TW202239773A - Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device - Google Patents

Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device Download PDF

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TW202239773A
TW202239773A TW111103644A TW111103644A TW202239773A TW 202239773 A TW202239773 A TW 202239773A TW 111103644 A TW111103644 A TW 111103644A TW 111103644 A TW111103644 A TW 111103644A TW 202239773 A TW202239773 A TW 202239773A
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group
mass
ring
monomer
resin composition
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木村明日香
利光恵理子
佐藤嘉秀
倉久稔
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日商三菱化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/22—Esters containing halogen
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
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    • H10K59/122—Pixel-defining structures or layers, e.g. banks
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    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
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Abstract

Provided is a photosensitive resin composition capable of achieving both adequate liquid repellency and ink jet application properties. The photosensitive resin composition of the present invention contains (A) a copolymer, (B) an alkali-soluble resin, and (D) a photopolymerizable compound, and the (A) copolymer contains a monomer (a1): monomer having an active group that generates radicals upon irradiation by active energy rays and a monomer (a2): a monomer having a fluorine atom and/or silicon atom, as constituent monomers.

Description

感光性樹脂組合物、硬化物、阻隔壁、有機電致發光元件、彩色濾光器及圖像顯示裝置Photosensitive resin composition, cured product, barrier rib, organic electroluminescent element, color filter, and image display device

本發明係關於一種感光性樹脂組合物、硬化物、阻隔壁、有機電致發光元件、彩色濾光器及圖像顯示裝置。  本案基於2021年1月29日於日本提出申請之專利特願2021-012736號主張優先權，並將其內容引用至本文中。The invention relates to a photosensitive resin composition, cured product, barrier wall, organic electroluminescent element, color filter and image display device. This case claims priority based on Japanese Patent Application No. 2021-012736 filed in Japan on January 29, 2021, and its content is incorporated herein.

一直以來，有機電致顯示器等中所含之有機電致發光元件係於基板上形成阻隔壁(隔牆)後，於由阻隔壁所圍成之區域內積層各種功能層而製造。作為容易地形成此種阻隔壁之方法，已知有藉由使用感光性樹脂組合物之光微影法而形成之方法。Conventionally, organic electroluminescence elements included in organic electroluminescence displays etc. are produced by forming barrier walls (partition walls) on a substrate and then laminating various functional layers in the area surrounded by the barrier walls. As a method of easily forming such a barrier rib, a method of forming by photolithography using a photosensitive resin composition is known.

又，作為於由阻隔壁所圍成之區域內積層各種功能層之方法，已知有如下方法：首先製備包含構成功能層之材料之油墨，繼而，將所製備之油墨注入至由阻隔壁所圍成之區域內。於該方法中，從容易將特定量之油墨準確地注入至特定部位方面考慮，多數情況下採用噴墨法。Also, as a method of laminating various functional layers in a region surrounded by barrier ribs, there is known a method of first preparing ink containing materials constituting the functional layer, and then injecting the prepared ink into the area surrounded by barrier ribs. within the enclosed area. In this method, the inkjet method is often used in view of the ease of accurately injecting a specific amount of ink into a specific location.

進而，於使用油墨形成功能層之情形時，出於預防油墨向阻隔壁附著、或防止被注入至鄰接之區域間之油墨彼此混合之目的等，有時要求對阻隔壁賦予撥油墨性(撥液性)。Furthermore, when using ink to form a functional layer, for the purpose of preventing ink from adhering to the barrier wall or preventing ink injected into adjacent regions from mixing with each other, it is sometimes required to impart ink repellency (repellent) to the barrier wall. liquid).

於藉由噴墨法形成有機發光層之情形時，為了防止有機發光元件之空心，或者積層平坦之有機發光層，由阻隔壁所圍成之區域(以下，亦稱為開口部)必須具有油墨容易潤濕擴散之性質。In the case of forming the organic light-emitting layer by the inkjet method, in order to prevent the hollow of the organic light-emitting element or to build up a flat organic light-emitting layer, the area surrounded by the barrier ribs (hereinafter also referred to as the opening) must have ink The property of easy wetting and spreading.

專利文獻1中記載有如下含氟硬化性樹脂及組合物，其於用於保護膜之塗佈材料之紫外線硬化型硬塗材用途中，於防污性方面有效果，且具有聚(全氟伸烷基醚鏈)及光聚合起始能力。Patent Document 1 describes a fluorine-containing curable resin and composition that are effective in antifouling properties in the application of ultraviolet-curable hard coating materials used as coating materials for protective films, and have poly(perfluoro alkylene ether chain) and photopolymerization initiation ability.

專利文獻2中記載有藉由使用包含具有多環式飽和烴骨架及乙烯性雙鍵之丙烯酸系樹脂之感光性組合物，於UV(Ultra Violet，紫外線)洗淨處理後撥油墨性亦良好。  [先前技術文獻]  [專利文獻]Patent Document 2 describes that by using a photosensitive composition containing an acrylic resin having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond, the ink repellency is also good after UV (Ultra Violet, ultraviolet) cleaning treatment. [Prior technical literature] [Patent literature]

[專利文獻1]日本專利第5353632號公報  [專利文獻2]國際公開第2019/146680號[Patent Document 1] Japanese Patent No. 5353632 [Patent Document 2] International Publication No. 2019/146680

[發明所欲解決之問題][Problem to be solved by the invention]

本發明人等進行研究，結果得知，專利文獻1中所記載之組合物不易進行利用顯影之圖案化而製作阻隔壁。又，當使用專利文獻2中所記載之組合物形成阻隔壁，藉由噴墨法將油墨塗佈於由阻隔壁所圍成之區域中時，有時油墨不易潤濕擴散。As a result of studies by the present inventors, it was found that the composition described in Patent Document 1 is not easily patterned by image development to produce barrier ribs. Also, when barrier ribs are formed using the composition described in Patent Document 2, and ink is applied to a region surrounded by the barrier ribs by an inkjet method, the ink may not easily wet and spread.

因此，本發明之目的在於提供一種能夠同時實現充分之撥液性與噴墨塗佈性之感光性樹脂組合物。  又，本發明提供一種使感光性樹脂組合物硬化而成之硬化物、包含硬化物之阻隔壁、具備阻隔壁之有機電致發光元件、具備阻隔壁之彩色濾光器、以及包含有機電致發光元件之圖像顯示裝置及包含彩色濾光器之圖像顯示裝置。  [解決問題之技術手段]Therefore, an object of the present invention is to provide a photosensitive resin composition capable of simultaneously achieving sufficient liquid repellency and inkjet coating properties. Also, the present invention provides a cured product obtained by curing the photosensitive resin composition, a barrier rib comprising the cured product, an organic electroluminescence element having a barrier rib, a color filter having a barrier rib, and an organic electroluminescence element comprising a barrier rib. An image display device of a light-emitting element and an image display device including a color filter. [Technical means to solve problems]

本發明人等進行努力研究，結果發現藉由組合使用特定共聚物、鹼可溶性樹脂及光聚合性化合物，可解決上述課題，從而完成本發明。  即，本發明之主旨如下所述。As a result of earnest research, the inventors of the present invention found that the above-mentioned problems can be solved by using a specific copolymer, an alkali-soluble resin, and a photopolymerizable compound in combination, and completed the present invention. That is, the gist of the present invention is as follows.

[1]一種感光性樹脂組合物，其係含有(A)共聚物、(B)鹼可溶性樹脂及(D)光聚合性化合物者，且  上述(A)共聚物含有下述單體(a1)及下述單體(a2)作為構成單體。  單體(a1)：具有藉由照射活性能量線而產生自由基之活性基之單體  單體(a2)：具有氟原子及/或矽原子之單體  [2]如[1]之感光性樹脂組合物，其中上述單體(a2)係具有氟原子之單體。  [3]如[2]之感光性樹脂組合物，其中上述單體(a2)係具有氟烷基之單體。  [4]如[3]之感光性樹脂組合物，其中上述單體(a2)係具有下述式(1)所表示之基之單體。  -CFXR f・・・式(1)  (式(1)中，X為氫原子、氟原子或三氟甲基，R f為可具有醚性氧原子之碳數1以上且20以下之氟烷基、或氟原子)  [5]如[1]至[4]中任一項之感光性樹脂組合物，其中上述(A)共聚物中之氟原子含量為5～40質量%。  [6]如[1]至[5]中任一項之感光性樹脂組合物，其中上述單體(a1)中之活性基為選自由二苯甲酮基、苯乙酮基、α-羥基酮基、α-胺基酮基、α-二酮基及α-二酮二烷基縮醛基所組成之群中之一種以上。  [7]如[1]至[6]中任一項之感光性樹脂組合物，其進而含有(C)光聚合起始劑。  [8]如[1]至[7]中任一項之感光性樹脂組合物，其進而含有(E)著色劑。  [9]如[1]至[8]中任一項之感光性樹脂組合物，其用於形成阻隔壁。  [10]一種硬化物，其係使如[1]至[9]中任一項之感光性樹脂組合物硬化而成。  [11]一種阻隔壁，其包含如[10]之硬化物。  [12]一種有機電致發光元件，其具備如[11]之阻隔壁。  [13]一種彩色濾光器，其包含發光性奈米晶粒，且具備如[11]之阻隔壁。  [14]一種圖像顯示裝置，其包含如[12]之有機電致發光元件。  [15]一種圖像顯示裝置，其包含如[13]之彩色濾光器。  [發明之效果] [1] A photosensitive resin composition comprising (A) a copolymer, (B) an alkali-soluble resin, and (D) a photopolymerizable compound, wherein the (A) copolymer contains the following monomer (a1) And the following monomer (a2) is used as a constituent monomer. Monomer (a1): a monomer having active radicals that generate free radicals by irradiating active energy rays Monomer (a2): a monomer having a fluorine atom and/or a silicon atom [2] as in [1] A resin composition wherein the above-mentioned monomer (a2) is a monomer having a fluorine atom. [3] The photosensitive resin composition according to [2], wherein the monomer (a2) is a monomer having a fluoroalkyl group. [4] The photosensitive resin composition according to [3], wherein the monomer (a2) is a monomer having a group represented by the following formula (1). -CFXR f・・・Formula (1) (In formula (1), X is a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R f is a halothane with a carbon number of 1 to 20 that may have an etheric oxygen atom group, or fluorine atom) [5] The photosensitive resin composition according to any one of [1] to [4], wherein the fluorine atom content in the above-mentioned (A) copolymer is 5 to 40% by mass. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the active group in the above-mentioned monomer (a1) is selected from the group consisting of benzophenone group, acetophenone group, and α-hydroxyl group. One or more of the group consisting of ketone group, α-aminoketone group, α-diketone group and α-diketone dialkyl acetal group. [7] The photosensitive resin composition according to any one of [1] to [6], which further contains (C) a photopolymerization initiator. [8] The photosensitive resin composition according to any one of [1] to [7], which further contains (E) a colorant. [9] The photosensitive resin composition according to any one of [1] to [8], which is used for barrier rib formation. [10] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [9]. [11] A barrier rib comprising the hardened product according to [10]. [12] An organic electroluminescent device comprising the barrier rib according to [11]. [13] A color filter comprising luminescent nanocrystal grains and having barrier walls as described in [11]. [14] An image display device comprising the organic electroluminescent element according to [12]. [15] An image display device comprising the color filter of [13]. [Effect of Invention]

藉由本發明，可提供一種能夠同時實現充分之撥液性與噴墨塗佈性之感光性樹脂組合物。According to the present invention, it is possible to provide a photosensitive resin composition capable of simultaneously achieving sufficient liquid repellency and inkjet coating properties.

以下，詳細地說明本發明。以下記載為本發明之實施方式之一例，本發明只要不超出其主旨，則並不特定為該等。  於本發明中，「(甲基)丙烯酸」意指「丙烯酸及/或甲基丙烯酸」。  於本發明中，「全部固形物成分」意指感光性樹脂組合物中之溶劑以外之全部成分，溶劑以外之成分即便於常溫下為液體，其成分亦不含於溶劑中，而包含於全部固形物成分中。  於本發明中，使用「～」表示之數值範圍意指包含「～」前後所記載之數值作為下限值及上限值之範圍。  於本發明中，「A及/或B」意指A及B之一者或兩者，具體而言，意指A、B、或A及B。  於本發明中，「(共)聚合物」意指包含均聚物(homopolymer)與共聚物(copolymer)兩者，又，「多元酸(酸酐)」意指「多元酸及/或多元酸酐」。  於本發明中，重量平均分子量意指利用GPC(凝膠滲透層析法)之聚苯乙烯換算之重量平均分子量(Mw)。  於本發明中，酸值表示有效固形物成分換算之酸值，係藉由中和滴定算出。Hereinafter, the present invention will be described in detail. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these unless the gist is exceeded. In the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid". In the present invention, "total solid content" means all the components in the photosensitive resin composition except the solvent. Even if the components other than the solvent are liquid at normal temperature, their components are not included in the solvent, but included in the entire in the solid content. In the present invention, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present invention, "A and/or B" means one or both of A and B, specifically, A, B, or A and B. In the present invention, "(co)polymer" means both homopolymer (homopolymer) and copolymer (copolymer), and "polyacid (anhydride)" means "polyacid and/or polyanhydride" . In the present invention, the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography). In the present invention, the acid value represents the acid value in terms of effective solid content, which is calculated by neutralization titration.

於本發明中，阻隔壁材係指隔牆材、壁材、屏障材，同樣地，阻隔壁係指隔牆、壁、屏障。  於本發明中，發光部(像素部)係指於施加電能之情形時放出光之部分。In the present invention, barrier wall materials refer to partition wall materials, wall materials, and barrier materials, and similarly, barrier wall materials refer to partition walls, walls, and barriers. In the present invention, a light-emitting portion (pixel portion) refers to a portion that emits light when electric energy is applied.

[1]感光性樹脂組合物  本發明之感光性樹脂組合物含有(A)共聚物、(B)鹼可溶性樹脂、及(D)光聚合性化合物，且(A)共聚物含有下述單體(a1)及單體(a2)作為構成單體。本發明之感光性樹脂組合物亦可視需要進而含有其他成分，例如亦可含有(C)光聚合起始劑、(E)著色劑、(F)鏈轉移劑等。[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) copolymer, (B) alkali-soluble resin, and (D) photopolymerizable compound, and (A) copolymer contains the following monomers (a1) and monomer (a2) serve as constituent monomers. The photosensitive resin composition of this invention may further contain other components as needed, for example, (C) photopolymerization initiator, (E) coloring agent, (F) chain transfer agent etc. may be contained.

於本發明中，阻隔壁例如係於主動驅動型有機電致發光元件中用於劃分功能層(有機層、發光部)者，例如係用於藉由向所劃分之區域(像素區域) 噴出作為用以構成功能層之材料之油墨並進行乾燥，形成包含功能層及阻隔壁之像素者。In the present invention, the barrier rib is used, for example, to divide the functional layer (organic layer, light-emitting part) in the active-driven organic electroluminescent element, for example, it is used to spray the divided region (pixel region) as The ink used to form the material of the functional layer is dried to form a pixel including the functional layer and barrier ribs.

[1-1]感光性樹脂組合物之成分及組成  本發明之感光性樹脂組合物含有(A)共聚物、(B)鹼可溶性樹脂及(D)光聚合性化合物。[1-1] Components and composition of the photosensitive resin composition The photosensitive resin composition of the present invention contains (A) a copolymer, (B) an alkali-soluble resin, and (D) a photopolymerizable compound.

[1-1-1](A)成分；共聚物  本發明之(A)共聚物含有以下單體(a1)及單體(a2)作為構成單體。即，本發明之(A)共聚物含有來自單體(a1)之結構單元及來自單體(a2)之結構單元。  單體(a1)：具有藉由照射活性能量線而產生自由基之活性基之單體  單體(a2)：具有氟原子及/或矽原子之單體  於使用本發明之感光性樹脂組合物形成阻隔壁之情形時，若對塗佈有感光性樹脂組合物之塗膜照射活性能量線，則自(A)共聚物之活性基產生自由基，以所產生之自由基為起點，與(D)光聚合性化合物進行聚合反應，故認為(A)共聚物容易固定化於塗膜表面附近。其結果為，即便經過將曝光後之塗膜顯影之步驟，亦可維持阻隔壁上表面之撥液性，因此認為於使用噴墨法，將油墨塗佈於由阻隔壁所圍成之區域例如像素部時，可抑制鄰接之像素部間之混色之產生。[1-1-1] Component (A); Copolymer The (A) copolymer of the present invention contains the following monomer (a1) and monomer (a2) as constituent monomers. That is, (A) copolymer of this invention contains the structural unit derived from the monomer (a1) and the structural unit derived from the monomer (a2). Monomer (a1): a monomer having active radicals that generate free radicals by irradiating active energy rays Monomer (a2): a monomer having a fluorine atom and/or a silicon atom Used in the photosensitive resin composition of the present invention In the case of forming a barrier wall, when active energy rays are irradiated to the coating film coated with the photosensitive resin composition, free radicals are generated from the active radicals of the (A) copolymer, and starting from the generated free radicals, and ( D) Since the photopolymerizable compound proceeds to a polymerization reaction, it is considered that the (A) copolymer is easily immobilized near the surface of the coating film. As a result, even after the step of developing the exposed coating film, the liquid repellency of the upper surface of the barrier ribs can be maintained. Therefore, it is considered that when using the inkjet method, the ink is applied to the area surrounded by the barrier ribs, such as In the case of a pixel portion, the occurrence of color mixture between adjacent pixel portions can be suppressed.

[單體(a1)]  單體(a1)係具有藉由照射活性能量線而產生自由基之活性基(以下，亦簡稱為「活性基」)之單體。除了活性基以外，單體(a1)還進而具有用以使各單體共聚之自由基聚合性基。[Monomer (a1)] The monomer (a1) is a monomer having an active group (hereinafter also simply referred to as "active group") that generates free radicals by irradiation with active energy rays. The monomer (a1) further has a radical polymerizable group for copolymerizing each monomer in addition to the active group.

作為單體(a1)之活性基，只要係具有藉由照射活性能量線而產生自由基之結構(具有光聚合起始性之結構)者即可。作為具有光聚合起始性之結構，可採用公知之各種結構，例如可例舉：奪氫型、電子轉移型、分子內裂解型。  作為活性基，例如可例舉：二苯甲酮基、苯乙酮基、安息香基、α-羥基酮基(例如自1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙酮之「2-羥基乙氧基中之羥基」中去除1個氫原子所得之基)、α-胺基酮基、α-二酮基、α-二酮二烷基縮醛基、蒽醌基、9-氧硫𠮿

Figure 111103644-A0304-1
基、氧膦基。從自由基產生效率較高方面出發，較佳為二苯甲酮基、苯乙酮基、α-羥基酮基、α-胺基酮基、α-二酮基、α-二酮二烷基縮醛基，更佳為二苯甲酮基、苯乙酮基、α-羥基酮基，尤佳為α-羥基酮基。As an active group of a monomer (a1), what is necessary is just what has the structure which generate|occur|produces a radical by irradiating an active energy ray (the structure which has photopolymerization initiation property). As the structure having photopolymerization initiation properties, various known structures can be employed, for example, hydrogen abstraction type, electron transfer type, and intramolecular cleavage type. As the active group, for example, benzophenone group, acetophenone group, benzoin group, α-hydroxyketone group (for example, from 1-[4-(2-hydroxyethoxy)-phenyl]-2 -Hydroxy-2-methyl-1-propanone The group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy group"), α-aminoketone group, α-diketone group, α-diketone group Ketone dialkyl acetal group, anthraquinone group, 9-oxothiol
Figure 111103644-A0304-1
base, phosphinyl group. From the aspect of high free radical generation efficiency, benzophenone group, acetophenone group, α-hydroxy ketone group, α-amino ketone group, α-diketone group, α-diketone dialkyl group are preferred The acetal group is more preferably a benzophenone group, an acetophenone group, and an α-hydroxyketone group, and is especially preferably an α-hydroxyketone group.

作為單體(a1)所具有之自由基聚合性基，可例舉包含自由基聚合性不飽和鍵(碳-碳雙鍵等)之官能基，例如可例舉(甲基)丙烯醯基、乙烯基。The radical polymerizable group contained in the monomer (a1) may, for example, be a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), for example, a (meth)acryl group, vinyl.

作為單體(a1)，從(A)共聚物之合成容易性、活性基導入量之調整容易性之觀點出發，較佳為具有活性基之(甲基)丙烯酸酯。  作為單體(a1)，例如可例舉：4-甲基丙烯醯氧基二苯甲酮、甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯，較佳為甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯。  單體(a1)可單獨使用一種，亦可併用兩種以上。The monomer (a1) is preferably a (meth)acrylate having an active group from the viewpoint of easiness of synthesis of the (A) copolymer and easiness of adjustment of the amount of active group introduced. Examples of the monomer (a1) include: 4-methacryloxybenzophenone, methacrylic acid 2-[4-(2-hydroxy-2-methyl-1-oxopropyl) Phenoxy]ethyl ester, preferably 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate. The monomer (a1) may be used alone or in combination of two or more.

[單體(a2)]  單體(a2)係具有氟原子及/或矽原子之單體。除了氟原子及/或矽原子以外，單體(a2)還進而具有用以使各單體共聚之自由基聚合性基。單體(a2)之自由基聚合性基與單體(a1)之自由基聚合性基同樣。[Monomer (a2)] The monomer (a2) is a monomer having a fluorine atom and/or a silicon atom. The monomer (a2) further has a radical polymerizable group for copolymerizing each monomer in addition to the fluorine atom and/or the silicon atom. The radical polymerizable group of the monomer (a2) is the same as that of the monomer (a1).

基於單體(a2)之單元對硬化物賦予撥水性及撥油性之至少一種，有助於硬化物之撥液性。  若(A)共聚物具有基於單體(a2)之單元，則於形成感光性樹脂組合物之塗膜時，(A)共聚物容易偏析於塗膜表面側。若(A)共聚物偏析於塗膜表面側，則塗膜表面側之基於單體(a2)之單元之濃度增高，可高效率地對硬化物表面賦予撥液性。The unit based on the monomer (a2) imparts at least one of water repellency and oil repellency to the cured product, and contributes to the liquid repellency of the cured product. If the (A) copolymer has a unit based on the monomer (a2), when forming a coating film of the photosensitive resin composition, the (A) copolymer is likely to segregate on the surface side of the coating film. When the (A) copolymer is segregated on the surface of the coating film, the concentration of units derived from the monomer (a2) on the surface of the coating film increases, and liquid repellency can be efficiently imparted to the surface of the cured product.

藉由(A)共聚物偏析於塗膜表面側，塗膜表面側之活性基之濃度增高，於照射活性能量線時，自(A)共聚物之活性基產生自由基，以所產生之自由基為起點，與(D)光聚合性化合物進行聚合反應，故認為(A)共聚物容易固定化於塗膜表面附近。其結果為，即便經過將曝光後之塗膜顯影之步驟，亦可維持阻隔壁上表面之撥液性，因此認為於使用噴墨法，將油墨塗佈於由阻隔壁所圍成之區域例如像素部時，可抑制鄰接之像素部間之混色之產生。  塗膜之硬化度可藉由感光性樹脂組合物中之自由基聚合性基的量及活性基之量、即，(A)共聚物及(C)光聚合起始劑之量或製版時之曝光量等進行調整。By segregating the (A) copolymer on the surface side of the coating film, the concentration of active groups on the surface side of the coating film increases, and when irradiating active energy rays, free radicals are generated from the active radicals of the (A) copolymer, and the generated free radicals Since the polymerization reaction proceeds with the (D) photopolymerizable compound as a starting point, the (A) copolymer is considered to be easily immobilized near the surface of the coating film. As a result, even after the step of developing the exposed coating film, the liquid repellency of the upper surface of the barrier ribs can be maintained. Therefore, it is considered that when using the inkjet method, the ink is applied to the area surrounded by the barrier ribs, such as In the case of a pixel portion, the occurrence of color mixture between adjacent pixel portions can be suppressed. The degree of hardening of the coating film can be determined by the amount of radically polymerizable groups and the amount of active groups in the photosensitive resin composition, that is, the amount of (A) copolymer and (C) photopolymerization initiator or the amount of Adjust the exposure, etc.

從撥液性之觀點出發，單體(a2)較佳為具有氟原子。只要具有氟原子，則其結構並無特別限定，例如較佳為包含選自具有氟烷基之單體及具有氟伸烷基之單體中的一種以上。從藉由熱分解產生之成分之揮發性成分較少、合成時不生成易凝膠方面出發，更佳為具有氟烷基之單體。From the viewpoint of liquid repellency, the monomer (a2) preferably has a fluorine atom. The structure is not particularly limited as long as it has a fluorine atom. For example, it preferably contains at least one selected from monomers having a fluoroalkyl group and monomers having a fluoroalkylene group. A monomer having a fluoroalkyl group is more preferable in terms of less volatile components of the components produced by thermal decomposition and no easy gel formation during synthesis.

作為單體(a2)中之氟烷基，較佳為具有下述通式(1)所表示之結構。  -CFXR f・・・式(1)  (式(1)中，X為氫原子、氟原子或三氟甲基，R f為可具有醚性氧原子之碳數1以上且20以下之氟烷基、或氟原子) The fluoroalkyl group in the monomer (a2) preferably has a structure represented by the following general formula (1). -CFXR f・・・Formula (1) (In formula (1), X is a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R f is a halothane with a carbon number of 1 to 20 that may have an etheric oxygen atom group, or fluorine atom)

式(1)中之R f之碳數為1以上，較佳為2以上，更佳為3以上，進而較佳為5以上，又，為20以下，較佳為10以下，更佳為6以下。藉由設為下限值以上，有表現出撥液性之傾向。又，藉由設為上限值以下，有改善與構成感光性樹脂組合物之其他成分之相溶性之傾向。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為2～20，進而較佳為3～10，尤佳為5～6。 The carbon number of R f in the formula (1) is 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and is 20 or less, preferably 10 or less, more preferably 6 the following. By making it more than the lower limit, liquid repellency tends to be expressed. Moreover, there exists a tendency for the compatibility with the other component which comprises a photosensitive resin composition to improve by making it below an upper limit. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 2-20, further preferably 3-10, especially preferably 5-6.

作為具有氟烷基與自由基聚合性基之化合物，例如可例舉具有氟烷基之(甲基)丙烯酸酯，作為具有氟烷基之(甲基)丙烯酸酯，更佳為具有全氟烷基之(甲基)丙烯酸酯。As a compound having a fluoroalkyl group and a radically polymerizable group, for example, a (meth)acrylate having a fluoroalkyl group is exemplified. As a (meth)acrylate having a fluoroalkyl group, a perfluoroalkyl group is more preferable. Based (meth)acrylate.

作為含有氟烷基之(甲基)丙烯酸酯，例如可例舉：丙烯酸2,2,2-三氟乙酯(大阪有機化學工業公司製造，Viscoat 3F)、丙烯酸2,2,3,3-四氟丙酯(大阪有機化學工業公司製造，Viscoat 4F)、丙烯酸1H,1H,5H-八氟戊酯(大阪有機化學工業公司製造，Viscoat 8F)、甲基丙烯酸1H,1H,5H-八氟戊酯(大阪有機化學工業公司製造，Viscoat 8FM)、丙烯酸1H,1H,2H,2H-十三氟辛酯(大阪有機化學工業公司製造，Viscoat 13F)、丙烯酸1H,1H,2H,2H-九氟己酯(Unimatec公司製造，CHEMINOX FAAC-4)、甲基丙烯酸1H,1H,2H,2H-九氟己酯(Unimatec公司製造，CHEMINOX FAMAC-4)、甲基丙烯酸1H,1H,2H,2H-十三氟辛酯(Unimatec公司製造，CHEMINOX FAMAC-6)。Examples of fluoroalkyl-containing (meth)acrylates include 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 3F), 2,2,3,3- Tetrafluoropropyl ester (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 4F), 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8F), 1H,1H,5H-octafluoromethacrylate Amyl ester (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 8FM), 1H, 1H, 2H, 2H-tridecylfluorooctyl (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat 13F), acrylate 1H, 1H, 2H, 2H-nine Fluorohexyl ester (manufactured by Unimatec, CHEMINOX FAAC-4), 1H,1H,2H,2H-nonafluorohexyl methacrylate (manufactured by Unimatec, CHEMINOX FAMAC-4), 1H,1H,2H,2H methacrylate -Tridecafluorooctyl (manufactured by Unimatec, CHEMINOX FAMAC-6).

作為單體(a2)中之氟伸烷基，並無特別限定，例如可例舉：-CF 2-O-、-(CF 2) 2-O-、-(CF 2) 3-O-、-CF 2-C(CF 3)O-、-C(CF 3)-CF 2-O-及具有該等重複單元之二價基。其中，從相溶性之觀點出發，較佳為具有氟伸烷基醚鏈。  作為具有氟伸烷基與自由基聚合性基之化合物，例如可例舉以下單體。 The fluoroalkylene group in the monomer (a2) is not particularly limited, and examples thereof include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O-, -C(CF 3 )-CF 2 -O- and divalent groups having these repeating units. Among these, it is preferable to have a fluoroalkylene ether chain from the viewpoint of compatibility. Examples of the compound having a fluoroalkylene group and a radical polymerizable group include the following monomers.

[化1]

Figure 02_image001
[chemical 1]
Figure 02_image001

上述式中，PFPE表示全氟伸烷基聚醚鏈。  單體(a2)可單獨使用一種，亦可併用兩種以上。In the above formula, PFPE represents a perfluoroalkylene polyether chain. The monomer (a2) may be used alone or in combination of two or more.

[單體(a3)]  (A)共聚物亦可進而含有具有氫供與性官能基之單體(a3)作為構成單體。除了氫供與性官能基以外，單體(a3)還進而具有用以使各單體共聚之自由基聚合性基。單體(a3)之自由基聚合性基與單體(a1)之自由基聚合性基同樣。  尤其是於單體(a1)具有奪氫型活性基之情形時，較佳為包含基於單體(a3)之單元。若(A)共聚物具有基於單體(a3)之單元，則有可抑制由來自感光性樹脂組合物之塗膜表面之氧所引起之聚合抑制，可有效地進行塗膜之硬化，使其容易地表現出撥液性之傾向。  作為氫供與性官能基，例如可例舉：羥基、胺基、巰基、醯胺基。從有效率地進行硬化反應，與氧自由基之反應性較高之觀點出發，較佳為羥基、胺基、醯胺基。[Monomer (a3)] (A) The copolymer may further contain a monomer (a3) having a hydrogen donating functional group as a constituent monomer. The monomer (a3) further has a radical polymerizable group for copolymerizing each monomer in addition to the hydrogen donating functional group. The radical polymerizable group of the monomer (a3) is the same as the radical polymerizable group of the monomer (a1). Especially when the monomer (a1) has a hydrogen abstraction type active group, it is preferred to include a unit based on the monomer (a3). If the (A) copolymer has a unit based on the monomer (a3), it can suppress polymerization inhibition caused by oxygen from the surface of the coating film of the photosensitive resin composition, and can effectively harden the coating film, making it Easily exhibit liquid-diaphoric tendencies. The hydrogen donating functional group includes, for example, a hydroxyl group, an amino group, a mercapto group, and an amide group. From the viewpoint of efficient hardening reaction and high reactivity with oxygen radicals, hydroxyl groups, amino groups, and amido groups are preferred.

作為單體(a3)，從化合物之合成容易性與氫供與性官能基導入量之調整容易性之觀點出發，較佳為具有氫供與性官能基之(甲基)丙烯酸酯或(甲基)丙烯醯胺類。The monomer (a3) is preferably (meth)acrylate or (meth)acrylate having a hydrogen-donating functional group from the viewpoint of the ease of synthesis of the compound and the ease of adjustment of the amount of hydrogen-donating functional group introduced. base) acrylamides.

作為單體(a3)，例如可例舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、反丁烯二酸單丁基羥酯、伊康酸單丁基羥酯等含羥基單體；N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-乙烯基己內醯胺、N-乙烯基吡咯啶酮、N-異丙基(甲基)丙烯醯胺、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸2-[(丁基胺基)羰基]氧基]乙酯、N,N-二甲基胺基丙基(甲基)丙烯醯胺、N,N-二乙基胺基丙基(甲基)丙烯醯胺、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、(甲基)丙烯酸N,N-二乙基胺基丙酯、N,N-二甲基胺基乙基(甲基)丙烯醯胺、N,N-二乙基胺基乙基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、乙烯基乙醯胺等含胺基或醯胺基單體。從於與活性基之併用中硬化促進效果優異方面出發，較佳為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(N,N-二甲基丙烯醯胺、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯，從可抑制由氧所引起之聚合抑制，可有效地進行硬化，使其容易地表現出撥液性之觀點出發，更佳為(甲基)丙烯酸N,N-二乙基胺基乙酯。  單體(a3)可單獨使用一種，亦可併用兩種以上。Examples of the monomer (a3) include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 6-Hydroxyhexyl, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-Hydroxylauryl (meth)acrylate, Monobutyl Hydroxy Fumarate, Hydroxyl-containing monomers such as monobutyl hydroxy itaconate; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-vinylcaprolactone Amide, N-vinylpyrrolidone, N-isopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, 2-[(meth)acrylate Butylamino)carbonyl]oxy]ethyl ester, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide , N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate Esters, N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, (meth)acrylmorpholine, Amino or amido-containing monomers such as vinyl acetamide. From the viewpoint of excellent hardening accelerating effect in combination with an active group, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferable. , (N,N-Dimethacrylamide, N,N-Dimethylaminoethyl (meth)acrylate, N,N-Diethylaminoethyl (meth)acrylate, can inhibit From the point of view that the polymerization inhibition caused by oxygen can be effectively cured to easily exhibit liquid repellency, N,N-diethylaminoethyl (meth)acrylate is more preferable. Monomer ( a3) One type may be used alone, or two or more types may be used in combination.

