所表示之環氧樹脂。藉 由使用式（3)之環氧樹脂，可提供靈敏度與溶解性之平衡 優異’且像紊邊緣之清晰性 '密著性優異之¥色感光性樹 脂組成物。 [化2] 1376569(1) In the formula (1), a plurality of R1 each independently represent a hydrogen atom, an alkyl group having a carbon number of i to 12, a halogen atom or a phenyl group which may have a substituent, and 丨 represents an integer of ^4. In the benzene type epoxy resin, an epoxy resin represented by the following formula (1) is preferably used, and an epoxy resin represented by the following formula (3) is particularly preferably used. By using the epoxy resin of the formula (3), it is possible to provide a color-sensitive photosensitive resin composition which is excellent in the balance between sensitivity and solubility and which is excellent in the sharpness of the turbid edge. [化2] 1376569
盤（式（2 )、（3)中’複數個〇別獨立表示氣原子碳 為1〜12之烷基、齒素原子或可具有取代基之苯基η 表不1〜4之整數1為平均值，表示q〜1g之數以小於 i為佳。） ' -又，聯苯型壤氧樹月旨令，亦可以使用由下式⑷所表 :之環氧樹脂為佳。藉由使用式（4)之環氧樹脂，可提供 靈敏度與溶解性之平衡優里， 八 卞銜馒異且像素邊緣之清晰性、密著 優異之著色感光性樹脂組成物。 [化3]In the disk (in the formulas (2) and (3), the plural number of the gas is 1 to 12, the dentate atom or the phenyl group which may have a substituent. The integer 1 of 1 to 4 is The average value indicates that the number of q to 1 g is preferably less than i.) '-In addition, the biphenyl type oxy-tree tree may also use an epoxy resin represented by the following formula (4): By using the epoxy resin of the formula (4), it is possible to provide a photosensitive resin composition which is excellent in balance between sensitivity and solubility, and which is excellent in the sharpness of the edge of the pixel and excellent in adhesion. [Chemical 3]
.R3 )中複數個R3分別獨立表示氫原子、碳數為夏 〜12之烧基、自素原子或者可具有取代基之苯基。m為平 均值，表示0〜10之數，以小於1為佳。） 1376569 〈含有乙烯性不飽和基之羧酸化合物（a2) > 作為含有乙烯性不飽和基之羧酸化合物（a2)，以分子 中含有丙烯基或曱基丙烯基等反應性乙烯性雙鍵之一元羧 酸化合物為佳。作為如此之含有乙烯性不飽和基之羧酸化 合物’可列舉：丙烯酸、曱基丙烯酸、石-笨乙烯基丙烯酸、 /3-糠基丙烯酸、〇：-氰基桂皮酸、桂皮酸等。該含有乙烯 性不飽和基之羧酸化合物（a2)可單獨或者組合2種以上 使用。 作為使環氧化合物（al)與含有乙烯性不飽和基之羧酸 化合物（a2)進行反應之方法，可使用眾所周知之方法。 例如可列舉如下方法以三乙胺、苄基乙胺等三級胺，十 二烧基三甲基氯化銨、四甲基氣化銨、四乙基氯化銨、节 基三乙基氣化銨等四級銨鹽，吡啶，三苯基膦等作為觸媒， 使環氧化合物（al)與含有乙烯性不飽和基之羧酸化合物 (a2)，於有機溶劑中’以50〜15〇〇c之反應溫度反應數小 時〜數十小時。 環氧化合物（al)與含有乙烯性不飽和基之羧酸化合物 (a2)之反應中之使用量比’以環氧化合物（ai)之環氧 當量與含有乙烯性不飽和基之缓酸化合物（a2)的緩酸當 量之比計’通常為1 : 0.5〜1 : 2，以1 : 〇.8〜1 : 1.25為 佳，更佳為1: 1。藉由設為上述範圍，而具有交聯效率提 尚之傾向，故較好。 〈多元酸酐（a3) > 12 夕疋酸If(a3)係具有2個以上絲之缓酸的酸酐包 括八有至7 2㈣笨環之化合物。作為如此之多元酸酐 ⑷)’例如可列舉如下式⑴所表示之具有聯苯骨架的 酸野、如下式（6)所表示之以有機基鍵結2個苯環之酸針。 [化4] 〇The plurality of R3 in .R3) independently represent a hydrogen atom, a pyridyl group having a carbon number of 12 to 12, a self-priming atom or a phenyl group which may have a substituent. m is an average value, indicating a number from 0 to 10, preferably less than one. 1376569 <Carboxylic acid compound (a2) containing an ethylenically unsaturated group > As a carboxylic acid compound (a2) containing an ethylenically unsaturated group, a reactive ethylenic group such as a propenyl group or a mercaptopropenyl group is contained in the molecule. One of the bond carboxylic acid compounds is preferred. Examples of the carboxylic acid compound containing an ethylenically unsaturated group include acrylic acid, mercaptoacrylic acid, stone-stact vinyl acrylic acid, /3-mercaptoacrylic acid, fluorene-cyanocinnamic acid, cinnamic acid and the like. The carboxylic acid compound (a2) containing an ethylenically unsaturated group may be used singly or in combination of two or more. As a method of reacting the epoxy compound (al) with the carboxylic acid compound (a2) containing an ethylenically unsaturated group, a well-known method can be used. For example, the following method may be exemplified by a tertiary amine such as triethylamine or benzylethylamine, a tridecyltrimethylammonium chloride, a tetramethylammonium halide, a tetraethylammonium chloride or a benzylidene group. a quaternary ammonium salt such as ammonium, pyridine, triphenylphosphine or the like as a catalyst, and an epoxy compound (al) and a carboxylic acid compound (a2) containing an ethylenically unsaturated group in an organic solvent '50 to 15 The reaction temperature of 〇〇c is reacted for several hours to several tens of hours. The ratio of use of the epoxy compound (al) to the carboxylic acid compound (a2) containing an ethylenically unsaturated group is 'epoxy equivalent of the epoxy compound (ai) and the acid-lowering compound containing an ethylenically unsaturated group The ratio of the slow acid equivalent of (a2) is usually 1: 0.5 to 1: 2, preferably 1: 〇. 8 to 1: 1.25, more preferably 1:1. It is preferable to have a tendency to improve the crosslinking efficiency by setting it as the above range. <Polyureic acid anhydride (a3) > 12 Evening acid If (a3) is an acid anhydride having two or more silky acid retardants, and includes a compound having eight to seven (4) acyclic rings. For example, the acid anhydride having a biphenyl skeleton represented by the following formula (1) and an acid needle in which two benzene rings are bonded by an organic group represented by the following formula (6) can be mentioned. [化4] 〇
〇〇
(式（6)中，R4表示碳數為之可具有取代基的伸 烷基。） 藉由使用上述具有2個以上羧基之羧酸的酸酐，可於光 聚合性化合物（A)中導入至少2個笨環。 又，除上述具有至少2個苯環之酸酐以外，多元酸酐 (a3)亦可含有其他多元酸酐。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 笨一甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二曱酸酐、甲 基六氫鄰苯二曱酸酐、甲基四氫鄰笨二曱酸酐、偏苯三曱 酸酐、均苯四曱酸二酐、二苯甲酮四羧酸二酐（BTDA)、3-曱基六氫鄰笨二曱酸酐、4_甲基六氫鄰苯二甲酸酐、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 13 1376569 苯二甲酸酐、3-曱基四氫鄰笨二甲酸酐、4-甲基四氫鄰苯 二曱酸酐、3-乙基四氫鄰笨二甲酸酐、4乙基四氫鄰苯二 甲酸野。該等多元酸酐可單獨或者組合2種以上使用。 衣氧化。物（&1)與含有乙稀性不飽和基之叛酸化合物 U2)反應後，進而與多元酸酐U3)反應之方法，可使 用眾所周知之方法。又’使用量比，以環氧化合物（al) 與含有乙稀性不飽和基之_化合物U2)之反應物中的(In the formula (6), R4 represents an alkylene group having a carbon number which may have a substituent.) By using an acid anhydride of a carboxylic acid having two or more carboxyl groups, at least a photopolymerizable compound (A) can be introduced into the photopolymerizable compound (A). 2 stupid rings. Further, the polybasic acid anhydride (a3) may contain 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, o-dosyl anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl group. Hexahydrophthalic anhydride, methyltetrahydro o-benzoic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), 3-mercapto-6 Hydrogen o-phthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrogenate 13 1376569 benzene Formic anhydride, 3-mercaptotetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic acid. These polybasic acid anhydrides can be used individually or in combination of 2 or more types. Clothing oxidation. The method of reacting the compound (&1) with the acid-reducing compound U2) containing an ethylenically unsaturated group and further reacting it with the polybasic acid anhydride U3) can be carried out by a known method. Further, the ratio of use is in the reaction of the epoxy compound (al) with the compound U2 containing an ethylenically unsaturated group.