[單體(a4)]  從使(A)共聚物更有效地偏析於塗膜表面之觀點出發，(A)共聚物亦可進而含有具有碳數4以上之烷基之單體(a4)作為構成單體。除了碳數4以上之烷基以外，單體(a4)還進而具有用以使各單體共聚之自由基聚合性基。單體(a4)之自由基聚合性基與單體(a1)之自由基聚合性基同樣。[Monomer (a4)] From the viewpoint of making the (A) copolymer segregate more effectively on the surface of the coating film, the (A) copolymer may further contain a monomer (a4) having an alkyl group having 4 or more carbon atoms as form a monomer. The monomer (a4) further has a radical polymerizable group for copolymerizing each monomer in addition to the alkyl group having 4 or more carbon atoms. The radical polymerizable group of the monomer (a4) is the same as that of the monomer (a1).

碳數4以上之烷基可為直鏈狀、支鏈狀、環狀中之任一種。環狀烷基可為單環式，亦可為多環式。從使(A)共聚物更有效地偏析於塗膜表面之觀點出發，烷基較佳為直鏈狀。  從使(A)共聚物更有效地偏析於塗膜表面之觀點出發，碳數4以上之烷基之碳數較佳為4～30，更佳為6～20，進而較佳為6～18。The alkyl group having 4 or more carbon atoms may be linear, branched or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. The alkyl group is preferably linear from the viewpoint of more effectively segregating the (A) copolymer on the surface of the coating film. From the viewpoint of making the (A) copolymer segregate more effectively on the surface of the coating film, the carbon number of the alkyl group having 4 or more carbon atoms is preferably 4-30, more preferably 6-20, and still more preferably 6-18 .

作為單體(a4)，可例舉具有碳數4以上之烷基與自由基聚合性基之化合物，從化合物之合成容易性與碳數4以上之烷基導入量之調整容易性的觀點出發，較佳為具有碳數4以上之烷基之(甲基)丙烯酸烷基酯。  作為單體(a4)，例如可例舉：(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸二環戊烯氧基乙酯、三環癸烷(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸金剛烷基酯，較佳為包含具有直鏈狀之碳數4以上之烷基之(甲基)丙烯酸烷基酯。作為具有直鏈狀之碳數4以上之烷基之(甲基)丙烯酸烷基酯，例如，若考慮製造容易性，則更佳為(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸硬脂酯，尤佳為(甲基)丙烯酸硬脂酯。  單體(a4)可單獨使用一種，亦可併用兩種以上。The monomer (a4) may, for example, be a compound having an alkyl group having 4 or more carbon atoms and a radically polymerizable group. From the viewpoint of ease of compound synthesis and ease of adjustment of the amount of alkyl group having 4 or more carbon atoms introduced , preferably an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms. Examples of the monomer (a4) include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, ( Decyl Methacrylate, Isodecyl (Meth)acrylate, Lauryl (Meth)acrylate, Myristyl (Meth)acrylate, Cetyl (Meth)acrylate, (Meth)acrylic acid Stearyl, Isostearyl (meth)acrylate, Tridecyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Tricyclodecane (meth)acrylate, Dicyclopentyl (meth)acrylate, isomethacrylate (meth)acrylate, and adamantyl (meth)acrylate are preferably (meth) containing an alkyl group having a straight chain of 4 or more carbon atoms. Alkyl acrylate. As the alkyl (meth)acrylate having a straight-chain alkyl group having 4 or more carbon atoms, for example, 2-ethylhexyl (meth)acrylate, (methyl ) octyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, especially stearyl (meth)acrylate. The monomer (a4) may be used alone or in combination of two or more.

(A)共聚物亦可視需要進而具有基於單體(a1)、單體(a2)、單體(a3)及單體(a4)以外之其他單體之單元作為構成單體。作為其他單體，例如可例舉具有自由基聚合性基，且不具有活性基、碳數4以上之烷基、氟原子及氫供與性官能基之化合物。  作為其他單體，例如可例舉：丙烯酸、甲基丙烯酸、丁烯酸、伊康酸、反丁烯二酸、順丁烯二酸、檸康酸等含羧基單體及該等之鹽；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯等(甲基)丙烯酸酯；(甲基)丙烯腈等含氮單體；苯乙烯、α-甲基苯乙烯、二乙烯苯、乙烯基甲苯等苯乙烯系化合物、丙酸乙烯酯、乙酸乙烯酯等乙烯酯；含磷乙烯基系單體；氯乙烯、偏二氯乙烯等鹵化乙烯；丁二烯等共軛二烯。(A) The copolymer may further have units derived from monomers other than monomer (a1), monomer (a2), monomer (a3) and monomer (a4) as constituent monomers, if necessary. Examples of other monomers include compounds having a radical polymerizable group and not having an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, and a hydrogen-donating functional group. Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and their salts; (Meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene, α-methyl Styrene compounds such as styrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and vinylidene chloride; butadiene and other conjugated dienes.

活性基可存在於(A)共聚物之主鏈之末端，亦可存在於基於構成(A)共聚物之單體(monomer)之單元中。  (A)共聚物較佳為於分子中具有複數個活性基。藉此，有可提高塗膜表面附近之活性基之濃度之傾向。  (A)共聚物之每1 g之活性基之含量較佳為0.1 mmol/g以上，更佳為0.5 mmol/g以上，進而較佳為0.8 mmol/g以上，又，較佳為2.5 mmol/g以下，更佳為2.0 mmol/g以下。若活性基之含量為上述範圍之下限值以上，則有硬化性更優異，可表現出較高撥液性之傾向。又，若為上限值以下，則有感光性樹脂組合物之儲存穩定性更優異之傾向。上述上限及下限可任意地組合，例如，較佳為0.1～2.5 mmol/g，更佳為0.5～2.5 mmol/g，進而較佳為0.8～2.0 mmol/g。The active group may exist at the terminal of the main chain of (A) copolymer, and may exist in the unit based on the monomer (monomer) which comprises (A) copolymer. (A) The copolymer preferably has a plurality of active groups in the molecule. This tends to increase the concentration of active groups near the surface of the coating film. (A) The active group content per 1 g of the copolymer is preferably at least 0.1 mmol/g, more preferably at least 0.5 mmol/g, still more preferably at least 0.8 mmol/g, and more preferably at least 2.5 mmol/g g or less, more preferably 2.0 mmol/g or less. When the content of the active group is more than the lower limit of the above range, the curability is more excellent, and it tends to exhibit higher liquid repellency. Moreover, there exists a tendency for the storage stability of a photosensitive resin composition to be more excellent as it is below an upper limit. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 0.1-2.5 mmol/g, more preferably 0.5-2.5 mmol/g, still more preferably 0.8-2.0 mmol/g.

基於單體(a1)之單元相對於構成(A)共聚物之全部單元之合計質量的比率較佳為1質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，尤佳為30質量%以上，又，較佳為99質量%以下，更佳為90質量%以下，進而較佳為80質量%以下，更進而較佳為70質量%以下，尤佳為60質量%以下。上述上限及下限可任意地組合，例如，較佳為1～99質量%，更佳為10～90質量%，進而較佳為20～80質量%，更進而較佳為30～70質量%，尤佳為30～60質量%。若基於單體(a1)之單元之比率為上述範圍之下限值以上，則有硬化性更優異，可表現出較高撥液性之傾向。若為上限值以下，則有感光性樹脂組合物之保存穩定性更優異之傾向。The ratio of the unit based on the monomer (a1) to the total mass of all units constituting the (A) copolymer is preferably at least 1% by mass, more preferably at least 10% by mass, still more preferably at least 20% by mass, especially Preferably at least 30% by mass, more preferably at most 99% by mass, more preferably at most 90% by mass, further preferably at most 80% by mass, still more preferably at most 70% by mass, especially preferably at most 60% by mass the following. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-99 mass %, more preferably 10-90 mass %, further preferably 20-80 mass %, still more preferably 30-70 mass %, Most preferably, it is 30-60 mass %. When the ratio of the unit based on a monomer (a1) is more than the lower limit of the said range, it will become more excellent in curability, and it will tend to express a high liquid repellency. There exists a tendency for the storage stability of a photosensitive resin composition to be more excellent as it is below an upper limit.

基於單體(a2)之單元相對於構成(A)共聚物之全部單元之合計質量的比率例如為1質量%以上，較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上，更進而較佳為20質量%以上，尤佳為25質量%。又，較佳為70質量%以下，更佳為60質量%以下，進而較佳為50質量%以下。上述上限及下限可任意地組合，例如，較佳為1～70質量%，更佳為5～60質量%，進而較佳為10～50質量%，更進而較佳為15～50質量%，尤佳為20～50質量%，極佳為25～50質量%。若基於單體(a2)之單元之比率為上述範圍之下限值以上，則有可更有效地表現出撥液性之傾向。若為上限值以下，則有(A)共聚物與(D)光聚合性化合物之相溶性更優異之傾向。The ratio of the unit based on the monomer (a2) to the total mass of all units constituting the (A) copolymer is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably It is 15 mass % or more, More preferably, it is 20 mass % or more, Especially preferably, it is 25 mass %. Moreover, it is preferably 70 mass % or less, more preferably 60 mass % or less, and still more preferably 50 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-70 mass %, more preferably 5-60 mass %, further preferably 10-50 mass %, still more preferably 15-50 mass %, Especially preferably, it is 20-50 mass %, Most preferably, it is 25-50 mass %. When the ratio of the unit based on a monomer (a2) is more than the lower limit of the said range, it exists in the tendency which can express liquid repellency more effectively. It exists in the tendency for the compatibility of (A) copolymer and (D) photopolymerizable compound to be more excellent as it is below an upper limit.

相對於基於單體(a1)之單元100質量%，基於單體(a2)之單元相對於基於單體(a1)之單元之比率較佳為10質量%，更佳為30質量%以上，進而較佳為50質量%以上，尤佳為70質量%。又，較佳為500質量%以下，更佳為300質量%以下，進而較佳為100質量%以下。例如，較佳為10～500質量%，更佳為30～300質量%，進而較佳為50～100質量%，更進而較佳為70～100質量%。  若基於單體(a2)之單元相對於基於單體(a1)之單元的比率為上述範圍之下限值以上，則有可表現出較高撥液性之傾向。若為上限值以下，則有以較低之紫外線照射量亦可表現出撥液性之傾向。又，有(A)共聚物與(D)光聚合性化合物之相溶性更優異之傾向。The ratio of the unit based on the monomer (a2) to the unit based on the monomer (a1) is preferably 10 mass %, more preferably 30 mass % or more, with respect to 100 mass % of the unit based on the monomer (a1), and It is preferably at least 50% by mass, particularly preferably 70% by mass. Moreover, it is preferably at most 500 mass %, more preferably at most 300 mass %, and still more preferably at most 100 mass %. For example, it is preferably 10 to 500 mass %, more preferably 30 to 300 mass %, still more preferably 50 to 100 mass %, still more preferably 70 to 100 mass %. If the ratio of the unit based on the monomer (a2) to the unit based on the monomer (a1) is more than the lower limit of the above range, it tends to exhibit a higher liquid repellency. When it is below the upper limit, liquid repellency tends to be expressed even with a relatively low amount of ultraviolet irradiation. Moreover, there exists a tendency for the compatibility of (A) copolymer and (D) photopolymerizable compound to be more excellent.

於(A)共聚物含有單體(a3)作為構成單體之情形時，基於單體(a3)之單元相對於構成(A)共聚物之全部單元之合計質量的比率較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。又，較佳為80質量%以下，更佳為60質量%以下，進而較佳為50質量%以下，尤佳為40質量%以下。上述上限及下限可任意地組合，例如，較佳為1～80質量%，更佳為1～60質量%，進而較佳為3～50質量%，尤佳為5～40質量%。若基於單體(a3)之單元之比率為上述範圍內，則有可更有效地表現出撥液性之傾向。When the (A) copolymer contains the monomer (a3) as a constituent monomer, the ratio of the unit based on the monomer (a3) to the total mass of all units constituting the (A) copolymer is preferably 1% by mass or more, more preferably at least 3% by mass, and still more preferably at least 5% by mass. Moreover, it is preferably at most 80 mass %, more preferably at most 60 mass %, still more preferably at most 50 mass %, particularly preferably at most 40 mass %. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-80 mass%, more preferably 1-60 mass%, further preferably 3-50 mass%, especially preferably 5-40 mass%. When the ratio of the unit based on a monomer (a3) exists in the said range, it exists in the tendency which can express liquid repellency more effectively.

於(A)共聚物含有單體(a4)作為構成單體之情形時，基於單體(a4)之單元相對於構成(A)共聚物之全部單元之合計質量的比率較佳為1質量%以上，更佳為5質量%以上，進而較佳為10質量%以上，更進而較佳為20質量%以上，尤佳為25質量%以上。又，較佳為80質量%以下，更佳為70質量%以下，進而較佳為60質量%以下，尤佳為50質量%以下。上述上限及下限可任意地組合，例如，較佳為1～80質量%，更佳為5～70質量%，進而較佳為10～60質量%，更進而較佳為20～50質量%，尤佳為25～50質量%。若基於單體(a4)之單元之比率為上述範圍內，則有可更有效地表現出撥液性之傾向。When the (A) copolymer contains the monomer (a4) as a constituent monomer, the ratio of the unit based on the monomer (a4) to the total mass of all units constituting the (A) copolymer is preferably 1% by mass Above, more preferably at least 5% by mass, more preferably at least 10% by mass, still more preferably at least 20% by mass, especially preferably at least 25% by mass. Moreover, it is preferably at most 80 mass %, more preferably at most 70 mass %, still more preferably at most 60 mass %, particularly preferably at most 50 mass %. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-80 mass %, more preferably 5-70 mass %, further preferably 10-60 mass %, still more preferably 20-50 mass %, More preferably, it is 25 to 50% by mass. When the ratio of the unit based on a monomer (a4) exists in the said range, it exists in the tendency which can express liquid repellency more effectively.

(A)共聚物中之氟原子含量較佳為5質量%以上，更佳為10質量%以上，進而較佳為12質量%以上，更進而較佳為15質量%以上，尤佳為18質量%以上。又，較佳為40質量%以下，更佳為35質量%以下，進而較佳為30質量%以下。上述上限及下限可任意地組合，例如，較佳為5～40質量%，更佳為10～35質量%，進而較佳為12～35質量%，更進而較佳為15～30質量%，尤佳為18～30質量%。若(A)共聚物中之氟原子含量為上述範圍之下限值以上，則有阻隔壁之上表面之撥液性變高之傾向。又，若為上述範圍之上限值以下，則有與其他材料之相溶性變良好之傾向。(A) The content of fluorine atoms in the copolymer is preferably at least 5% by mass, more preferably at least 10% by mass, further preferably at least 12% by mass, still more preferably at least 15% by mass, particularly preferably at least 18% by mass %above. Moreover, it is preferably 40 mass % or less, more preferably 35 mass % or less, still more preferably 30 mass % or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-40 mass %, more preferably 10-35 mass %, further preferably 12-35 mass %, still more preferably 15-30 mass %, Most preferably, it is 18-30 mass %. When the content of fluorine atoms in the (A) copolymer is more than the lower limit of the above range, the liquid repellency of the upper surface of the barrier rib tends to increase. Moreover, there exists a tendency for the compatibility with other materials to become favorable as it is below the upper limit of the said range.

(A)共聚物之重量平均分子量(Mw)較佳為1000以上，更佳為10000以上，進而較佳為50000以上，更進而較佳為100000以上。又，較佳為500000以下，更佳為300000以下，進而較佳為200000以下。上述上限及下限可任意地組合，例如，較佳為1000～500000，更佳為10000～300000，進而較佳為50000～200000，尤佳為100000～200000。若Mw為上述範圍之下限值以上，則有可更有效地表現出撥液性之傾向。若為上限值以下，則有感光性樹脂組合物之塗佈性更優異之傾向。(A) The weight average molecular weight (Mw) of the copolymer is preferably at least 1,000, more preferably at least 10,000, still more preferably at least 50,000, still more preferably at least 100,000. Moreover, it is preferably 500,000 or less, more preferably 300,000 or less, and still more preferably 200,000 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1,000-500,000, more preferably 10,000-300,000, further preferably 50,000-200,000, especially preferably 100,000-200,000. When Mw is more than the lower limit value of the said range, it exists in the tendency which can express a liquid repellency more effectively. It exists in the tendency for the coating property of a photosensitive resin composition to be more excellent as it is below an upper limit.

(A)共聚物之Mw為藉由凝膠滲透層析法(GPC)測定之標準聚苯乙烯換算之值。詳細測定條件如下述實施例中所記載。(A) Mw of the copolymer is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC). The detailed measurement conditions are as described in the following Examples.

(A)共聚物之玻璃轉移溫度(Tg)較佳為-30℃以上，更佳為0℃以上，進而較佳為25℃以上，又，較佳為180℃以下，更佳為150℃以下，進而較佳為100℃以下。上述上限及下限可任意地組合，例如，較佳為-30～180℃，更佳為0～150℃，進而較佳為25～100℃。若Tg為上述範圍之下限值以上，則有可更有效地表現出撥液性之傾向。若為上限值以下，則有(A)共聚物與(D)光聚合性化合物之相溶性更優異之傾向。(A) The glass transition temperature (Tg) of the copolymer is preferably -30°C or higher, more preferably 0°C or higher, further preferably 25°C or higher, and preferably 180°C or lower, more preferably 150°C or lower , and more preferably below 100°C. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably -30-180°C, more preferably 0-150°C, still more preferably 25-100°C. When Tg is more than the lower limit value of the said range, it exists in the tendency which can express a liquid repellency more effectively. It exists in the tendency for the compatibility of (A) copolymer and (D) photopolymerizable compound to be more excellent as it is below an upper limit.

(A)共聚物例如可藉由使包含單體(a1)及單體(a2)之單體成分聚合所獲得。單體成分亦可視需要進而包含單體(a3)、單體(a4)及其他單體中之任一種以上。(A) The copolymer can be obtained by polymerizing the monomer component containing a monomer (a1) and a monomer (a2), for example. The monomer component may further contain any one or more of monomers (a3), monomers (a4) and other monomers as needed.

單體成分之聚合典型地係於聚合起始劑之存在下進行。聚合時，亦可視需要併用鏈轉移劑。  作為聚合方法，可例舉：溶液聚合、懸浮聚合、塊狀聚合、乳化聚合等公知之方法，其中，從操作較簡便且生產性較高方面出發，較佳為溶液聚合。Polymerization of the monomeric components is typically carried out in the presence of a polymerization initiator. During polymerization, a chain transfer agent may also be used in combination if necessary. The polymerization method may, for example, be known methods such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc. Among them, solution polymerization is preferable in terms of easier operation and higher productivity.

本發明之感光性樹脂組合物中之(A)共聚物之含有比率並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.01質量%以上，更佳為0.05質量%以上，進而較佳為0.1質量%以上，更進而較佳為0.25質量%以上，又，較佳為30質量%以下，更佳為20質量%以下，進而較佳地10質量%以下，更進而較佳為5質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～30質量%，更佳為0.05～20質量%，進而較佳為0.1～10質量%，尤佳為0.25～5質量%。藉由設為上述下限值以上，有撥油墨性提高之傾向。藉由設為上述上限值以下，有與其他成分之相溶性提高之傾向。The content ratio of (A) copolymer in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably 0.01% by mass or more, more preferably 0.05% by mass in the total solid content of the photosensitive resin composition more than 0.1% by mass, more preferably at least 0.25% by mass, more preferably at most 30% by mass, more preferably at most 20% by mass, further preferably at most 10% by mass, and still more preferably at most 0.25% by mass. Preferably it is 5 mass % or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 0.01-30 mass%, more preferably 0.05-20 mass%, further preferably 0.1-10 mass%, especially preferably 0.25-5 mass%. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for the compatibility with other components to improve by making it below the said upper limit.

[1-1-2](B)成分；鹼可溶性樹脂  本發明之感光性樹脂組合物含有(B)鹼可溶性樹脂。作為鹼可溶性樹脂，只要為能夠利用鹼性顯影液進行顯影之樹脂，則並無特別限定。於本發明中，(B)鹼可溶性樹脂係不同於(A)共聚物之成分，於存在相當於(A)共聚物之鹼可溶性樹脂之情形時，係作為(A)共聚物處理。作為鹼可溶性樹脂，可例舉含有羧基及/或羥基之各種樹脂。其中，從獲得適度之錐角之阻隔壁，可抑制由後烘烤時之阻隔壁表面之熱熔融所引起之撥液劑的流出而保持撥油墨性等觀點出發，較佳為具有羧基之樹脂。[1-1-2] Component (B); Alkali-soluble resin The photosensitive resin composition of the present invention contains (B) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it can be developed with an alkaline developing solution. In the present invention, the (B) alkali-soluble resin is a component different from the (A) copolymer, and when an alkali-soluble resin corresponding to the (A) copolymer exists, it is treated as the (A) copolymer. Various resins containing a carboxyl group and/or a hydroxyl group are mentioned as an alkali-soluble resin. Among them, from the viewpoint of obtaining a barrier wall with a moderate taper angle, suppressing the outflow of the liquid-repellent agent caused by thermal melting of the surface of the barrier wall during post-baking, and maintaining ink repellency, resins having carboxyl groups are preferred. .

[具有乙烯性雙鍵之鹼可溶性樹脂(b)]  於本發明之感光性樹脂組合物中，(B)鹼可溶性樹脂較佳為包含具有乙烯性雙鍵之鹼可溶性樹脂(b)(以下，有時簡稱為「鹼可溶性樹脂(b)」)。藉由包含具有乙烯性雙鍵之鹼可溶性樹脂(b)，感度變高，藉由抑制顯影時之撥液劑流出，有所獲得之阻隔壁之撥油墨性變高之傾向。[Alkali-soluble resin (b) having an ethylenic double bond] In the photosensitive resin composition of the present invention, the (B) alkali-soluble resin preferably includes an alkali-soluble resin (b) having an ethylenic double bond (hereinafter, Sometimes referred to simply as "alkali-soluble resin (b)"). By containing the alkali-soluble resin (b) which has an ethylenic double bond, sensitivity becomes high, and the ink repellency of the obtained barrier rib tends to become high by suppressing the outflow of the liquid repellent agent at the time of image development.

具有乙烯性雙鍵之鹼可溶性樹脂(b)之具體結構並無特別限定，從顯影溶解性之觀點出發，較佳為環氧(甲基)丙烯酸酯樹脂(b1)及/或丙烯酸共聚樹脂(b2)，從釋氣減少之觀點出發，更佳為環氧(甲基)丙烯酸酯樹脂(b1)。The specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited, but epoxy (meth)acrylate resin (b1) and/or acrylic copolymer resin ( b2), from the viewpoint of reducing outgassing, epoxy (meth)acrylate resin (b1) is more preferable.

[環氧(甲基)丙烯酸酯樹脂(b1)]  環氧(甲基)丙烯酸酯樹脂(b1)係於環氧樹脂上加成具有乙烯性不飽和鍵(乙烯性雙鍵)之酸或酯化合物，進而加成多元酸或其酸酐而成之樹脂。例如可例舉藉由在環氧樹脂之環氧基上開環加成具有乙烯性不飽和鍵之酸之羧基，於環氧樹脂上經由酯鍵(-COO-)加成乙烯性不飽和鍵，並且於此時所產生之羥基上加成多元酸酐之一個羧基而成者。又，亦可例舉於加成多元酸酐時，同時添加多元醇進行加成而成者。進而，使具有能夠反應之官能基之化合物進而與上述反應中所獲得之樹脂的羧基反應所獲得之樹脂亦包含於環氧(甲基)丙烯酸酯樹脂(b1)中。  如此，環氧(甲基)丙烯酸酯樹脂於化學結構上實質上不具有環氧基，且並不限定於「(甲基)丙烯酸酯」，但由於環氧化合物(環氧樹脂)為原料，且「(甲基)丙烯酸酯」為代表例，故依照習慣如此進行命名。  又，作為環氧(甲基)丙烯酸酯系樹脂(b1)，從圖案化性之觀點出發，可更適宜地使用於主鏈具有芳香族環者。[Epoxy (meth)acrylate resin (b1)] Epoxy (meth)acrylate resin (b1) is an acid or ester with an ethylenically unsaturated bond (ethylenic double bond) added to the epoxy resin compound, and then add polybasic acid or its anhydride to resin. For example, by adding the carboxyl group of an acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin through ring-opening, and adding an ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) , and a carboxyl group of polybasic acid anhydride is added to the hydroxyl group generated at this time. Moreover, when adding a polybasic acid anhydride, what added and added a polyhydric alcohol simultaneously is also mentioned. Furthermore, the epoxy (meth)acrylate resin (b1) also contains the resin obtained by making the compound which has a reactive functional group react with the carboxyl group of the resin obtained by the said reaction. In this way, epoxy (meth)acrylate resin does not have epoxy group substantially in chemical structure, and is not limited to "(meth)acrylate", but since epoxy compound (epoxy resin) is used as a raw material, And "(meth)acrylate" is a representative example, so it is named according to the custom. Also, as the epoxy (meth)acrylate resin (b1), those having an aromatic ring in the main chain can be more suitably used from the viewpoint of patternability.

此處，環氧樹脂亦包括藉由熱硬化形成樹脂以前之原料化合物在內表述，作為其環氧樹脂，可自公知之環氧樹脂中適當選擇使用。又，環氧樹脂可使用使酚性化合物與表鹵醇反應所獲得之化合物。作為酚性化合物，較佳為具有二價或者二價以上之酚性羥基之化合物，可為單體，亦可為聚合物。  具體而言，例如可例舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、聯苯酚醛清漆環氧樹脂、三苯酚環氧樹脂、苯酚與二環戊二烯之聚合物之環氧化物、二羥基茀型環氧樹脂、二羥基伸烷氧基茀型環氧樹脂、9,9-雙(4'-羥基苯基)茀之二縮水甘油醚化物、1,1-雙(4'-羥基苯基)金剛烷之二縮水甘油醚化物，可適宜地使用於主鏈具有芳香族環者。Here, the epoxy resin is also described including raw material compounds before forming a resin by thermosetting, and as the epoxy resin, it can be appropriately selected from known epoxy resins. Moreover, the compound obtained by making a phenolic compound and epihalohydrin react can be used for an epoxy resin. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenol Aldehyde varnish epoxy resin, trisphenol epoxy resin, epoxide of polymer of phenol and dicyclopentadiene, dihydroxy fluorine type epoxy resin, dihydroxy alkeneoxy fluorine type epoxy resin, 9,9 -Diglycidyl etherate of bis(4'-hydroxyphenyl) terpene and diglycidyl etherate of 1,1-bis(4'-hydroxyphenyl)adamantane can be suitably used in main chains with aromatic Ringer.

其中，從硬化膜強度之觀點出發，較佳為雙酚A型環氧樹脂、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、苯酚與二環戊二烯之聚合物之環氧化物、9,9-雙(4'-羥基苯基)茀之環氧化物，進而較佳為雙酚A型環氧樹脂。Among them, bisphenol A type epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, epoxy resin of polymer of phenol and dicyclopentadiene are preferable from the viewpoint of the strength of the cured film. , 9,9-bis(4'-hydroxyphenyl) oxirane epoxide, and more preferably bisphenol A epoxy resin.

作為具有乙烯性不飽和鍵之酸，例如可例舉：(甲基)丙烯酸、丁烯酸、順丁烯二酸、反丁烯二酸、檸康酸、季戊四醇三(甲基)丙烯酸酯琥珀酸酐加成物、季戊四醇三(甲基)丙烯酸酯四氫鄰苯二甲酸酐加成物、二季戊四醇五(甲基)丙烯酸酯琥珀酸酐加成物、二季戊四醇五(甲基)丙烯酸酯鄰苯二甲酸酐加成物、二季戊四醇五(甲基)丙烯酸酯四氫鄰苯二甲酸酐加成物、(甲基)丙烯酸與ε-己內酯之反應產物。其中，從感度之觀點出發，較佳為(甲基)丙烯酸。Examples of the acid having an ethylenically unsaturated bond include: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinate Acid anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride Diformic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth)acrylic acid and ε-caprolactone. Among them, (meth)acrylic acid is preferable from the viewpoint of sensitivity.

作為多元酸(酸酐)，例如可例舉：琥珀酸、順丁烯二酸、伊康酸、鄰苯二甲酸、四氫鄰苯二甲酸、3-甲基四氫鄰苯二甲酸、4-甲基四氫鄰苯二甲酸、3-乙基四氫鄰苯二甲酸、4-乙基四氫鄰苯二甲酸、六氫鄰苯二甲酸、3-甲基六氫鄰苯二甲酸、4-甲基六氫鄰苯二甲酸、3-乙基六氫鄰苯二甲酸、4-乙基六氫鄰苯二甲酸、偏苯三甲酸、均苯四甲酸、二苯甲酮四羧酸、聯苯四羧酸、及該等之酸酐。該等可單獨使用一種，亦可併用兩種以上。該等之中，從減少顯影後之像素部之殘渣之觀點出發，較佳為琥珀酸酐、順丁烯二酸酐、伊康酸酐，更佳為琥珀酸酐。As the polybasic acid (acid anhydride), for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4- Methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4 -Methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, Biphenyltetracarboxylic acid, and their anhydrides. These may be used alone or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferable, and succinic anhydride is more preferable from the viewpoint of reducing the residue of the pixel portion after image development.

藉由使用多元醇，有可增大環氧(甲基)丙烯酸酯樹脂(b1)之分子量，向分子中導入分支，可取得分子量與黏度之平衡之傾向。又，有可增加酸基向分子中之導入率，可取得感度或密接性等之平衡之傾向。  作為多元醇，例如可例舉：三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三羥甲基乙烷、1,2,3-丙三醇。該等可單獨使用一種，亦可併用兩種以上。By using a polyol, the molecular weight of the epoxy (meth)acrylate resin (b1) can be increased, branches can be introduced into the molecule, and a balance between molecular weight and viscosity can be obtained. Also, it tends to increase the introduction rate of acid groups into the molecule, and to achieve a balance of sensitivity and adhesiveness. Examples of polyols include trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. These may be used alone or in combination of two or more.

環氧(甲基)丙烯酸酯樹脂(b1)之酸值並無特別限定，較佳為10 mgKOH/g以上，更佳為20 mgKOH/g以上，進而較佳為40 mgKOH/g以上，更進而較佳為60 mgKOH/g以上，又，較佳為200 mgKOH/g以下，更佳為180 mgKOH/g以下，進而較佳為150 mgKOH/g以下，更進而較佳為120 mgKOH/g以下，尤佳為100 mgKOH/g以下。上述上限及下限可任意地組合，例如，較佳為10～200 mgKOH/g，更佳為10～180 mgKOH/g，進而較佳為20～150 mgKOH/g，更進而較佳為40～120 mgKOH/g，尤佳為60～100 mgKOH/g。藉由設為上述下限值以上，殘渣容易減少。又，藉由設為上述上限值以下，有元件發光時之釋氣減少之傾向。The acid value of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, further preferably 40 mgKOH/g or more, and still more preferably More preferably 60 mgKOH/g or more, and preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, further preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less, More preferably, it is 100 mgKOH/g or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-200 mgKOH/g, more preferably 10-180 mgKOH/g, further preferably 20-150 mgKOH/g, still more preferably 40-120 mgKOH/g, preferably 60-100 mgKOH/g. Residues are easy to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for the outgassing at the time of a device to emit light to reduce by making it below the said upper limit.

環氧(甲基)丙烯酸酯樹脂(b1)之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為2000以上，進而較佳為3000以上，更進而較佳為4000以上，特別較佳為5000以上，尤佳為6000以上，最佳為7000以上，又，較佳為30000以下，更佳為20000以下，進而較佳為15000以下，尤佳為10000以下。上述上限及下限可任意地組合，較佳為1000～30000，更佳為2000～30000，進而較佳為3000～20000，更進而較佳為4000～20000，特別較佳為5000～15000，尤佳為6000～15000，最佳為7000～10000。藉由設為上述下限值以上，有元件發光時之釋氣減少之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably at least 1000, more preferably at least 2000, further preferably at least 3000, still more preferably at least 4000 , particularly preferably at least 5,000, particularly preferably at least 6,000, most preferably at least 7,000, and more preferably at most 30,000, more preferably at most 20,000, further preferably at most 15,000, and most preferably at most 10,000. The above upper and lower limits can be combined arbitrarily, preferably 1000-30000, more preferably 2000-30000, further preferably 3000-20000, still more preferably 4000-20000, especially preferably 5000-15000, especially preferably 6000-15000, preferably 7000-10000. There exists a tendency for the outgassing at the time of a device to emit light to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

於(B)鹼可溶性樹脂包含環氧(甲基)丙烯酸酯樹脂(b1)之情形時，(B)鹼可溶性樹脂中所含之環氧(甲基)丙烯酸酯樹脂(b1)之含量並無特別限定，較佳為30質量%以上，更佳為50質量%以上，進而較佳為70質量%以上，更進而較佳為80質量%以上，尤佳為90質量%以上，又，通常為100質量%以下。上述上限及下限可任意地組合，例如，較佳為30～100質量%，更佳為50～100質量%，進而較佳為70～100質量%，更進而較佳為80～100質量%，尤佳為90～100質量%。藉由設為上述下限值以上，有釋氣減少之傾向。In the case where (B) alkali-soluble resin contains epoxy (meth)acrylate resin (b1), the content of epoxy (meth)acrylate resin (b1) contained in (B) alkali-soluble resin does not have Especially limited, preferably at least 30% by mass, more preferably at least 50% by mass, further preferably at least 70% by mass, still more preferably at least 80% by mass, especially preferably at least 90% by mass, and usually 100% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 30-100 mass %, more preferably 50-100 mass %, further preferably 70-100 mass %, still more preferably 80-100 mass %, More preferably, it is 90 to 100% by mass. There exists a tendency for outgassing to reduce by setting it as more than the said lower limit.

環氧(甲基)丙烯酸酯樹脂(b1)可藉由先前公知之方法合成。具體而言，可使用如下方法：使上述環氧樹脂溶解於有機溶劑中，於觸媒與熱聚合抑制劑之共存下，添加上述具有乙烯性不飽和鍵之酸或酯化合物進行加成反應，進而添加多元酸或其酸酐繼續反應。Epoxy (meth)acrylate resin (b1) can be synthesize|combined by the method known previously. Specifically, the following method can be used: dissolving the above-mentioned epoxy resin in an organic solvent, and adding the above-mentioned acid or ester compound having an ethylenically unsaturated bond in the presence of a catalyst and a thermal polymerization inhibitor to carry out an addition reaction, Furthermore, polybasic acid or its anhydride is added and reaction is continued.

作為有機溶劑，例如可例舉：甲基乙基酮、環己酮、二乙二醇乙醚乙酸酯、丙二醇單甲醚乙酸酯。作為觸媒，例如可例舉：三乙基胺、苄基二甲基胺、三苄基胺等三級胺類；氯化四甲基銨、氯化甲基三乙基銨、氯化四乙基銨、氯化四丁基銨、氯化三甲基苄基銨等四級銨鹽類；三苯基膦等磷化合物；三苯基銻等銻類。作為熱聚合抑制劑，例如可例舉：對苯二酚、對苯二酚單甲醚、甲基對苯二酚。  該等可單獨使用一種，亦可併用兩種以上。Examples of the organic solvent include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. As the catalyst, for example, tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; tetramethylammonium chloride, methyltriethylammonium chloride, tetramethylammonium chloride, Quaternary ammonium salts such as ethylammonium, tetrabutylammonium chloride, and trimethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine; antimony such as triphenylantimony. As a thermal polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone are mentioned, for example. One of these can be used alone, or two or more can be used in combination.

相對於環氧樹脂之環氧基之1化學當量，具有乙烯性不飽和鍵之酸或酯化合物可使用較佳為成為0.7～1.3化學當量、更佳為成為0.9～1.1化學當量之量。加成反應時之溫度較佳為60～150℃，更佳為80～120℃。相對於加成反應中所產生之羥基之1化學當量，多元酸(酸酐)可使用較佳為成為0.1～1.2化學當量、更佳為成為0.2～1.1化學當量之量。The acid or ester compound having an ethylenically unsaturated bond can be used in an amount of preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction is preferably from 60 to 150°C, more preferably from 80 to 120°C. The polybasic acid (acid anhydride) can be used in an amount of preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of hydroxyl groups generated in the addition reaction.

從元件發光時之釋氣之觀點出發，環氧(甲基)丙烯酸酯樹脂(b1)較佳為含有選自由包含下述通式(i)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-1)(以下，有時稱為「環氧(甲基)丙烯酸酯樹脂(b1-1)」)、包含下述通式(ii)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-2)(以下，有時稱為「環氧(甲基)丙烯酸酯樹脂(b1-2)」)、及包含下述通式(iii)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-3)(以下，有時稱為「環氧(甲基)丙烯酸酯樹脂(b1-3)」)所組成之群中之至少一種。From the viewpoint of outgassing when the device emits light, the epoxy (meth)acrylate resin (b1) preferably contains an epoxy (meth)acrylate selected from a partial structure represented by the following general formula (i) Ester resin (b1-1) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b1-1)"), epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (ii) base) acrylate resin (b1-2) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b1-2)"), and one containing a partial structure represented by the following general formula (iii) At least one kind selected from the group consisting of epoxy (meth)acrylate resin (b1-3) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-3)").

該等之中，從減少元件發光時之釋氣之觀點出發，環氧(甲基)丙烯酸酯樹脂(b1)較佳為包含含有下述通式(i)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-1)，更佳為包含下述通式(i)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-1)。作為原因之一，推測如下等：藉由具有剛直之主骨架，對熱不易分解。Among them, the epoxy (meth)acrylate resin (b1) preferably contains epoxy ( The meth)acrylate resin (b1-1) is more preferably an epoxy (meth)acrylate resin (b1-1) containing a partial structure represented by the following general formula (i). As one of the reasons, it is presumed that it is difficult to decompose by heat by having a rigid main skeleton.

[化2]

Figure 02_image003
[Chem 2]
Figure 02_image003

式(i)中，R a表示氫原子或甲基，R b表示可具有取代基之二價烴基。式(i)中之苯環亦可進而經任意取代基取代。*表示鍵結鍵。 In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * Indicates a bonded bond.

(R b)  式(i)中，R b表示可具有取代基之二價烴基。  作為二價烴基，可例舉：二價脂肪族基、二價芳香族環基、將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基。 (R b ) In formula (i), R b represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may, for example, be a divalent aliphatic group, a divalent aromatic ring group, or a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

二價脂肪族基可例舉：直鏈狀、支鏈狀、環狀脂肪族基。該等之中，從顯影溶解性之觀點出發，較佳為直鏈狀脂肪族基，另一方面，從減少顯影液向曝光部之滲透之觀點出發，較佳為環狀脂肪族基。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為3～15，進而較佳為6～10。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The divalent aliphatic group may, for example, be a straight-chain, branched or cyclic aliphatic group. Among them, a straight-chain aliphatic group is preferable from the viewpoint of image development solubility, and a cyclic aliphatic group is preferable from the viewpoint of reducing penetration of a developing solution into an exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 3-15, still more preferably 6-10. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為二價直鏈狀脂肪族基，例如可例舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正己基、伸正庚基。該等之中，從減少殘渣之觀點出發，較佳為亞甲基。  作為二價支鏈狀脂肪族基，例如可例舉於上述二價直鏈狀脂肪族基中具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基作為側鏈之結構。  二價環狀脂肪族基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～5。藉由設為上述下限值以上，有殘膜率提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。作為二價環狀脂肪族基，例如可例舉：自環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環之環去除2個氫原子所得之基。該等之中，從顯影密接性之觀點出發，較佳為自金剛烷環去除2個氫原子所得之基。Examples of the divalent straight-chain aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. Among them, methylene is preferred from the viewpoint of reducing residues. Examples of the divalent branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl, tertiary butyl as the structure of the side chain. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 1-5, still more preferably 2-5. By setting it as more than the said lower limit, there exists a tendency for a residual film rate to improve. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. As the divalent cyclic aliphatic group, for example, one selected from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norberane ring, an isobornane ring, and an adamantane ring The base obtained by removing 2 hydrogen atoms from the ring. Among them, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of image development adhesiveness.

作為二價脂肪族基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基，從合成容易性之觀點出發，較佳為未經取代。Examples of substituents that a divalent aliphatic group may have include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, from the viewpoint of ease of synthesis From a viewpoint, it is preferably unsubstituted.

作為二價芳香族環基，可例舉二價芳香族烴環基及二價芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。上述上限及下限可任意地組合，例如，較佳為4～20，更佳為5～15，進而較佳為6～10。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。As a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-20, more preferably 5-15, still more preferably 6-10. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為二價芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環。作為二價芳香族烴環基，例如可例舉：具有2個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 111103644-A0304-2
環、聯三伸苯環、苊環、螢蒽環、茀環。  作為二價芳香族雜環基中之芳香族雜環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可例舉：具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等之中，從光硬化性之觀點出發，較佳為具有2個自由原子價之苯環、萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 111103644-A0304-2
ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, and oxadiazoles having two free atomic valences. ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, Benzisothiazole ring, Benzimidazole ring, Pyridine ring, Pyridine ring, Pyridine ring, Pyrimidine ring, Trinyl ring, Quinoline ring, Isoquinoline ring, Gheoline ring, Quinoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. Among them, a benzene ring and a naphthalene ring having two free atomic valences are preferable from the viewpoint of photocurability, and a benzene ring having two free atomic valences is more preferable.

作為二價芳香族環基可具有之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基、縮水甘油醚基。該等之中，從硬化性之觀點出發，較佳為未經取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group are mentioned, for example. Among these, unsubstituted is preferable from the viewpoint of curability.

作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，可例舉將1個以上之上述二價脂肪族基與1個以上之上述二價芳香族環基連結而成之基。  二價脂肪族基之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  二價芳香族環基之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。As a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups, one or more divalent aliphatic groups and one or more divalent aliphatic groups A group formed by linking aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，例如可例舉下述式(i-A)～(i-F)所表示之基。該等之中，從骨架之剛直性與膜之疏水化之觀點出發，較佳為下述式(i-A)所表示之基。化學式中之*表示鍵結鍵。As a group which connected one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the group represented by following formula (i-A) - (i-F) is mentioned, for example. Among these, a group represented by the following formula (i-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film. The * in the chemical formula represents a bonding bond.

[化3]

Figure 02_image005
[Chem 3]
Figure 02_image005

式(i)中之苯環亦可進而經任意取代基取代。作為式(i)中之苯環之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。取代基之數量亦並無特別限定，只要於化學方面容許，則可為1個，亦可為2個以上。  從硬化性之觀點出發，較佳為未經取代。The benzene ring in formula (i) may be further substituted with any substituent. As a substituent of the benzene ring in formula (i), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not particularly limited, and may be one or two or more as long as it is chemically acceptable. From the viewpoint of hardenability, it is preferably unsubstituted.

從顯影溶解性之觀點出發，式(i)所表示之部分結構較佳為下述式(i-1)所表示之部分結構。From the viewpoint of image development solubility, the partial structure represented by formula (i) is preferably a partial structure represented by the following formula (i-1).

[化4]

Figure 02_image007
[chemical 4]
Figure 02_image007

式(i-1)中，R a及R b與式(i)含義相同。R 1表示可具有取代基之碳數1～4之二價烴基。*表示鍵結鍵。式(i-1)中之苯環亦可進而經任意取代基取代。 In formula (i-1), R a and R b have the same meaning as in formula (i). R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Indicates a bonded bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

(R 1)  式(i-1)中，R 1表示可具有取代基之碳數1～4之二價烴基。作為二價烴基，可例舉伸烷基、伸烯基。 (R 1 ) In the formula (i-1), R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. The divalent hydrocarbon group may, for example, be an alkylene group or an alkenylene group.

伸烷基可為直鏈，亦可為支鏈，但從顯影溶解性之觀點出發，較佳為直鏈。其碳數並無特別限定，通常為1以上，較佳為2以上，又，較佳為4以下，更佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～4，更佳為1～3，進而較佳為2～3。藉由設為上述下限值以上，有殘膜率增高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣產生量減少之傾向。The alkylene group may be a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of image development solubility. The carbon number is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or less, more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-4 are preferable, 1-3 are more preferable, 2-3 are still more preferable. By setting it as more than the said lower limit, there exists a tendency for a residual film rate to increase. Moreover, there exists a tendency for the outgassing generation amount at the time of device light emission to reduce by making it below the said upper limit.

作為伸烷基，例如可例舉：亞甲基、伸乙基、伸丙基、伸丁基，從釋氣減少之觀點出發，較佳為亞甲基、伸乙基，更佳為伸乙基。Examples of the alkylene group include: methylene group, ethylidene group, propylidene group, and butylene group. From the viewpoint of reducing outgassing, methylene group and ethylidene group are preferred, and ethylidene group is more preferred. base.

伸烯基可為直鏈，亦可為支鏈，但從顯影溶解性之觀點出發，較佳為直鏈。其碳數並無特別限定，通常為2以上，又，較佳為4以下，更佳為3以下。例如，較佳為2～4，更佳為2～3。藉由設為上述下限值以上，有殘膜率增高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣產生量減少之傾向。The alkenylene group may be a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of image development solubility. The carbon number is not particularly limited, but is usually 2 or more, preferably 4 or less, more preferably 3 or less. For example, 2-4 are preferable, and 2-3 are more preferable. By setting it as more than the said lower limit, there exists a tendency for a residual film rate to increase. Moreover, there exists a tendency for the outgassing generation amount at the time of device light emission to reduce by making it below the said upper limit.

作為伸烯基，例如可例舉：伸乙烯基、伸丙烯基、伸丁烯基，從釋氣之觀點出發，較佳為伸乙烯基。As an alkenylene group, a vinylene group, a propenyl group, and a butylene group are mentioned, for example, A vinylene group is preferable from a viewpoint of outgassing.

碳數1～4之二價烴基可具有之取代基並無特別限定，例如可例舉：鹵素原子、烷氧基、苯甲醯基、羥基，從合成容易性之觀點出發，較佳為未經取代。The substituent that the divalent hydrocarbon group having 1 to 4 carbon atoms may have is not particularly limited, for example, a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group are mentioned. superseded.

該等之中，從釋氣減少之觀點出發，R 1較佳為碳數1～4之二價伸烷基，更佳為亞甲基或伸乙基，進而較佳為伸乙基。 Among them, from the viewpoint of reducing outgassing, R 1 is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylylene group, and still more preferably an ethylylene group.

環氧(甲基)丙烯酸酯樹脂(b1-1)1分子中所含之式(i-1)所表示之部分結構可為1種，亦可為2種以上。The partial structure represented by the formula (i-1) contained in 1 molecule of epoxy (meth)acrylate resin (b1-1) may be 1 type, and may be 2 or more types.

環氧(甲基)丙烯酸酯樹脂(b1-1)1分子中所含之式(i)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為2以上，進而較佳為3以上，又，較佳為10以下，更佳為8以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～10，進而較佳為3～8。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The number of partial structures represented by the formula (i) contained in the epoxy (meth)acrylate resin (b1-1) 1 molecule is not particularly limited, preferably 1 or more, more preferably 2 or more, and even more preferably It is preferably at least 3, more preferably at most 10, more preferably at most 8. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-10, still more preferably 3-8. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

環氧(甲基)丙烯酸酯樹脂(b1-1)1分子中所含之式(i-1)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為2以上，進而較佳為3以上，又，較佳為10以下，更佳為8以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～10，進而較佳為3～8。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The number of partial structures represented by the formula (i-1) contained in the molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, Furthermore, it is preferably 3 or more, and more preferably 10 or less, and more preferably 8 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-10, still more preferably 3-8. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

以下例舉環氧(甲基)丙烯酸酯樹脂(b1-1)之具體例。Specific examples of the epoxy (meth)acrylate resin (b1-1) are given below.

[化5]

Figure 02_image009
[chemical 5]
Figure 02_image009

[化6]

Figure 02_image011
[chemical 6]
Figure 02_image011

[化7]

Figure 02_image013
[chemical 7]
Figure 02_image013

[化8]

Figure 02_image015
[chemical 8]
Figure 02_image015

[化9]

Figure 02_image017
[chemical 9]
Figure 02_image017

[化10]

Figure 02_image019
[chemical 10]
Figure 02_image019

[化11]

Figure 02_image021
[chemical 11]
Figure 02_image021

作為另一態樣，從顯影密接性之觀點出發，環氧(甲基)丙烯酸酯樹脂(b1)較佳為包含下述式(ii)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-2)。As another aspect, from the viewpoint of developing adhesiveness, the epoxy (meth)acrylate resin (b1) is preferably epoxy (meth)acrylate containing a partial structure represented by the following formula (ii) Resin (b1-2).

[化12]

Figure 02_image023
[chemical 12]
Figure 02_image023

式(ii)中，R c分別獨立地表示氫原子或甲基。R d表示具有環狀烴基作為側鏈之二價烴基。*表示鍵結鍵。 In formula (ii), R c each independently represent a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Indicates a bonded bond.

(R d)  式(ii)中，R d表示具有環狀烴基作為側鏈之二價烴基。  作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R d ) In the formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為4～30，進而較佳為6～20，尤佳為8～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環。該等之中，從顯影密接性之觀點出發，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, especially preferably 15 or less . The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 4-30, further preferably 6-20, especially preferably 8-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norberane ring, isobornane ring, and adamantane ring. . Among them, an adamantane ring is preferable from the viewpoint of image development adhesiveness.

芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為10以下，更佳為5以下，進而較佳為4以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～5，進而較佳為3～4。藉由設為上述下限值以上，有殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。  作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，更進而較佳為10以上，尤佳為12以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為6～40，進而較佳為8～30，更進而較佳為10～20，尤佳為12～15。藉由設為上述下限值以上，有殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。  作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 111103644-A0304-2
環、聯三伸苯環、苊環、螢蒽環、茀環。該等之中，從圖案化特性之觀點出發，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably 4 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-5, still more preferably 3-4. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, especially preferably 12 or more, and preferably 40 or less, more preferably 30 or less, more preferably 20 or less, particularly preferably 15 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-40, further preferably 8-30, still more preferably 10-20, especially preferably 12-15. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit. As the aromatic ring in the aromatic ring group, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 111103644-A0304-2
ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. Among them, from the viewpoint of patterning properties, a fennel ring is preferable.

具有環狀烴基作為側鏈之二價烴基中之二價烴基並無特別限定，例如可例舉：二價脂肪族基、二價芳香族環基、將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基。The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, for example, a divalent aliphatic group, a divalent aromatic ring group, a combination of one or more divalent aliphatic groups and A group formed by linking one or more divalent aromatic ring groups.

二價脂肪族基可例舉直鏈狀、支鏈狀、環狀脂肪族基。該等之中，從顯影溶解性之觀點出發，較佳為直鏈狀脂肪族基，另一方面，從減少顯影液向曝光部之滲透之觀點出發，較佳為環狀脂肪族基。其碳數通常為1以上，較佳為3以上，更佳為6以上，又，較佳為25以下，更佳為20以下，進而較佳為15以下。上述上限及下限可任意地組合，例如，較佳為1～25，更佳為3～20，進而較佳為6～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The divalent aliphatic group may, for example, be a straight-chain, branched or cyclic aliphatic group. Among them, a straight-chain aliphatic group is preferable from the viewpoint of image development solubility, and a cyclic aliphatic group is preferable from the viewpoint of reducing penetration of a developing solution into an exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-25, more preferably 3-20, still more preferably 6-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為二價直鏈狀脂肪族基，例如可例舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸正己基、伸正庚基。該等之中，從殘渣之觀點出發，較佳為亞甲基。  作為二價支鏈狀脂肪族基，例如可例舉於上述二價直鏈狀脂肪族基中具有甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基作為側鏈之結構。  二價環狀脂肪族基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為二價環狀脂肪族基，例如可例舉：自環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環去除2個氫原子所得之基。該等之中，從顯影密接性之觀點出發，較佳為自金剛烷環去除2個氫原子所得之基。Examples of the divalent straight-chain aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. Among them, methylene is preferable from the viewpoint of residue. Examples of the divalent branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second Butyl, tertiary butyl as the structure of the side chain. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. As a divalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norberane ring, an isobornane ring, and an adamantane ring can be mentioned. The base derived from 2 hydrogen atoms. Among them, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of image development adhesiveness.

作為二價脂肪族基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基，從合成容易性之觀點出發，較佳為未經取代。Examples of substituents that a divalent aliphatic group may have include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, from the viewpoint of ease of synthesis From a viewpoint, it is preferably unsubstituted.

作為二價芳香族環基，較佳為二價芳香族烴環基及二價芳香族雜環基。其碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～30，更佳為5～20，進而較佳為6～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are preferable. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-30, more preferably 5-20, still more preferably 6-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為二價芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環。作為二價芳香族烴環基，例如可例舉：具有2個自由原子價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 111103644-A0304-2
環、聯三伸苯環、苊環、螢蒽環、茀環。  作為二價芳香族雜環基中之芳香族雜環，可為單環，亦可為縮合環。作為二價芳香族雜環基，例如可例舉：具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等之中，從光硬化性之觀點出發，較佳為具有2個自由原子價之苯環、萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 111103644-A0304-2
ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, and oxadiazoles having two free atomic valences. ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, Benzisothiazole ring, Benzimidazole ring, Pyridine ring, Pyridine ring, Pyridine ring, Pyrimidine ring, Trinyl ring, Quinoline ring, Isoquinoline ring, Gheoline ring, Quinoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. Among them, a benzene ring and a naphthalene ring having two free atomic valences are preferable from the viewpoint of photocurability, and a benzene ring having two free atomic valences is more preferable.

作為二價芳香族環基可具有之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。該等之中，從硬化性之觀點出發，較佳為未經取代。As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. Among these, unsubstituted is preferable from the viewpoint of curability.

作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，可例舉將1個以上之上述二價脂肪族基與1個以上之上述二價芳香族環基連結而成之基。  二價脂肪族基之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  二價芳香族環基之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為1～5，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。As a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups, one or more divalent aliphatic groups and one or more divalent aliphatic groups A group formed by linking aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為將1個以上之二價脂肪族基與1個以上之二價芳香族環基連結而成之基，例如可例舉式(i-A)～(i-F)所表示之基等。該等之中，從減少殘渣之觀點出發，較佳為式(i-C)所表示之基。As a group which connected one or more divalent aliphatic groups and one or more divalent aromatic ring groups, the groups represented by formula (i-A) - (i-F) etc. are mentioned, for example. Among them, the group represented by the formula (i-C) is preferable from the viewpoint of reducing residues.

對於該等二價烴基，作為側鏈之環狀烴基之鍵結態樣並無特別限定，例如可例舉利用側鏈取代脂肪族基或芳香族環基之1個氫原子之態樣、或包含脂肪族基之1個碳原子而構成作為側鏈之環狀烴基之態樣。For these divalent hydrocarbon groups, the bonding state of the cyclic hydrocarbon group as a side chain is not particularly limited, for example, a state in which one hydrogen atom of an aliphatic group or an aromatic ring group is replaced by a side chain, or A form in which one carbon atom of an aliphatic group constitutes a cyclic hydrocarbon group as a side chain.

從顯影密接性之觀點出發，式(ii)所表示之部分結構較佳為下述式(ii-1)所表示之部分結構。From the viewpoint of image development adhesiveness, the partial structure represented by formula (ii) is preferably a partial structure represented by the following formula (ii-1).

[化13]

Figure 02_image025
[chemical 13]
Figure 02_image025

式(ii-1)中，R c與式(ii)含義相同。R α表示可具有取代基之一價環狀烴基。n為1以上之整數。式(ii-1)中之苯環亦可進而經任意取代基取代。*表示鍵結鍵。 In formula (ii-1), R c has the same meaning as formula (ii). R α represents a valent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. * Indicates a bonded bond.

(R α)  式(ii-1)中，R α表示可具有取代基之一價環狀烴基。  作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R α ) In the formula (ii-1), R α represents a valent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為6以下，更佳為4以下，進而較佳為3以下。上述上限及下限可任意地組合，例如，較佳為1～6，更佳為1～4，進而較佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  又，脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為4～30，進而較佳為6～20，尤佳為8～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環。該等之中，從顯影密接性之觀點出發，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, 1-6 are preferable, 1-4 are more preferable, 2-3 are still more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, especially preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 4-30, further preferably 6-20, especially preferably 8-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norberane ring, isobornane ring, and adamantane ring. . Among them, an adamantane ring is preferable from the viewpoint of image development adhesiveness.

芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為10以下，更佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～10，進而較佳為3～5。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數通常為4以上，較佳為5以上，更佳為6以上，又，較佳為30以下，更佳為20以下，進而較佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～30，更佳為5～20，進而較佳為6～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、茀環。該等之中，從顯影密接性之觀點出發，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-10, still more preferably 3-5. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-30, more preferably 5-20, still more preferably 6-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring in the aromatic ring group includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of image development adhesiveness, fennel ring is preferable.

作為環狀烴基可具有之取代基，例如可例舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基，從合成容易性之觀點出發，較佳為未經取代。Examples of substituents that a cyclic hydrocarbon group may have include: methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. An alkyl group with 1 to 5 carbons; an alkoxy group with 1 to 5 carbons such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; replace.

n表示1以上之整數，但較佳為2以上，又，較佳為3以下。例如，較佳為1～3，更佳為2～3。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。n represents an integer of 1 or more, but is preferably 2 or more, and is preferably 3 or less. For example, 1-3 are preferable, and 2-3 are more preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

該等之中，從牢固之膜硬化度與電特性之觀點出發，R α較佳為一價脂肪族環基，更佳為金剛烷基。 Among them, R α is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group, from the standpoint of firm film hardening and electrical properties.

如上所述，式(ii-1)中之苯環亦可進而經任意取代基取代。作為取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。取代基之數量亦並無特別限定，可為1個，亦可為2個以上。從硬化性之觀點出發，較佳為未經取代。As mentioned above, the benzene ring in formula (ii-1) may be further substituted with any substituent. As a substituent, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

以下例舉式(ii-1)所表示之部分結構之具體例。Specific examples of the partial structure represented by formula (ii-1) are given below.

[化14]

Figure 02_image027
[chemical 14]
Figure 02_image027

[化15]

Figure 02_image029
[chemical 15]
Figure 02_image029

[化16]

Figure 02_image031
[chemical 16]
Figure 02_image031

[化17]

Figure 02_image033
[chemical 17]
Figure 02_image033

[化18]

Figure 02_image035
[chemical 18]
Figure 02_image035

從顯影密接性之觀點出發，上述式(ii)所表示之部分結構較佳為下述式(ii-2)所表示之部分結構。From the viewpoint of image development adhesiveness, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-2).

[化19]

Figure 02_image037
[chemical 19]
Figure 02_image037

式(ii-2)中，R c與式(ii)含義相同。R β表示可具有取代基之二價環狀烴基。式(ii-2)中之苯環亦可進而經任意取代基取代。*表示鍵結鍵。 In formula (ii-2), R c has the same meaning as formula (ii). R β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. * Indicates a bonded bond.

(R β)  式(ii-2)中，R β表示可具有取代基之二價環狀烴基。  作為環狀烴基，可例舉脂肪族環基或芳香族環基。 (R β ) In the formula (ii-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～5。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  又，脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為35以下，進而較佳為30以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為6～35，進而較佳為8～30。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為脂肪族環基中之脂肪族環，可例舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環。該等之中，從顯影密接性之觀點出發，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-5. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, further preferably 30 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-35, still more preferably 8-30. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aliphatic ring in the aliphatic ring group may, for example, be a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norberane ring, an isobornane ring or an adamantane ring. Among them, an adamantane ring is preferable from the viewpoint of image development adhesiveness.

芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為10以下，較佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～10，進而較佳為3～5。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而較佳為10以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為6～30，進而較佳為8～20，尤佳為10～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、茀環。該等之中，從顯影密接性之觀點出發，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-10, still more preferably 3-5. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably It is less than 20, preferably less than 15. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-30, further preferably 8-20, especially preferably 10-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring in the aromatic ring group includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of image development adhesiveness, fennel ring is preferable.

作為環狀烴基可具有之取代基，例如可例舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基。該等之中，從合成之簡易性之觀點出發，較佳為未經取代。Examples of substituents that a cyclic hydrocarbon group may have include: methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. Alkyl group with 1 to 5 carbons; alkoxy group with 1 to 5 carbons such as methoxy and ethoxy; hydroxyl group; nitro group; cyano group; carboxyl group. Among these, unsubstituted is preferable from the viewpoint of the ease of synthesis.

該等之中，從硬化性之觀點出發，R β較佳為二價脂肪族環基，更佳為二價金剛烷環基。  作為另一態樣，從顯影密接性之觀點出發，R β較佳為二價芳香族環基，更佳為二價茀環基。 Among these, R β is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of hardenability. As another aspect, R β is preferably a divalent aromatic ring group, more preferably a divalent oxene ring group, from the viewpoint of image development adhesiveness.

式(ii-2)中之苯環亦可進而經任意取代基取代。作為式(ii-2)中之苯環之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。取代基之數量亦並無特別限定，可為1個，亦可為2個以上。從硬化性之觀點出發，較佳為未經取代。The benzene ring in formula (ii-2) may be further substituted with any substituent. As a substituent of the benzene ring in formula (ii-2), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

以下例舉式(ii-2)所表示之部分結構之具體例。Specific examples of the partial structure represented by the formula (ii-2) are given below.

[化20]

Figure 02_image039
[chemical 20]
Figure 02_image039

[化21]

Figure 02_image041
[chem 21]
Figure 02_image041

[化22]

Figure 02_image043
[chem 22]
Figure 02_image043

[化23]

Figure 02_image045
[chem 23]
Figure 02_image045

從硬化性之觀點出發，式(ii)所表示之部分結構較佳為下述式(ii-3)所表示之部分結構。From the viewpoint of curability, the partial structure represented by formula (ii) is preferably a partial structure represented by the following formula (ii-3).

[化24]

Figure 02_image047
[chem 24]
Figure 02_image047

式(ii-3)中，R c及R d與式(ii)含義相同。R 1與式(i-1)含義相同。*表示鍵結鍵。 In formula (ii-3), R c and R d have the same meaning as formula (ii). R 1 has the same meaning as in formula (i-1). * Indicates a bonded bond.

環氧(甲基)丙烯酸酯樹脂(b1-2)1分子中所含之式(ii-3)所表示之部分結構可為1種，亦可為2種以上。The partial structure represented by the formula (ii-3) contained in 1 molecule of epoxy (meth)acrylate resin (b1-2) may be 1 type, and may be 2 or more types.

環氧(甲基)丙烯酸酯樹脂(b1-2)1分子中所含之式(ii)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為3以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為1～15，進而較佳為3～10。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and, Preferably it is 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-15, still more preferably 3-10. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為進而另一態樣，從減少元件發光時之釋氣之觀點出發，環氧(甲基)丙烯酸酯樹脂(b1)較佳為包含下述通式(iii)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-3)。As yet another aspect, from the viewpoint of reducing outgassing when the device emits light, the epoxy (meth)acrylate resin (b1) is preferably an epoxy resin containing a partial structure represented by the following general formula (iii) (meth)acrylate resin (b1-3).

[化25]

Figure 02_image049
[chem 25]
Figure 02_image049

式(iii)中，R e表示氫原子或甲基，γ表示單鍵、-CO-、可具有取代基之伸烷基、或可具有取代基之二價環狀烴基。式(iii)中之苯環亦可進而經任意取代基取代。*表示鍵結鍵。 In formula (iii), R e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (iii) may be further substituted with any substituent. * Indicates a bonded bond.

(γ)  式(iii)中，γ表示單鍵、-CO-、可具有取代基之伸烷基、或可具有取代基之二價環狀烴基。(γ) In formula (iii), γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

伸烷基可為直鏈狀，亦可為支鏈狀，但從顯影溶解性之觀點出發，較佳為直鏈狀，從顯影密接性之觀點出發，較佳為支鏈狀。其碳數並無特別限定，通常為1以上，較佳為2以上，又，較佳為6以下，更佳為4以下。上述上限及下限可任意地組合，例如，較佳為1～6，更佳為2～4。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The alkylene group may be linear or branched, but is preferably linear from the viewpoint of image development solubility, and preferably branched from the viewpoint of image development adhesiveness. The carbon number is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-6, more preferably 2-4. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為伸烷基，例如可例舉：亞甲基、伸乙基、伸丙基、伸丁基、伸己基、伸庚基，從同時實現顯影密接性與顯影溶解性之觀點出發，較佳為亞甲基、伸乙基、伸丙基，更佳為二甲基亞甲基(2,2-伸丙基)。Examples of the alkylene group include methylene, ethylene, propylidene, butylene, hexylene, and heptyl. From the viewpoint of achieving both developing adhesiveness and developing solubility, preferred is Methylene, ethylidene, propylidene, more preferably dimethylmethylene (2,2-propylidene).

作為伸烷基可具有之取代基，例如可例舉：甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基，從同時實現顯影密接性與顯影溶解性之觀點出發，較佳為未經取代。As the substituent that the alkylene group may have, for example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; From the viewpoint of image development solubility, it is preferably unsubstituted.

作為二價環狀烴基，可例舉二價脂肪族環基或二價芳香族環基。The divalent cyclic hydrocarbon group may, for example, be a divalent aliphatic ring group or a divalent aromatic ring group.

脂肪族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，又，較佳為10以下，更佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～5。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  又，脂肪族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，又，較佳為40以下，更佳為35以下，進而較佳為30以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為6～35，進而較佳為8～30。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為脂肪族環基中之脂肪族環，例如可例舉：環己烷環、環庚烷環、環癸烷環、環十二烷環、降𦯉烷環、異冰片烷環、金剛烷環。該等之中，從顯影密接性之觀點出發，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-5. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, further preferably 30 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-35, still more preferably 8-30. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norberane ring, isobornane ring, and adamantane ring. . Among them, an adamantane ring is preferable from the viewpoint of image development adhesiveness.

芳香族環基所具有之環之數量並無特別限定，通常為1以上，較佳為2以上，更佳為3以上，又，較佳為10以下，更佳為5以下。上述上限及下限可任意地組合，例如，較佳為1～10，更佳為2～10，進而較佳為3～5。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基，可例舉芳香族烴環基、芳香族雜環基。芳香族環基之碳數通常為4以上，較佳為6以上，更佳為8以上，進而較佳為10以上，又，較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為15以下。上述上限及下限可任意地組合，例如，較佳為4～40，更佳為6～30，進而較佳為8～20，尤佳為10～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族環基中之芳香族環，例如可例舉：苯環、萘環、蒽環、菲環、茀環。該等之中，從顯影密接性之觀點出發，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-10, more preferably 2-10, still more preferably 3-5. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 Below, preferably below 15. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-30, further preferably 8-20, especially preferably 10-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. The aromatic ring in the aromatic ring group includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, from the viewpoint of image development adhesiveness, fennel ring is preferable.

作為環狀烴基可具有之取代基，例如可例舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、異戊基等碳數1～5之烷基；甲氧基、乙氧基等碳數1～5之烷氧基；羥基；硝基；氰基；羧基，從合成之簡易性之觀點出發，較佳為未經取代。Examples of substituents that a cyclic hydrocarbon group may have include: methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. An alkyl group with 1 to 5 carbons; an alkoxy group with 1 to 5 carbons such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; superseded.