0H基之莫耳數、與多元酸野（a3)之酸奸基的當量比計， 通常為 1 : 1 ^ 1 : 1u 1 . Λ n 1 υ· 1以1 · Ο·8〜1 ·· 0.2為佳。藉由設 為上述範圍，而具有對顯影液之溶解性變成適度之傾向， 故較好® 使環氧化合物ui)與含有乙歸性不飽和基之缓酸化合 物（⑴之反應物，進而與多元酸酐（a3)反應而獲得之 樹脂的酸價，以樹脂固形分計，以10〜150mgKOH/g為佳， 更佳為70〜110rag_/g。藉由將樹脂之酸價設為1〇The molar ratio of the molar number of the 0H group to the acidity base of the polyacid field (a3) is usually 1: 1 ^ 1 : 1u 1 . Λ n 1 υ · 1 to 1 · Ο·8~1 ·· 0.2 is better. When it is set to the above range, the solubility in the developer tends to be moderate, so that the epoxy compound ui) and the acid-suppressing compound containing the ethylenically unsaturated group ((1) are further reacted with The acid value of the resin obtained by the reaction of the polybasic acid anhydride (a3) is preferably from 10 to 150 mgKOH/g, more preferably from 70 to 110 rag/g, based on the solid content of the resin. The acid value of the resin is set to 1 Torr.
mgKOH/g以上，可獲得充分之對顯影液的溶解性；又藉 由設為150 mgK〇H/g以下，可獲得充分之硬化性，且可^ 表面性良好。 又，樹脂之質量平均分子量以1000〜40000為佳更佳 為2000〜3000(^藉由將質量平均分子量設為1〇〇〇以上， 可提高耐熱性及膜強度；又，藉由設為4〇〇〇〇以下，可獲 得充分之對顯影液的溶解性。 又，作為具有乙烯性不飽和基之樹脂，可以使用分子内 具有咔哚結構（CardoStructure)之樹脂為佳。具有咔哚 1376569 結構之樹脂的耐熱性及耐化學性高，故藉由用於光聚合性 化合物（A) t，可提高著色感光性樹脂組成物之耐熱性及 对化學性。例如，可以使用下式⑺所表示之樹脂為佳。 [化5] HOOC~Y—C0— 〇.When it is more than mgKOH/g, sufficient solubility in the developer can be obtained, and by setting it to 150 mgK〇H/g or less, sufficient hardenability can be obtained, and the surface property can be improved. Further, the mass average molecular weight of the resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 3,000 (the heat resistance and the film strength can be improved by setting the mass average molecular weight to 1 Torr or more); In the following, a sufficient solubility in the developer can be obtained. Further, as the resin having an ethylenically unsaturated group, a resin having a fluorene structure (CardoStructure) in the molecule can be preferably used. Since the resin is high in heat resistance and chemical resistance, the photopolymerizable compound (A) t can improve the heat resistance and chemical properties of the colored photosensitive resin composition. For example, it can be represented by the following formula (7). The resin is better. [Chemical 5] HOOC~Y—C0— 〇.
COOH -X—0—C0—Z—C0—〇 COOHCOOH -X—0—C0—Z—C0—〇 COOH
O-CO-Y-COOH □ (7)O-CO-Y-COOH □ (7)
式（7)中，X為下式（8)所表示之基。 [化6]In the formula (7), X is a group represented by the following formula (8). [Chemical 6]
又式（7)中，Y係自順丁烯二酸酐、丁二酸酐、亞 曱基丁-酸酐、鄰苯二曱酸酐、四氫鄰苯二甲酸酐、六氫 鄰苯二甲酸酐、甲基内亞甲基四氫鄰苯二甲酸酐、氣橋酸 酐甲基四氫鄰苯二甲酸野、戊二㈣等二中除去 羧酸酐基（-C0-0-C0-)之殘基。 ,—«I —不丫啊四 、二酐、聯苯四羧酸二酐（BPDA)、二苯醚四羧酸二酐 四敌Sic—Sf巾除去2個缓酸酐基之殘基。 《具有乙烯性不飽和基之單體 15 < S ) 1376569 具有乙烯性不飽和基之單體中，有單官能單體及多官能 單體。 作為單官能單體，可列舉：（甲基）丙烯醯胺、羥甲基（甲 基）丙烯酿胺、曱氧基曱基（甲基）丙烯醯胺、乙氧基甲基（甲 基）丙烯酿胺、丙氧基甲基（甲基）丙烯醯胺、丁氧基甲氧基 甲基（甲基）丙烯醯胺、N-羥甲基（甲基）丙烯醯胺、N-羥基 甲基（曱基）丙烯醯胺、（甲基）丙烯酸、反丁烯二酸、順丁 烯二酸、順丁稀二酸酐、亞甲基丁二酸、亞甲基丁二酸酐、 甲基順丁烯二酸、曱基順丁烯二酸酐、丁烯酸、2-丙烯醯 胺基-2-甲基丙磺酸、第三丁基丙烯醯胺磺酸、（甲基）丙烯 破fi旨、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯墓） 丙烯酸-2-乙基己酯、（甲基）丙烯酸環己酯、（曱基）丙烯酸 -2-羥基乙酯、（甲基）丙烯酸-2-羥基丙酯、（甲基）丙烯酸 -2-羥基丁酯、（曱基）丙烯酸-2-苯氡基_2_羥基丙酯、鄰苯 二甲酸-2-(甲基）丙烯醯氧基-2-羥基丙酯、單（甲基）丙烯 酸甘油酯、（曱基）丙烯酸四氫糠基甲酯、（曱基）丙烯酸二 甲胺酯、（甲基）丙烯酸縮水甘法酯、（曱基）丙烯酸_2, 2, 2-三氟乙酯、（甲基）丙稀酸-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或 者組合2種以上使用。 另一方面，作為多官能單體，可列舉：乙二醇二（甲基） 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（甲基）丙烯酸酯、新戊二醇二（甲基） 1376569 丙烯酸酯、1，6-己二醇二（甲基）丙烯酸酯、三羥曱基丙烷 二（甲基）丙烯酸g旨、二（曱基）丙烤酸甘油酯、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（曱基）丙烯酸酯、季 戊四醇三（曱基）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.（甲基）丙稀 酸5旨、2,2-雙（4-(曱基）丙烯醯氧基二乙氧基苯基）丙烷、 2, 2-雙（4-(甲基）丙烯醯氧基聚乙氧基苯基）丙烷、（曱基） 丙烯酸2-羥基-3-(曱基）丙烯醯氧基丙酯、乙二醇二縮水 甘油醚二（甲基）丙烯酸酯、二乙二醇二縮水甘油醚二（曱基） 另烯酸酯、鄰苯二甲酸二縮水甘油酯二（甲基）丙烯綾酯、 二丙稀酸甘油酯、甘油聚縮水甘油醚聚（甲基）丙稀酸酯、 (曱基）丙烯酸胺甲酸乙酯（即，甲苯二異氰酸酯）、三甲基 六亞甲基二異氰酸酯及六亞曱基二異氰酸酯等與（甲基）丙 烯酸-2-羥基乙酯之反應物、亞曱基雙（甲基）丙烯醯胺、（甲 基）丙烯醯胺亞甲醚、多元醇與N-羥曱基（曱基）丙烯醯胺 之縮合物等多官能單體或三丙烯基縮甲醛（triacryl formal)等。該等多官能單體可單獨或者組合2種以上使 用0 相對於著色感光性樹脂組成物之固形分，該具有乙烯性 不飽和基之單體的含量範圍以5〜50質量％為佳，更佳為 10〜40質量％。藉由設為上述範圍，而具有易於取得靈敏 度、顯影性、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形分，光聚合性化合 17 旦（A)之含量範圍以5〜5〇質量％為佳，更佳為10〜40質 ❶藉由叹為上述範圍，而具有易於取得靈敏度顯影性、 解析性之平衡的傾向，故較好。 [斥墨性化合物（β)] 斥墨性化合物（Β)係至少使含有環氧基之丙烯酸系單 體（Μ)、可與該含有環氧基之丙烯酸系單體（μ)共聚合 之氣系單體（b2)進行共聚合而獲得之共聚物。換言之， 本發明中，使用具有環氧基之氟系化合物作為上述斥墨性 化合物（B)。藉由使用如此之斥墨性化合物⑴可提供 斥墨性非常優異之著色感光性樹脂組成物。 <含有環氡基之丙烯酸系單體（bl) > 作為含有環氧基之丙烯酸系單體（bl),可列舉：（甲基） 丙烯酸縮水甘油酯、由了式（9)〜（11) ~表示之脂環族 環氧化合物、使（甲基）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、使於側鏈上具有 羥基或羧基之丙烯酸系單體的羥基或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等。其中，以 (甲基）丙烯酸縮水甘油酯為佳。該等含有環氧基之丙烯酸 系單體（bl)可單獨或者組合2種以上使用。 [化7]Further, in the formula (7), Y is derived from maleic anhydride, succinic anhydride, decylene succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and The residue of the carboxylic acid anhydride group (-C0-0-C0-) is removed from the group of methylenetetrahydrophthalic anhydride, gas bridge anhydride methyltetrahydrophthalic acid, and pentane (tetra). ,—«I — 丫 丫 tetra, dianhydride, biphenyl tetracarboxylic dianhydride (BPDA), diphenyl ether tetracarboxylic dianhydride Four enemy Sic-Sf towel removes the residue of two slow anhydride groups. <<Monomer having ethylenically unsaturated group 15 < S ) 1376569 Among the monomers having an ethylenically unsaturated group, there are a monofunctional monomer and a polyfunctional monomer. Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, decyl fluorenyl (meth) acrylamide, and ethoxymethyl (methyl). Acrylamine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyl Base (fluorenyl) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, cis-succinic anhydride, methylene succinic acid, methylene succinic anhydride, methyl cis Butenedioic acid, mercapto maleic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide, and (meth)acryl , (ethyl) methacrylate, butyl (meth) acrylate tomb) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (A 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenylhydrazino-2-hydroxypropyl (meth) acrylate, -2-(methyl) phthalate Propylene oxime-2-hydroxyl Ester, glyceryl mono(meth)acrylate, tetrahydrofurfuryl methyl (meth) acrylate, dimethyl amide (meth) acrylate, glycidyl (meth) acrylate, (mercapto) acrylate 2, 2-trifluoroethyl ester, (meth)acrylic acid-2, 2, 3,3-tetrafluoropropyl ester, (meth)acrylic acid half ester of phthalic acid derivative, and the like. These monofunctional monomers may be used alone or in combination of two or more. On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth) acrylate, polypropylene glycol bis(indenyl) acrylate, butanediol di(meth) acrylate, neopentyl glycol di(methyl) 1376569 acrylate, 1,6-hexanediol II ( Methyl) acrylate, trihydroxymercaptopropane di(meth)acrylic acid g, bis(indenyl)propane glyceride, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Acrylate, pentaerythritol di(decyl) acrylate, pentaerythritol tri(decyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) propylene Acid 5, 2,2-bis(4-(indenyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxybenzene Base) propane, (fluorenyl) 2-hydroxy-3-acrylate Propylene methoxypropyl ester, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether bis(indenyl) enoate, diglycidyl phthalate Di(meth) propylene oxime ester, dipropylene glyceride, glycerol polyglycidyl ether poly(methyl) acrylate, (mercapto) acrylate