該等之中，從減少殘渣之觀點出發，γ較佳為可具有取代基之伸烷基，更佳為二甲基亞甲基。Among them, γ is preferably an alkylene group which may have a substituent, more preferably a dimethylmethylene group, from the viewpoint of reducing residue.

式(iii)中之苯環亦可進而經任意取代基取代。作為式(iii)中之苯環之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。取代基之數量亦並無特別限定，可為1個，亦可為2個以上。從硬化性之觀點出發，較佳為未經取代。The benzene ring in formula (iii) may be further substituted with any substituent. As a substituent of the benzene ring in formula (iii), for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group may be mentioned. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

從顯影溶解性之觀點出發，式(iii)所表示之部分結構較佳為下述式(iii-1)所表示之部分結構。From the viewpoint of image development solubility, the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1).

[化26]

Figure 02_image051
[chem 26]
Figure 02_image051

式(iii-1)中，R e及γ與式(iii)含義相同。R 1與式(i-1)含義相同。*表示鍵結鍵。式(iii-1)中之苯環亦可進而經任意取代基取代。 In formula (iii-1), R e and γ have the same meanings as in formula (iii). R 1 has the same meaning as in formula (i-1). * Indicates a bonded bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

式(iii-1)中之苯環亦可進而經任意取代基取代。作為式(iii-1)中之苯環之取代基，例如可例舉：羥基、甲基、甲氧基、乙基、乙氧基、丙基、丙氧基。取代基之數量亦並無特別限定，可為1個，亦可為2個以上。從硬化性之觀點出發，較佳為未經取代。The benzene ring in formula (iii-1) may be further substituted with any substituent. As a substituent of the benzene ring in formula (iii-1), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

環氧(甲基)丙烯酸酯樹脂(b1-3)1分子中所含之式(iii)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為5以上，進而較佳為10以上，又，較佳為18以下，更佳為15以下。上述上限及下限可任意地組合，例如，較佳為1～18，更佳為5～18，進而較佳為10～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The number of partial structures represented by the formula (iii) contained in the epoxy (meth)acrylate resin (b1-3) 1 molecule is not particularly limited, preferably 1 or more, more preferably 5 or more, and more preferably It is preferably at least 10, more preferably at most 18, more preferably at most 15. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-18, more preferably 5-18, still more preferably 10-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

環氧(甲基)丙烯酸酯樹脂(b1-3)1分子中所含之式(iii-1)所表示之部分結構之數量並無特別限定，較佳為1以上，更佳為3以上，進而較佳為5以上，又，較佳為18以下，更佳為15以下。上述上限及下限可任意地組合，例如，較佳為1～18，更佳為3～18，進而較佳為5～15。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The number of partial structures represented by the formula (iii-1) contained in the epoxy (meth)acrylate resin (b1-3)1 molecule is not particularly limited, preferably 1 or more, more preferably 3 or more, Furthermore, it is preferably 5 or more, and is preferably 18 or less, more preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-18, more preferably 3-18, still more preferably 5-15. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

以下例舉環氧(甲基)丙烯酸酯樹脂(b1-3)之具體例。Specific examples of the epoxy (meth)acrylate resin (b1-3) are given below.

[化27]

Figure 02_image053
[chem 27]
Figure 02_image053

[化28]

Figure 02_image055
[chem 28]
Figure 02_image055

[化29]

Figure 02_image057
[chem 29]
Figure 02_image057

[丙烯酸共聚樹脂(b2)]  從硬化性之觀點出發，丙烯酸共聚樹脂(b2)較佳為於側鏈具有乙烯性雙鍵者。[Acrylic copolymer resin (b2)] From the viewpoint of curability, the acrylic copolymer resin (b2) preferably has an ethylenic double bond in a side chain.

丙烯酸共聚樹脂(b2)之中，從顯影溶解性之觀點出發，較佳為包含下述通式(I)所表示之部分結構之丙烯酸共聚樹脂(b2-1)。Among the acrylic copolymer resins (b2), an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I) is preferable from the viewpoint of image development solubility.

[化30]

Figure 02_image059
[chem 30]
Figure 02_image059

式(I)中，R A及R B分別獨立地表示氫原子或甲基。*表示鍵結鍵。 In formula (I), R A and R B each independently represent a hydrogen atom or a methyl group. * Indicates a bonded bond.

從顯影性之觀點出發，式(I)所表示之部分結構較佳為下述通式(I-1)所表示之部分結構。From the viewpoint of developability, the partial structure represented by the formula (I) is preferably a partial structure represented by the following general formula (I-1).

[化31]

Figure 02_image061
[chem 31]
Figure 02_image061

式(I-1)中，R A及R B與式(I)含義相同。R 1與式(i-1)含義相同。 In formula (I-1), R A and R B have the same meaning as formula (I). R 1 has the same meaning as in formula (i-1).

從感度之觀點出發，式(I)所表示之部分結構較佳為下述式(I-2)所表示之部分結構。From the viewpoint of sensitivity, the partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (I-2).

[化32]

Figure 02_image063
[chem 32]
Figure 02_image063

式(I-2)中，R A及R B與式(I)含義相同。 In formula (I-2), R A and R B have the same meaning as formula (I).

於丙烯酸共聚樹脂(b2-1)包含式(I)所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I)所表示之部分結構之含量並無特別限定，較佳為5莫耳%以上，更佳為20莫耳%以上，進而較佳為30莫耳%以上，更進而較佳為50莫耳%以上，尤佳為70莫耳%以上，最佳為80莫耳%以上，又，較佳為99莫耳%以下，更佳為97莫耳%以下，進而較佳為95莫耳%以下。上述上限及下限可任意地組合，例如，較佳為5～99莫耳%，更佳為20～99莫耳%，進而較佳為30～97莫耳%，更進而較佳為50～97莫耳%，尤佳為70～95莫耳%，最佳為80～95莫耳%。藉由設為上述下限值以上，有殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the formula (I), the content of the partial structure represented by the formula (I) contained in the acrylic copolymer resin (b2-1) is not particularly limited , preferably more than 5 mole %, more preferably more than 20 mole %, more preferably more than 30 mole %, more preferably more than 50 mole %, especially preferably more than 70 mole %, most preferably It is preferably at least 80 mol%, and more preferably at most 99 mol%, more preferably at most 97 mol%, further preferably at most 95 mol%. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-99 mol%, more preferably 20-99 mol%, further preferably 30-97 mol%, even more preferably 50-97 mol%. Mole %, preferably 70-95 mole %, most preferably 80-95 mole %. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit.

於丙烯酸共聚樹脂(b2-1)包含式(I-1)所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I-1)所表示之部分結構之含量並無特別限定，較佳為1莫耳%以上，更佳為5莫耳%以上，進而較佳為8莫耳%以上，更進而較佳為10莫耳%以上，又，較佳為99莫耳%以下，更佳為60莫耳%以下，進而較佳為40莫耳%以下，更進而較佳為30莫耳%以下，尤佳為20莫耳%以下。上述上限及下限可任意地組合，例如，較佳為1～99莫耳%，更佳為1～60莫耳%，進而較佳為5～40莫耳%，更進而較佳為8～30莫耳%，尤佳為10～20莫耳%。藉由設為上述下限值以上，有感度變高，殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the formula (I-1), the content of the partial structure represented by the formula (I-1) contained in the acrylic copolymer resin (b2-1) It is not particularly limited, but it is preferably at least 1 mol%, more preferably at least 5 mol%, further preferably at least 8 mol%, still more preferably at least 10 mol%, and more preferably at least 99 mol%. Mole% or less, more preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, especially preferably 20 mol% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-99 mol%, more preferably 1-60 mol%, further preferably 5-40 mol%, even more preferably 8-30 Mole %, preferably 10-20 Mole %. By making it more than the said lower limit, there exists a tendency for a sensitivity to become high and a residue to reduce. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit.

於丙烯酸共聚樹脂(b2-1)包含式(I-2)所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I-2)所表示之部分結構之含量並無特別限定，較佳為10莫耳%以上，更佳為20莫耳%以上，進而較佳為30莫耳%以上，更進而較佳為40莫耳%以上，尤佳為50莫耳%以上，最佳為70莫耳%以上，又，較佳為99莫耳%以下，更佳為95莫耳%以下，進而較佳為90莫耳%以下，尤佳為85莫耳%以下。上述上限及下限可任意地組合，例如，較佳為10～99莫耳%，更佳為20～99莫耳%，進而較佳為30～95莫耳%，更進而較佳為40～95莫耳%，尤佳為50～90莫耳%，最佳為70～85莫耳%。藉由設為上述下限值以上，有感度變高之傾向。又，藉由設為上述上限值以下，有顯影性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the formula (I-2), the content of the partial structure represented by the formula (I-2) contained in the acrylic copolymer resin (b2-1) It is not particularly limited, but it is preferably at least 10 mol %, more preferably at least 20 mol %, further preferably at least 30 mol %, still more preferably at least 40 mol %, and most preferably at least 50 mol % % or more, preferably more than 70 mol%, and preferably less than 99 mol%, more preferably less than 95 mol%, further preferably less than 90 mol%, especially preferably less than 85 mol% . The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-99 mol%, more preferably 20-99 mol%, further preferably 30-95 mol%, even more preferably 40-95 mol%. Mole %, preferably 50-90 mole %, most preferably 70-85 mole %. There exists a tendency for sensitivity to become high by setting it as more than the said lower limit. Moreover, it exists in the tendency for developability to improve by making it below the said upper limit.

於丙烯酸共聚樹脂(b2-1)包含式(I)所表示之部分結構之情形時，此外可包含之部分結構並無特別限定，從顯影密接性之觀點出發，例如較佳為包含下述通式(I')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains a partial structure represented by formula (I), the partial structure that can be included is not particularly limited, but from the viewpoint of image development adhesiveness, for example, it is preferable to include the following general A partial structure represented by formula (I').

[化33]

Figure 02_image065
[chem 33]
Figure 02_image065

式(I')中，R D表示氫原子或甲基，R E表示可具有取代基之烷基、可具有取代基之芳基(芳香族環基)、或可具有取代基之烯基。 In formula (I'), RD represents a hydrogen atom or a methyl group, and RE represents an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group), or an optionally substituted alkenyl group.

(R E)  式(I')中，R E表示可具有取代基之烷基、可具有取代基之芳基、或可具有取代基之烯基。  作為R E中之烷基，可例舉：直鏈狀、支鏈狀或環狀烷基。其碳數較佳為1以上，更佳為3以上，進而較佳為5以上，又，較佳為20以下，更佳為18以下，進而較佳為16以下，更進而較佳為14以下，尤佳為12以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為1～18，進而較佳為3～16，更進而較佳為3～14，尤佳為5～12。藉由設為上述下限值以上，有膜強度增高，顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 ( RE ) In formula (I'), RE represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. The alkyl group in R E may, for example, be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less , preferably below 12. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, further preferably 3-16, still more preferably 3-14, especially preferably 5-12. By setting it as more than the said lower limit, film strength becomes high and image development adhesiveness tends to improve. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烷基，例如可例舉：甲基、乙基、環己基、二環戊基、十二烷基。該等之中，從膜強度之觀點出發，較佳為二環戊基、十二烷基，更佳為二環戊基。  作為烷基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。As an alkyl group, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group are mentioned, for example. Among these, dicyclopentyl and dodecyl are preferred from the viewpoint of film strength, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, phenyl group, The carboxyl group, acryl group, and methacryl group are preferably hydroxyl groups and oligoglycol groups from the viewpoint of developability.

作為R E中之芳基(芳香族環基)，可例舉一價芳香族烴環基、一價芳香族雜環基。其碳數較佳為4以上，更佳為6以上，又，較佳為24以下，更佳為22以下，進而較佳為20以下，尤佳為18以下。上述上限及下限可任意地組合，例如，較佳為4～24，更佳為4～22，進而較佳為6～20，尤佳為6～18。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。  作為芳香族烴環基中之芳香族烴環，可為單環，亦可為縮合環，例如可例舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 111103644-A0304-2
環、聯三伸苯環、苊環、螢蒽環、茀環。  作為芳香族雜環基中之芳香族雜環基，可為單環，亦可為縮合環，例如可例舉：呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等之中，從硬化性之觀點出發，較佳為苯環基、萘環基，更佳為苯環基。  作為芳基可具有之取代基，例如可例舉：甲基、乙基、丙基、甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。 The aryl group (aromatic ring group) in R E may, for example, be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group. The carbon number is preferably at least 4, more preferably at least 6, and is preferably at most 24, more preferably at most 22, further preferably at most 20, especially preferably at most 18. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-24, more preferably 4-22, further preferably 6-20, especially preferably 6-18. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit. As the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group, it can be a single ring or a condensed ring, such as: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 111103644-A0304-2
ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. As the aromatic heterocyclic group in the aromatic heterocyclic group, it may be a single ring or a condensed ring, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrrole ring, Azole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, Furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridyl ring, pyridyl ring, pyrimidine ring, triglyceride ring, quinoline ring, Isoquinoline ring, zeoline ring, quinoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. Among them, from the viewpoint of curability, preferred are benzene ring group and naphthalene ring group, more preferably benzene ring group. As substituents that the aryl group may have, for example, methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, low A polyethylene glycol group, a phenyl group, and a carboxyl group are preferably a hydroxyl group and an oligoethylene glycol group from the viewpoint of developability.

作為R E中之烯基，可例舉：直鏈狀、支鏈狀或環狀烯基。其碳數較佳為2以上，又，較佳為22以下，更佳為20以下，進而較佳為18以下，更進而較佳為16以下，尤佳為14以下。例如，較佳為2～22，更佳為2～20，進而較佳為2～18，更進而較佳為2～16，尤佳為2～14。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 The alkenyl group in R E may, for example, be linear, branched or cyclic alkenyl. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, especially preferably 14 or less. For example, it is preferably 2-22, more preferably 2-20, still more preferably 2-18, still more preferably 2-16, especially preferably 2-14. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烯基，例如可例舉：乙烯基、丙烯基、丁烯基、環己烯基。該等之中，從硬化性之觀點出發，較佳為乙烯基、丙烯基，更佳為乙烯基。  作為烯基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。As an alkenyl group, a vinyl group, a propenyl group, a butenyl group, and a cyclohexenyl group are mentioned, for example. Among them, from the viewpoint of curability, vinyl and acryl are preferred, and vinyl is more preferred. Examples of substituents that an alkenyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoglycol, phenyl, The carboxyl group is preferably a hydroxyl group or an oligoethylene glycol group from the viewpoint of developability.

該等之中，從顯影性之觀點出發，作為R E，較佳為烷基、烯基，更佳為烷基，進而較佳為二環戊基。 Among them, from the viewpoint of developability, R E is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and still more preferably a dicyclopentyl group.

於丙烯酸共聚樹脂(b2-1)包含式(I')所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I')所表示之部分結構之含量並無特別限定，較佳為0.5莫耳%以上，更佳為1莫耳%以上，進而較佳為1.5莫耳%以上，尤佳為2莫耳%以上，又，較佳為90莫耳%以下，更佳為70莫耳%以下，進而較佳為50%莫耳以下，更進而較佳為30莫耳%以下，尤佳為10莫耳%以下。上述上限及下限可任意地組合，例如，較佳為0.5～90莫耳%，更佳為0.5～70莫耳%，進而較佳為1～50%莫耳，更進而較佳為1.5～30莫耳%，尤佳為2～10莫耳%。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the formula (I'), the content of the partial structure represented by the formula (I') contained in the acrylic copolymer resin (b2-1) has no Particularly limited, preferably at least 0.5 mol%, more preferably at least 1 mol%, further preferably at least 1.5 mol%, particularly preferably at least 2 mol%, and more preferably at most 90 mol% , more preferably less than 70 mol %, more preferably less than 50 mol %, still more preferably less than 30 mol %, especially preferably less than 10 mol %. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 0.5-90 mol%, more preferably 0.5-70 mol%, further preferably 1-50% mol, even more preferably 1.5-30 Mole %, preferably 2-10 Mole %. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

於丙烯酸共聚樹脂(b2-1)包含式(I)所表示之部分結構之情形時，從耐熱性、膜強度之觀點出發，較佳為進而包含式(I'')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains a partial structure represented by formula (I), it is preferable to further contain a partial structure represented by formula (I'') from the viewpoint of heat resistance and film strength.

[化34]

Figure 02_image067
[chem 34]
Figure 02_image067

式(I'')中，R F表示氫原子或甲基，R G表示可具有取代基之烷基、可具有取代基之烯基、羥基、羧基、鹵素原子、可具有取代基之烷氧基、硫醇基、或可具有取代基之烷基硫醚基。t表示0～5之整數。 In the formula (I''), R F represents a hydrogen atom or a methyl group, R G represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, or an alkoxy group that may have a substituent group, thiol group, or alkylsulfide group which may have a substituent. t represents an integer of 0-5.

(R G)  式(I'')中，R G表示可具有取代基之烷基、可具有取代基之烯基、羥基、羧基、鹵素原子、可具有取代基之烷氧基、硫醇基、或可具有取代基之烷基硫醚基。  作為R G中之烷基，可例舉：直鏈狀、支鏈狀或環狀烷基。其碳數較佳為1以上，更佳為3以上，進而較佳為5以上，又，較佳為20以下，更佳為18以下，進而較佳為16以下，更進而較佳為14以下，尤佳為12以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為1～18，進而較佳為3～16，更進而較佳為3～14，尤佳為5～12。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 (R G ) In the formula (I''), R G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, or a thiol group , or an alkylsulfide group which may have a substituent. The alkyl group in R G may, for example, be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less , preferably below 12. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, further preferably 3-16, still more preferably 3-14, especially preferably 5-12. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烷基，例如可例舉：甲基、乙基、環己基、二環戊基、十二烷基。該等之中，從顯影密接性之觀點出發，較佳為二環戊基、十二烷基，更佳為二環戊基。  作為烷基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。As an alkyl group, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group are mentioned, for example. Among them, dicyclopentyl and dodecyl are preferable from the viewpoint of image development adhesiveness, and dicyclopentyl is more preferable. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, phenyl group, The carboxyl group, acryl group, and methacryl group are preferably hydroxyl groups and oligoglycol groups from the viewpoint of developability.

作為R G中之烯基，可例舉：直鏈狀、支鏈狀或環狀烯基。其碳數較佳為2以上，又，較佳為22以下，更佳為20以下，進而較佳為18以下，更進而較佳為16以下，尤佳為14以下。上述上限及下限可任意地組合，例如，較佳為2～22，更佳為2～20，進而較佳為2～18，更進而較佳為2～16，尤佳為2～14。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 The alkenyl group in R G may, for example, be linear, branched or cyclic alkenyl. The carbon number is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less, especially preferably 14 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 2-22, more preferably 2-20, further preferably 2-18, still more preferably 2-16, especially preferably 2-14. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烯基，例如可例舉：乙烯基、丙烯基、丁烯基、環己烯基。該等之中，從硬化性之觀點出發，較佳為乙烯基、丙烯基，更佳為乙烯基。  作為烯基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。As an alkenyl group, a vinyl group, a propenyl group, a butenyl group, and a cyclohexenyl group are mentioned, for example. Among them, from the viewpoint of curability, vinyl and acryl are preferred, and vinyl is more preferred. Examples of substituents that an alkenyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoglycol, phenyl, The carboxyl group is preferably a hydroxyl group or an oligoethylene glycol group from the viewpoint of developability.

作為R G中之鹵素原子，可例舉：氟原子、氯原子、溴原子、碘原子，該等之中，從撥油墨性之觀點出發，較佳為氟原子。 The halogen atom in RG may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, a fluorine atom is preferred from the viewpoint of ink repellency.

作為R G中之烷氧基，可例舉：直鏈狀、支鏈狀或環狀烷氧基。其碳數較佳為1以上，又，較佳為20以下，更佳為18以下，進而較佳為16以下，更進而較佳為14以下，尤佳為12以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為1～18，進而較佳為1～16，更進而較佳為1～14，尤佳為1～12。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 The alkoxy group in R G may, for example, be a linear, branched or cyclic alkoxy group. The carbon number is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, still more preferably at most 14, and especially preferably at most 12. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, further preferably 1-16, still more preferably 1-14, especially preferably 1-12. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烷氧基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。Examples of substituents that an alkoxy group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, phenyl group , carboxyl group, acryl group, methacryl group, from the viewpoint of developability, preferably a hydroxyl group and an oligoethylene glycol group.

作為R G中之烷基硫醚基，可例舉：直鏈狀、支鏈狀或環狀烷基硫醚基。其碳數較佳為1以上，又，較佳為20以下，更佳為18以下，進而較佳為16以下，更進而較佳為14以下，尤佳為12以下。上述上限及下限可任意地組合，例如，較佳為1～20，更佳為1～18，進而較佳為1～16，更進而較佳為1～14，尤佳為1～12。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。 As the alkyl sulfide group in R G , linear, branched or cyclic alkyl sulfide groups may, for example, be mentioned. The carbon number is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, still more preferably at most 14, and especially preferably at most 12. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, further preferably 1-16, still more preferably 1-14, especially preferably 1-12. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

作為烷基硫醚基，例如可例舉：甲基硫醚基、乙基硫醚基、丙基硫醚基、丁基硫醚基。該等之中，從顯影性之觀點出發，較佳為甲基硫醚基、乙基硫醚基。  作為烷基硫醚基中之烷基可具有之取代基，例如可例舉：甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基、丙烯醯基、甲基丙烯醯基，從顯影性之觀點出發，較佳為羥基、低聚乙二醇基。As an alkyl sulfide group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group are mentioned, for example. Among these, methyl sulfide group and ethyl sulfide group are preferable from the viewpoint of developability. Examples of substituents that the alkyl group in the alkylsulfide group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoethylene A glycol group, a phenyl group, a carboxyl group, an acryl group, a methacryl group, and a hydroxyl group and an oligoethylene glycol group are preferable from a viewpoint of developability.

該等之中，從顯影性之觀點出發，作為R G，較佳為羥基、羧基，更佳為羧基。 Among them, from the viewpoint of developability, R G is preferably a hydroxyl group or a carboxyl group, more preferably a carboxyl group.

(t)  式(I'')中，t表示0～5之整數。從顯影性之觀點出發，較佳為0～2，更佳為0～1，進而較佳為0。(t) In formula (I''), t represents an integer from 0 to 5. From the viewpoint of developability, it is preferably 0-2, more preferably 0-1, and still more preferably 0.

於丙烯酸共聚樹脂(b2-1)包含式(I'')所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I'')所表示之部分結構之含量並無特別限定，較佳為1莫耳%以上，更佳為2莫耳%以上，進而較佳為3莫耳%以上，尤佳為5莫耳%以上，又，較佳為90莫耳%以下，更佳為70莫耳%以下，進而較佳為50莫耳%以下，更進而較佳為30莫耳%以下，尤佳為20莫耳%以下，最佳為10莫耳%以下。上述上限及下限可任意地組合，例如，較佳為1～90莫耳%，更佳為1～70莫耳%，進而較佳為2～50莫耳%，更進而較佳為2～30莫耳%，尤佳為3～20莫耳%，最佳為5～10莫耳%。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the formula (I''), the content of the partial structure represented by the formula (I'') contained in the acrylic copolymer resin (b2-1) It is not particularly limited, but it is preferably at least 1 mol%, more preferably at least 2 mol%, further preferably at least 3 mol%, especially preferably at least 5 mol%, and more preferably 90 mol% % or less, more preferably less than 70 mol%, more preferably less than 50 mol%, even more preferably less than 30 mol%, especially preferably less than 20 mol%, most preferably less than 10 mol% . The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-90 mol%, more preferably 1-70 mol%, further preferably 2-50 mol%, even more preferably 2-30 Mole %, preferably 3-20 Mole %, most preferably 5-10 Mole %. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

於丙烯酸共聚樹脂(b2-1)包含式(I)所表示之部分結構之情形時，從顯影性之觀點出發，較佳為進而包含下述通式(I''')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains a partial structure represented by formula (I), it is preferable to further contain a partial structure represented by the following general formula (I''') from the viewpoint of developability .

[化35]

Figure 02_image069
[chem 35]
Figure 02_image069

上述式(I''')中，R H表示氫原子或甲基。 In the above formula (I'''), R H represents a hydrogen atom or a methyl group.

於丙烯酸共聚樹脂(b2-1)包含式(I''')所表示之部分結構之情形時，丙烯酸共聚樹脂(b2-1)中所含之式(I''')所表示之部分結構之含量並無特別限定，較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為30莫耳%以上，又，較佳為90莫耳%以下，更佳為80莫耳%以下，進而較佳為70莫耳%以下，尤佳為50莫耳%以下。上述上限及下限可任意地組合，例如，較佳為5～90莫耳%，更佳為5～80莫耳%，進而較佳為10～70莫耳%，尤佳為30～50莫耳%。藉由設為上述下限值以上，有殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains a partial structure represented by the formula (I'''), the partial structure represented by the formula (I''') contained in the acrylic copolymer resin (b2-1) The content is not particularly limited, preferably more than 5 mol%, more preferably more than 10 mol%, more preferably more than 30 mol%, and preferably less than 90 mol%, more preferably 80 mol%. Mole% or less, more preferably 70 mole% or less, especially preferably 50 mole% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-90 mol%, more preferably 5-80 mol%, further preferably 10-70 mol%, especially preferably 30-50 mol% %. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit.

丙烯酸共聚樹脂(b2)之酸值並無特別限定，較佳為5 mgKOH/g以上，更佳為10 mgKOH/g以上，進而較佳為20 mgKOH/g以上，更進而較佳為25 mgKOH/g以上，又，較佳為100 mgKOH/g以下，更佳為80 mgKOH/g以下，進而較佳為60 mgKOH/g以下，更進而較佳為40 mgKOH/g以下。上述上限及下限可任意地組合，例如，較佳為5～100 mgKOH/g，更佳為10～80 mgKOH/g，進而較佳為20～60 mgKOH/g，更進而較佳為25～40 mgKOH/g。藉由設為上述下限值以上，有殘渣減少之傾向。又，藉由設為上述上限值以下，有顯影密接性提高之傾向。The acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably at least 5 mgKOH/g, more preferably at least 10 mgKOH/g, still more preferably at least 20 mgKOH/g, still more preferably at least 25 mgKOH/g g or more, and preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, further preferably 60 mgKOH/g or less, still more preferably 40 mgKOH/g or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-100 mgKOH/g, more preferably 10-80 mgKOH/g, further preferably 20-60 mgKOH/g, still more preferably 25-40 mgKOH/g. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. Moreover, there exists a tendency for image development adhesiveness to improve by making it below the said upper limit.

丙烯酸共聚樹脂(b2)之重量平均分子量(Mw)並無特別限定，較佳為1000以上，更佳為2000以上，進而較佳為3000以上，更佳為4000以上，尤佳為5000以上，又，較佳為30000以下，更佳為20000以下，進而較佳為15000以下，更佳為10000以下。尤佳為8000以下。上述上限及下限可任意地組合，例如，較佳為1000～30000，更佳為2000～20000，進而較佳為3000～15000，更進而較佳為4000～10000，尤佳為5000～8000。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有殘渣減少之傾向。The weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, but is preferably at least 1000, more preferably at least 2000, further preferably at least 3000, more preferably at least 4000, especially preferably at least 5000, and , preferably less than 30,000, more preferably less than 20,000, further preferably less than 15,000, more preferably less than 10,000. Preferably it is below 8000. The above upper and lower limits can be combined arbitrarily, for example, preferably 1000-30000, more preferably 2000-20000, further preferably 3000-15000, still more preferably 4000-10000, especially preferably 5000-8000. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.

於(B)鹼可溶性樹脂包含丙烯酸共聚樹脂(b2)之情形時，(B)鹼可溶性樹脂中所含之丙烯酸共聚樹脂(b2)之含量並無特別限定，較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上，尤佳為20質量%以上，又，通常較佳為100質量%以下，更佳為80質量%以下，進而較佳為50質量%以下。上述上限及下限可任意地組合，例如，較佳為5～100質量%，更佳為10～100質量%，進而較佳為15～80質量%，尤佳為20～50質量%。藉由設為上述下限值以上，有顯影溶解性變良好之傾向。藉由設為上述上限值以下，有錐角變高之傾向。When the (B) alkali-soluble resin contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably Preferably at least 10% by mass, more preferably at least 15% by mass, especially preferably at least 20% by mass, and usually preferably at most 100% by mass, more preferably at most 80% by mass, further preferably at most 50% by mass the following. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-100 mass%, more preferably 10-100 mass%, further preferably 15-80 mass%, especially preferably 20-50 mass%. Image development solubility tends to become favorable by setting it as more than the said lower limit. There exists a tendency for taper angle to become high by making it below the said upper limit.

於(B)鹼可溶性樹脂中，可單獨含有環氧(甲基)丙烯酸酯樹脂(b1)及丙烯酸共聚樹脂(b2)中之任一種，亦可含有兩者。進而，於(B)鹼可溶性樹脂中，亦可含有鹼可溶性樹脂(b)以外之鹼可溶性樹脂。In (B) alkali-soluble resin, any one of epoxy (meth)acrylate resin (b1) and acrylic copolymer resin (b2) may be contained independently, and both may be contained. Furthermore, alkali-soluble resins other than alkali-soluble resin (b) may be contained in (B) alkali-soluble resin.

於感光性樹脂組合物之全部固形物成分中，本發明之感光性樹脂組合物中之(B)鹼可溶性樹脂之含量較佳為5質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，更進而較佳為30質量%以上，尤佳為40質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，進而較佳為70質量%以下。上述上限及下限可任意地組合，例如，較佳為5～90質量%，更佳為10～90質量%，進而較佳為20～80質量%，更進而較佳為30～70質量%。藉由設為上述下限值以上，有顯影性提高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣減少之傾向。In the total solid content of the photosensitive resin composition, the content of (B) alkali-soluble resin in the photosensitive resin composition of the present invention is preferably at least 5% by mass, more preferably at least 10% by mass, and even more preferably It is at least 20% by mass, more preferably at least 30% by mass, especially preferably at least 40% by mass, and more preferably at most 90% by mass, more preferably at most 80% by mass, further preferably at most 70% by mass . The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-90 mass%, more preferably 10-90 mass%, further preferably 20-80 mass%, still more preferably 30-70 mass%. There exists a tendency for developability to improve by making it more than the said lower limit. Moreover, there exists a tendency for the outgassing at the time of a device to emit light to reduce by making it below the said upper limit.

於本發明之感光性樹脂組合物包含環氧(甲基)丙烯酸酯樹脂(b1)之情形時，環氧(甲基)丙烯酸酯樹脂(b1)之含量並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為5質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，更進而較佳為30質量%以上，尤佳為40質量%以上，又，較佳為90質量%以下，更佳為70質量%以下，進而較佳為60質量%以下，尤佳為50質量%以下。上述上限及下限可任意地組合，例如，較佳為5～90質量%，更佳為10～90質量%，進而較佳為20～70質量%，更進而較佳為30～60質量%，尤佳為40～50質量%。藉由設為上述下限值以上，有顯影性提高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣減少之傾向。In the case where the photosensitive resin composition of the present invention includes epoxy (meth)acrylate resin (b1), the content of epoxy (meth)acrylate resin (b1) is not particularly limited. In the total solid content of the substance, it is preferably at least 5% by mass, more preferably at least 10% by mass, more preferably at least 20% by mass, still more preferably at least 30% by mass, and most preferably at least 40% by mass , Also, preferably at most 90% by mass, more preferably at most 70% by mass, further preferably at most 60% by mass, especially preferably at most 50% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-90% by mass, more preferably 10-90% by mass, further preferably 20-70% by mass, still more preferably 30-60% by mass, More preferably, it is 40 to 50% by mass. There exists a tendency for developability to improve by making it more than the said lower limit. Moreover, there exists a tendency for the outgassing at the time of a device to emit light to reduce by making it below the said upper limit.

又，於本發明之感光性樹脂組合物包含丙烯酸共聚樹脂(b2)之情形時，丙烯酸共聚樹脂(b2)之含量並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為5質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，更進而較佳為30質量%以上，尤佳為40質量%以上，又，較佳為90質量%以下，更佳為80質量%以下，進而較佳為70質量%以下。上述上限及下限可任意地組合，例如，較佳為5～90質量%，更佳為10～90質量%，進而較佳為20～80質量%，更進而較佳為30～70質量%。藉由設為上述下限值以上，有顯影性提高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣減少之傾向。In addition, when the photosensitive resin composition of the present invention contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) is not particularly limited, but preferably It is at least 5% by mass, more preferably at least 10% by mass, more preferably at least 20% by mass, still more preferably at least 30% by mass, especially preferably at least 40% by mass, and more preferably at most 90% by mass , more preferably 80% by mass or less, further preferably 70% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-90 mass%, more preferably 10-90 mass%, further preferably 20-80 mass%, still more preferably 30-70 mass%. There exists a tendency for developability to improve by making it more than the said lower limit. Moreover, there exists a tendency for the outgassing at the time of a device to emit light to reduce by making it below the said upper limit.

又，感光性樹脂組合物之全部固形物成分中之(B)鹼可溶性樹脂及(D)光聚合性化合物之含量的合計較佳為5質量%以上，更佳為10質量%以上，進而較佳為30質量%以上，更進而較佳為50質量%以上，尤佳為70質量%以上，進而尤佳為80質量%以上，最佳為90質量%以上，又，較佳為99質量%以下，更佳為97質量%以下，進而較佳為95質量%以下。上述上限及下限可任意地組合，例如，較佳為5～99質量%，更佳為10～99質量%，進而較佳為30～99質量%，更進而較佳為50～97質量%，特別較佳為70～97質量%，尤佳為80～95質量%，最佳為90～95質量%。藉由設為上述下限值以上，有硬化性提高之傾向。又，藉由設為上述上限值以下，有元件發光時之釋氣減少之傾向。In addition, the total content of the (B) alkali-soluble resin and (D) photopolymerizable compound in the total solid content of the photosensitive resin composition is preferably at least 5% by mass, more preferably at least 10% by mass, and even more preferably Preferably at least 30% by mass, more preferably at least 50% by mass, especially preferably at least 70% by mass, still more preferably at least 80% by mass, most preferably at least 90% by mass, and more preferably at least 99% by mass It is less than or equal to 97% by mass, more preferably less than or equal to 95% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-99% by mass, more preferably 10-99% by mass, further preferably 30-99% by mass, still more preferably 50-97% by mass, Especially preferably, it is 70-97 mass %, Especially preferably, it is 80-95 mass %, Most preferably, it is 90-95 mass %. There exists a tendency for curability to improve by making it more than the said lower limit. Moreover, there exists a tendency for the outgassing at the time of a device to emit light to reduce by making it below the said upper limit.

作為感光性樹脂組合物中之(B)鹼可溶性樹脂相對於(D)光聚合性化合物之調配比，相對於(D)光聚合性化合物100質量份，較佳為50質量份以上，更佳為60質量份以上，進而較佳為70質量份以上，尤佳為80質量份以上，又，較佳為500質量份以下，更佳為400質量份以下，進而較佳為300質量份以下。全部上限及下限可任意地組合，例如，較佳為50～500質量份，更佳為60～400質量份，進而較佳為70～300質量份。藉由設為上述下限值以上，有顯影密接性提高之傾向。又，藉由設為上述上限值以下，有硬化性提高之傾向。The ratio of (B) alkali-soluble resin to (D) photopolymerizable compound in the photosensitive resin composition is preferably 50 parts by mass or more, more preferably 100 parts by mass of (D) photopolymerizable compound It is 60 mass parts or more, more preferably 70 mass parts or more, especially preferably 80 mass parts or more, and preferably 500 mass parts or less, more preferably 400 mass parts or less, still more preferably 300 mass parts or less. All upper limits and lower limits can be combined arbitrarily, for example, Preferably it is 50-500 mass parts, More preferably, it is 60-400 mass parts, More preferably, it is 70-300 mass parts. Image development adhesiveness tends to improve by making it more than the said lower limit. Moreover, there exists a tendency for curability to improve by making it below the said upper limit.

[1-1-3](C)成分；光聚合起始劑  本發明之感光性樹脂組合物亦可進而含有不同於(A)共聚物之(C)光聚合起始劑。(C)光聚合起始劑只要為利用活性光線使(D)光聚合性化合物聚合，例如使(D)光聚合性化合物所具有之乙烯性不飽和鍵聚合之化合物，則並無特別限定。[1-1-3] Component (C); Photopolymerization initiator The photosensitive resin composition of the present invention may further contain (C) a photopolymerization initiator different from the (A) copolymer. The (C) photopolymerization initiator is not particularly limited as long as it polymerizes the (D) photopolymerizable compound with active light, for example, polymerizes the ethylenically unsaturated bond of the (D) photopolymerizable compound.

於本發明之感光性樹脂組合物包含(C)光聚合起始劑之情形時，可使用該領域中通常使用之光聚合起始劑。作為此種光聚合起始劑，例如可例舉：日本專利特開昭59-152396號公報、日本專利特開昭61-151197號公報中所記載之包含二茂鈦化合物之茂金屬化合物；日本專利特開2000-56118號公報中所記載之六芳基聯咪唑衍生物類；日本專利特開平10-39503號公報記載之鹵甲基化㗁二唑衍生物類、鹵甲基均三𠯤衍生物類、N-苯基甘胺酸等N-芳基-α-胺基酸類、N-芳基-α-胺基酸鹽類、N-芳基-α-胺基酸酯類等自由基活性劑、α-胺烷基苯酮衍生物類；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報等中所記載之肟酯系化合物。When the photosensitive resin composition of this invention contains (C) photoinitiator, the photoinitiator normally used in this field can be used. As such a photopolymerization initiator, for example, a metallocene compound containing a titanocene compound described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; Hexaarylbiimidazole derivatives described in Japanese Patent Laid-Open No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-triazole derivatives described in Japanese Patent Laid-Open No. 10-39503 Species, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radicals Active agents, α-aminoalkylphenone derivatives; oxime ester compounds described in JP-A-2000-80068, JP-A-2006-36750, etc.

作為茂金屬化合物，例如可例舉：二氯化二環戊二烯基鈦、二環戊二烯基二苯基鈦、二環戊二烯基雙(2,3,4,5,6-五氟苯基)鈦、二環戊二烯基雙(2,3,5,6-四氟苯基)鈦、二環戊二烯基雙(2,4,6-三氟苯基)鈦、二環戊二烯基二(2,6-二氟苯基)鈦、二環戊二烯基二(2,4-二氟苯基)鈦、二(甲基環戊二烯基)雙(2,3,4,5,6-五氟苯基)鈦、二(甲基環戊二烯基)雙(2,6-二氟苯基)鈦、二環戊二烯基[2,6-二氟-3-(吡咯-1-基)-苯基]鈦。As the metallocene compound, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6- Pentafluorophenyl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienylbis(2,4,6-trifluorophenyl)titanium , Dicyclopentadienyl bis (2,6-difluorophenyl) titanium, dicyclopentadienyl bis (2,4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, dicyclopentadienyl[2, 6-Difluoro-3-(pyrrol-1-yl)-phenyl]titanium.

作為聯咪唑衍生物類，例如可例舉：2-(2'-氯苯基)-4,5-二苯基咪唑二聚物、2-(2'-氯苯基)-4,5-雙(3'-甲氧基苯基)咪唑二聚物、2-(2'-氟苯基)-4,5-二苯基咪唑二聚物、2-(2'-甲氧基苯基)-4,5-二苯基咪唑二聚物、(4'-甲氧基苯基)-4,5-二苯基咪唑二聚物。Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5- Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl )-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

作為鹵甲基化㗁二唑衍生物類，例如可例舉：2-三氯甲基-5-(2'-苯并呋喃基)-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-苯并呋喃基)乙烯基]-1,3,4-㗁二唑、2-三氯甲基-5-[β-(2'-(6''-苯并呋喃基)乙烯基)]-1,3,4-㗁二唑、2-三氯甲基-5-呋喃基-1,3,4-㗁二唑。Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloro Methyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6' '-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

作為鹵甲基均三𠯤衍生物類，例如可例舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)均三𠯤、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)均三𠯤、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)均三𠯤、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)均三𠯤。Examples of the halomethyl-s-trimethanium derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trimethanone, 2-(4-methoxy Nylnaphthyl)-4,6-bis(trichloromethyl)-s-trimethanone, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-trimethanone, 2-( 4-Ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)same.

作為α-胺烷基苯酮衍生物類，例如可例舉：2-甲基-1[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-嗎啉基苯基)丁烷-1-酮、3,6-雙(2-甲基-2-嗎啉基丙醯基)-9-辛基咔唑。Examples of α-aminoalkylphenone derivatives include: 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4 -morpholinylphenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-octylcarbazole.

作為(C)光聚合起始劑，尤其是從感度或製版性方面出發，肟酯系化合物較有效，例如於使用包含酚性羥基之鹼可溶性樹脂之情形時，從感度方面出發變得不利，故此種感度優異之肟酯系化合物尤其有用。肟酯系化合物由於光反應之量子產率較高，所生成之自由基之活性較高，故對熱反應較穩定，少量即能夠獲得高感度之感光性樹脂組合物。As (C) photopolymerization initiator, especially in terms of sensitivity and plate making, oxime ester compounds are more effective, for example, when using an alkali-soluble resin containing phenolic hydroxyl group, it becomes disadvantageous in terms of sensitivity, Therefore, such oxime ester compounds with excellent sensitivity are particularly useful. Due to the high quantum yield of the photoreaction and the high activity of the generated free radicals, the oxime ester compound is relatively stable to the thermal reaction, and a photosensitive resin composition with high sensitivity can be obtained with a small amount.

作為肟酯系化合物，例如可例舉下述通式(IV)所表示之化合物。As an oxime ester type compound, the compound represented by following general formula (IV), for example is mentioned.

[化36]

Figure 02_image071
[chem 36]
Figure 02_image071

式(IV)中，R 21a表示氫原子、可具有取代基之烷基、或可具有取代基之芳香族環基。  R 21b表示包含芳香環之任意取代基。  R 22a表示可具有取代基之烷醯基、或可具有取代基之芳醯基。  n表示0或1之整數。 In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents an optional substituent including an aromatic ring. R 22a represents an alkanoyl group which may have a substituent, or an arayl group which may have a substituent. n represents an integer of 0 or 1.

R 21a中之烷基之碳數並無特別限定，從對溶劑之溶解性、感度、噴墨塗佈性之觀點出發，較佳為1以上，更佳為2以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。作為烷基，例如可例舉：甲基、乙基、丙基、環戊基乙基、丙基。  作為烷基可具有之取代基，例如可例舉：芳香族環基、羥基、羧基、鹵素原子、胺基、醯胺基、4-(2-甲氧基-1-甲基)乙氧基-2-甲基苯基、N-乙醯-N-乙醯氧基胺基。作為烷基，從合成容易性之觀點出發，較佳為未經取代。 The number of carbon atoms in the alkyl group in R 21a is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and more preferably 20 from the viewpoint of solvent solubility, sensitivity, and inkjet coating properties. or less, more preferably 15 or less, still more preferably 10 or less. As an alkyl group, a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group are mentioned, for example. Examples of substituents that the alkyl group may have include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amine group, amido group, 4-(2-methoxy-1-methyl)ethoxy group -2-methylphenyl, N-acetyl-N-acetyloxyamino. The alkyl group is preferably unsubstituted from the viewpoint of ease of synthesis.

作為R 21a中之芳香族環基，較佳為芳香族烴環基及芳香族雜環基。芳香族環基之碳數並無特別限定，從對感光性樹脂組合物之溶解性之觀點出發，較佳為5以上。又，從顯影性之觀點出發，較佳為30以下，更佳為20以下，進而較佳為12以下。上述上限及下限可任意地組合，例如，較佳為5～30，更佳為5～20，進而較佳為5～12。 The aromatic ring group in R 21a is preferably an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Moreover, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 5-30, more preferably 5-20, still more preferably 5-12.

作為芳香族環基，例如可例舉：苯基、萘基、吡啶基、呋喃基，該等之中，從顯影性之觀點出發，較佳為苯基、萘基，更佳為苯基。  作為芳香族環基可具有之取代基，例如可例舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基、烷氧基、該等取代基連結而成之基，從顯影性之觀點出發，較佳為烷基、烷氧基、將該等連結而成之基，更佳為連結後之烷氧基。  該等之中，從噴墨塗佈性之觀點出發，較佳為R 21a可具有取代基之烷基。 As an aromatic ring group, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group are mentioned, for example, Among these, a phenyl group and a naphthyl group are preferable from a developable viewpoint, and a phenyl group is more preferable. The substituents that the aromatic ring group may have include, for example, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amido groups, alkyl groups, alkoxy groups, and groups formed by linking these substituents. From the perspective of developability From the standpoint, it is preferably an alkyl group, an alkoxy group, or a group formed by linking them, and more preferably an alkoxy group after linking. Among them, from the viewpoint of inkjet coatability, R 21a is preferably an alkyl group which may have a substituent.

作為R 21b，較佳為可經取代之咔唑基、可經取代之9-氧硫𠮿

Figure 111103644-A0304-1
基、可經取代之二苯硫醚基、可經取代之茀基、可經取代之吲哚基。該等之中，從噴墨塗佈性之觀點出發，較佳為可經取代之二苯硫醚基。 R 21b is preferably carbazolyl which may be substituted, or 9-oxothiol which may be substituted
Figure 111103644-A0304-1
group, diphenylsulfide group which may be substituted, fenyl group which may be substituted, indolyl group which may be substituted. Among these, diphenylsulfide groups which may be substituted are preferred from the viewpoint of inkjet coatability.

R 22a中之烷醯基之碳數並無特別限定，從對溶劑之溶解性或感度之觀點出發，較佳為2以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下，更佳為5以下。作為烷醯基，例如可例舉：乙醯基(acetyl)、乙醯基(ethanoyl)、丙醯基、丁醯基。  作為烷醯基可具有之取代基，例如可例舉：芳香族環基、羥基、羧基、鹵素原子、胺基、醯胺基。作為烷醯基，從合成容易性之觀點出發，較佳為未經取代。 The carbon number of the alkyl group in R 22a is not particularly limited, but from the viewpoint of solubility or sensitivity to solvents, it is preferably at least 2, preferably at most 20, more preferably at most 15, and still more preferably 10 or less, more preferably 5 or less. As an alkyl group, an acetyl group (acetyl), an ethanoyl group (ethanoyl), a propionyl group, and a butyryl group are mentioned, for example. Examples of substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amido group. The alkanoyl group is preferably unsubstituted from the viewpoint of easiness of synthesis.

R 22a中之芳醯基之碳數並無特別限定，從對溶劑之溶解性或感度之觀點出發，較佳為7以上，更佳為8以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。作為芳醯基，例如可例舉苯甲醯基、萘甲醯基。  作為芳醯基可具有之取代基，例如可例舉：羥基、羧基、鹵素原子、胺基、醯胺基、烷基。作為芳醯基，從合成容易性之觀點出發，較佳為未經取代。  該等之中，從感度之觀點出發，較佳為R 22a可具有取代基之烷醯基，更佳為未經取代之烷醯基，進而較佳為乙醯基。 The carbon number of the aryl group in R 22a is not particularly limited, but from the viewpoint of solubility or sensitivity to solvents, it is preferably 7 or more, more preferably 8 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. As an aryl group, a benzoyl group and a naphthyl group are mentioned, for example. As a substituent which an aramide group may have, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, and an alkyl group are mentioned, for example. The aryl group is preferably unsubstituted from the viewpoint of ease of synthesis. Among them, from the viewpoint of sensitivity, R 22a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably an acetyl group.

例如可使用日本專利第4454067號公報、國際公開2002/100903號、國際公開2012/45736號、國際公開2015/36910號、國際公開2006/18973號、國際公開2008/78678號、日本專利第4818458號公報、國際公開2005/80338號、國際公開2008/75564號、國際公開2009/131189號、國際公開2009/131189號、國際公開2010/133077號、國際公開2010/102502號、國際公開2012/68879號中所記載之光聚合起始劑。For example, Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012/45736, International Publication No. 2015/36910, International Publication No. 2006/18973, International Publication No. 2008/78678, and Japanese Patent No. 4818458 can be used. Gazette, International Publication No. 2005/80338, International Publication No. 2008/75564, International Publication No. 2009/131189, International Publication No. 2009/131189, International Publication No. 2010/133077, International Publication No. 2010/102502, International Publication No. 2012/68879 The photopolymerization initiator described in.

光聚合起始劑可單獨使用一種，亦可組合兩種以上使用。於光聚合起始劑中，為了提高感度，可視需要調配與圖像曝光之光源之波長對應之增感色素、聚合促進劑。作為增感色素，例如可例舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報中所記載之𠮿

Figure 111103644-A0304-1
色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中所記載之具有雜環之香豆素色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中所記載之3-酮香豆素化合物；日本專利特開平6-19240號公報中所記載之吡咯亞甲基色素；日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報中所記載之具有二烷基胺基苯骨架之色素。The photopolymerization initiator may be used alone or in combination of two or more. In the photopolymerization initiator, in order to increase the sensitivity, a sensitizing pigment and a polymerization accelerator corresponding to the wavelength of the light source for image exposure may be formulated as needed. As a sensitizing dye, for example, the phospholipids described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756 can be cited.
Figure 111103644-A0304-1
Pigment; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, the coumarin pigment with a heterocycle; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open 5- The 3-ketocoumarin compound described in the No. 289335 bulletin; the pyrromethene pigment described in the Japanese Patent Laid-Open Publication No. 6-19240; Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japan Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, and Japanese Patent Laid-Open No. 5-107761 A pigment having a dialkylaminobenzene skeleton described in the gazette, Japanese Patent Laid-Open No. 5-210240, and Japanese Patent Laid-Open No. 4-288818.

該等增感色素之中，較佳為含胺基之增感色素，更佳為於同一分子內具有胺基及苯基之化合物。例如，進而較佳為4,4'-二甲基胺基二苯甲酮、4,4'-二乙基胺基二苯甲酮、2-胺基二苯甲酮、4-胺基二苯甲酮、4,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、3,4-二胺基二苯甲酮等二苯甲酮系化合物；2-(對二甲基胺基苯基)苯并㗁唑、2-(對二乙基胺基苯基)苯并㗁唑、2-(對二甲基胺基苯基)苯并[4,5]苯并㗁唑、2-(對二甲基胺基苯基)苯并[6,7]苯并㗁唑、2,5-雙(對二乙基胺基苯基)-1,3,4-㗁唑、2-(對二甲基胺基苯基)苯并噻唑、2-(對二乙基胺基苯基)苯并噻唑、2-(對二甲基胺基苯基)苯并咪唑、2-(對二乙基胺基苯基)苯并咪唑、2,5-雙(對二乙基胺基苯基)-1,3,4-噻二唑、(對二甲基胺基苯基)吡啶、(對二乙基胺基苯基)吡啶、(對二甲基胺基苯基)喹啉、(對二乙基胺基苯基)喹啉、(對二甲基胺基苯基)嘧啶、(對二乙基胺基苯基)嘧啶等含對二烷基胺基苯基化合物。該等之中，尤佳為4,4'-二烷基胺基二苯甲酮。  增感色素可單獨使用一種，亦可併用兩種以上。Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. For example, further preferred are 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminodiphenone Benzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone compounds;2 -(p-Dimethylaminophenyl)benzoxazole, 2-(p-Diethylaminophenyl)benzoxazole, 2-(p-Dimethylaminophenyl)benzo[4, 5] benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3 ,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl) Benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethyl Aminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethyl p-dialkylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine and other p-dialkylaminophenyl compounds. Among these, 4,4'-dialkylaminobenzophenone is particularly preferable. One kind of sensitizing pigment can be used alone, or two or more kinds can be used in combination.

作為聚合促進劑，例如可使用對二甲基胺基苯甲酸乙酯、苯甲酸2-二甲基胺基乙酯等芳香族胺；正丁基胺、N-甲基二乙醇胺等脂肪族胺。聚合促進劑可單獨使用一種，亦可併用兩種以上。As a polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as n-butylamine and N-methyldiethanolamine can be used . A polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

於本發明之感光性樹脂組合物含有(C)光聚合起始劑之情形時，(C)光聚合起始劑之含有比率並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.01質量%以上，更佳為0.1質量%以上，進而較佳為1質量%以上，更進而較佳為2質量%以上，尤佳為3質量%以上，又，較佳為25質量%以下，更佳為20質量%以下，進而較佳為15質量%以下，更進而較佳為10質量%以下，尤佳為7質量%以下，最佳為5質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～25質量%，更佳為0.01～20質量%，進而較佳為0.1～15質量%，更進而較佳為1～10質量%，特別較佳為2～7質量%，更佳為3～5質量%。藉由設為上述下限值以上，有撥油墨性提高之傾向。藉由設為上述上限值以下，有殘渣減少之傾向。In the case where the photosensitive resin composition of the present invention contains (C) photopolymerization initiator, the content ratio of (C) photopolymerization initiator is not particularly limited, and the total solid content of the photosensitive resin composition , preferably more than 0.01% by mass, more preferably more than 0.1% by mass, more preferably more than 1% by mass, more preferably more than 2% by mass, especially preferably more than 3% by mass, and more preferably 25% by mass Mass % or less, more preferably 20 mass % or less, further preferably 15 mass % or less, still more preferably 10 mass % or less, especially preferably 7 mass % or less, most preferably 5 mass % or less. The upper and lower limits above can be combined arbitrarily, for example, preferably 0.01-25% by mass, more preferably 0.01-20% by mass, further preferably 0.1-15% by mass, still more preferably 1-10% by mass, Especially preferably, it is 2-7 mass %, More preferably, it is 3-5 mass %. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

作為感光性樹脂組合物中之(C)光聚合起始劑相對於(D)光聚合性化合物之調配比，相對於(D)光聚合性化合物100質量份，較佳為1質量份以上，更佳為5質量份以上，進而較佳為10質量份以上，更進而較佳為15質量份以上，尤佳為20質量份以上，又，較佳為200質量份以下，更佳為100質量份以下，進而較佳為50質量份以下，尤佳為30質量份以下。上述上限及下限可任意地組合，例如，較佳為1～200質量份，更佳為5～200質量份，進而較佳為10～100質量份，更進而較佳為15～50質量份，尤佳為20～30質量份。藉由設為上述下限值以上，有撥油墨性提高之傾向。藉由設為上述上限值以下，有殘渣減少之傾向。The compounding ratio of (C) photopolymerization initiator to (D) photopolymerizable compound in a photosensitive resin composition is preferably 1 mass part or more with respect to 100 mass parts of (D) photopolymerizable compound, More preferably at least 5 parts by mass, more preferably at least 10 parts by mass, still more preferably at least 15 parts by mass, especially preferably at least 20 parts by mass, and more preferably at most 200 parts by mass, more preferably at least 100 parts by mass It is not more than 50 parts by mass, more preferably not more than 50 parts by mass, especially preferably not more than 30 parts by mass. The upper and lower limits above can be combined arbitrarily, for example, preferably 1-200 parts by mass, more preferably 5-200 parts by mass, further preferably 10-100 parts by mass, still more preferably 15-50 parts by mass, Most preferably, it is 20-30 mass parts. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

[1-1-4](D)成分；光聚合性化合物  本發明之感光性樹脂組合物含有(D)光聚合性化合物。認為藉由包含(D)光聚合性化合物，成為高感度。  於本發明中，(D)光聚合性化合物係不同於(A)共聚物之成分，於存在相當於(A)共聚物之光聚合性化合物之情形時，係作為(A)共聚物處理。  作為此處所使用之光聚合性化合物，意指分子內具有1個以上乙烯性不飽和鍵(乙烯性雙鍵)之化合物，從聚合性、交聯性、及可擴大伴隨其之曝光部與非曝光部之顯影液溶解性之差異等方面出發，較佳為分子內具有2個以上乙烯性不飽和鍵之化合物。又，進而較佳為其不飽和鍵為來自(甲基)丙烯醯氧基者，即，(甲基)丙烯酸酯化合物。[1-1-4] Component (D); photopolymerizable compound The photosensitive resin composition of the present invention contains (D) a photopolymerizable compound. It is considered that high sensitivity is achieved by including (D) a photopolymerizable compound. In the present invention, the (D) photopolymerizable compound is a component different from the (A) copolymer, and when there is a photopolymerizable compound corresponding to the (A) copolymer, it is treated as the (A) copolymer. The photopolymerizable compound used here means a compound having one or more ethylenically unsaturated bonds (ethylenically double bonds) in the molecule. From the viewpoint of the difference in solubility of the developer in the exposed part, etc., a compound having two or more ethylenically unsaturated bonds in the molecule is preferable. Furthermore, it is more preferable that the unsaturated bond is derived from a (meth)acryloxy group, that is, a (meth)acrylate compound.

於本發明之感光性樹脂組合物中，作為(D)光聚合性化合物，尤其理想為使用1分子中具有2個以上乙烯性不飽和鍵之多官能乙烯性單體。多官能乙烯性單體所具有之乙烯性不飽和基之數量並無特別限定，較佳為2個以上，更佳為3個以上，進而較佳為4個以上，尤佳為5個以上，又，較佳為15個以下，更佳為10個以下，進而較佳為8個以下，尤佳為7個以下。上述上限及下限可任意地組合，例如，較佳為2～15個，更佳為3～10個，進而較佳為4～8個，尤佳為5～7個。藉由設為上述下限值以上，有聚合性提高而成為高感度之傾向。藉由設為上述上限值以下，有顯影性變得更良好之傾向。  作為(D)光聚合性化合物，例如可例舉：脂肪族多羥基化合物與不飽和羧酸之酯；芳香族多羥基化合物與不飽和羧酸之酯；藉由脂肪族多羥基化合物、芳香族多羥基化合物等多元羥基化合物與不飽和羧酸及多元羧酸之酯化反應所獲得之酯。In the photosensitive resin composition of this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more ethylenically unsaturated bonds in 1 molecule as (D) photopolymerizable compound. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, especially preferably 5 or more, Moreover, it is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 2-15, more preferably 3-10, further preferably 4-8, especially preferably 5-7. By setting it as more than the said lower limit, there exists a tendency for polymerizability to improve and to become high sensitivity. There exists a tendency for developability to become more favorable by making it below the said upper limit. As (D) photopolymerizable compounds, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aliphatic polyhydroxy compounds, aromatic Esters obtained by the esterification reaction of polyhydroxy compounds such as polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

作為脂肪族多羥基化合物與不飽和羧酸之酯，例如可例舉：乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二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、甘油丙烯酸酯等脂肪族多羥基化合物之丙烯酸酯；將該等化合物之丙烯酸酯替換為甲基丙烯酸酯而成之甲基丙烯酸酯；將該等化合物之丙烯酸酯替換為伊康酸酯而成之伊康酸酯；將該等化合物之丙烯酸酯替換為丁烯酸酯而成之丁烯酸酯；將該等化合物之丙烯酸酯替換為順丁烯二酸酯而成之順丁烯二酸酯。Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate and other aliphatic polyol acrylate; Methacrylate obtained by replacing acrylate of these compounds with methacrylate; Iconate obtained by replacing acrylate of these compounds with itaconate; Crotonate esters obtained by crotonate esters; maleate esters obtained by substituting maleate esters for acrylate esters of these compounds.

作為芳香族多羥基化合物與不飽和羧酸之酯，例如可例舉：對苯二酚二丙烯酸酯、對苯二酚二甲基丙烯酸酯、間苯二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、鄰苯三酚三丙烯酸酯等芳香族多羥基化合物之丙烯酸酯及甲基丙烯酸酯。  作為藉由脂肪族多羥基化合物、芳香族多羥基化合物等多元羥基化合物與不飽和羧酸及多元羧酸之酯化反應所獲得之酯，未必為單一物，例如可例舉：丙烯酸、鄰苯二甲酸、及乙二醇之縮合物；丙烯酸、順丁烯二酸、及二乙二醇之縮合物；甲基丙烯酸、對苯二甲酸及季戊四醇之縮合物；丙烯酸、己二酸、丁二醇及甘油之縮合物。Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol diacrylate Acrylates and methacrylates of aromatic polyhydroxy compounds such as methacrylates and pyrogallol triacrylate. The ester obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids does not necessarily have to be a single substance. Examples include: acrylic acid, o-phthalic acid Condensates of diformic acid and ethylene glycol; Condensates of acrylic acid, maleic acid and diethylene glycol; Condensates of methacrylic acid, terephthalic acid and pentaerythritol; Acrylic acid, adipic acid, butanediol Condensate of alcohol and glycerin.

作為本發明之感光性樹脂組合物中所使用之光聚合性化合物的上述以外之例，例如，如使聚異氰酸酯化合物與含羥基之(甲基)丙烯酸酯、或聚異氰酸酯化合物與多元醇及含羥基之(甲基)丙烯酸酯反應所獲得之胺基甲酸酯(甲基)丙烯酸酯類；如多元環氧化合物與含羥基之(甲基)丙烯酸酯或(甲基)丙烯酸之加成反應物之環氧丙烯酸酯類；伸乙基雙丙烯醯胺等丙烯醯胺類；鄰苯二甲酸二烯丙酯等烯丙酯類；鄰苯二甲酸二乙烯酯等含乙烯基之化合物較有用。  作為胺基甲酸酯(甲基)丙烯酸酯類，例如可例舉：DPHA-40H、UX-5000、UX-5002D-P20、UX-5003D、UX-5005(日本化藥公司製造)、U-2PPA、U-6LPA、U-10PA、U-33H、UA-53H、UA-32P、UA-1100H(新中村化學工業公司製造)、UA-306H、UA-510H、UF-8001G(協榮社化學公司製造)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(日本合成化學工業公司製造)。As an example of the photopolymerizable compound used in the photosensitive resin composition of the present invention other than the above, for example, a polyisocyanate compound and a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound and a polyol and a polyol containing Urethane (meth)acrylates obtained by the reaction of (meth)acrylates of hydroxyl groups; such as the addition reaction of polyepoxides and hydroxyl-containing (meth)acrylates or (meth)acrylic acid Epoxy acrylates; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are more useful . As urethane (meth)acrylates, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U- 2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd. company), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

該等之中，從適當之錐角與感度之觀點出發，作為(D)光聚合性化合物，較佳為使用酯(甲基)丙烯酸酯類或胺基甲酸酯(甲基)丙烯酸酯類，更佳為使用二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、鄰苯二甲酸2-三(甲基)丙烯醯氧基甲基乙酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯之二元酸酐加成物、季戊四醇三(甲基)丙烯酸酯之二元酸酐加成物。  該等可單獨使用一種，亦可併用兩種以上。Among them, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as (D) photopolymerizable compound from the viewpoint of appropriate taper angle and sensitivity. , more preferably dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tri(meth)acryloxymethylethyl phthalate, pentaerythritol tetra(methyl) ) acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate dibasic anhydride adduct, pentaerythritol tri(meth)acrylate dibasic anhydride adduct. One of these can be used alone, or two or more can be used in combination.

於本發明之感光性樹脂組合物中，(D)光聚合性化合物之分子量並無特別限定，從感度、撥油墨性、錐角之觀點出發，較佳為100以上，更佳為150以上，進而較佳為200以上，更進而較佳為300以上，尤佳為400以上，最佳為500以上，又，較佳為1000以下，更佳為700以下。上述上限及下限可任意地組合，例如，較佳為100～1000，更佳為150～1000，進而較佳為200～1000，更進而較佳為300～700，尤佳為400～700，最佳為500～700。  (D)光聚合性化合物之碳數並無特別限定，從感度、撥油墨性、錐角之觀點出發，較佳為7以上，更佳為10以上，進而較佳為15以上，更進而較佳為20以上，尤佳為25以上，又，較佳為50以下，更佳為40以下，進而較佳為35以下，尤佳為30以下。上述上限及下限可任意地組合，例如，較佳為7～50，更佳為10～50，進而較佳為15～40，更進而較佳為20～35，尤佳為25～30。  從感度、撥油墨性、錐角之觀點出發，較佳為酯(甲基)丙烯酸酯類、環氧(甲基)丙烯酸酯類、及胺基甲酸酯(甲基)丙烯酸酯類，其中，進而較佳為季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等3官能以上之酯(甲基)丙烯酸酯類、鄰苯二甲酸2,2,2-三(甲基)丙烯醯氧基甲基乙酯、二季戊四醇五(甲基)丙烯酸酯之二元酸酐加成物等對3官能以上之酯(甲基)丙烯酸酯類之酸酐之加成物。In the photosensitive resin composition of the present invention, the molecular weight of (D) the photopolymerizable compound is not particularly limited, but is preferably 100 or more, more preferably 150 or more, from the viewpoints of sensitivity, ink repellency, and cone angle. Furthermore, it is more preferably 200 or more, still more preferably 300 or more, especially preferably 400 or more, most preferably 500 or more, and is preferably 1000 or less, more preferably 700 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 100-1000, more preferably 150-1000, further preferably 200-1000, still more preferably 300-700, especially preferably 400-700, most preferably The best is 500-700. (D) The carbon number of the photopolymerizable compound is not particularly limited, but it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, and still more preferably from the viewpoint of sensitivity, ink repellency, and taper angle. It is preferably at least 20, particularly preferably at least 25, more preferably at most 50, more preferably at most 40, still more preferably at most 35, especially preferably at most 30. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 7-50, more preferably 10-50, further preferably 15-40, still more preferably 20-35, especially preferably 25-30. From the viewpoint of sensitivity, ink repellency, and taper angle, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, among which , and more preferably three or more functional esters such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. ) acrylates, 2,2,2-tri(meth)acryloxymethylethyl phthalate, dibasic anhydride adducts of dipentaerythritol penta(meth)acrylate, etc. The adducts of anhydrides of ester (meth)acrylates.

於感光性樹脂組合物之全部固形物成分中，本發明之感光性樹脂組合物中之(D)光聚合性化合物之含量較佳為5質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，更進而較佳為30質量%以上，尤佳為40質量%以上，又，較佳為80質量%以下，更佳為70質量%以下，進而較佳為60質量%以下，更進而較佳為55質量%以下，尤佳為50質量%以下。上述上限及下限可任意地組合，例如，較佳為5～80質量%，更佳為10～70質量%，進而較佳為20～60質量%，更進而較佳為30～55質量%，尤佳為40～50質量%。藉由設為上述下限值以上，有成為適當之內部硬化性之傾向。藉由設為上述上限值以下，有顯影性變良好之傾向。In the total solid content of the photosensitive resin composition, the content of the (D) photopolymerizable compound in the photosensitive resin composition of the present invention is preferably at least 5% by mass, more preferably at least 10% by mass, and even more preferably Preferably at least 20% by mass, more preferably at least 30% by mass, especially preferably at least 40% by mass, more preferably at most 80% by mass, more preferably at most 70% by mass, still more preferably at most 60% by mass Below, more preferably below 55% by mass, especially preferably below 50% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-80 mass %, more preferably 10-70 mass %, further preferably 20-60 mass %, still more preferably 30-55 mass %, More preferably, it is 40 to 50% by mass. There exists a tendency which becomes suitable internal hardening property by making it more than the said lower limit. There exists a tendency for developability to become favorable by making it below the said upper limit.