urethane (ie, toluene diisocyanate), top three Reaction of hexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, fluorenylene bis(meth) acrylamide, (meth) acrylamide A polyfunctional monomer such as a condensation product of a methyl ether, a polyhydric alcohol, and a N-hydroxydecyl (decyl) acrylamide, or a triacryl formal or the like. These polyfunctional monomers may be used singly or in combination of two or more kinds with respect to the solid content of the colored photosensitive resin composition, and the content of the monomer having an ethylenically unsaturated group is preferably from 5 to 50% by mass, more preferably Good for 10 to 40% by mass. When it is in the above range, it tends to be easy to obtain a balance between sensitivity, developability, and analytical property, which is preferable. With respect to the solid content of the colored photosensitive resin composition, the content of the photopolymerizable compound 17 (A) is preferably 5 to 5 % by mass, more preferably 10 to 40 % by sighing the above range. It is preferable because it has a tendency to easily obtain a balance between sensitivity developability and analytical property. [Ink Repellent Compound (β)] The ink repellent compound (Β) is obtained by copolymerizing at least an epoxy group-containing acrylic monomer (Μ) with the epoxy group-containing acrylic monomer (μ). A copolymer obtained by copolymerizing a gas monomer (b2). In other words, in the present invention, a fluorine-based compound having an epoxy group is used as the ink-repellent compound (B). By using such an ink repellent compound (1), it is possible to provide a colored photosensitive resin composition which is excellent in ink repellency. <Acrylic group-containing acrylic monomer (b1) > Examples of the epoxy group-containing acrylic monomer (bl) include glycidyl (meth)acrylate and the formula (9) to (() 11) an alicyclic epoxy compound represented by ~, a monomer obtained by reacting a carboxyl group of (meth)acrylic acid with an epoxy group of a difunctional or higher epoxy compound, and having a hydroxyl group or a carboxyl group in a side chain A monomer or the like obtained by reacting a hydroxyl group or a carboxyl group of an acrylic monomer with an epoxy group of a difunctional or higher epoxy compound. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing acrylic monomers (b1) may be used alone or in combination of two or more. [Chemistry 7]
1376569 (式（10)、（11)中’R5表示氫原子或甲基，m表示1〜 1 〇之整數’ 1及n分別獨立表示1〜3之整數。） 相對於斥墨性化合物（Β)，自含有環氧基之丙烯酸系單 體（bl)衍生的單元之含量範圍以質量％為佳，更佳 為5〜15質量％。藉由設為上述範圍，而具有斥墨性提高之 傾向，故較好。 〈氟系單體（b2) > 作為氟系單體（b2)’以具有乙浠性不飽和基，可與含 有環氧基之㈣酸系單體（M)共聚合者為佳 。作為如此 之氟系單體(b2)’可列舉由下式（12)所表示之化合物等。 該等氟系單體（b2 )可單獨或者組合2種以上使用。 [化8] CXlX2== CX3~^ CK^k-i C-M O^e- Rf (12) 19 1376569 (式U2)巾，γ分別獨立表示氫原子或ι原子， X3表示氫原子1原子、甲基或全氟甲基，χ5表示氯 原子、氟原子或全氟甲基，Rf表示碳數為卜4()之含_ 基或者碳數為2〜100之具有驗鍵之含說院基，a表示〇〜3 之整數，b及C分別獨立表示〇或丨。） 相對於斥墨性化合物⑴，自氣系單體（b2)衍生的單 元之含量範圍以3〇〜8G質量％為佳’更佳為4g〜6g質量％。1376569 (In the formulae (10) and (11), 'R5 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 1 '. 1 and n each independently represent an integer of 1 to 3.) Relative to an ink repellent compound (Β) The content of the unit derived from the epoxy group-containing acrylic monomer (b1) is preferably in the range of mass%, more preferably from 5 to 15% by mass. The above range is preferable because it has a tendency to improve ink repellency. <Fluorated monomer (b2) > As the fluorine-based monomer (b2)', it is preferred to have an ethylenically unsaturated group and to copolymerize with the (iv) acid-based monomer (M) having an epoxy group. Examples of such a fluorine-based monomer (b2)' include a compound represented by the following formula (12). These fluorine-based monomers (b2) may be used alone or in combination of two or more. CXlX2== CX3~^ CK^ki CM O^e- Rf (12) 19 1376569 (Formula U2) towel, γ independently represents a hydrogen atom or ι atom, and X3 represents a hydrogen atom of 1 atom, methyl or Perfluoromethyl, χ5 represents a chlorine atom, a fluorine atom or a perfluoromethyl group, and Rf represents a phenyl group having a carbon number of 4 () or a carbon number of 2 to 100. An integer of 〇~3, b and C respectively represent 〇 or 丨. With respect to the ink repellent compound (1), the content of the unit derived from the gas monomer (b2) is preferably from 3 to 8 g% by mass, more preferably from 4 g to 6 g% by mass.
藉由設為上述範圍，而具有斥墨性以及與著色感光性樹脂 組成物之其他成分的相溶性趨於良好之傾向，故較好： 又，於氟系單體（b2)中，以具有_(CF2)rF(r=i〜i〇) 所表示之基者為佳。…〜8為佳，更佳為2〜6。藉由具 有上述基，而具有斥墨性以及與著色感光性樹脂組成物之 其他成分的相溶性趨於良好之傾向，故較好。 <含有羧基之丙烯酸系單體（b3)〉 • 斥墨性化合物（B)係以進而與含线基之丙稀酸系單 (3),、聚。而獲得之共聚物為佳。藉由與含有缓基之 丙稀酸系單體（b3)共聚合，可調整斥墨性化合物⑴之 酸價’從而可獲得充分的對顯影液之溶解性。 作為如上述之含有羧基之丙烯酸系單體（M)，可列舉： 由下式（13)所表示之化合物、順丁稀二酸、亞甲基丁二 甲基順丁烯一酸、丁烯酸等。其中以(甲基)丙烯酸 為佳，特佳為曱基丙稀酸。該等含有缓基之丙稀酸系單體 (b3)可單獨或者組合2種以上使用。 1376569 [化9] R6In the above range, the ink repellency and the compatibility with other components of the colored photosensitive resin composition tend to be good, so that it is preferable to have a fluorine-based monomer (b2). The base represented by _(CF2)rF(r=i~i〇) is preferred. ...~8 is better, more preferably 2~6. The ink repellency and the compatibility with other components of the colored photosensitive resin composition tend to be good by having the above-mentioned groups, which is preferable. <A carboxyl group-containing acrylic monomer (b3)> The ink repellent compound (B) is further agglomerated with a linear group-containing acrylic acid (3). The copolymer obtained is preferred. By copolymerizing with the acrylic acid monomer (b3) containing a slow group, the acid value of the ink repellent compound (1) can be adjusted to obtain a sufficient solubility in the developer. The above-mentioned carboxyl group-containing acrylic monomer (M) includes a compound represented by the following formula (13), cis-butyl diacid, methylene butylene dimethyl-butanic acid, and butene. Acid, etc. Among them, (meth)acrylic acid is preferred, and mercaptoacrylic acid is particularly preferred. These acrylic acid-containing monomers (b3) containing a buffer group may be used alone or in combination of two or more. 1376569 [Chemical 9] R6
I C (13)I C (13)
II
COOH . (式（13)中’ R6表示氫原子或碳數為 相對於斥墨性化合物（B)，自含有/ 1〜5之烷基。） (b3)衍生的單元之含量範圍以〇 竣基之丙烯酸系單體 為1〜15質量%。藉由設為上述範圍，而2°且質量%為佳，更佳 • 解性趨於適度之傾向，故較好。 /、有對顯影液之溶 根據需要，可使其他單體與斥墨性化合物 Μ》 作為如此之其他單體，可列舉上述具有乙埽性不飽和基° 單體。其中，以丙稀㈣單體為佳。相對於斥墨性化人 ⑻，自該其他單體衍生的單元之含量以g〜2g質量％ 佳0COOH. (In the formula (13), R6 represents a hydrogen atom or a carbon number relative to the ink repellent compound (B), and contains an alkyl group of /1 to 5%.) The content of the unit derived from (b3) is in the range of 〇竣The acrylic monomer is 1 to 15% by mass. It is preferable to set it as the above range, and it is preferable that 2° and mass% are preferable, and the solutionability tends to be moderate. / There is a solution to the developer. The other monomer and the ink repellent compound may be used as such other monomers, and the above-mentioned monomer having an ethylenically unsaturated group can be mentioned. Among them, propylene (tetra) monomer is preferred. The content of the unit derived from the other monomer is from g to 2 g% by mass relative to the ink repellent person (8).