[1-1-5](E)著色劑  為了將阻隔壁著色，本發明之感光性樹脂組合物亦可含有著色劑。作為著色劑，可使用顏料、染料等公知之著色劑。  本發明中所使用之(E)著色劑之種類並無特別限定，可使用顏料，亦可使用染料。該等之中，從耐久性之觀點出發，較佳為使用顏料。[1-1-5] (E) Colorant The photosensitive resin composition of the present invention may contain a colorant for coloring the barrier ribs. As a coloring agent, well-known coloring agents, such as a pigment and a dye, can be used. The type of (E) coloring agent used in the present invention is not particularly limited, and pigments and dyes can also be used. Among them, it is preferable to use a pigment from the viewpoint of durability.

(E)著色劑中所含之顏料可為1種，亦可為2種以上。尤其是從於可見區域中均勻地遮光之觀點出發，較佳為2種以上。  可用作(E)著色劑之顏料之種類並無特別限定，例如可例舉有機顏料或無機顏料。該等之中，從控制感光性樹脂組合物之透過波長而有效率地使其硬化之觀點出發，較佳為使用有機顏料。  作為有機顏料，可例舉有機著色顏料或有機黑色顏料。此處，有機著色顏料意指呈現黑色以外之顏色之有機顏料，可例舉：紅色顏料、橙色顏料、藍色顏料、紫色顏料、綠色顏料、黃色顏料等。(E) The pigment contained in a coloring agent may be 1 type, and may be 2 or more types. In particular, from the viewpoint of uniformly shielding light in the visible region, two or more types are preferred. The kind of pigments that can be used as (E) coloring agent is not particularly limited, for example, organic pigments or inorganic pigments can be mentioned. Among them, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the photosensitive resin composition and efficiently curing it. The organic pigment may, for example, be an organic colored pigment or an organic black pigment. Here, the organic colored pigment means an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

有機顏料之中，從紫外線吸收性之觀點出發，較佳為使用有機著色顏料。  有機著色顏料可單獨使用一種，亦可併用兩種以上。尤其是於用於遮光性之用途之情形時，更佳為組合使用顏色不同之有機著色顏料，進而較佳為使用呈現接近黑色之顏色之有機著色顏料之組合。Among organic pigments, it is preferable to use an organic colored pigment from the viewpoint of ultraviolet absorbing property. One type of organic coloring pigment can be used alone, or two or more types can be used in combination. In particular, when it is used for light-shielding purposes, it is more preferable to use a combination of organic coloring pigments of different colors, and it is more preferable to use a combination of organic coloring pigments showing a color close to black.

該等有機顏料之化學結構並無特別限定，例如可例舉：偶氮系、酞菁系、喹吖酮系、苯并咪唑酮系、異吲哚啉酮系、二㗁𠯤系、陰丹士林系、苝系。以下，以顏料編號表示可使用之顏料之具體例。以下例舉之「C.I.顏料紅2」等用語意指色料索引(C.I.)。The chemical structure of these organic pigments is not particularly limited, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxane-based, indan-based Shilin Department, Perylene Department. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. The following terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).

作為紅色顏料，可例舉：C.I.顏料紅1、2、3、4、5、6、7、8、9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48：1、48：2、48：3、48：4、49、49：1、49：2、50：1、52：1、52：2、53、53：1、53：2、53：3、57、57：1、57：2、58：4、60、63、63：1、63：2、64、64：1、68、69、81、81：1、81：2、81：3、81：4、83、88、90：1、101、101：1、104、108、108：1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276。  其中，從遮光性、分散性之觀點出發，可較佳地例舉：C.I.顏料紅48：1、122、149、168、177、179、194、202、206、207、209、224、242、254，可進而較佳地例舉：C.I.顏料紅177、209、224、254。  再者，從分散性或遮光性方面出發，較佳為使用C.I.顏料紅177、254、272，於利用紫外線使感光性樹脂組合硬化之情形時，作為紅色顏料，較佳為使用紫外線吸收率較低者，從該觀點出發，更佳為使用C.I.顏料紅254、272。Examples of red pigments include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53 :1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 ,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200 ,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249 ,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276 . Among them, from the viewpoint of opacity and dispersibility, C.I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, which can be further preferably exemplified: C.I. Pigment Red 177, 209, 224, 254. Furthermore, from the perspective of dispersibility or light-shielding, it is preferable to use C.I. Pigment Red 177, 254, 272. When using ultraviolet rays to harden the photosensitive resin combination, as a red pigment, it is preferable to use If it is lower, from this point of view, it is more preferable to use C.I. Pigment Red 254, 272.

作為橙色(orange)顏料，可例舉：C.I.顏料橙1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79。  其中，從分散性或遮光性之觀點出發，較佳為使用C.I.顏料橙13、43、64、72，於利用紫外線使感光性樹脂組合硬化之情形時，作為橙色顏料，較佳為使用紫外線吸收率較低者，從該觀點出發，更佳為使用C.I.顏料橙64、72。Examples of orange pigments include: C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, it is preferable to use C.I. Pigment Orange 13, 43, 64, and 72 from the viewpoint of dispersibility or light-shielding properties, and when the combination of photosensitive resins is hardened by ultraviolet rays, it is preferable to use ultraviolet absorbing If the rate is lower, it is more preferable to use C.I. Pigment Orange 64 and 72 from this point of view.

作為藍色顏料，可例舉：C.I.顏料藍1、1：2、9、14、15、15：1、15：2、15：3、15：4、15：6、16、17、19、25、27、28、29、33、35、36、56、56：1、60、61、61：1、62、63、66、67、68、71、72、73、74、75、76、78、79。  其中，從遮光性之觀點出發，可較佳地例舉：C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、60，可進而較佳地例舉C.I.顏料藍15：6。  再者，從分散性或遮光性方面出發，較佳為使用C.I.顏料藍15：6、16、60，於利用紫外線使感光性樹脂組合硬化之情形時，作為藍色顏料，較佳為使用紫外線吸收率較低者，從該觀點出發，更佳為使用C.I.顏料藍60。Examples of blue pigments include: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78,79. Among them, from the viewpoint of light-shielding properties, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, and more preferably C.I. Pigment Blue 15:6. Furthermore, it is preferable to use C.I. Pigment Blue 15:6, 16, or 60 in terms of dispersibility or light-shielding properties. When using ultraviolet rays to harden the photosensitive resin combination, it is preferable to use ultraviolet rays as blue pigments. If the absorption rate is low, it is more preferable to use C.I. Pigment Blue 60 from this point of view.

作為紫色顏料，可例舉：C.I.顏料紫1、1：1、2、2：2、3、3：1、3：3、5、5：1、14、15、16、19、23、25、27、29、31、32、37、39、42、44、47、49、50。  其中，從遮光性之觀點出發，可較佳地例舉C.I.顏料紫19、23，可進而較佳地例舉C.I.顏料紫23。  再者，從分散性或遮光性方面出發，較佳為使用C.I.顏料紫23、29，於利用紫外線使感光性樹脂組合硬化之情形時，作為紫色顏料，較佳為使用紫外線吸收率較低者，從該觀點出發，更佳為使用C.I.顏料紫29。Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25 , 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferably exemplified from the viewpoint of light-shielding properties, and C.I. Pigment Violet 23 is further preferably exemplified. Furthermore, in terms of dispersibility or light-shielding properties, it is preferable to use C.I. Pigment Violet 23 and 29. When using ultraviolet rays to harden the photosensitive resin combination, as purple pigments, it is preferable to use those with lower ultraviolet absorption rate. , from this point of view, it is more preferable to use C.I. Pigment Violet 29.

作為除了紅色顏料、橙色顏料、藍色顏料、紫色顏料以外可使用之有機著色顏料，例如可例舉綠色顏料、黃色顏料等。  作為綠色顏料，可例舉：C.I.顏料綠1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55。  其中，可較佳地例舉C.I.顏料綠7、36。  作為黃色顏料，可例舉：C.I.顏料黃1、1：1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35：1、36、36：1、37、37：1、40、41、42、43、48、53、55、61、62、62：1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127：1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191：1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208。  其中，可較佳地例舉：C.I.顏料黃83、117、129、138、139、150、154、155、180、185，可進而較佳地例舉：C.I.顏料黃83、138、139、150、180。As an organic coloring pigment which can be used other than a red pigment, an orange pigment, a blue pigment, and a purple pigment, a green pigment, a yellow pigment, etc. are mentioned, for example. Examples of green pigments include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 . Among them, C.I. Pigment Green 7, 36 can be preferably exemplified. Examples of yellow pigments include: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 , 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81 ,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133 ,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169 ,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198 , 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferably: C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably: C.I. Pigment Yellow 83, 138, 139, 150 , 180.

該等之中，從遮光性、或撥油墨性之觀點出發，較佳為使用選自由紅色顏料、橙色顏料、藍色顏料及紫色顏料所組成之群中之至少一種。Among them, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and purple pigments from the viewpoint of light-shielding properties or ink-repelling properties.

該等之中，從硬化性、或撥油墨性之觀點出發，較佳為含有以下之顏料中之至少一種以上。  紅色顏料：C.I.顏料紅177、254、272  橙色顏料：C.I.顏料橙43、64、72  藍色顏料：C.I.顏料藍15：6、60  紫色顏料：C.I.顏料紫23、29Among them, it is preferable to contain at least one or more of the following pigments from the viewpoint of curability or ink repellency. Red Pigment: C.I. Pigment Red 177, 254, 272 Orange Pigment: C.I. Pigment Orange 43, 64, 72 Blue Pigment: C.I. Pigment Blue 15: 6, 60 Purple Pigment: C.I. Pigment Violet 23, 29

又，從遮光性之觀點出發，較佳為使用有機黑色顏料作為(E)著色劑。作為有機黑色顏料，可例舉：苯胺黑、苝黑或以下通式(2)所表示之有機黑色顏料。其中，從遮光性、分散性之觀點出發，更佳為式(2)所表示之有機黑色顏料。Moreover, it is preferable to use an organic black pigment as (E) coloring agent from a light-shielding viewpoint. Examples of the organic black pigment include aniline black, perylene black, or an organic black pigment represented by the following general formula (2). Among them, the organic black pigment represented by the formula (2) is more preferable from the viewpoint of light-shielding properties and dispersibility.

[化37]

Figure 02_image073
[chem 37]
Figure 02_image073

又，亦可使用無機顏料。作為無機黑色顏料，可例舉：碳黑、乙炔黑、燈黑、骨黑、石墨、鐵黑、花青黑、鈦黑等。該等之中，從遮光性、分散性之觀點出發，可較佳地使用碳黑。In addition, inorganic pigments can also be used. As an inorganic black pigment, carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, titanium black, etc. are mentioned. Among them, carbon black is preferably used from the viewpoint of light-shielding properties and dispersibility.

於使用顏料時，亦可併用公知之分散劑或分散助劑以使該顏料可不凝聚而穩定地存在於感光性樹脂組合物中。When using a pigment, a well-known dispersing agent or a dispersing aid can also be used together so that this pigment can exist stably in a photosensitive resin composition without aggregation.

於本發明之感光性樹脂組合物含有(E)著色劑之情形時，作為著色劑之含量，從製版性與顏色特性之觀點出發，於感光性樹脂組合物之全部固形物成分中，較佳為60質量%以下，更佳為40質量%以下。下限並無特別限定，較佳為0.01質量%以上。  作為另一態樣，若於感光性樹脂組合物中包含著色劑，則有阻隔壁之硬化性降低而阻隔壁之撥液性降低，亦容易產生釋氣之傾向。因此，較理想為感光性樹脂組合物中之著色劑之含量較低，例如，相對於感光性樹脂組合物之全部固形物成分，較佳為20質量%以下，更佳為10質量%以下。When the photosensitive resin composition of the present invention contains the (E) colorant, the content of the colorant is preferably from the viewpoint of plate making properties and color properties in the total solid content of the photosensitive resin composition It is 60 mass % or less, More preferably, it is 40 mass % or less. The lower limit is not particularly limited, but is preferably 0.01% by mass or more. As another aspect, if a colorant is included in the photosensitive resin composition, the curability of the barrier wall will decrease, the liquid repellency of the barrier wall will decrease, and outgassing will tend to occur. Therefore, it is desirable that the content of the coloring agent in the photosensitive resin composition be low, for example, with respect to the total solid content of the photosensitive resin composition, it is preferably 20% by mass or less, more preferably 10% by mass or less.

[1-1-6](F)鏈轉移劑  本發明之感光性樹脂組合物亦可含有(F)鏈轉移劑。藉由包含鏈轉移劑，有改善由表面附近之氧抑制等所引起之自由基失活而可提高表面硬化性，且錐角變高之傾向。又，藉由提高表面硬化性，有可抑制撥液劑流出，容易將撥液劑固定於阻隔壁之表面附近而接觸角增高之傾向。  作為(F)鏈轉移劑，例如可例舉含巰基化合物、或四氯化碳，從有鏈轉移效果較高之傾向方面出發，更佳為含巰基化合物。含巰基化合物由於S-H鍵結能較小，故容易產生斷鍵，容易引起鏈轉移反應，故有可提高表面硬化性之傾向。[1-1-6] (F) Chain transfer agent The photosensitive resin composition of the present invention may also contain (F) chain transfer agent. Inclusion of a chain transfer agent tends to improve surface hardening properties by improving radical deactivation caused by oxygen inhibition near the surface, and the taper angle tends to become higher. In addition, by improving the surface hardening property, the outflow of the liquid-repellent agent can be suppressed, and the liquid-repellent agent tends to be easily fixed near the surface of the barrier wall, thereby increasing the contact angle. As the (F) chain transfer agent, for example, a mercapto-containing compound or carbon tetrachloride can be exemplified, and a mercapto-containing compound is more preferable in terms of a tendency to have a higher chain transfer effect. Due to the small S-H bonding energy, mercapto-containing compounds are prone to bond breaking and chain transfer reactions, so there is a tendency to improve surface hardening.

鏈轉移劑中，從錐角、表面硬化性之觀點出發，較佳為具有芳香族環之含巰基化合物與脂肪族系之含巰基化合物。  作為脂肪族系之含巰基化合物，例如可例舉：丁二醇雙(3-巰基丙酸酯)、丁二醇雙巰基乙酸酯、乙二醇雙(3-巰基丙酸酯)、乙二醇雙巰基乙酸酯、三羥甲基丙烷三(3-巰基丙酸酯)、三羥甲基丙烷三巰基乙酸酯、三硫代丙酸三羥基乙酯、季戊四醇四(3-巰基丙酸酯)、季戊四醇三(3-巰基丙酸酯)、丁二醇雙(3-巰基丁酸酯)、乙二醇雙(3-巰基丁酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇三(3-巰基丁酸酯)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮。Among the chain transfer agents, from the viewpoint of cone angle and surface hardening properties, mercapto-containing compounds having an aromatic ring and aliphatic mercapto-containing compounds are preferable. As the aliphatic mercapto group-containing compound, for example, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), Glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis(3-mercaptopropionate) propionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3 -mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 ,5-tris𠯤-2,4,6(1H,3H,5H)-trione.

該等之中，較佳為三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)、季戊四醇三(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇三(3-巰基丁酸酯)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮，更佳為季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)。  (F)鏈轉移劑可單獨使用一種，亦可併用兩種以上。Among these, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane Tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)- 1,3,5-Tri-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate). (F) One kind of chain transfer agent may be used alone, or two or more kinds may be used in combination.

從提高撥油墨性之觀點出發，作為(F)鏈轉移劑，較適宜為組合選自由2-巰基苯并噻唑、2-巰基苯并咪唑、及2-巰基苯并㗁唑所組成之群中之一種以上與光聚合起始劑，用作光聚合起始劑系，更適宜為與聯咪唑衍生物類組合。例如可使用2-巰基苯并噻唑，亦可使用2-巰基苯并咪唑，亦可併用2-巰基苯并噻唑與2-巰基苯并咪唑。  作為另一態樣，從表面硬化性之觀點出發，較佳為使用選自由季戊四醇四(3-巰基丙酸酯)、及季戊四醇四(3-巰基丁酸酯)所組成之群中之一種或兩種以上。From the viewpoint of improving ink repellency, as (F) chain transfer agent, it is more suitable to be selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole One or more photopolymerization initiators are used as a photopolymerization initiator system, and it is more suitable to combine with biimidazole derivatives. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination. As another aspect, from the viewpoint of surface hardening, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Two or more.

於本發明之感光性樹脂組合物包含(F)鏈轉移劑之情形時，其含量並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.01質量%以上，更佳為0.025質量%以上，進而較佳為0.05質量%以上，更進而較佳為0.1質量%以上，尤佳為1質量%以上，又，較佳為5質量%以下，更佳為4質量%以下，進而較佳為3質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～5質量%，更佳為0.025～5質量%，進而較佳為0.05～4質量%，更進而較佳為0.1～4質量%，尤佳為1～3質量%。藉由設為上述下限值以上，有表面硬化性變高，撥液性變高之傾向。又，藉由設為上述上限值以下，有容易形成所需圖案之傾向。When the photosensitive resin composition of the present invention contains (F) chain transfer agent, its content is not particularly limited, but it is preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition, more preferably It is at least 0.025% by mass, more preferably at least 0.05% by mass, still more preferably at least 0.1% by mass, especially preferably at least 1% by mass, and more preferably at most 5% by mass, more preferably at most 4% by mass , and more preferably 3% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 0.01-5 mass %, more preferably 0.025-5 mass %, further preferably 0.05-4 mass %, still more preferably 0.1-4 mass %, Especially preferably, it is 1-3 mass %. Surface hardening property becomes high by making it more than the said lower limit, and there exists a tendency for liquid repellency to become high. Moreover, it exists in the tendency which forms a desired pattern easily by making it below the said upper limit.

作為鏈轉移劑，作為併用具有芳香族環之含巰基化合物與脂肪族系之含巰基化合物時之其含量，相對於具有芳香族環之含巰基化合物100質量份，脂肪族系之含巰基化合物較佳為10質量份以上，更佳為50質量份以上，進而較佳為80質量份以上，又，較佳為400質量份以下，更佳為300質量份以下，進而較佳為200質量份以下，尤佳為150質量份以下。上述上限與下限可任意地組合，例如，較佳為10～400質量份，更佳為10～300質量份，進而較佳為50～200質量份，尤佳為80～150質量份。藉由設為上述下限值以上，有撥油墨性變高之傾向。又，藉由設為上述上限值以下，有感度變高之傾向。As a chain transfer agent, as the content when using an aromatic ring-containing mercapto-group compound and an aliphatic-based mercapto-group-containing compound in combination, the aliphatic-based mercapto-group-containing compound is relatively small relative to 100 parts by mass of the aromatic ring-containing mercapto-group-containing compound. Preferably at least 10 parts by mass, more preferably at least 50 parts by mass, more preferably at least 80 parts by mass, more preferably at most 400 parts by mass, more preferably at most 300 parts by mass, further preferably at most 200 parts by mass , preferably 150 parts by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-400 mass parts, more preferably 10-300 mass parts, further preferably 50-200 mass parts, especially preferably 80-150 mass parts. There exists a tendency for ink repellency to become high by making it more than the said lower limit. Moreover, there exists a tendency for sensitivity to become high by making it below the said upper limit.

於本發明之感光性樹脂組合物包含(F)鏈轉移劑及(C)光聚合起始劑之情形時，作為感光性樹脂組合物中之(F)鏈轉移劑相對於(C)光聚合起始劑之調配比，相對於(C)光聚合起始劑100質量份，較佳為1質量份以上，更佳為5質量份以上，進而較佳為10質量份以上，尤佳為20質量份以上，又，較佳為500質量份以下，更佳為400質量份以下，進而較佳為300質量份以下，更進而較佳為200質量份以下，尤佳為150質量份以下。上述上限及下限可任意地組合，例如，較佳為10～500質量份，更佳為10～400質量份，進而較佳為20～300質量份，更進而較佳為20～200質量份，尤佳為20～150質量份。藉由設為上述下限值以上，有表面硬化性變高，撥液性變高之傾向。又，藉由設為上述上限值以下，有容易形成所需圖案之傾向。In the case where the photosensitive resin composition of the present invention includes (F) chain transfer agent and (C) photopolymerization initiator, as (F) chain transfer agent in the photosensitive resin composition relative to (C) photopolymerization The mixing ratio of the initiator is preferably at least 1 part by mass, more preferably at least 5 parts by mass, further preferably at least 10 parts by mass, and especially preferably at least 20 parts by mass relative to 100 parts by mass of the (C) photopolymerization initiator. More preferably, it is not more than 500 parts by mass, more preferably not more than 400 parts by mass, further preferably not more than 300 parts by mass, still more preferably not more than 200 parts by mass, especially preferably not more than 150 parts by mass. The upper and lower limits above can be combined arbitrarily, for example, preferably 10-500 parts by mass, more preferably 10-400 parts by mass, further preferably 20-300 parts by mass, still more preferably 20-200 parts by mass, Most preferably, it is 20-150 mass parts. Surface hardening property becomes high by making it more than the said lower limit, and there exists a tendency for liquid repellency to become high. Moreover, it exists in the tendency which forms a desired pattern easily by making it below the said upper limit.

[1-1-7](G)成分；撥液劑  本發明之感光性樹脂組合物亦可進而含有不同於(A)共聚物之(G)撥液劑。作為(G)撥液劑，較佳為具有交聯基之含氟原子樹脂。認為藉由含有具有交聯基之含氟原子樹脂，可對所獲得之阻隔壁之表面賦予撥油墨性，故可使所獲得之阻隔壁防止每一像素之混色。[1-1-7] Component (G); liquid repellent The photosensitive resin composition of the present invention may further contain (G) liquid repellent which is different from (A) copolymer. As (G) the liquid repellent, preferably a fluorine atom-containing resin having a crosslinking group. It is considered that ink repellency can be imparted to the surface of the obtained barrier rib by containing the fluorine atom-containing resin having a crosslinking group, so that the obtained barrier rib can prevent color mixing of each pixel.

作為交聯基，例如可例舉環氧基或乙烯性不飽和基，從抑制撥液劑向顯影液流出之觀點出發，較佳為乙烯性不飽和基。  藉由使用具有交聯基之撥液劑，於使所形成之塗佈膜曝光時可使其表面之交聯反應加速，撥液劑因顯影處理而不易流出，其結果為，認為可使所獲得之阻隔壁表現出較高之撥油墨性。As a crosslinking group, an epoxy group or an ethylenically unsaturated group is mentioned, for example, From a viewpoint of suppressing the outflow of a liquid-repellent agent to a developing solution, an ethylenically unsaturated group is preferable. By using a liquid-repelling agent having a cross-linking group, the cross-linking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed, and the liquid-repelling agent is not easy to flow out due to the development treatment. The obtained barrier ribs showed high ink repellency.

又，有作為含氟原子樹脂之(G)撥液劑於阻隔壁之表面配向，發揮防止油墨之暈開或混色之作用之傾向。更詳細而言，有如下傾向：發揮防止因具有氟原子之基排斥油墨，油墨越過阻隔壁進入鄰接之區域所引起之油墨的暈開或混色之作用。Also, the (G) liquid-repelling agent of the fluorine atom-containing resin tends to be aligned on the surface of the barrier wall to prevent ink from blurring or color mixing. More specifically, it tends to prevent the ink from blurring or color mixing caused by the base having fluorine atoms repelling the ink and the ink crossing the barrier wall into the adjacent area.

具有交聯基之含氟原子樹脂較佳為具有全氟烷基及全氟伸烷基醚鏈中之任一者或兩者。藉由具有全氟烷基及全氟伸烷基醚鏈中之任一者或兩者，有含氟原子樹脂進而容易於阻隔壁表面配向，表現出更高之撥油墨性，進而防止油墨之暈開或混色之傾向。The fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having either or both of the perfluoroalkyl group and the perfluoroalkylene ether chain, the resin containing fluorine atoms is easy to align on the surface of the barrier wall, showing higher ink repellency, and preventing the ink from being separated. Tendency to smear or mix colors.

作為全氟烷基，例如可例舉：全氟丁基、全氟己基、全氟辛基。作為全氟伸烷基醚鏈，例如可例舉：-CF 2-O-、-(CF 2) 2-O-、-(CF 2) 3-O-、-CF 2-C(CF 3)O-、-C(CF 3)-CF 2-O-及具有該等重複單元之二價基。 As a perfluoroalkyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group are mentioned, for example. Examples of perfluoroalkylene ether chains include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 ) O-, -C(CF 3 )-CF 2 -O- and divalent groups having these repeating units.

作為具有交聯基之含氟原子樹脂，例如可例舉：具有環氧基及全氟烷基之丙烯酸共聚樹脂、具有環氧基及全氟伸烷基醚鏈之丙烯酸共聚樹脂、具有乙烯性不飽和基及全氟烷基之丙烯酸共聚樹脂、具有乙烯性不飽和基及全氟伸烷基醚鏈之丙烯酸共聚樹脂、具有環氧基及全氟烷基之環氧(甲基)丙烯酸酯樹脂、具有環氧基及全氟伸烷基醚鏈之環氧(甲基)丙烯酸酯樹脂、具有乙烯性不飽和基及全氟烷基之環氧(甲基)丙烯酸酯樹脂、具有乙烯性不飽和基及全氟伸烷基醚鏈之環氧(甲基)丙烯酸酯樹脂。該等之中，從撥油墨性之觀點出發，較佳為具有乙烯性不飽和基及全氟烷基之丙烯酸共聚樹脂、具有乙烯性不飽和基及全氟伸烷基醚鏈之丙烯酸共聚樹脂，進而較佳為具有乙烯性不飽和基及全氟伸烷基醚鏈之丙烯酸共聚樹脂。As the fluorine atom-containing resin having a crosslinking group, for example: acrylic copolymer resin having epoxy group and perfluoroalkyl group, acrylic copolymer resin having epoxy group and perfluoroalkylene ether chain, vinyl resin Acrylic copolymer resin with unsaturated group and perfluoroalkyl group, acrylic copolymer resin with ethylenically unsaturated group and perfluoroalkyl ether chain, epoxy (meth)acrylate with epoxy group and perfluoroalkyl group Resin, epoxy (meth)acrylate resin with epoxy group and perfluoroalkylene ether chain, epoxy (meth)acrylate resin with ethylenically unsaturated group and perfluoroalkyl group, vinyl Epoxy (meth)acrylate resin with unsaturated groups and perfluoroalkylene ether chains. Among these, from the viewpoint of ink repellency, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains are preferred. , and more preferably an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain.

作為該等具有交聯基之含氟原子樹脂之市售品，可使用以如下等商品名於市面上有售之含氟有機化合物：DIC公司製造之「MEGAFAC(註冊商標、下同)F116」、「MEGAFACF120」、「MEGAFACF142D」、「MEGAFACF144D」、「MEGAFACF150」、「MEGAFACF160」、「MEGAFACF171」、「MEGAFACF172」、「MEGAFACF173」、「MEGAFACF177」、「MEGAFACF178A」、「MEGAFACF178K」、「MEGAFACF179」、「MEGAFACF183」、「MEGAFACF184」、「MEGAFACF191」、「MEGAFACF812」、「MEGAFACF815」、「MEGAFACF824」、「MEGAFACF833」、「MEGAFACRS101」、「MEGAFACRS102」「MEGAFACRS105」、「MEGAFACRS201」、「MEGAFACRS202」、「MEGAFACRS301」、「MEGAFACRS303」「MEGAFACRS304」、「MEGAFACRS401」、「MEGAFACRS402」、「MEGAFACRS501」、「MEGAFACRS502」、「MEGAFACRS-72-K」、「MEGAFACRS-78」、「MEGAFACRS-90」、「DEFENSA(註冊商標、下同) MCF300」、「DEFENSA MCF310」、「DEFENSA MCF312」、「DEFENSA MCF323」；3M Japan公司製造之「Fluorad FC430」、「Fluorad FC431」、「FC-4430」、「FC4432」；AGC公司製造之「AsahiGuard(註冊商標) AG710」；「Surflon(註冊商標、下同) S-382」、「Surflon SC-101」、「Surflon SC-102」、「Surflon SC-103」、「Surflon SC-104」、「Surflon SC-105」、「Surflon SC-106」。  該等之中，作為具有乙烯性不飽和基及全氟伸烷基之丙烯酸共聚樹脂，可適宜地使用「MEGAFACRS-72-K」、「MEGAFACRS-78」、「MEGAFACRS-90」。As commercial products of such fluorine atom-containing resins having crosslinking groups, fluorine-containing organic compounds commercially available under the following trade names: "MEGAFAC (registered trademark, the same below) F116" manufactured by DIC Corporation can be used , "MEGAFACF120", "MEGAFACF142D", "MEGAFACF144D", "MEGAFACF150", "MEGAFACF160", "MEGAFACF171", "MEGAFACF172", "MEGAFACF173", "MEGAFACF177", "MEGAFACF178A", "MEGAFACF178K", "MEGAFACF179", " MEGAFACF183", "MEGAFACF184", "MEGAFACF191", "MEGAFACF812", "MEGAFACF815", "MEGAFACF824", "MEGAFACF833", "MEGAFACRS101", "MEGAFACRS102", "MEGAFACRS105", "RSMEGAFACRS,201", "MEGAFACRS202", "301GA" "MEGAFACRS303", "MEGAFACRS304", "MEGAFACRS401", "MEGAFACRS402", "MEGAFACRS501", "MEGAFACRS502", "MEGAFACRS-72-K", "MEGAFACRS-78", "MEGAFACRS-90", "DEFENSA (registered trademark, Same) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323"; "Fluorad FC430", "Fluorad FC431", "FC-4430", "FC4432" manufactured by 3M Japan; AsahiGuard (registered trademark) AG710"; "Surflon (registered trademark, the same below) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106". Among these, "MEGAFACRS-72-K", "MEGAFACRS-78", and "MEGAFACRS-90" can be suitably used as an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group.

具有交聯基之含氟原子樹脂中之含氟原子比率並無特別限制，於具有交聯基之含氟原子樹脂中，較佳為5質量%以上，更佳為10質量%以上，進而較佳為20質量%以上，更進而較佳為25質量%以上。又，較佳為50質量%以下，更佳為35質量%以下。上述上限及下限可任意地組合，例如，較佳為5～50質量%，更佳為10～50質量%，進而較佳為20～35質量%，尤佳為25～35質量%。藉由設為上述下限值以上，有可抑制向像素部流出之傾向。藉由設為上述上限值以下，有顯示出較高之接觸角之傾向。The ratio of fluorine atoms in the fluorine atom-containing resin with a crosslinking group is not particularly limited, and in the fluorine atom-containing resin with a crosslinking group, it is preferably at least 5% by mass, more preferably at least 10% by mass, and even more preferably It is preferably at least 20% by mass, more preferably at least 25% by mass. Also, it is preferably at most 50% by mass, more preferably at most 35% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-50 mass%, more preferably 10-50 mass%, further preferably 20-35 mass%, especially preferably 25-35 mass%. By setting it as more than the said lower limit, there exists a tendency for the outflow to a pixel part to be suppressed. There exists a tendency for a high contact angle to be shown by making it below the said upper limit.

具有交聯基之含氟原子樹脂之分子量並無特別限制，可為低分子量之化合物，亦可為高分子量體。高分子量體由於由後烘烤引起之流動性得以抑制，可抑制自阻隔壁流出，故較佳。於為具有交聯基之含氟原子樹脂高分子量體之情形時，具有交聯基之含氟原子樹脂之數量平均分子量較佳為100以上，更佳為500以上，且進而較佳為100000以下，更佳為10000以下。上述上限及下限可任意地組合，例如，較佳為100～100000，更佳為500～10000。The molecular weight of the fluorine atom-containing resin having a crosslinking group is not particularly limited, and may be a low-molecular-weight compound or a high-molecular-weight compound. A high-molecular-weight body is preferable because fluidity due to post-baking can be suppressed and flow out from barrier ribs can be suppressed. In the case of a high molecular weight body of a fluorine atom-containing resin having a crosslinking group, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably at least 100, more preferably at least 500, and further preferably at most 100,000 , more preferably less than 10,000. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 100-100000, more preferably 500-10000.

於本發明之感光性樹脂組合物含有(G)撥液劑之情形時，本發明之感光性樹脂組合物中之(G)撥液劑之含有比率並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.01質量%以上，更佳為0.1質量%以上，進而較佳為0.5質量%以上，又，較佳為5質量%以下，更佳為3質量%以下，進而較佳為2質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～5質量%，更佳為0.1～3質量%，進而較佳為0.5～2質量%。藉由設為上述下限值以上，有撥油墨性提高之傾向。藉由設為上述上限值以下，有於形成阻隔壁後將油墨塗佈於像素部時容易獲得均勻之塗膜之傾向。When the photosensitive resin composition of the present invention contains the (G) liquid repellent, the content ratio of the (G) liquid repellent in the photosensitive resin composition of the present invention is not particularly limited. In the total solid content, it is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, further preferably at least 0.5% by mass, and is preferably at most 5% by mass, more preferably at most 3% by mass, Furthermore, it is more preferable that it is 2 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 0.01-5 mass %, more preferably 0.1-3 mass %, still more preferably 0.5-2 mass %. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By setting it as below the said upper limit, when ink is apply|coated to a pixel part after forming a barrier rib, it exists in the tendency which becomes easy to obtain a uniform coating film.