作為使含有環氧基之丙烯酸系_⑴）、貌系單體 (b2)、含有羧基之丙烯酸系單體（b3)以及根據需之苴 他單體進行反應轉得共聚物之方法，可使^所周知: 方法。 斥墨性化合物（B)之質量平均分子量以2〇〇〇〜5〇〇〇〇 為佳，更佳為5000〜2〇〇〇〇。藉由將質量平均分子量設為 2000以上，可提高耐熱性及膜強度；又，藉由設為5〇〇〇〇 以下，可獲得充分之對顯影液的溶解性。 21 1376569 又’斥墨性化合物（B)之含量以光聚合性化合物（a) 與斥墨性化合物（B)之質量比為99. 9 : 0. 1〜70 : 30為佳。 藉由wt為上述範圍’而具有易於取得靈敏度、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-羥基環己基苯酮、 2-經基-2-.曱基-1-苯基丙烧-1-鋼、卜[4-(2 -經基乙氧基） 本基]-2-經基-2-甲基-1-丙烧-1鲷、i-(4-異丙基苯基）—2一 經基-2-甲基丙烧-1-酮、1-(4-十二烧基笨基）_2 —羥基_2_ 甲基丙烧-1-酮、2, 2-二曱氧基-1，2-二苯基乙烷-卜酮、雙 (4-二曱胺基笨基）酮、2-甲基-1-[4-(甲硫基）苯基]_2一味 啉基丙烷-1-酮、2-苄基-2-二曱胺基-1-(4-咪啉基苯基）_ 丁烷-1-酮、乙酮-l-[9-乙基-6-(2-曱基苯曱醯基）_叩_咔 吐-3-基]-1-(鄰乙醯肟）、2, 4, 6-三曱基笨曱醯基二苯基氧 化膦、4-苯曱醯基-4’-甲基二曱基硫醚、4-二甲胺基苯甲 酸、4-二曱胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙醋、4_ 二曱胺基苯甲酸丁酯、4-二甲胺基-2-乙基己基苯甲酸、4_ 二甲胺基-2-異戊基苯曱酸、苄基-沒-甲氧基乙基縮駿、节 基二甲基縮酮、1-苯基-1，2-丙二酮-2-(鄰乙氧基幾基） 肟、鄰苯甲醯基苯甲酸甲酯、2, 4-二乙基噻噸酮、2_氣嚷 嘲酮（2-〇11〇1"〇1加€«3111:11〇1^)、2,4-二甲基嗟嗍調、1-氣_4-丙氧 基噻噸酮、噻噸、2-氣噻噸、2,4-二乙基噻噸、2_甲基嗔 嘲、2-異丙基°塞嘲、2-乙基蒽酿、八曱基蒽酿、1，2_苯幷 22 1376569 蒽醌、2, 3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、 過氧化異丙笨、2-酼基苯幷咪唑、2-巯基笨幷噚唑、2_毓 基笨幷噻唑' 2_(鄰氯苯基）_4,5_二（間甲氧基笨基）_咪唑 二聚物、二笨甲酮、2-氯二苯甲_、p，p，_雙（二曱胺基） 二苯甲酮、4, 4，-雙（二乙胺基）二苯甲酮、4, 4，_二氯二苯 甲酮、3,3-二甲基-4-甲氧基二苯甲酮、二苯基乙二酮、安 息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香 正丁鍵、安息香異丁謎、安息香丁键、苯乙酮、2,2 -二乙 氧基苯乙酮、對二曱基苯乙酮、對二甲胺基苯丙酮、二氯 苯乙酮、三氣苯乙酮、對第三丁基苯乙酮、對二曱胺基苯 乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、 α-二氯-4-笨氧基苯乙酮、嘆嘴酮、2_甲基嗟嘲酮、2-異丙基嗓嘲酮、二苯幷環庚酮、4 -二甲胺基苯甲酸戊酯、 9一苯基吖啶、I 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、2, 4, 6_ 三（三氣甲基）-均三嗪' 2_曱基_46_雙（三氣甲基）均三 噪、2-[2-(5-曱基呋喃-2-基）乙烯基]一4, 6-雙（三氣曱基）-均三嗓、2-[2-(吱喃-2-基）乙烯基]_4,6-雙（三氯甲基）-均三嗪、2-[2-(4-二乙胺基-2-曱基苯基）乙烯基]_4,6_雙 (三氣甲基）-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）_46_ 雙（三氣甲基）-均三嗪、2-(4-乙氧基苯乙烯基）-4, 6-雙（三 氯甲基）-均三嗪、2-(4-正丁氧基苯基）-4, 6-雙（三氣曱 基）-均三嗪、2,4-雙-三氣甲基_6_(3_溴_4-甲氧基）苯基- 23 1376569 均一秦2,4-雙-二氯甲基_6_(2_溴_4_甲氧幻苯基一均三 秦2,4雙二氯甲基_6_(3_溴_4甲氧幻苯乙稀基苯基_ 均一桊2, 4-雙-二氯子基_6_(2_演氧基）苯乙稀基苯 基均一秦等纟中，就靈敏度方面而言尤其以使用肪系 光聚合起始劑為佳。該等光聚合起始劑可單獨或者組合2 種以上使用。 相對於著色感光性樹脂組成物之固形分，光聚合起始劑 (C)之含量以〇 5〜30質量％為佳，更佳為1〜2〇質量％ 之範圍。藉由設為上述範圍，可獲得充分之耐熱性、耐化 學性’又’可提高成膜性’抑制光硬化不良。 [著色劑（D )] 作為著色劑（D) ’可列舉碳黑或鈦黑等遮光劑。又，亦 可使用 Cu、Fe、Mn、Cr、Co、Ni、V、Zn、Se、Mg、Ca、 Sr、Ba、Pd、Ag、Cd、In、Sn、Sb、Hg、Pb、Bi、Si 及 A1 等之各種金屬氧化物、複合氧化物、金屬硫化物、金屬硫 酸鹽或金屬碳酸鹽等無機顏料。 作為碳黑’可使用槽黑（channe 1 b 1 ack)、爐黑、熱碳 黑（thermal black)、燈黑等眾所周知之碳黑，特別是槽 黑因遮光性優異故較適於使用。又，亦可使用由樹脂包覆 之碳黑。具體而言，可列舉：將碳黑以及與存在於碳黑表 面之叛基、經基、羰基具有反應性之樹脂混合，於5〇〜38〇 度下進行加熱而獲得的由樹脂包覆之碳黑；於水-有機溶劑 混合系統或水-界面活性劑混合系統中分散乙烯性單體，而 24 1376569 於聚合起始劍之在& 存在下進订自由基聚合或自由基共聚合而 獲得的由樹^包覆之碳黑等^該由樹脂包覆之碳黑與未經 樹如包覆之碳黑相tt，導電性低，故於用作液晶顯示器等 之表色遽光片的情形時，可形成漏電少可靠性高的低耗 電顧示器。 作為著色劑，可於上述無機顏肖中添加有機顏料作為輔 助顏料。藉由適當選擇添加呈現無機顏料之補色的有機顏 料，可獲得如下效果。例如，碳黑係呈略帶紅色之黑色。 •目此’藉由於碳黑中添加呈紅色之補色，亦即藍色的有機 顏料作為輔助顏料，使得碳黑之紅色消失，整體呈較佳之 黑色。相料無機顏料與有機顏料之合言十，有冑顏料之使 用範圍以1〇〜80質量％為佳，較佳為20〜60質量％，更佳 為20〜40質量％。 "作為上述無機顏料及有機顏料，可使用利用分散劑以適 當濃度分散顏料而獲得之溶液。例如，作為無機顏料，可 φ 列舉：御國色素公司製造之碳分散液CF Black (含有濃度 為20%之碳）、御國色素公司製造之碳分散液CF Biack (含 有24%之咼電阻碳）、御國色素公司製造之鈦黑分散液 Black (含有20%之黑鈦顏料）。又’作為有機顏料，例如 可列舉：御國色素公司製造之藍顏料分散液CF blue (含 有20%之藍顏料）、御國色素公司製造之紫顏料分散液（含 有10%之紫顏料）等。又’作為分散劑’以使用聚乙稀亞 胺系、胺基甲酸乙醋樹脂系、丙稀酸樹脂系之高分子分散 劑為佳。 25 < S > 1376569 相對於著色感光性樹脂組成物之固形分，著色劑之含量 以10〜70質量％為佳。藉由將含量設為質量％以下，可 抑制光硬化不良；又，藉由設為1〇質量％以上，可獲得充 分之遮光性。又，於如下所述使用本發明之著色感光性樹 脂組成物來成膜黑色矩陣時，以將著色劑之濃度調整為每 1 Am膜厚之OD(〇ptical Density，光學密度）值成為 1.5以上為佳。若每i μιη膜厚之〇D值為ι·5以上則在 用於液a日顯7F||之黑色矩陣的情形時，可獲得充分之對比 度。 [溶劑] 本發明之著色感光性樹㈣成物以含㈣以稀釋之 劑為佳。作為該溶劑，例如可列舉：乙二醇單甲謎、乙 醇單乙趟、乙二醇單正 單甲-、二乙二醇單㈣、二：!…、二乙二 一乙—醇單正丙醚、二乙二 單正丁醚、三乙二醇單甲醚、_ • 甲醚、丙二醇I, 二乙二醇皁乙醚、丙二醇. 二丙二醇單甲H 年丙鍵、丙二醇單正丁謎 二丙二醇單T _ 早乙醚、二丙二醇單正丙醚 (聚)二醇》。丁醚 '三丙二醇單甲醚、三丙二醇單乙醚」 (聚)烷一醇早烷基醚類；乙 辟平 乙—二乙二醇單d'乙酸醋、乙二醇j 酸醋、丙二醇單甲_乙_、丙^ 醇單乙^ 燒二醇單燒基越乙酸醋類；二：一：單乙_乙酸醋等(聚 基乙基醚、二乙二醇、：醇-甲醚、二乙二醇， 四氫呋喃等其他醚類；甲差 26 1376569 乙基輞、環己酮、2-庚酮、3-庚酮等_類；2-羥基丙酸曱 龍、2-羥基丙酸乙酯等乳酸烷基酯類；2_羥基_2_曱基丙酸 乙酯、3-甲氡基丙酸甲酯、3-曱氧基丙酸乙酯、3_乙氧基 丙酸甲酯、3-乙氧基丙酸乙酯、乙氡基乙酸乙酯、羥基乙 酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3一甲氧基丁酯、 乙酸3-曱基-3-曱氧基丁酯、丙酸3-甲基_3_甲氧基丁酯、 乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸 異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙 酉曰、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、 丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙 酯、2-側氧丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族 烴類；N-曱基吡咯啶酮、N，N_:甲基甲醯胺、N N_二曱基 乙醯胺等醯胺類等。該等溶劑可單獨或者組合2種以上^ 用。 相對於著色感光性樹脂組成物之固形分質量份，溶 劑之含量以50〜500質量份為佳。 [其他成分] 本發明之著色感光性樹脂組成物中可根據需要而含有 添加劑。作為添加劑，可列舉：熱聚合抑制劑、消泡劑、 界面活性劑、敏化劑、硬化促進劑、光交聯劑、光敏劑、 分散劑、分散助劑、填充劑、密著促進劑、抗氧化劑紫 外線吸收劑、抗凝集劑等。 ' 27 1376569 [著色感光性樹脂組成物之調配方法] 本發明之著色感光性樹脂組成物，係藉由以攪拌機將上 述各成分全部混合而獲得。再者，可使用過濾器進行過濾， 以使所獲得之混合物變得均勻。 [彩色濾光片之製造方法]As a method of reacting an epoxy group-containing acrylic _(1)), a morphene monomer (b2), a carboxyl group-containing acrylic monomer (b3), and a ruthenium monomer as needed, to obtain a copolymer, ^ Known: Method. The mass average molecular weight of the ink repellent compound (B) is preferably 2 Å to 5 Å, more preferably 5,000 Å to 2 Å. By setting the mass average molecular weight to 2,000 or more, heat resistance and film strength can be improved, and by setting it to 5 Torr or less, sufficient solubility in a developing solution can be obtained. The ratio of the content of the photopolymerizable compound (a) to the ink repellent compound (B) is 99. 9 : 0. 1 to 70 : 30 is preferable. It is preferred that the weight is in the above range, and it is easy to obtain a balance between sensitivity, developability, decomposability, and ink repellent property. [Photopolymerization Initiator (C)] As the photopolymerization initiator (C), 1-hydroxycyclohexyl benzophenone, 2-cyano-2-indenyl-1-phenylpropanone-1 - steel, [4-(2-propenylethoxy) benzyl]-2-yl-2-methyl-1-propan-1-yl, i-(4-isopropylphenyl)- 2-mono-2-methylpropan-1-one, 1-(4-dodecylphenyl)_2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy- 1,2-diphenylethane-butanone, bis(4-didecylamino) ketone, 2-methyl-1-[4-(methylthio)phenyl]_2monosylpropanylpropane- 1-ketone, 2-benzyl-2-didecylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone-l-[9-ethyl-6-(2 -mercaptobenzoyl)_叩_咔t-3-yl]-1-(o-ethylidene), 2,4,6-tridecyl adenyl diphenylphosphine oxide, 4-benzene Mercapto-4'-methyldidecyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-diguanylaminobenzoate, 4-dimethylaminobenzoic acid ethyl acetate, 4-diamine Butyl benzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-non-methoxyethyl shrink, section Dimethyl ketal, 1-phenyl-1 , 2-propanedione-2-(o-ethoxymethyl) hydrazine, methyl phthaloyl benzoate, 2, 4-diethyl thioxanthone, 2 嚷 嚷 嚷 ( (2-〇 11〇1"〇1 plus €«3111:11〇1^), 2,4-dimethylhydrazine, 1-gas_4-propoxythioxanthone, thioxanthene, 2-gas thioxanthene, 2,4-Diethyl thioxanthene, 2-methyl oxime, 2-isopropyl hydrazine, 2-ethyl broth, octagonal broth, 1,2 benzoquinone 22 1376569 蒽醌, 2, 3-diphenylanthracene, azobisisobutyronitrile, benzammonium peroxide, isopropylidene peroxide, 2-mercaptobenzimidazole, 2-mercaptopurine, 2_mercapto幷thiazole ' 2 —(o-chlorophenyl)_4,5-di(m-methoxyphenyl)_imidazole dimer, dimercapto ketone, 2-chlorobenzonitrile, p,p, _bis (two Guanyl) benzophenone, 4, 