於本發明之感光性樹脂組合物含有具有交聯基之含氟原子樹脂之情形時，本發明之感光性樹脂組合物中之具有交聯基之含氟原子樹脂的含有比率並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.01質量%以上，更佳為0.1質量%以上，進而較佳為0.5質量%以上，又，較佳為5質量%以下，更佳為3質量%以下，進而較佳為2質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～5質量%，更佳為0.1～3質量%，進而較佳為0.5～2質量%。藉由設為上述下限值以上，有撥油墨性提高之傾向。藉由設為上述上限值以下，有於形成阻隔壁後將油墨塗佈於像素部時容易獲得均勻之塗膜之傾向。When the photosensitive resin composition of the present invention contains a fluorine atom-containing resin having a crosslinking group, the content ratio of the fluorine atom-containing resin having a crosslinking group in the photosensitive resin composition of the present invention is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, still more preferably at least 0.5% by mass, and more preferably at most 5% by mass. It is 3 mass % or less, More preferably, it is 2 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 0.01-5 mass %, more preferably 0.1-3 mass %, still more preferably 0.5-2 mass %. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By setting it as below the said upper limit, when ink is apply|coated to a pixel part after forming a barrier rib, it exists in the tendency which becomes easy to obtain a uniform coating film.

[1-1-8]塗佈性提昇劑、顯影改良劑  為了提高塗佈性或顯影溶解性，本發明之感光性樹脂組合物亦可含有塗佈性提昇劑或顯影改良劑。  作為塗佈性提昇劑或顯影改良劑，例如可使用公知之界面活性劑。  界面活性劑可出於提高作為感光性樹脂組合物之塗佈液之塗佈性、及塗佈膜之顯影性等目的而使用，其中，較佳為氟系界面活性劑或聚矽氧系界面活性劑。  尤其是從具有於顯影時自未曝光部去除感光性樹脂組合物之殘渣之作用，且具有呈現潤濕性之功能方面出發，較佳為聚矽氧系界面活性劑，進而較佳為聚醚改性聚矽氧系界面活性劑。[1-1-8] Coatability enhancer, development improver In order to improve coatability or development solubility, the photosensitive resin composition of the present invention may also contain a coatability enhancer or a development improver. As a coatability improver or development improver, for example, a known surfactant can be used. Surfactants can be used for the purpose of improving the applicability of the coating solution as a photosensitive resin composition, and the developability of the coating film. Among them, fluorine-based surfactants or polysiloxane-based surfactants are preferred. active agent. In particular, polysiloxane-based surfactants are preferable, and polyethers are more preferable because they have the effect of removing the residue of the photosensitive resin composition from the unexposed portion during development, and have the function of exhibiting wettability. Modified polysiloxane surfactant.

作為氟系界面活性劑，較適宜為於末端、主鏈及側鏈中之至少任一部位具有氟烷基或氟伸烷基之化合物。具體而言，可例舉：1,1,2,2-四氟辛基(1,1,2,2-四氟丙基)醚、1,1,2,2-四氟辛基己醚、八乙二醇二(1,1,2,2-四氟丁基)醚、六乙二醇二(1,1,2,2,3,3-六氟戊基)醚、八丙二醇二(1,1,2,2-四氟丁基)醚、六丙二醇二(1,1,2,2,3,3-六氟戊基)醚、全氟十二烷基磺酸鈉、1,1,2,2,8,8,9,9,10,10-十氟十二烷、1,1,2,2,3,3-六氟癸烷等。作為該等之市售品，例如可例舉：BM Chemie公司製造之「BM-1000」、「BM-1100」；DIC公司製造之「MEGAFACF470」、「MEGAFACF475」、「MEGAFACF554」、「MEGAFACF559」；3M Japan公司製造之「FC430」；NEOS公司製造之「DFX-18」。As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at least any one of the terminal, the main chain, and the side chain is preferable. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1 ,1,2,2,8,8,9,9,10,10-decadecafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Such commercially available products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie Corporation; "MEGAFACF470", "MEGAFACF475", "MEGAFACF554" and "MEGAFACF559" manufactured by DIC Corporation; "FC430" manufactured by 3M Japan Corporation; "DFX-18" manufactured by NEOS Corporation.

作為聚矽氧系界面活性劑，例如可例舉：東麗道康寧公司製造之「DC3PA」、「SH7PA」、「DC11PA」、「SH21PA」、「SH28PA」、「SH29PA」、「8032Additive」、「SH8400」；BYK-Chemie公司製造之「BYK(註冊商標、下同)323」、「BYK330」。  作為界面活性劑，亦可包含氟系界面活性劑及聚矽氧系界面活性劑以外之其他界面活性劑，作為其他界面活性劑，例如可例舉：非離子性、陰離子性、陽離子性、兩性界面活性劑。Examples of polysiloxane surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400" manufactured by Toray Dow Corning Co., Ltd. "; "BYK (registered trademark, the same below) 323" and "BYK330" manufactured by BYK-Chemie. As the surfactant, other surfactants other than fluorine-based surfactants and polysiloxane-based surfactants may be included. Examples of other surfactants include: nonionic, anionic, cationic, and amphoteric Surfactant.

作為非離子性界面活性劑，例如可例舉：聚氧乙烯烷基醚類、聚氧乙烯聚氧丙烯烷基醚類、聚氧乙烯烷基苯醚類、聚氧乙烯烷基酯類、聚氧乙烯脂肪酸酯類、甘油脂肪酸酯類、聚氧乙烯甘油脂肪酸酯類、季戊四醇脂肪酸酯類、聚氧乙烯季戊四醇脂肪酸酯類、山梨醇酐脂肪酸酯類、聚氧乙烯山梨醇酐脂肪酸酯類、山梨醇脂肪酸酯類、聚氧乙烯山梨醇脂肪酸酯類。作為該等之市售品，例如可例舉：花王公司製造之「Emulgen(註冊商標。下同)104P」、「Emulgen A60」等聚氧乙烯系界面活性劑等。As the nonionic surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl ethers, Oxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan Alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters. Examples of such commercially available products include polyoxyethylene-based surfactants such as "Emulgen (registered trademark; the same below) 104P" and "Emulgen A60" manufactured by Kao Corporation.

作為陰離子性界面活性劑，例如可例舉：烷基磺酸鹽類、烷基苯磺酸鹽類、烷基萘磺酸鹽類、聚氧乙烯烷基醚磺酸鹽類、烷基硫酸鹽類、烷基硫酸酯鹽類、高級醇硫酸酯鹽類、脂肪族醇硫酸酯鹽類、聚氧乙烯烷基醚硫酸鹽類、聚氧乙烯烷基苯醚硫酸鹽類、烷基磷酸酯鹽類、聚氧乙烯烷基醚磷酸鹽類、聚氧乙烯烷基苯醚磷酸鹽類、特殊高分子系界面活性劑。其中，較佳為特殊高分子系界面活性劑，進而較佳為特殊多羧酸型高分子系界面活性劑。作為陰離子性界面活性劑，例如，烷基硫酸酯鹽類可例舉花王公司製造之「Emal(註冊商標)10」等，烷基萘磺酸鹽類可例舉花王公司製造之「Pelex(註冊商標) NB-L」等，特殊高分子系界面活性劑可例舉花王公司製造之「Homogenol(註冊商標、下同) L-18」、「Homogenol L-100」等。Examples of anionic surfactants include: alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkyl sulfates Alkyl sulfates, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates Classes, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants. Among them, a special polymer-based surfactant is preferred, and a special polycarboxylic acid-type polymer-based surfactant is further preferred. As an anionic surfactant, for example, "Emal (registered trademark) 10" manufactured by Kao Corporation can be exemplified for alkyl sulfate ester salts, and "Pelex (registered trademark)" manufactured by Kao Corporation for alkylnaphthalene sulfonates can be exemplified. Trademark) NB-L", etc. Special polymer surfactants include "Homogenol (registered trademark, the same below) L-18" and "Homogenol L-100" manufactured by Kao Corporation.

作為陽離子性界面活性劑，例如可例舉：四級銨鹽類、咪唑啉衍生物類、烷基胺鹽類。作為兩性界面活性劑，例如可例舉：甜菜鹼型化合物類、咪唑鎓鹽類、咪唑啉類、胺基酸類。該等之中，較佳為四級銨鹽類，進而較佳為硬脂基三甲基銨鹽類。作為陽離子性界面活性劑或良性界面活性劑，例如，作為烷基胺鹽類，可例舉花王公司製造之「Acetamin(註冊商標)24」，作為四級銨鹽類，可例舉花王公司製造之「Quartamin(註冊商標、下同)24P」、「Quartamin86W」。  界面活性劑可單獨使用一種，亦可併用兩種以上。例如可例舉：聚矽氧系界面活性劑/氟系界面活性劑之組合、聚矽氧系界面活性劑/特殊高分子系界面活性劑之組合、氟系界面活性劑/特殊高分子系界面活性劑之組合。其中，較佳為聚矽氧系界面活性劑/氟系界面活性劑之組合。該聚矽氧系界面活性劑/氟系界面活性劑之組合中，例如可例舉：BYK-Chemie公司製造之「BYK-300」或「BYK-330」/NEOS公司製造之「DFX-18」、BYK-Chemie公司製造之「BYK-300」、「BYK-330」/AGC SEIMI CHEMICAL公司製造之「S-393」、BYK-Chemie公司製造之「BYK-300」或「BYK-330」/DIC公司製造之「F-554」或「F-559」、Shin-Etsu Silicones公司製造之「KP340」/DIC公司製造之「F-478」或「F-475」、東麗道康寧公司製造之「SH7PA」/大金公司製造之「DS-401」、NUC公司製造之「L-77」/3M Japan公司製造之「FC4430」。  作為顯影改良劑，例如亦可使用包含有機羧酸或其酸酐之公知之顯影改良劑。  於本發明之感光性樹脂組合物包含塗佈性提昇劑或顯影改良劑之情形時，從感度之觀點出發，於感光性樹脂組合物之全部固形物成分中，塗佈性提昇劑或顯影改良劑之含量較佳為分別為20質量%以下，更佳為分別為10質量%以下。As a cationic surfactant, quaternary ammonium salts, imidazoline derivatives, and alkylamine salts are mentioned, for example. As the amphoteric surfactant, for example, betaine-type compounds, imidazolium salts, imidazolines, and amino acids may be mentioned. Among these, quaternary ammonium salts are preferred, and stearyl trimethylammonium salts are further preferred. As a cationic surfactant or a benign surfactant, for example, "Acetamin (registered trademark) 24" manufactured by Kao Corporation can be mentioned as an alkylamine salt, and "Acetamin (registered trademark) 24" manufactured by Kao Corporation can be mentioned as a quaternary ammonium salt. "Quartamin (registered trademark, the same below) 24P" and "Quartamin86W". One type of surfactant can be used alone, or two or more types can be used in combination. Examples include: a combination of polysiloxane-based surfactant/fluorine-based surfactant, a combination of polysiloxane-based surfactant/special polymer-based surfactant, a combination of fluorine-based surfactant/special polymer-based interface Combination of active agents. Among them, a combination of polysiloxane-based surfactant/fluorine-based surfactant is preferable. In the combination of the polysiloxane-based surfactant/fluorine-based surfactant, for example, "BYK-300" or "BYK-330" manufactured by BYK-Chemie Co., Ltd./"DFX-18" manufactured by NEOS Corporation , "BYK-300" manufactured by BYK-Chemie, "BYK-330"/"S-393" manufactured by AGC SEIMI CHEMICAL, "BYK-300" or "BYK-330" manufactured by BYK-Chemie/DIC "F-554" or "F-559" manufactured by the company, "KP340" manufactured by Shin-Etsu Silicones, "F-478" or "F-475" manufactured by DIC Corporation, "SH7PA" manufactured by Toray Dow Corning Corporation "/"DS-401" manufactured by Daikin Corporation, "L-77" manufactured by NUC Corporation/"FC4430" manufactured by 3M Japan Corporation. As the development improving agent, for example, a known development improving agent containing an organic carboxylic acid or an anhydride thereof can also be used. In the case where the photosensitive resin composition of the present invention contains a coatability improver or a development improver, from the viewpoint of sensitivity, in the total solid content of the photosensitive resin composition, the coatability improver or the development improver The contents of the agents are preferably 20% by mass or less, more preferably 10% by mass or less.

[1-1-9]紫外線吸收劑  本發明之感光性樹脂組合物亦可含有紫外線吸收劑。紫外線吸收劑係出於如下目的而添加者：藉由利用紫外線吸收劑吸收曝光所使用之光源之特定波長來控制光硬化分佈。藉由包含紫外線吸收劑，有可獲得改善顯影後之錐角形狀，或減少顯影後殘留於非曝光部之殘渣等效果之傾向。作為紫外線吸收劑，從抑制光聚合起始劑之光吸收之觀點出發，例如可使用於波長250 nm至400 nm之間具有吸收極大值之化合物。  作為紫外線吸收劑，例如可例舉：苯并三唑系化合物、三𠯤系化合物、二苯甲酮化合物、苯甲酸酯化合物、桂皮酸衍生物、萘衍生物、蒽及其衍生物、二萘化合物、啡啉化合物、染料。  該等紫外線吸收劑可單獨使用一種，亦可併用兩種以上。  作為苯并三唑系化合物，例如可例舉：2-(5甲基-2-羥基苯基)苯并三唑、2-(2-羥基-5-第三丁基苯基)-2H-苯并三唑、3-[3-第三丁基-5-(5-氯-2H-苯并三唑-2-基)-4-羥基苯基]丙酸辛酯、3-[3-第三丁基-5-(5-氯-2H-苯并三唑-2-基)-4-羥基苯基]丙酸乙基己酯、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-2H-苯并三唑、2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并三唑、2-(3,5-二-第三戊基-2-羥基苯基)苯并三唑、2-(2'-羥基-5'-第三辛基苯基)苯并三唑、3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸庚酯、3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸辛酯、3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸壬酯、2-(2H-苯并三唑-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚。該等之中，從錐角與曝光感度之觀點出發，較佳為3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸庚酯、3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸辛酯、3-[3-第三丁基-5-(2H-苯并三唑-2-基)-4-羥基苯基]丙酸壬酯、該等之混合物。[1-1-9] Ultraviolet absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling photohardening distribution by absorbing the specific wavelength of the light source used for exposure with the ultraviolet absorber. By including the ultraviolet absorber, there is a tendency to obtain effects such as improving the taper angle shape after development or reducing the residue remaining in the non-exposed portion after development. As the ultraviolet absorber, from the viewpoint of suppressing the light absorption of the photopolymerization initiator, for example, a compound having an absorption maximum value at a wavelength of 250 nm to 400 nm can be used. As the ultraviolet absorber, for example, benzotriazole-based compounds, trioxane-based compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, di Naphthalene compounds, phenanthroline compounds, dyes. These ultraviolet absorbers may be used alone or in combination of two or more. Examples of benzotriazole-based compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H- Benzotriazole, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-th Tributyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethylhexyl propionate, 2-[2-hydroxy-3,5-bis(α ,α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole, 3- [3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]heptyl propionate, 3-[3-tert-butyl-5-(2H-benzene Triazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] Nonyl propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole- 2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. Among these, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propane is preferred from the viewpoint of cone angle and exposure sensitivity. Heptyl acid, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5 -(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]nonyl propionate, mixtures thereof.

作為市售之苯并三唑系化合物，例如可例舉：SUMISORB(註冊商標、下同)200、SUMISORB250、SUMISORB300、SUMISORB340、SUMISORB350(住友化學公司製造)、JF77、JF78、JF79、JF80、JF83(城北化學工業公司製造)、TINUVIN(註冊商標、下同) PS、TINUVIN99-2、TINUVIN109、TINUVIN384-2、TINUVIN326、TINUVIN900、TINUVIN928、TINUVIN1130(BASF公司製造)、EVERSORB70、EVERSORB71、EVERSORB72、EVERSORB73、EVERSORB74、EVERSORB75、EVERSORB76、EVERSORB234、EVERSORB77、EVERSORB78、EVERSORB80、EVERSORB81(臺灣永光化學工業公司製造)、Tomisorb(註冊商標、下同)100、Tomisorb600(APICorporation公司製造)、SEESORB(註冊商標、下同)701、SEESORB702、SEESORB703、SEESORB704、SEESORB706、SEESORB707、SEESORB709(Shipro Kasei公司製造)、RUVA-93(大塚化學公司製造)。Examples of commercially available benzotriazole-based compounds include SUMISORB (registered trademark, the same below) 200, SUMISORB250, SUMISORB300, SUMISORB340, SUMISORB350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 ( Chengbei Chemical Industry Co., Ltd.), TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, 4EVERSORB EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Yongguang Chemical Industry Co., Ltd.), Tomisorb (registered trademark, the same below) 100, Tomisorb600 (manufactured by API Corporation), SEESORB (registered trademark, the same below) 701, SEESORB702 , SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Shipro Kasei), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

作為三𠯤系化合物，例如可例舉：2-[4,6-二(2,4-二甲苯基)-1,3,5-三𠯤-2-基]-5-辛氧基苯酚、2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤-2-基]-5-[3-(十二烷氧基)-2-羥基丙氧基]苯酚、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤與2-乙基己基縮水甘油醚之反應產物、2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三𠯤。該等之中，從錐角與曝光感度之觀點出發，較佳為羥基苯基三𠯤化合物。  作為市售之三𠯤系化合物，例如可例舉：TINUVIN400、TINUVIN405、TINUVIN460、TINUVIN477、TINUVIN479(BASF公司製造)等。Examples of trioxane-based compounds include: 2-[4,6-bis(2,4-xylyl)-1,3,5-trizil-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri-2-yl]-5-[3-(dodecyloxy)-2-hydroxyl Propoxy]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethanone and 2-ethylhexyl The reaction product of glycidyl ether, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-tributoxyphenyl. Among them, a hydroxyphenyl trisanthene compound is preferable from the viewpoint of the cone angle and exposure sensitivity. As the commercially available tertiary compound, for example, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 (manufactured by BASF Corporation) and the like may be mentioned.

作為其他紫外線吸收劑，例如可例舉：SUMISORB130(住友化學公司製造)、EVERSORB10、EVERSORB11、EVERSORB12(臺灣永光化學工業公司製造)、Tomisorb800(APICorporation公司製造)、SEESORB100、SEESORB101、SEESORB101S、SEESORB102、SEESORB103、SEESORB105、SEESORB106、SEESORB107、SEESORB151(Shipro Kasei公司製造)等二苯甲酮化合物；SUMISORB400(住友化學公司製造)、水楊酸苯酯等苯甲酸酯化合物；桂皮酸2-乙基己酯、對甲氧基桂皮酸2-乙基己酯、甲氧基肉桂酸異丙酯、甲氧基肉桂酸異戊酯等桂皮酸衍生物；α-萘酚、β-萘酚、α-萘酚甲醚、α-萘酚乙醚、1,2-二羥基萘、1,3-二羥基萘、1,4-二羥基萘、1,5-二羥基萘、1,6-二羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,3-二羥基萘、2,6-二羥基萘、2,7-二羥基萘等萘衍生物；蒽、9,10-二羥基蒽等蒽及其衍生物；偶氮系染料、二苯甲酮系染料、胺基酮系染料、喹啉系染料、蒽醌系染料、二苯基氰基丙烯酸酯系染料、三𠯤系染料、對胺基苯甲酸系染料等染料。該等之中，從曝光感度之觀點出發，較佳為使用桂皮酸衍生物、萘衍生物，尤佳為使用桂皮酸衍生物。As other ultraviolet absorbers, for example, SUMISORB130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongguang Chemical Industry Co., Ltd.), Tomisorb800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, Benzophenone compounds such as SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Shipro Kasei); benzoate compounds such as SUMISORB400 (manufactured by Sumitomo Chemical Co., Ltd.), phenyl salicylate; 2-ethylhexyl cinnamate, p- Cinnamic acid derivatives such as 2-ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthol, β-naphthol, α-naphthol A Ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other naphthalene derivatives; anthracene, 9,10-dihydroxynaphthalene Anthracene and its derivatives such as anthracene; azo-based dyes, benzophenone-based dyes, aminoketone-based dyes, quinoline-based dyes, anthraquinone-based dyes, diphenylcyanoacrylate-based dyes, and triphenylcyanoacrylate-based dyes , p-aminobenzoic acid dyes and other dyes. Among them, it is preferable to use a cinnamic acid derivative and a naphthalene derivative from the viewpoint of exposure sensitivity, and it is particularly preferable to use a cinnamic acid derivative.

於本發明之感光性樹脂組合物包含紫外線吸收劑之情形時，於感光性樹脂組合物之全部固形物成分中，感光性樹脂組合物中之紫外線吸收劑之含量較佳為0.01質量%以上，更佳為0.05質量%以上，進而較佳為0.1質量%以上，更進而較佳為0.5質量%以上，尤佳為1質量%以上，又，較佳為15質量%以下，更佳為10質量%以下，進而較佳為5質量%以下，尤佳為3質量%以下。上述上限及下限可任意地組合，例如，較佳為0.01～15質量%，更佳為0.05～15質量%，進而較佳為0.1～10質量%，更進而較佳為0.5～5質量%，尤佳為1～3質量%。藉由設為上述下限值以上，有錐角增大之傾向。又，藉由設為上述上限值以下，有成為高感度之傾向。When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the photosensitive resin composition is preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition, More preferably at least 0.05% by mass, more preferably at least 0.1% by mass, still more preferably at least 0.5% by mass, especially preferably at least 1% by mass, more preferably at most 15% by mass, more preferably at most 10% by mass % or less, more preferably 5 mass % or less, particularly preferably 3 mass % or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 0.01-15 mass %, more preferably 0.05-15 mass %, further preferably 0.1-10 mass %, still more preferably 0.5-5 mass %, Most preferably, it is 1-3 mass %. By setting it as more than the said lower limit, there exists a tendency for a taper angle to become large. Moreover, there exists a tendency for it to become high sensitivity by making it below the said upper limit.

於本發明之感光性樹脂組合物包含紫外線吸收劑之情形時，作為相對於(C)光聚合起始劑之調配比，相對於(C)光聚合起始劑100質量份，較佳為1質量份以上，更佳為10質量份以上，進而較佳為30質量份以上，更進而較佳為50質量份以上，尤佳為80質量份以上，又，較佳為500質量份以下，更佳為300質量份以下，進而較佳為200質量份以下，尤佳為150質量份以下。上述上限及下限可任意地組合，例如，較佳為10～500質量份，更佳為30～300質量份，進而較佳為50～200質量份，尤佳為80～150質量份。藉由設為上述下限值以上，有錐角增大之傾向。又，藉由設為上述上限值以下，有成為高感度之傾向。When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the compounding ratio to (C) photopolymerization initiator is preferably 1 with respect to 100 parts by mass of (C) photopolymerization initiator More than 10 parts by mass, more preferably more than 30 parts by mass, more preferably more than 50 parts by mass, especially preferably more than 80 parts by mass, and preferably less than 500 parts by mass, more preferably Preferably, it is 300 mass parts or less, More preferably, it is 200 mass parts or less, Most preferably, it is 150 mass parts or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-500 mass parts, more preferably 30-300 mass parts, still more preferably 50-200 mass parts, especially preferably 80-150 mass parts. By setting it as more than the said lower limit, there exists a tendency for a taper angle to become large. Moreover, there exists a tendency for it to become high sensitivity by making it below the said upper limit.

[1-1-10]聚合抑制劑  本發明之感光性樹脂組合物亦可含有聚合抑制劑。認為藉由含有聚合抑制劑，自由基聚合受到抑制，故可增大所獲得之阻隔壁之錐角。  作為聚合抑制劑，例如可例舉：對苯二酚、對苯二酚單甲醚、甲基對苯二酚、甲氧基苯酚、2,6-二第三丁基-4-甲酚(BHT)。該等之中，從聚合抑制能力之觀點出發，較佳為甲基對苯二酚、甲氧基苯酚，更佳為甲基對苯二酚。[1-1-10] Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is considered that radical polymerization is suppressed by containing a polymerization inhibitor, so that the cone angle of the obtained barrier rib can be increased. As a polymerization inhibitor, for example, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-methylphenol ( BHT). Among these, methylhydroquinone and methoxyphenol are preferable, and methylhydroquinone is more preferable from the viewpoint of polymerization inhibiting ability.

聚合抑制劑可單獨使用一種，亦可併用兩種以上。通常，於製造(B)鹼可溶性樹脂時，樹脂中有時會包含聚合抑制劑，可將其用作本發明之感光性樹脂組合物中所含之聚合抑制劑，亦可於感光性樹脂組合物之製造時，除了添加樹脂中所含之聚合抑制劑以外，還添加與其相同或不同之聚合抑制劑。A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. Usually, when the (B) alkali-soluble resin is produced, the resin sometimes contains a polymerization inhibitor, which can be used as the polymerization inhibitor contained in the photosensitive resin composition of the present invention, and can also be combined with the photosensitive resin. In addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor is added during the production of the product.

於本發明之感光性樹脂組合物包含聚合抑制劑之情形時，於感光性樹脂組合物之全部固形物成分中，感光性樹脂組合物中之聚合抑制劑之含量較佳為0.0005質量%以上，更佳為0.001質量%以上，進而較佳為0.01質量%以上，又，較佳為0.3質量%以下，更佳為0.2質量%以下，進而較佳為0.1質量%以下。上述上限及下限可任意地組合，例如，較佳為0.0005～0.3質量%，更佳為0.001～0.2質量%，進而較佳為0.01～0.1質量%。藉由設為上述下限值以上，有可提高錐角之傾向。又，藉由設為上述上限值以下，有可保持高感度之傾向。When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin composition is preferably 0.0005% by mass or more in the total solid content of the photosensitive resin composition, More preferably, it is at least 0.001% by mass, still more preferably at least 0.01% by mass, and more preferably at most 0.3% by mass, more preferably at most 0.2% by mass, still more preferably at most 0.1% by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 0.0005-0.3 mass %, more preferably 0.001-0.2 mass %, still more preferably 0.01-0.1 mass %. There exists a tendency for a taper angle to be made high by setting it as more than the said lower limit. Moreover, there exists a tendency for high sensitivity to be maintained by making it below the said upper limit.

[1-1-11]矽烷偶合劑  本發明之感光性樹脂組合物為了改善與基板之密接性，亦可含有矽烷偶合劑。作為矽烷偶合劑，例如可使用環氧系、甲基丙烯酸系、胺基系、咪唑系之矽烷偶合劑。從密接性提高之觀點出發，尤佳為環氧系、咪唑系之矽烷偶合劑。  於本發明之感光性樹脂組合物包含矽烷偶合劑之情形時，從密接性之觀點出發，於感光性樹脂組合物之全部固形物成分中，矽烷偶合劑之含量較佳為20質量%以下，更佳為15質量%以下。[1-1-11] Silane coupling agent The photosensitive resin composition of the present invention may also contain a silane coupling agent in order to improve the adhesion with the substrate. As the silane coupling agent, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used, for example. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred. When the photosensitive resin composition of the present invention contains a silane coupling agent, from the viewpoint of adhesion, the content of the silane coupling agent is preferably 20% by mass or less in the total solid content of the photosensitive resin composition. More preferably, it is 15 mass % or less.

[1-1-12]磷酸系密接提昇劑  為了改善與基板之密接性，本發明之感光性樹脂組合物亦可含有磷酸系密接提昇劑。作為磷酸系密接提昇劑，較佳為含(甲基)丙烯醯氧基之磷酸酯類，其中，較佳為下述通式(Va)、(Vb)、(Vc)所表示者。[1-1-12] Phosphoric acid-based adhesion enhancer In order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may also contain a phosphoric acid-based adhesion enhancer. As the phosphoric acid-based adhesion improving agent, (meth)acryloxy-containing phosphoric acid esters are preferable, and among them, those represented by the following general formulas (Va), (Vb), and (Vc) are preferable.

[化38]

Figure 02_image075
[chem 38]
Figure 02_image075

式(Va)、(Vb)、(Vc)中，R 8表示氫原子或甲基，r及r'為1～10之整數，s為1、2或3。 In the formulas (Va), (Vb), and (Vc), R 8 represents a hydrogen atom or a methyl group, r and r' are integers ranging from 1 to 10, and s is 1, 2 or 3.

於本發明之感光性樹脂組合物含有磷酸系密接提昇劑之情形時，其含量並無特別限定，於感光性樹脂組合物之全部固形物成分中，較佳為0.1質量%以上，更佳為0.2質量%以上，進而較佳為0.3質量%以上，又，較佳為5質量%以下，更佳為3質量%以下，進而較佳為1質量%以下。上述上限及下限可任意地組合，例如，較佳為0.1～5質量%，更佳為0.2～3質量%，進而較佳為0.3～1質量%。藉由設為上述下限值以上，有與基板之密接性提高之傾向。又，藉由設為上述上限值以下，有表面硬化性提高之傾向。When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion improving agent, its content is not particularly limited, but it is preferably 0.1% by mass or more in the total solid content of the photosensitive resin composition, more preferably 0.2 mass % or more, more preferably 0.3 mass % or more, and preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 0.1-5 mass %, more preferably 0.2-3 mass %, still more preferably 0.3-1 mass %. There exists a tendency for the adhesiveness with a board|substrate to improve by making it more than the said lower limit. Moreover, surface hardening property exists in the tendency for it to improve by making it below the said upper limit.

[1-1-13]溶劑  本發明之感光性樹脂組合物通常含有溶劑，且於使上述各成分溶解或分散於溶劑中之狀態下使用。作為溶劑，並無特別限制，例如可例舉以下所記載之有機溶劑。[1-1-13] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state where the above-mentioned components are dissolved or dispersed in the solvent. It does not specifically limit as a solvent, For example, the organic solvent described below is mentioned.

乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丁醚、丙二醇第三丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丁醚、甲氧基甲基戊醇、二丙二醇單乙醚、二丙二醇單甲醚、3-甲基-3-甲氧基丁醇、3-甲氧基-1-丁醇、三乙二醇單甲醚、三乙二醇單乙醚、三丙二醇甲醚等二醇單烷基醚類；乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚、二乙二醇二丁醚、二丙二醇二甲醚等二醇二烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、乙酸甲氧基丁酯、乙酸3-甲氧基丁酯、乙酸甲氧基戊酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單正丁醚乙酸酯、二丙二醇單甲醚乙酸酯、三乙二醇單甲醚乙酸酯、三乙二醇單乙醚乙酸酯、乙酸3-甲基-3-甲氧基丁酯、乙酸3-甲氧基-1-丁酯等二醇烷基醚乙酸酯類；乙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己醇二乙酸酯等二醇二乙酸酯類；環己醇乙酸酯等烷乙酸酯類；戊醚、二乙醚、二丙醚、二異丙醚、二丁醚、二戊醚、乙基異丁醚、二己醚等醚類；丙酮、甲基乙基酮、甲基戊基酮、甲基異丙基酮、甲基異戊基酮、二異丙基酮、二異丁基酮、甲基異丁基酮、環己酮、乙基戊基酮、甲基丁基酮、甲基己基酮、甲基壬基酮、甲氧基甲基戊酮等酮類；甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丁二醇、二乙二醇、二丙二醇、三乙二醇、甲氧基甲基戊醇、甘油、苄醇等一元或多元醇類；正戊烷、正辛烷、二異丁烯、正己烷、己烯、異戊二烯、二戊烯、十二烷等脂肪族烴類；環己烷、甲基環己烷、甲基環己烯、聯環己烷等脂環式烴類；苯、甲苯、二甲苯、異丙苯等芳香族烴類；甲酸戊酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸戊酯、異丁酸甲酯、乙二醇乙酸酯、丙酸乙酯、丙酸丙酯、丁酸丁酯、丁酸異丁酯、異丁酸甲酯、辛酸乙酯、硬脂酸丁酯、苯甲酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、γ-丁內酯等鏈狀或環狀酯類；3-甲氧基丙酸、3-乙氧基丙酸等烷氧基羧酸類；氯丁烷、氯戊烷等鹵代烴類；甲氧基甲基戊酮等醚酮類；乙腈、苯甲腈等腈類：四氫呋喃、二甲基四氫呋喃、二甲氧基四氫呋喃等四氫呋喃類等。Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Butanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and other glycol monoalkyl ethers; ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers ;Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid 3 - Glycol alkyl ether acetates such as methyl-3-methoxybutyl ester and 3-methoxy-1-butyl acetate; ethylene glycol diacetate, 1,3-butanediol diethyl Diol diacetates such as esters and 1,6-hexanol diacetate; alkane acetates such as cyclohexanol acetate; pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether Ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone Diisobutyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones such as Methanol, Ethanol, Propanol, Butanol, Hexanol, Cyclohexanol, Ethylene Glycol, Propylene Glycol, Butylene Glycol, Diethylene Glycol, Dipropylene Glycol, Triethylene Glycol, Methoxymethylpentyl Alcohol, glycerol, benzyl alcohol and other monohydric or polyhydric alcohols; n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene, dodecane and other aliphatic hydrocarbons; cyclohexyl Alicyclic hydrocarbons such as alkane, methylcyclohexane, methylcyclohexene, and dicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, and acetic acid Ethyl, Butyl Acetate, Propyl Acetate, Amyl Acetate, Methyl Isobutyrate, Ethylene Glycol Acetate, Ethyl Propionate, Propyl Propionate, Butyl Butyrate, Isobutyl Butyrate, Isobutyrate Methyl Butyrate, Ethyl Octanoate, Butyl Stearate, Ethyl Benzoate, Methyl 3-Ethoxypropionate, Ethyl 3-Ethoxypropionate, Methyl 3-Methoxypropionate, Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters; 3-methoxypropionate Alkoxy carboxylic acids such as acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile: Tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran and other tetrahydrofuran class etc.

作為符合上述之市售之溶劑，例如可例舉：礦油精、Varsol＃2、Apco＃18 solvent、Apcothinner、Socalsolvent No.1及No.2、Solvesso＃150、Shell TS28 solvent、卡必醇、乙基卡必醇、丁基卡必醇、甲基溶纖劑、乙基溶纖劑、乙基溶纖劑乙酸酯、甲基溶纖劑乙酸酯、二乙二醇二甲醚(均為商品名)。As the above-mentioned commercially available solvents, for example, mineral spirits, Varsol #2, Apco #18 solvent, Apcothinner, Socalsolvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, carbitol, Ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether ( are trade names).