4,-bis(diethylamino)benzophenone, 4, 4,-dichlorobenzophenone, 3,3-dimethyl-4-methoxy Benzophenone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl bond, benzoin dibutyl mystery, benzoin butyl bond, acetophenone, 2,2 - two Ethoxyacetophenone Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, tri-o-acetophenone, p-tert-butylacetophenone, p-diamylacetophenone, p-tert-butyltrichlorobenzene Ethyl ketone, p-tert-butyldichloroacetophenone, α-dichloro-4-p-oxyacetophenone, scrotonone, 2-methylpyridone, 2-isopropylpyridone, two Phenylcycloheptanone, amyl 4-dimethylaminobenzoate, 9-phenyl acridine, I 7_bis-(9-acridinyl)heptane, 1,5-bis-(9-acridine Pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2, 4, 6_ tris(trimethylmethyl)-s-triazine ' 2 fluorenyl _46 _ bis (tri-gas methyl) are three-noise, 2-[2-(5-fluorenylfuran-2-yl)vinyl]- 4,6-bis(triseodecyl)-homo-trimium, 2- [2-(indol-2-yl)vinyl]_4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-mercaptophenyl) Vinyl]_4,6_bis(trismethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trimethylmethyl) )_s-triazine, 2_(4-methoxyphenyl)_46_bis(trimethylmethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloro) Methyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trimethylsulfonyl)-s-triazine, 2,4-bis-trismethylmethyl_6_( 3_bromo- 4-methoxy)phenyl- 23 1376569 homo-Qin 2,4-bis-dichloromethyl_6_(2_bromo-4-methoxyphenyl)-mono-di-qin 2,4 double-two Chloromethyl_6_(3_bromo-4-methoxymethoxyphenylphenyl)-homo- 2,4-bis-dichlorophenyl_6_(2_methoxy)phenethylphenyl homogen In the case of the oxime, it is particularly preferable to use a photopolymerization initiator in terms of sensitivity. These photopolymerization initiators may be used alone or in combination of two or more. The content of the photopolymerization initiator (C) is preferably from 5 to 30% by mass, more preferably from 1 to 2% by mass, based on the solid content of the coloring photosensitive resin composition. When it is in the above range, sufficient heat resistance and chemical resistance can be obtained, and the film formability can be improved to suppress photohardening failure. [Colorant (D)] As the colorant (D) ', a light-shielding agent such as carbon black or titanium black may be mentioned. Further, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si may also be used. And inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates such as A1. As the carbon black, a well-known carbon black such as chanel black (brown), furnace black, thermal black, or lamp black can be used, and in particular, the groove black is excellent in light-shielding property, and therefore it is suitable for use. Further, carbon black coated with a resin can also be used. Specifically, a resin which is obtained by mixing carbon black and a resin reactive with a thiol, a trans group or a carbonyl group which are present on the surface of the carbon black, and heating at 5 to 38 Torr is used. Carbon black; dispersing the ethylenic monomer in a water-organic solvent mixing system or a water-surfactant mixing system, and 24 1376569 in the presence of a polymerization starting sword in the presence of & The obtained carbon black coated by the tree ^ such as the carbon black coated with the resin and the carbon black which is not coated with the tree, has low conductivity, and thus is used as a color grading sheet for a liquid crystal display or the like. In this case, a low power consumption indicator with less leakage and high reliability can be formed. As the coloring agent, an organic pigment can be added as an auxiliary pigment to the above inorganic pigment. By appropriately selecting and adding an organic pigment which exhibits a complementary color of an inorganic pigment, the following effects can be obtained. For example, carbon black is a reddish black. • By the way, by adding a red complementary color to the carbon black, that is, a blue organic pigment as an auxiliary pigment, the red color of the carbon black disappears, and the overall color is preferably black. In general, the use of the pigment inorganic pigment and the organic pigment is preferably from 1 to 80% by mass, preferably from 20 to 60% by mass, more preferably from 20 to 40% by mass. " As the above inorganic pigment and organic pigment, a solution obtained by dispersing a pigment at an appropriate concentration with a dispersing agent can be used. For example, as an inorganic pigment, φ can be listed as a carbon dispersion CF Black (containing 20% carbon) manufactured by Yuki Co., Ltd., and a carbon dispersion CF Biack manufactured by Yuki Co., Ltd. (containing 24% of ruthenium resistance carbon). ), Titanium Black Dispersion Black (containing 20% black titanium pigment) manufactured by Yuguo Pigment Co., Ltd. In addition, as the organic pigment, for example, a blue pigment dispersion liquid CF blue (containing 20% of a blue pigment) manufactured by Yuki Co., Ltd., and a purple pigment dispersion liquid (containing 10% of a purple pigment) manufactured by Yuki Co., Ltd., etc. . Further, as the dispersing agent, a polymer dispersing agent such as a polyethyleneimine-based compound, an urethane-based acetal resin or an acrylic resin-based polymer is preferably used. 25 < S > 1376569 The content of the colorant is preferably 10 to 70% by mass based on the solid content of the colored photosensitive resin composition. By setting the content to the mass% or less, the photocuring failure can be suppressed, and by setting it to 1% by mass or more, sufficient light blocking property can be obtained. Further, when a black matrix is formed by using the colored photosensitive resin composition of the present invention as described below, the density of the colorant is adjusted to an OD (optical density) value of 1.5 or more per 1 Am film thickness. It is better. If the 〇D value of the film thickness per i μιη is ι·5 or more, a sufficient contrast can be obtained in the case of the black matrix for the liquid a 7D||. [Solvent] The colored photosensitive tree (IV) of the present invention preferably contains (4) a diluent. Examples of the solvent include ethylene glycol monomethyl mystery, ethanol monoethyl hydrazine, ethylene glycol mono-n-mono-, diethylene glycol mono (four), two: ..., and diethyldithioacetate. Propyl ether, diethylenedi-n-butyl ether, triethylene glycol monomethyl ether, _ • methyl ether, propylene glycol I, diethylene glycol soap ether, propylene glycol. dipropylene glycol monomethyl H-year-old bond, propylene glycol single-square Dipropylene glycol mono T _ early diethyl ether, dipropylene glycol mono-n-propyl ether (poly) diol. Butane ether 'tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether" (poly) alkane alcohol early alkyl ether; Bipping B-diethylene glycol single d' acetic acid vinegar, ethylene glycol j vinegar, propylene glycol single A_B_, 丙^ Alcohol, single ethyl, diol, monoalkyl ketone, acetic acid vinegar; two: one: single ethyl acetate vinegar, etc. (polyethyl ether, diethylene glycol, alcohol-methyl ether, Diethylene glycol, tetrahydrofuran and other ethers; A difference 26 1376569 ethyl hydrazine, cyclohexanone, 2-heptanone, 3-heptanone, etc.; 2-hydroxypropionic acid guanidine, 2-hydroxypropionic acid Ethyl lactate such as ester; ethyl 2-hydroxy-2-propenyl propionate, methyl 3-methyl mercaptopropionate, ethyl 3-methoxyoxypropionate, methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, ethyl acetoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-mercaptoacetate -3-decyloxybutyl ester, 3-methyl-3-methoxybutyrate propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid Amyl ester, isoamyl acetate, n-butyl propionate, acetamidine butyrate, n-propyl butyrate, butyric acid Other esters such as propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate; An aromatic hydrocarbon such as toluene or xylene; an amide such as N-decylpyrrolidone, N,N_:methylformamide or N N-didecylacetamide. These solvents may be used alone or in combination. The content of the solvent is preferably 50 to 500 parts by mass based on the solid content of the coloring photosensitive resin composition. [Other Components] The colored photosensitive resin composition of the present invention can be used as needed. The additive is contained. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing agent, a dispersing aid, a filler, and a sealant. Promoter, antioxidant ultraviolet absorber, anti-aggregation agent, etc. ' 27 1376569 [Preparation method of coloring photosensitive resin composition] The colored photosensitive resin composition of the present invention is obtained by mixing all of the above components by a stirrer And get. Again, you can use filtering Filtered, so that the obtained mixture became homogeneous. [Production method of the color filter]
首先’使用輥式塗佈機、反向塗佈機（reverse coater )、棒式塗佈機等接觸轉印型塗佈裝置或者旋塗機 (旋轉式塗佈裝置）、淋幕式塗裝機（curtain f 1〇w c〇ater) 等非接觸型塗佈裝置，將本發明之著色感光性樹脂組成物 塗佈於基板上。基板係使用具有透光性之基板。 繼而，使所塗佈之著色感光性樹脂組成物乾燥而形成塗 膜。乾燥方法並無特別限定，例如可使用如下方法中之任 一方法：（ι)利用加熱板於80〜12(rc、較佳為9〇〜1〇(rc 之溫度乾燥6G〜120秒之方法；（2)於室溫下放置數小時First, 'contact roll transfer coating device such as roll coater, reverse coater, bar coater, or spin coating machine (rotary coating device), curtain coating machine A non-contact type coating device such as (curtain f 1 〇 wc 〇 ater) applies the colored photosensitive resin composition of the present invention to a substrate. As the substrate, a substrate having light transmissivity is used. Then, the applied colored photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited. For example, any of the following methods may be used: (1) using a hot plate at 80 to 12 (rc, preferably 9 〇 to 1 〇 (the temperature of rc is dried for 6 G to 120 seconds) (2) placed at room temperature for several hours
〜數日之方法；（3)於暖風加熱器或紅外線加熱器中放置 數十分鐘〜數小時而除去溶劑之方法。 繼而’透過負型光罩，對該塗膜照射紫外線、準分子雷 射光等活性能量線，使其部分曝光。能量線之照射量根據 著色感光性樹脂組成物之組成而有所不同，例如以〜 2000 mJ/cm2左右為佳。 繼而’利用顯影液對曝光後之膜進行顯影，從而使其 成所期望之形狀的圖案。顯影方法並無特別限定，例如 使用浸潰法、噴霧法等。作為顯影液，可_..單乙_ 28 1376569 二乙醇胺、三乙醇胺等有機系之物f，或者氫氧化納、氯 氧化鉀、碳酸鈉、氨、四級銨鹽等之水溶液。 繼而，於2G(TC左右對顯影後之圖案進行後烘烤處理。 此時，以將所形成之圖案全面曝光為佳。藉此可形成具 有規疋圖案形狀之黑色矩陣。 繼而’將R、G、B各色墨水自喷墨嘴喷出至由黑色矩陣 所區劃之各區域，以熱或光使積蓄之墨水硬化。藉此，可 製造彩色濾光片。 [實施例] <實施例1 > 使用下述樹脂（A—1)、與作為單體（A—3)之季戊四 醇四丙烯酸酯’作為光聚合性化合物（A)。 [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，一面將雙酚苐型 環氧樹脂235 g (環氧當量235 )、四甲基氯化銨110 mg、 2, 6-二-第三丁基-4-甲基苯紛100 mg、以及丙烯酸72.0 g，於90°C至100t進行加熱使其熔解後，緩慢升溫至 120°C。此間，測定酸價，連續加熱攪拌約12小時，直至 酸價成為小於1.0 mgKOH/g為止。繼而冷卻至室溫，獲得 無色透明之固體狀雙酚第型環氧丙烯酸酯。 繼而，於所獲得之上述雙酚葬型環氧丙烯酸酯307.0 g 中，添加丙二醇單曱醚乙酸酯（PGMEA) 350 g並使其溶解 29 1376569 後，混合二苯甲酮四羧酸二酐8〇 5 g以及漠化四乙基銨i g ’於1⑽至115»c反應4小時。確㈣㈣消失後混 合1’2,3,6-四氫鄰苯二甲酸# 38 〇 g，於_反應6小 時，獲得樹脂（A-卜再者，利用紅外（IR)光譜確認酸 酐基之消失。所獲得之樹脂（Α〜υ以Gpc測定之質量平 均分子量為5000,酸價為80 mg K〇H/ge利用乙酸3_甲氧 基丁酯將該樹脂（A—1)之固形分濃度調整為55質量 使用下述化合物（B — 1)，作為斥墨性化合物（B)。 [化合物（B—1)之合成] 化合物（B—1)之合成方法如下所述。 將甲基丙烯酸縮水甘油酯16 g、氟系單體（CH2=c(CH3) COOCH2CH2(CF2)eF) 100 g、甲基丙烯酸異莰酯5〇 g、作為 鏈轉移劑之正十二硫醇7 g、2, 2’-偶氮雙（4-甲氧基-2, 4-二甲基戊腈）2 g’溶解於乙酸3-甲氧基丁酯384 g中，於 氮氣環境中以60°C進行攪拌並使其聚合，獲得共聚物。所 獲得之化合物（B - 1 )以GPC測定之質量平均分子量為98 00。再者’利用乙酸3-甲氧基丁酯將該化合物（b_i)之 固形分濃度調整為30質量％。 使用化合物（C — 1 )(汽巴精化（Ciba Specialty Chemical )公司製造，IRGACURE OXE 02)，作為光聚合起 始劑（C )。 使用著色劑（D— 1)(御國色素公司製造，CF Black : 碳黑25質量％，溶劑：乙酸3-曱氧基丁酯），作為著色劑 30 1376569 (D)。 將上述各成分與溶劑（乙酸3_甲氧基丁酯：環己綱= 60 : 40 )以表1之比例進行調配，利用攪拌機混合2小時 後，以5 yin之薄膜過濾器進行過濾，調配著色感光性樹 脂組成物。再者，表1中之數值表示質量份。 <實施例2〜4 '比較例1〜7 > 除於實施例1中，將（A)、（B)、（C).、（D)成分以表【、 2所示之調配量進行調配以外，以與實施例丨相同之方式 調配著色感光性樹脂組成物。再者，表2中之數值表示暂 量份。 表1、2中所記載之各成分如下所述。 [樹脂（A -2)之合成] 將Epikote YX4000H (曰本環氧樹脂公司製造，環氧當 夏192) 400 g、二笨基膦.4 g、丙稀酸153 g、乙酸3-甲 氧基丁酯60G g進行混合，於90〜i〇(rc反應。其後，添 加四氫鄰苯二曱酸酐40 g以及聯苯四缓酸二酐360 g作為 多元酸酐，使其進一步反應，藉此獲得具有聯苯骨架之樹 脂（A — 2 )。該樹脂（A — 2 )以GPC測定之質量平均分子量 為7000，酸價為90 mg KOH/g。再者，利用乙酸3-曱氧基 丁酯將該樹脂（A—2)之固形分濃度調整為50質量％。 [化合物（B — 2)之合成] 將曱基丙烯酸縮水甘油酯24 g、氟系單體（ch2=C(CH3) 31 1376569 C00CH2CH2(CF〇6F) 100 g、曱基丙烯酸異莰酯25 g、甲基 丙烯酸甲酯25 g、作為鏈轉移劑之正十二硫醇7 g、2,2’ -偶氮雙（4-曱氧基-2,4-二甲基戊腈）2 g，溶解於乙酸3二 曱氡基丁酯406 g中，於氮氣環境中以4〇。〇進行攪拌並使 其聚合，獲得共聚物。所獲得之化合物（B—2)以GPC測 定之質量平均分子量為10800。再者，利用乙酸3-曱氧基 丁醋，將該化合物（B—2)之固形分濃度調整為30質量％。 [化合物（B—3)之合成] 除於化合物（B—1)之合成中，不使用曱基丙烯酸縮水 甘油酯以外，以相同方式合成化合物（B_3)。所獲得之化 合物（B— 3)以GPC測定之質量平均分子量為89〇〇β再者， 利用乙酸3-甲氧基丁酯將該化合物（Β_3)之固形分濃度 調整為30質量％。 [化合物（Β—4)之合成] 將丙嗣 555_ 0 g、氟系單體（CH2=C(CH3)C00CH2CH2(CF2) eF) 72·〇 g、甲基丙烯酸12.0 g、甲基丙烯酸2_羥基乙醋 84. 〇 g、作為鏈轉移齊丨之正十二硫醇6. 9居、以及22, _ 偶氮又（4甲氧基_24_二甲基戊腈）3 2 g進行混合於氮 氣環境下搜拌並於4QC使其聚合18小時後，添加水進行 再沈殿精製’繼而利用石油⑽進行再沈殿精製，加以真空 乾燥而獲得聚合物1。 將聚合物1之100 g、異氰酸2_甲基丙稀酿氧基乙醋 32 1376569 41.7 g、二月桂酸二丁基錫0.17 g、2, 6-二-第三丁基-對 甲紛2.1 g以及丙_ 100 g進行混合，一邊加以檀拌、一 邊使其於30°C聚合18小時後’添加水進行再沈澱精製， 繼而以石油醚進行再沈澱精製，加以真空乾燥而獲得化合 物（B-4)。所獲得之化合物（B—4)以GPC測定之質量平 均分子量為9800 ^再者，該化合物（b-4)並不製成溶液 而直接使用。 <評價> 將上述實施例1〜4、比較例1〜6中調配之著色感光性 樹脂組成物塗佈於玻璃基板上後，於9〇t乾燥2分鐘，獲 得具有約2 em之膜厚的感光層。繼而，透過負型光罩， 以曝光量200 mJ/cm2對該感光層選擇性照射紫外線，使用 N-A3K (東京應化卫業製造）：純水25之溶液作為顯 影液’於25°C喷霧顯影60秒、，藉此形成圖案。盆後，藉 由對所形成m 22。(：實施3D分鐘之後烘烤處理，^ 成線寬為20 之格子狀黑色矩陣圖案/ 行有，以上述格 子之開口部成為200 ”x80 "之方式，形成黑色矩陣圖 案。繼而，以如下方式評價顯影性、斥墨性、像素區 之濕潤性。 (顯影性） 顯^性㈣可形錢案者記為〇,將可形_“圖案 不2良:記為△’將無法形成圖案者記為x。將結果 33 1376569 (斥墨性） 斥墨性係測定玻璃基板上所形成之圖案上的丙二醇單 甲醚乙.酸酯(PGMEA)之接觸角，將4〇。以上之情形記為〇， 將Ο X上且小於4〇之情形記為△，將小於。之情形記 為X。將結果示於表1、2中。 (像素區域内之濕潤性） 像素區域内之濕潤性係於所形成之格子内（像素區域 内）滴下20 pi之PGMEA，將PGMEA擴散至格子内之面積 的100%之情形記為◎，將擴散至80〜1〇〇%之情形記為〇， 將擴散至40〜80%之情形記為△，將小於4〇%之情形記為 X。將結果示於表1、2中。 …、~ a few days method; (3) a method of removing the solvent by placing it in a heater heater or an infrared heater for tens of minutes to several hours. Then, the coating film is irradiated with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask to partially expose it. The irradiation amount of the energy ray varies depending on the composition of the colored photosensitive resin composition, and is preferably, for example, about 2,000 mJ/cm2. Then, the exposed film is developed by a developing solution to have a pattern of a desired shape. The developing method is not particularly limited, and examples thereof include a dipping method, a spraying method, and the like. The developer may be an organic solution such as monoethyl _ 28 1376569 diethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium oxychloride, sodium carbonate, ammonia or a quaternary ammonium salt. Then, the pattern after development is subjected to post-baking treatment at about 2 G. At this time, it is preferable to comprehensively expose the formed pattern. Thereby, a black matrix having a regular pattern shape can be formed. Each of the G and B inks is ejected from the ink ejecting nozzle to each region partitioned by the black matrix, and the accumulated ink is hardened by heat or light. Thereby, a color filter can be manufactured. [Embodiment] <Example 1 > The following resin (A-1) and pentaerythritol tetraacrylate as monomer (A-3) were used as the photopolymerizable compound (A). [Synthesis of Resin (A-1)] Resin (A- 1) The synthesis method is as follows: One side is blown with air at a rate of 25 ml/min, and bisphenol quinone type epoxy resin 235 g (epoxy equivalent 235), tetramethylammonium chloride 110 mg, 2, 6-di-t-butyl-4-methylbenzene 100 mg, and 72.0 g of acrylic acid, heated at 90 ° C to 100 t, and then slowly heated to 120 ° C. During this time, the acid value was measured continuously. Heating and stirring for about 12 hours until the acid value becomes less than 1.0 mgKOH/g, and then cooled to room temperature to obtain a colorless transparent Solid bisphenol type epoxy acrylate. Then, in the obtained bisphenol borne epoxy acrylate 307.0 g, propylene glycol monoterpene ether acetate (PGMEA) 350 g was added and dissolved in 29 1376569 Mixing benzophenone tetracarboxylic dianhydride 8〇5 g and desertified tetraethylammonium ig ' at 1 (10) to 115»c for 4 hours. After confirming (4) (4) disappearing, mixing 1'2,3,6-tetrahydroortene Phthalic acid # 38 〇g, reacted for 6 hours to obtain a resin (A-B again, the disappearance of the acid anhydride group was confirmed by infrared (IR) spectroscopy. The obtained resin (mass average molecular weight measured by Gpc) It is 5000, the acid value is 80 mg K〇H/ge, and the solid content concentration of the resin (A-1) is adjusted to 55 mass by using 3-methoxybutyl acetate to use the following compound (B-1) as a repellent Ink compound (B) [Synthesis of compound (B-1)] The synthesis method of the compound (B-1) is as follows: 16 g of glycidyl methacrylate, a fluorine-based monomer (CH2=c (CH3) ) COOCH2CH2(CF2)eF) 100 g, isodecyl methacrylate 5〇g, n-dodecylmer 7 g as a chain transfer agent, 2, 2'-azobis(4-methoxy -2,4-Dimethylvaleronitrile) 2 g' was dissolved in 384 g of 3-methoxybutyl acetate, and stirred at 60 ° C under a nitrogen atmosphere to obtain a copolymer. The mass average molecular weight of the compound (B-1) measured by GPC was 98 00. Further, the solid content concentration of the compound (b_i) was adjusted to 30% by mass using 3-methoxybutyl acetate. The compound (C-1) (manufactured by Ciba Specialty Chemical Co., Ltd., IRGACURE OXE 02) was used as a photopolymerization initiator (C). A coloring agent (D-1) (manufactured by Yuki Co., Ltd., CF Black: carbon black 25 mass%, solvent: 3-decyloxybutyl acetate) was used as a coloring agent 30 1376569 (D). The above components and the solvent (3-methoxybutyl acetate: cycloheximide = 60: 40) were formulated in the ratio of Table 1, and mixed by a stirrer for 2 hours, and then filtered by a 5 yin membrane filter. The photosensitive resin composition is colored. Further, the numerical values in Table 1 represent parts by mass. <Examples 2 to 4 'Comparative Examples 1 to 7 > In addition to the first embodiment, the components (A), (B), (C)., and (D) were formulated in the amounts shown in Tables [2]. In the same manner as in Example 调, a coloring photosensitive resin composition was prepared in the same manner as in the formulation. Furthermore, the values in Table 2 indicate the temporary shares. The components described in Tables 1 and 2 are as follows. [Synthesis of Resin (A-2)] Epikote YX4000H (manufactured by Sakamoto Epoxy Co., Ltd., Epoxy xiaxia 192) 400 g, diphenylphosphine. 4 g, 153 g of acrylic acid, 3-methoxyacetic acid 60 g g of butyl butyl ester was mixed and reacted at 90 〇 〇 (rc reaction. Thereafter, 40 g of tetrahydrophthalic anhydride and 360 g of biphenyl tetrazoic acid dianhydride were added as a polybasic acid anhydride to further react. This obtained a resin (A-2) having a biphenyl skeleton. The resin (A-2) had a mass average molecular weight of 7,000 as determined by GPC and an acid value of 90 mg KOH/g. Further, 3-methoxyl acetate was used. Butyl ester was adjusted to a solid content concentration of the resin (A-2) to 50% by mass. [Synthesis of Compound (B-2)] 24 g of glycidyl methacrylate and a fluorine-based monomer (ch2=C (CH3) 31 1376569 C00CH2CH2 (CF〇6F) 100 g, isodecyl methacrylate 25 g, methyl methacrylate 25 g, as a chain transfer agent, n-dodecyl mercaptan 7 g, 2,2'-azo double 2 g of (4-nonyloxy-2,4-dimethylvaleronitrile), dissolved in 406 g of 3 dimercaptobutyl acetate, stirred and polymerized in a nitrogen atmosphere at 4 Torr. Obtaining copolymer The obtained compound (B-2) has a mass average molecular weight of 10,800 as measured by GPC. Further, the solid content concentration of the compound (B-2) is adjusted to 30% by mass using 3-methoxybutyl vinegar acetate. [Synthesis of Compound (B-3)] In the synthesis of the compound (B-1), the compound (B-3) was synthesized in the same manner except that glycidyl methacrylate was not used. The obtained compound (B-3) The mass average molecular weight measured by GPC was 89 〇〇β, and the solid content concentration of the compound (Β_3) was adjusted to 30% by mass using 3-methoxybutyl acetate. [Synthesis of Compound (Β-4) ] 嗣 555 _ 0 g, fluorine monomer (CH2 = C (CH3) C00CH2CH2 (CF2) eF) 72 · 〇 g, methacrylic acid 12.0 g, methacrylic acid 2 - hydroxyethyl vinegar 84. 〇 g, as Chain transfer of n-dodecyl mercaptan 6. 9 and 22, _ azo (4 methoxy _24_ dimethyl valeronitrile) 3 2 g were mixed and mixed under nitrogen atmosphere at 4QC After the polymerization was carried out for 18 hours, water was added to re-prepare the column, and then refined with oil (10), and then dried in a vacuum to obtain a poly 1. A 100 g of the polymer 1, 100% of the isocyanic acid oxyacetate 32 1376569 41.7 g, dibutyl tin dilaurate 0.17 g, 2,6-di-t-butyl-pair 2.1 g and propylene 100 g were mixed, and after being mixed with sandalwood, the mixture was polymerized at 30 ° C for 18 hours, and then water was added for reprecipitation purification, followed by reprecipitation purification with petroleum ether, followed by vacuum drying. Compound (B-4). The obtained compound (B-4) had a mass average molecular weight of 9800^ as determined by GPC. Further, the compound (b-4) was used as it was without being used as a solution. <Evaluation> The colored photosensitive resin compositions prepared in the above Examples 1 to 4 and Comparative Examples 1 to 6 were applied onto a glass substrate, and then dried at 9 Torr for 2 minutes to obtain a film having about 2 em. Thick photosensitive layer. Then, the photosensitive layer was selectively irradiated with ultraviolet light through a negative mask at an exposure amount of 200 mJ/cm 2 , and a solution of N-A3K (manufactured by Tokyo Chemical Industry Co., Ltd.): pure water 25 was used as a developing solution 'at 25 ° C. The film was developed by spray development for 60 seconds. After the basin, m 22 is formed by the pair. (: After 3D minutes, the baking process is performed, and a grid-like black matrix pattern/line having a line width of 20 is formed, and a black matrix pattern is formed so that the opening of the lattice becomes 200"x80 ". In the manner of evaluation, the developability, the ink repellency, and the wettability of the pixel region were evaluated. (Developability) The (4) shapeable money case was recorded as 〇, and the shape _ "pattern not good: marked as △" would not be able to form a pattern. The result is denoted by x. The result is 33 1376569 (ink repellency). The ink repellency is measured by measuring the contact angle of propylene glycol monomethyl ether acetate (PGMEA) on the pattern formed on the glass substrate, which is 4 〇. In the case of 〇, the case where Ο X is less than 4 记 is denoted by Δ, and the case where Ο is smaller than 。 is denoted by X. The results are shown in Tables 1 and 2. (Hardness in the pixel region) Wetting in the pixel region In the case where the PGMEA is dropped by 20 pi in the formed lattice (in the pixel region), the case where PGMEA is diffused to 100% of the area in the lattice is denoted by ◎, and the case where the diffusion is 80 to 1% is recorded as 〇 , the case of spreading to 40 to 80% is denoted by △, and the case of less than 4〇% is denoted by X. The results are shown in Tables 1 and 2. ...,
34 137656934 1376569
[表l ] 實施例1 實施例2 實施例3 實施例4 (A) A-1 160 180 — 180 A-2 —' — 180 — A-3 35 35 35 35 ⑻ B— 1 33 6.6 33 — B-2 — — — 6.6 B—3 — — — 一 B-4 — — — — (C) C— 1 20 20 20 20 ⑻ D-1 780 780 780 780 溶劑 1160 1160 1160 1160 顯影性 Δ 〇 〇 〇 斥墨性 〇 〇 〇 〇 像素區域内之濕潤性 〇 ◎ 〇 〇[Table 1] Example 1 Example 2 Example 3 Example 4 (A) A-1 160 180 - 180 A-2 - ' - 180 - A-3 35 35 35 35 (8) B - 1 33 6.6 33 - B -2 — — — 6.6 B—3 — — — A B-4 — — — — (C) C— 1 20 20 20 20 (8) D-1 780 780 780 780 Solvent 1160 1160 1160 1160 Developability Δ Repellent Wetness in the area of the ink 〇〇〇〇 pixel 〇 〇〇 〇〇
[表2] 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 (B) B— 1 — — — — — — B—2 — — — — — — B-3 — 16 33 50 — 33 B—4 — — — — 10 — (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 顯影性 〇 Δ X X X Δ 斥墨性 X X Δ Δ △ X 像素區域内之濕潤性 〇 X X X X X 由表1、2可知：於使用具有環氧基之化合物（B—1) 或化合物（B — 2 )作為斥墨性化合物（B )之實施例1〜4 < S ) 35 1376569 中，斥墨性.像素區域内之濕潤性均優異。此外，由於由黑 色矩陣區劃之像素區域濕潤性高，故認為可於該像素區域 均勻積蓄R、G、B各色墨水。與此相對，於使用化合物（β —3)或（β — 4)作為斥墨性化合物（B)之比較例2〜6中， 斥墨性劣於實施例1〜4，且像素區域内之濕潤性不良，顯 影性亦不良。又，於未使用斥墨性化合物（Β)之比較例i 中，像素區域内之濕潤性雖良好，但斥墨性顯著了降，無 法用於喷墨用途。 • 【圖式簡單說明】 無 【主要元件符號說明】 … 無 36[Table 2] 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 (B) B—1 — — — — — — B—2 — — — — — — B-3 — 16 33 50 — 33 B—4 — — — — 10 — (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 Developability 〇Δ XXX Δ Ink repellency XX Δ Δ △ X Wetness in the pixel area 〇XXXXX As shown in Tables 1, 2 : In the use of the epoxy group-containing compound (B-1) or the compound (B-2) as the ink repellent compound (B), in Examples 1 to 4 <S) 35 1376569, the ink repellent property is in the pixel region. Excellent wettability. Further, since the pixel region partitioned by the black matrix has high wettability, 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 Comparative Examples 2 to 6 in which the compound (β-3) or (β-4) was used as the ink repellent compound (B), the ink repellency was inferior to those in Examples 1 to 4, and in the pixel region. Poor wettability and poor developability. Further, in Comparative Example i in which the ink repellent compound (Β) was not used, although the wettability in the pixel region was good, the ink repellency was remarkably lowered, and it was not used for the ink jet application. • [Simple diagram description] None [Main component symbol description] ... None 36
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| JP5173543B2 (en) * | 2008-04-08 | 2013-04-03 | 東京応化工業株式会社 | Positive photosensitive resin composition |
| US8829070B2 (en) | 2009-08-31 | 2014-09-09 | Kabushiki Kaisha Toshiba | Ultraviolet-curable resin material for pattern transfer and magnetic recording medium manufacturing method using the same |
| TWI570509B (en) | 2010-10-05 | 2017-02-11 | Sumitomo Chemical Co | Coloring the photosensitive resin composition |
| JP4988032B2 (en) * | 2010-12-08 | 2012-08-01 | 株式会社東芝 | Method for manufacturing magnetic recording medium |
| JP5039199B2 (en) * | 2010-12-08 | 2012-10-03 | 株式会社東芝 | UV curable resin material used for pattern transfer |
| JP5744528B2 (en) * | 2011-01-11 | 2015-07-08 | 東京応化工業株式会社 | Colored photosensitive resin composition for touch panel, touch panel, and display device |
| JP6708367B2 (en) * | 2014-03-31 | 2020-06-10 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive resin composition for light-shielding film, light-shielding film and color filter obtained by curing the same |
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| JP2001281861A (en) * | 2000-04-03 | 2001-10-10 | Fujifilm Arch Co Ltd | Positive type photosensitive resin composition |
| WO2004042474A1 (en) * | 2002-11-06 | 2004-05-21 | Asahi Glass Company, Limited | Negative type photosensitive resin composition |
| JP2004198542A (en) * | 2002-12-16 | 2004-07-15 | Showa Denko Kk | Color filter black matrix resist composition and photosensitive composition used for same composition |
| JP3938375B2 (en) * | 2003-03-12 | 2007-06-27 | 三菱化学株式会社 | Photosensitive coloring composition, color filter, and liquid crystal display device |
| CN100356204C (en) * | 2003-03-12 | 2007-12-19 | 三菱化学株式会社 | Photosensitive composition, photosensitive color composition, color filter, and liquid crystal display equipemnt |
| JP4595374B2 (en) * | 2003-04-24 | 2010-12-08 | 住友化学株式会社 | Black photosensitive resin composition |
| JP4290483B2 (en) * | 2003-06-05 | 2009-07-08 | 新日鐵化学株式会社 | Photosensitive resin composition for black resist and light-shielding film formed using the same |
| JP5177933B2 (en) * | 2003-08-12 | 2013-04-10 | 東洋インキＳｃホールディングス株式会社 | Partition wall composition, pixel forming substrate using the same, and pixel forming method |
| JP4448381B2 (en) * | 2004-05-26 | 2010-04-07 | 東京応化工業株式会社 | Photosensitive composition |
| JP4611724B2 (en) * | 2004-12-03 | 2011-01-12 | 東京応化工業株式会社 | Photosensitive composition for forming light-shielding film, and black matrix formed with the photosensitive composition for forming light-shielding film |
| KR101321838B1 (en) * | 2005-07-20 | 2013-10-25 | 가부시키가이샤 아데카 | Alkaline-developable photosensitive colored composition |
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