溶劑可使感光性樹脂組合物中之各成分溶解或分散，係根據本發明之感光性樹脂組合物之使用方法來選擇，但從塗佈性之觀點出發，較佳為大氣壓下(1013.25 hPa)之沸點為60～280℃者，更佳為70～260℃者。例如，較佳為丙二醇單甲醚、3-甲氧基-1-丁醇、丙二醇單甲醚乙酸酯、乙酸3-甲氧基-1-丁酯。The solvent can dissolve or disperse the components in the photosensitive resin composition, and is selected according to the usage method of the photosensitive resin composition of the present invention, but from the viewpoint of coatability, it is preferably under atmospheric pressure (1013.25 hPa) The boiling point is 60-280°C, more preferably 70-260°C. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.

溶劑可單獨使用一種，亦可併用兩種以上。  溶劑較佳為以感光性樹脂組合物中之全部固形物成分較佳為成為10質量%以上、更佳為成為15質量%以上、進而較佳為成為18質量%以上、且較佳為成為90質量%以下、更佳為成為50質量%以下、進而較佳為成為40質量%以下、尤佳為成為30質量%以下之方式使用。上述上限及下限可任意地組合，例如，較佳為10～90質量%，更佳為10～50質量%，進而較佳為15～40質量%，尤佳為18～30質量%。藉由設為上述下限值以上，有即便對較高之膜厚亦可獲得塗膜之傾向。又，藉由設為上述上限值以下，有可獲得適度之塗佈均勻性之傾向。A solvent may be used individually by 1 type, and may use 2 or more types together. The solvent is preferably at least 10% by mass, more preferably at least 15% by mass, further preferably at least 18% by mass, and more preferably at least 90% of the total solid content in the photosensitive resin composition. % by mass or less, more preferably not more than 50 mass %, still more preferably not more than 40 mass %, most preferably not more than 30 mass %. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-90 mass%, more preferably 10-50 mass%, further preferably 15-40 mass%, especially preferably 18-30 mass%. By setting it as more than the said lower limit, there exists a tendency for a coating film to be obtained even with a high film thickness. Moreover, there exists a tendency for moderate coating uniformity to be acquired by making it below the said upper limit.

[1-2]感光性樹脂組合物之製備方法  本發明之感光性樹脂組合物係藉由利用攪拌機混合上述各成分來製備。再者，例如亦可使用膜濾器進行過濾，以使所製備之感光性樹脂組合物變均勻。[1-2] Preparation method of photosensitive resin composition The photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a mixer. Furthermore, for example, it is also possible to perform filtration using a membrane filter so that the prepared photosensitive resin composition can be made uniform.

[2]硬化物、阻隔壁及該等之形成方法  本發明之感光性樹脂組合物可適宜地用於形成阻隔壁、尤其是用以劃分有機電致發光元件之有機層(發光部)之阻隔壁。本發明之阻隔壁包含使本發明之感光性樹脂組合物硬化而成之硬化物。  使用本發明之感光性樹脂組合物形成阻隔壁之方法並無特別限定，可採用先前公知之方法。作為阻隔壁之形成方法，例如可例舉包括如下步驟之方法：塗佈步驟，其將感光性樹脂組合物塗佈於基板上，形成感光性樹脂組合物層；曝光步驟，其使感光性樹脂組合物層曝光。作為此種阻隔壁之形成方法，例如可例舉光微影法。[2] Cured products, barrier ribs, and methods for forming them wall. The barrier rib of this invention contains the hardened|cured material which hardened the photosensitive resin composition of this invention. The method of forming barrier ribs using the photosensitive resin composition of the present invention is not particularly limited, and previously known methods can be used. As a method for forming a barrier rib, for example, a method including the following steps can be cited: a coating step, which applies a photosensitive resin composition to a substrate to form a photosensitive resin composition layer; an exposure step, which makes the photosensitive resin composition The composition layer is exposed. As a method of forming such a barrier rib, photolithography may, for example, be mentioned.

於光微影法中，將感光性樹脂組合物塗佈於基板之形成阻隔壁之整個區域來形成感光性樹脂組合物層。使所形成之感光性樹脂組合物層相應於特定阻隔壁之圖案進行曝光，其後將所曝光之感光性樹脂組合物層顯影，而於基板上形成阻隔壁。In the photolithography method, the photosensitive resin composition is applied to the entire area of the substrate where the barrier ribs are formed to form a photosensitive resin composition layer. Expose the formed photosensitive resin composition layer corresponding to the pattern of the specific barrier ribs, and then develop the exposed photosensitive resin composition layer to form barrier ribs on the substrate.

用於形成阻隔壁之基板並無特別限定，係根據使用形成有阻隔壁之基板製造之有機電致發光元件之種類適當選擇。作為適宜之基板之材料，可例舉玻璃、或各種樹脂材料。作為樹脂材料，例如可例舉：聚對苯二甲酸乙二酯等聚酯；聚乙烯、及聚丙烯等聚烯烴；聚碳酸酯；聚(甲基)丙烯酸系樹脂；聚碸；聚醯亞胺。  該等基板之材料之中，從耐熱性優異方面出發，較佳為玻璃、及聚醯亞胺。又，亦可根據所製造之有機電致發光元件之種類，於形成阻隔壁之基板之表面預先設置ITO(Indium Tin Oxide，氧化銦錫)或ZnO(Indium Zinc Oxide，氧化銦鋅)等透明電極層。The substrate used to form the barrier ribs is not particularly limited, and is appropriately selected according to the type of organic electroluminescence element manufactured using the substrate on which the barrier ribs are formed. A suitable material for the substrate may, for example, be glass or various resin materials. As the resin material, for example, polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resins; amine. Among the materials of these substrates, glass and polyimide are preferable in terms of excellent heat resistance. Also, according to the type of organic electroluminescent element to be manufactured, transparent electrodes such as ITO (Indium Tin Oxide, indium tin oxide) or ZnO (Indium Zinc Oxide, indium zinc oxide) can be pre-set on the surface of the substrate forming the barrier ribs. Floor.

光微影法中之將感光性樹脂組合物塗佈於基板上之塗佈步驟中，於應形成阻隔壁之基板上，使用輥式塗佈機、反向塗佈機、棒式塗佈機等接觸轉印型塗佈裝置、或旋轉塗佈機(旋轉式塗佈裝置)、淋幕式平面塗佈機等非接觸型塗佈裝置塗佈感光性樹脂組合物，並視需要藉由乾燥去除溶劑，而形成感光性樹脂組合物層。In the coating step of coating the photosensitive resin composition on the substrate in the photolithography method, a roll coater, a reverse coater, and a bar coater are used on the substrate on which barrier walls are to be formed Non-contact coating devices such as contact transfer coating devices, such as spin coaters (rotary coating devices), and curtain type flat coaters, are used to coat the photosensitive resin composition, and if necessary, dry The solvent is removed to form a photosensitive resin composition layer.

塗佈量根據用途而有所不同，例如於阻隔壁之情形時，以按乾燥膜厚計，通常成0.5～30 μm、較佳為成為1～15 μm、尤佳為成為1～5 μm之方式塗佈。重要的是乾燥膜厚或最終形成之阻隔壁之高度於基板整個區域較均勻。若不均較小，則可抑制顯示裝置中所產生之不平整缺陷。The coating amount varies depending on the application. For example, in the case of a barrier wall, the dry film thickness is usually 0.5 to 30 μm, preferably 1 to 15 μm, and most preferably 1 to 5 μm. method of coating. It is important that the dry film thickness or the height of the resulting barrier ribs be relatively uniform over the entire area of the substrate. If the unevenness is small, unevenness defects generated in the display device can be suppressed.

向基板上供給感光性樹脂組合物後之乾燥較佳為利用使用有加熱板、IR(Infrared Radiation，紅外線輻射)烘箱、對流烘箱之乾燥方法。亦可組合不提供溫度，而於減壓腔室內進行乾燥之減壓乾燥法。Drying after supplying the photosensitive resin composition onto the substrate is preferably a drying method using a hot plate, an IR(Infrared Radiation) oven, or a convection oven. It is also possible to combine the reduced-pressure drying method of drying in a reduced-pressure chamber without providing temperature.

乾燥條件可根據溶劑成分之種類、所使用之乾燥機之性能等適當選擇。乾燥時間根據溶劑成分之種類、所使用之乾燥機之性能等，通常於40～130℃之溫度下於15秒～5分鐘之範圍內選擇，較佳為於50～110℃之溫度下於30秒～3分鐘之範圍內選擇。Drying conditions can be appropriately selected according to the type of solvent components, the performance of the dryer used, and the like. The drying time depends on the type of solvent components, the performance of the dryer used, etc., usually at a temperature of 40-130°C in the range of 15 seconds to 5 minutes, preferably at a temperature of 50-110°C at 30 Select from the range of seconds to 3 minutes.

繼而，於曝光步驟中，利用負型遮罩對感光性樹脂組合物照射紫外線、準分子雷射光等活性能量線，將感光性樹脂組合物層相應於阻隔壁之圖案而部分地曝光。曝光可使用高壓水銀燈、超高壓水銀燈、氙燈、碳弧燈等發出紫外線之光源。根據感光性樹脂組合物之組成曝光量亦有所不同，例如較佳為10～400 mJ/cm 2左右。 Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask to partially expose the photosensitive resin composition layer corresponding to the pattern of the barrier ribs. Exposure can use a light source that emits ultraviolet light, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp. The exposure amount varies depending on the composition of the photosensitive resin composition, for example, it is preferably about 10 to 400 mJ/cm 2 .

繼而，於顯影步驟中，利用顯影液使相應於阻隔壁之圖案進行了曝光之感光性樹脂組合物層顯影，藉此形成阻隔壁圖案。顯影方法並無特別限定，可使用浸漬法、噴霧法等。作為顯影液，例如可例舉：二甲基苄基胺、單乙醇胺、二乙醇胺、三乙醇胺等有機系顯影液；或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、四級銨鹽等水溶液。又，亦可於顯影液中添加消泡劑或界面活性劑。Next, in the developing step, the photosensitive resin composition layer exposed corresponding to the pattern of the barrier ribs is developed with a developer, thereby forming a barrier rib pattern. The image development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Examples of developing solutions include organic developing solutions such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine; or aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. . Moreover, you may add an antifoaming agent or surfactant to a developer.

其後，藉由對顯影後之阻隔壁圖案實施後烘烤而進行加熱硬化，可獲得阻隔壁。後烘烤較佳為於150～250℃下進行15～60分鐘。Thereafter, the barrier rib pattern can be obtained by post-baking the developed barrier rib pattern to heat-cure it. Post-baking is preferably carried out at 150-250° C. for 15-60 minutes.

於形成阻隔壁後亦可進行以洗淨未曝光部為目標之洗淨處理。洗淨方法並無特別限定，可例舉：電漿照射、準分子光照射、UV照射。於準分子光照射或UV照射中，藉由光照射，活性氧可將附著於像素部之有機物分解而去除。A cleaning treatment aimed at cleaning the unexposed portion may also be performed after the formation of the barrier ribs. The cleaning method is not particularly limited, and examples thereof include plasma irradiation, excimer light irradiation, and UV irradiation. In excimer light irradiation or UV irradiation, active oxygen decomposes and removes organic substances attached to the pixel portion by light irradiation.

[3]有機電致發光元件  本發明之有機電致發光元件具備本發明之阻隔壁。  使用藉由以上所說明之方法製造之具備阻隔壁圖案之基板，製造各種有機電致發光元件。形成有機電致發光元件之方法並無特別限定，但較佳為藉由上述方法於基板上形成阻隔壁之圖案，其後向基板上之由阻隔壁所圍成之區域內注入油墨而形成像素等有機層，藉此製造有機電致發光元件。  作為有機電致發光元件之類型，可例舉底部發光型或頂部發光型。  底部發光型例如係於積層有透明電極之玻璃基板上形成阻隔壁，並於由阻隔壁所圍成之開口部積層電洞傳輸層、發光層、電子傳輸層、金屬電極層而製作。頂部發光型例如係於積層有金屬電極層之玻璃基板上形成阻隔壁，並於由阻隔壁所圍成之開口部積層電子傳輸層、發光層、電洞傳輸層、透明電極層而製作。  作為發光層，可例舉如日本專利特開2009-146691號公報或日本專利第5734681號公報中所記載之有機電致發光層。亦可使用如日本專利第5653387號公報或日本專利第5653101號公報中所記載之量子點。[3] Organic electroluminescence element The organic electroluminescence element of the present invention has the barrier rib of the present invention. Various organic electroluminescence elements were produced using the substrate having the barrier rib pattern produced by the method described above. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to form a pattern of barrier ribs on the substrate by the above method, and then inject ink into the area surrounded by the barrier ribs on the substrate to form pixels and other organic layers to manufacture organic electroluminescence elements. As the type of organic electroluminescence element, a bottom emission type or a top emission type can be exemplified. Bottom emission type, for example, is formed by forming a barrier wall on a glass substrate laminated with a transparent electrode, and laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in the opening surrounded by the barrier wall. The top emission type, for example, forms a barrier wall on a glass substrate laminated with a metal electrode layer, and laminates an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the barrier wall. The light-emitting layer may, for example, be an organic electroluminescent layer described in Japanese Patent Application Laid-Open No. 2009-146691 or Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101 may also be used.

作為形成有機層形成用之油墨時所使用之溶劑，可使用水、有機溶劑、及該等之混合溶劑。有機溶劑只要能自注入油墨後形成之皮膜去除，則並無特別限定。作為有機溶劑，例如可例舉：甲苯、二甲苯、大茴香醚、均三甲苯、萘滿、環己基苯、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、甲醇、乙醇、異丙醇、乙酸乙酯、乙酸丁酯、3-苯氧基甲苯。又，可於油墨中例如添加界面活性劑、抗氧化劑、黏度調整劑、紫外線吸收劑。As the solvent used when forming the ink for forming an organic layer, water, an organic solvent, and a mixed solvent of these can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink. Examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Ethanol, Isopropanol, Ethyl Acetate, Butyl Acetate, 3-Phenoxytoluene. In addition, for example, a surfactant, an antioxidant, a viscosity modifier, and an ultraviolet absorber may be added to the ink.

作為向由阻隔壁所圍成之區域內注入油墨之方法，從能夠容易地將少量油墨注入至特定部位方面而言，較佳為噴墨法。用於有機層之形成油墨係根據所製造之有機電致發光元件之種類適當選擇。於藉由噴墨法注入油墨之情形時，油墨之黏度只要能夠將油墨自噴墨頭良好地噴出，則並無特別限定，但較佳為4～20 mPa・s，更佳為5～10 mPa・s。油墨之黏度可藉由油墨中之固形物成分含量之調整、溶劑之變更、黏度調整劑之添加等進行調整。As a method of injecting ink into the region surrounded by the barrier ribs, an inkjet method is preferable in that a small amount of ink can be easily injected into a specific portion. The ink used for forming the organic layer is appropriately selected according to the type of organic electroluminescence element to be produced. In the case of injecting ink by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected from the inkjet head well, but it is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa·s. mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, etc.

[4]彩色濾光器  本發明之彩色濾光器只要包含發光性奈米晶粒，且具備本發明之阻隔壁，則並無特別限定，可例舉於以阻隔壁劃分之區域中形成有像素者。[4] Color filter The color filter of the present invention is not particularly limited as long as it contains luminescent nanocrystal grains and has the barrier ribs of the present invention. Pixels.

圖1係具備本發明之阻隔壁之彩色濾光器之一例的模式剖視圖。如圖1所示，彩色濾光器100具備：基板10、設置於基板上之阻隔壁20、紅色像素30、綠色像素40、及藍色像素50。紅色像素30、綠色像素40、及藍色像素50係以依序重複之方式以晶格狀排列。阻隔壁20設置於該等鄰接之像素之間。換言之，該等鄰接之像素彼此被阻隔壁20劃分開。FIG. 1 is a schematic cross-sectional view of an example of a color filter provided with a barrier rib of the present invention. As shown in FIG. 1 , the color filter 100 includes: a substrate 10 , barrier ribs 20 disposed on the substrate, red pixels 30 , green pixels 40 , and blue pixels 50 . The red pixels 30 , the green pixels 40 , and the blue pixels 50 are arranged in a lattice in a sequentially repeated manner. The barrier wall 20 is disposed between the adjacent pixels. In other words, the adjacent pixels are separated from each other by the barrier ribs 20 .

於紅色像素30中包含紅色發光性奈米晶粒2，並且於綠色像素40中包含綠色發光性奈米晶粒1。藍色像素50係使來自光源之藍色光透過之像素。The red pixel 30 contains red light-emitting nanocrystal grains 2 , and the green pixel 40 contains green light-emitting nanocrystal grains 1 . The blue pixel 50 is a pixel that transmits blue light from a light source.

該等奈米晶粒係吸收激發光而發出螢光或磷光之奈米尺寸之結晶體，例如係利用穿透式電子顯微鏡或掃描式電子顯微鏡測定之最大粒徑為100 nm以下之結晶體。These nanocrystals are nanometer-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, for example, crystals with a maximum particle size of 100 nm or less measured by a transmission electron microscope or a scanning electron microscope.

發光性奈米晶粒係可藉由吸收特定波長之光，發出不同於所吸收之波長之波長之光(螢光或磷光)者，例如，紅色發光性奈米晶粒2係發出於605～665 nm之範圍內具有發光峰值波長之光(紅色光)者，綠色發光性奈米晶粒1係發出於500～560 nm之範圍內具有發光峰值波長之光(綠色光)者。Luminescent nanocrystals can emit light of a wavelength different from the absorbed wavelength (fluorescence or phosphorescence) by absorbing light of a specific wavelength. For example, red luminescent nanocrystals 2 are emitted at 605~ Those that have light emission peak wavelength (red light) within the range of 665 nm, and green light emitting nanocrystals 1 are those that emit light (green light) that has emission peak wavelength within the range of 500-560 nm.

根據井型電位模型之薛定諤波動方程式之解，發光性奈米晶粒所發出之光之波長(發光色)取決於發光性奈米晶粒之尺寸(例如粒徑)，但亦取決於發光性奈米晶粒所具有之能隙。因此，可藉由變更所使用之發光性奈米晶粒之構成材料及尺寸來選擇發光色。作為發光性奈米晶粒，可例舉量子點等。According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength (luminous color) of the light emitted by the luminescent nanocrystals depends on the size (such as particle size) of the luminescent nanocrystals, but also depends on the luminescence The energy gap possessed by nanocrystal grains. Therefore, the luminescent color can be selected by changing the constituent material and size of the luminescent nanocrystal grains used. Quantum dots etc. are mentioned as a luminous nanocrystal particle.

包含發光性奈米晶粒之彩色濾光器之製造方法並無特別限定，可例舉如下方法：準備具備由本發明之硬化物所構成之阻隔壁之基板，於利用阻隔壁劃分之區域中形成包含發光性奈米晶粒之層。形成包含發光性奈米晶粒之層之方法並無特別限定，例如可藉由如下方法製造：藉由噴墨方式使包含發光性奈米晶粒之油墨組合物選擇性地附著，並藉由活性能量線之照射或加熱使油墨組合物硬化。The method of manufacturing a color filter including luminescent nanocrystal grains is not particularly limited, and the following method is exemplified: prepare a substrate having a barrier rib made of the cured product of the present invention, and form it in a region divided by the barrier rib A layer comprising luminescent nanoparticles. The method of forming the layer containing the luminescent nanocrystal grains is not particularly limited. For example, it can be produced by the following method: selectively attaching the ink composition containing the luminescent nanocrystal grains by inkjet method, and by Irradiation or heating of active energy rays hardens the ink composition.

[5]圖像顯示裝置  本發明之圖像顯示裝置之一態樣包含本發明之有機電致發光元件。只要係包含本發明之有機電致發光元件者，則對圖像顯示裝置之型號或構造並無特別限制，例如可使用主動驅動型有機電致發光元件依據常法組裝。例如可藉由如「有機EL顯示器」(Ohmsha，2004年8月20日發行，時任靜士、安達千波矢、村田英幸著)中所記載之方法，形成本發明之圖像顯示裝置。例如亦可組合發出白色光之有機電致發光元件與彩色濾光器來進行圖像顯示，亦可組合RGB(Red Green Blue，紅綠藍)等發光色不同之有機電致發光元件來進行圖像顯示。[5] Image display device One aspect of the image display device of the present invention includes the organic electroluminescence device of the present invention. As long as it includes the organic electroluminescent element of the present invention, there is no particular limitation on the type or structure of the image display device. For example, an active-driven organic electroluminescent element can be used to assemble according to the usual method. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, by Shizushi Oka, Chihaya Adachi, and Hideyuki Murata). For example, an organic electroluminescent element that emits white light and a color filter can also be combined for image display, and an organic electroluminescent element with different luminescent colors such as RGB (Red Green Blue, red, green, blue) can also be combined for image display. like display.

本發明之圖像顯示裝置之另一態樣包含本發明之彩色濾光器。  作為圖像顯示裝置之種類，可例舉液晶顯示裝置、或包含有機電致發光元件之圖像顯示裝置等。於液晶顯示裝置之情形時，可例舉包含具備藍色LED之光源、及具備於每一像素部控制自光源發出之藍色光之電極之液晶層者。Another aspect of the image display device of the present invention includes the color filter of the present invention. The type of image display device may, for example, be a liquid crystal display device or an image display device including an organic electroluminescent element. In the case of a liquid crystal display device, a liquid crystal layer including a light source including a blue LED, and an electrode for controlling blue light emitted from the light source in each pixel portion is exemplified.

另一方面，關於包含有機電致發光元件之圖像顯示裝置，可例舉於和上述彩色濾光器之各像素部對應之位置配置有藍色發光之有機電致發光元件者。具體而言，可例舉日本專利特開2019-87746號公報中所記載之方式。  [實施例]On the other hand, an image display device including an organic electroluminescent element may, for example, be one in which an organic electroluminescent element emitting blue light is arranged at a position corresponding to each pixel portion of the above-mentioned color filter. Specifically, the method described in Japanese Patent Laid-Open No. 2019-87746 may be mentioned. [Example]

例舉實施例對本發明之感光性樹脂組合物進行說明，但本發明只要不超出其主旨，則並不限定於以下之實施例。  以下之實施例中所使用之感光性樹脂組合物之構成成分如下所述。Although an Example is given and the photosensitive resin composition of this invention is demonstrated, unless this invention exceeds the summary, it is not limited to a following Example. The components of the photosensitive resin composition used in the following examples are as follows.

共聚物(a-1)：  經過以下之合成例1、製造例1及製造例2之順序所獲得之以丙烯酸1H,1H,2H,2H-十三氟辛酯、甲基丙烯酸硬脂酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯(重量比：0.35/0.15/0.10/0.40)為構成單體之共聚物。  甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯相當於單體(a1)，丙烯酸1H,1H,2H,2H-十三氟辛酯相當於單體(a2)。Copolymer (a-1): 1H,1H,2H,2H-Tridecafluorooctyl acrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate (weight ratio: 0.35/0.15/0.10 /0.40) is a copolymer of monomers. 2-[4-(2-Hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate is equivalent to monomer (a1), acrylic acid 1H,1H,2H,2H-tridecyl Fluoroctyl is equivalent to monomer (a2).

(合成例1：甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯之合成)  將甲基丙烯酸酐(東京化成工業股份有限公司製造)減壓蒸餾，回收純度達到99.8%以上之餾分而獲得甲基丙烯酸酐之蒸餾物。減壓蒸餾係藉由於壓力30 pa下自室溫緩慢升溫至90℃之方法實施。  除此以外，使1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙酮(東京化成工業股份有限公司製造)22.4 g(0.1 mol)、及三乙基胺(東京化成工業股份有限公司製造)30.4 g(0.3 mol)溶解於二氯甲烷(東京化成工業股份有限公司製造)500 mL中。於室溫下於其中滴加上述甲基丙烯酸酐之蒸餾物23.1 g(0.15 mol)，並攪拌12小時。  利用離子交換水500 mL將所獲得之反應液洗淨3次，其後將有機相濃縮，將溶劑蒸餾去除。藉由管柱層析法(乙酸乙酯/己烷＝10/90(體積比))將殘留物純化，獲得目標化合物21.6 g (產率74%)。  藉由 1H-NMR(Nuclear Magnetic Resonance，核磁共振)分析，確認所獲得之化合物為甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯。 1H NMR (300 MHz, 氯仿-d): δ 8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1 Hz, 2H), 4.29 (dd, J = 5.5, 4.1 Hz, 3H), 1.94 (dd, J = 1.6, 1.0 Hz, 3H), 1.61 (s, 6H)。 (Synthesis Example 1: Synthesis of 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate) Methacrylic anhydride (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) is distilled under reduced pressure, and the distillate of methacrylic anhydride is obtained by recovering the distillate with a purity of more than 99.8%. Distillation under reduced pressure was carried out by slowly raising the temperature from room temperature to 90°C under a pressure of 30 Pa. In addition, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 30.4 g (0.3 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 mL of dichloromethane (manufactured by Tokyo Chemical Industry Co., Ltd.). 23.1 g (0.15 mol) of the distillate of the said methacrylic anhydride was dripped there at room temperature, and it stirred for 12 hours. The obtained reaction solution was washed three times with 500 mL of ion-exchanged water, and then the organic phase was concentrated, and the solvent was distilled off. The residue was purified by column chromatography (ethyl acetate/hexane=10/90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%). By 1 H-NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) analysis, it was confirmed that the obtained compound was methacrylic acid 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy ] ethyl ester. 1 H NMR (300 MHz, chloroform-d): δ 8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1 Hz, 2H), 4.29 (dd, J = 5.5, 4.1 Hz, 3H), 1.94 (dd, J = 1.6, 1.0 Hz, 3H), 1.61 (s, 6H).

(製造例1：共聚物(a-1)之製造)  於具備攪拌機、冷凝管及溫度計之燒瓶中添加甲基異丁基酮(MIBK)70份，繼而，對燒瓶內進行氮氣置換，升溫至65℃，歷時2小時滴加甲基丙烯酸2-[4-(2-羥基-2-甲基-1-氧代丙基)苯氧基]乙酯40質量份、甲基丙烯酸硬脂酯(三菱化學製造之「Acryester S」)15質量份、甲基丙烯酸2-乙基己酯(三菱化學製造之「Acryester EH」)20質量份、丙烯酸1H,1H,2H,2H-十三氟辛酯(大阪有機化學工業公司製造之「Viscoat 13F」)35質量份、作為聚合起始劑之2,2'-偶氮雙(2,4-二甲基戊腈)0.75質量份、及MIBK 78質量份之混合溶液。進而於2小時後，為了提高聚合率，投入2,2'-偶氮雙(2,4-二甲基戊腈)0.5質量份與MIBK 0.6質量份之混合液，並保持5小時。其後，藉由將反應液冷卻至40℃，獲得共聚物之MIBK溶液(溶液(a-1))。以下，將溶液(a-1)中之固形物成分稱為共聚物(a-1)。  溶液(a-1)之固形物成分(不揮發成分)為40質量%。共聚物(a-1)之重量平均分子量(Mw)為132000，共聚物(a-1)之每1 g之活性基之含量為1.31(mmol/g)。(Manufacturing Example 1: Manufacture of Copolymer (a-1)) 70 parts of methyl isobutyl ketone (MIBK) was added to a flask equipped with a stirrer, a condenser, and a thermometer, and then, the inside of the flask was replaced with nitrogen, and the temperature was raised to At 65°C, 40 parts by mass of 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, stearyl methacrylate ( "Acryester S" manufactured by Mitsubishi Chemical) 15 parts by mass, 2-ethylhexyl methacrylate ("Acryester EH" manufactured by Mitsubishi Chemical) 20 parts by mass, 1H,1H,2H,2H-tridecafluorooctyl acrylate ("Viscoat 13F" manufactured by Osaka Organic Chemical Industry Co., Ltd.) 35 parts by mass, 0.75 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and MIBK 78 by mass part of the mixed solution. Furthermore, after 2 hours, in order to increase a polymerization rate, the mixed liquid of 0.5 mass part of 2,2'- azobis (2, 4- dimethylvaleronitrile) and 0.6 mass part of MIBK was injected|thrown-in, and it held|maintained for 5 hours. Thereafter, by cooling the reaction liquid to 40° C., an MIBK solution of the copolymer (solution (a-1)) was obtained. Hereinafter, the solid content in the solution (a-1) is referred to as a copolymer (a-1). The solid content (non-volatile content) of the solution (a-1) was 40% by mass. The weight average molecular weight (Mw) of the copolymer (a-1) was 132,000, and the active group content per 1 g of the copolymer (a-1) was 1.31 (mmol/g).

於100 mL之滴液漏斗中投入製造例1中所製造之溶液(a-1)20質量份、MIBK 20質量份，進行移液操作直至變均勻。繼而於500 mL之燒杯中投入甲醇160質量份與攪拌棒，並進行攪拌。歷時10分鐘向甲醇溶液中滴加預先準備之滴液漏斗中之溶液(a-1)與MIBK之混合溶液。滴加結束後，進而進行30分鐘攪拌，其後停止攪拌。停止攪拌後，於燒杯之底面確認共聚物(a-1)之沈澱物之存在。去除上清液後，向燒杯中添加MIBK 30質量份，使沈澱物再溶解直至變均勻。與上述同樣地將再溶解後之溶液利用甲醇160質量份進行再沈澱純化，進而將所回收之沈澱物於80℃下進行2小時減壓乾燥，藉此獲得純化後之共聚物(a-1)。Put 20 parts by mass of the solution (a-1) and 20 parts by mass of MIBK prepared in Production Example 1 into a 100 mL dropping funnel, and perform pipetting until it becomes uniform. Then, 160 parts by mass of methanol and a stirring bar were put into a 500 mL beaker, and stirred. The mixed solution of solution (a-1) and MIBK in the dropping funnel prepared in advance was added dropwise to the methanol solution over 10 minutes. Stirring was performed for 30 minutes after completion|finish of dripping, and stirring was stopped after that. After the stirring was stopped, the presence of the precipitate of the copolymer (a-1) was confirmed on the bottom surface of the beaker. After removing the supernatant, 30 parts by mass of MIBK was added to the beaker to redissolve the precipitate until it became uniform. The redissolved solution was reprecipitated and purified with 160 parts by mass of methanol in the same manner as above, and the recovered precipitate was dried under reduced pressure at 80°C for 2 hours to obtain the purified copolymer (a-1 ).

共聚物(a-1)之重量平均分子量(Mw)係利用下述條件之凝膠層析法(GPC)進行測定。  (測定條件)  設備：Waters公司製造之「e2695」  管柱：東曹股份有限公司製造之「TSKgel Super H3000＋H4000＋H6000」  檢測器：示差折射率檢測器(RI檢測器/內置)  溶劑：四氫呋喃  溫度：40℃  流速：0.5 mL/min  注入量：10 μL  濃度：0.2質量%  校正試樣：單分散聚苯乙烯  校正法：聚苯乙烯換算The weight average molecular weight (Mw) of a copolymer (a-1) was measured by the gel chromatography (GPC) of the following conditions. (Measurement conditions) Equipment: "e2695" manufactured by Waters Co., Ltd. Column: "TSKgel Super H3000+H4000+H6000" manufactured by Tosoh Co., Ltd. Detector: Differential refractive index detector (RI detector/built-in) Solvent: Tetrahydrofuran Temperature: 40°C Flow rate: 0.5 mL/min Injection volume: 10 μL Concentration: 0.2% by mass Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion

鹼可溶性樹脂(b-1)：對以三環癸烷甲基丙烯酸酯/苯乙烯/甲基丙烯酸縮水甘油酯(莫耳比：0.3/0.1/0.6)為構成單體之共聚樹脂，相對於甲基丙烯酸縮水甘油酯使丙烯酸進行等量加成反應，進而以相對於上述共聚樹脂1莫耳成為0.36莫耳之方式使四氫鄰苯二甲酸酐進行加成反應而成之鹼可溶性丙烯酸共聚樹脂。藉由GPC測定之聚苯乙烯換算之重量平均分子量(Mw)為3100，固形物成分酸值為40 mgKOH/g。Alkali-soluble resin (b-1): for the copolymer resin composed of tricyclodecane methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6), relative to Glycidyl methacrylate is an alkali-soluble acrylic acid copolymer obtained by adding an equivalent amount of acrylic acid to 0.36 moles of tetrahydrophthalic anhydride relative to 1 mole of the above-mentioned copolymer resin. resin. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 3100, and the solid content acid value was 40 mgKOH/g.

光聚合性化合物(c-1)：二季戊四醇六丙烯酸酯(KAYARAD DPHA、日本化藥公司製造)Photopolymerizable compound (c-1): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

光聚合起始劑(d-1)：下述化學結構之化合物(肟酯系化合物)Photopolymerization initiator (d-1): a compound with the following chemical structure (oxime ester compound)

[化39]

Figure 02_image077
[chem 39]
Figure 02_image077

鏈轉移劑(f-1)：昭和電工公司製造 KarenzMT PE1(季戊四醇四(3-巰基丁酸酯)Chain transfer agent (f-1): KarenzMT PE1 (pentaerythritol tetrakis(3-mercaptobutyrate) manufactured by Showa Denko Co., Ltd.

添加劑-1：KAYAMER PM-21(日本化藥公司製造)Additive-1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)

分散劑-1：BYK-Chemie公司製造 BYK-LPN21116(胺值為70 mgKOH/g。酸值為1 mgKOH/g以下)Dispersant-1: BYK-LPN21116 manufactured by BYK-Chemie (Amine value: 70 mgKOH/g. Acid value: 1 mgKOH/g or less)

溶劑-1：丙二醇單甲醚乙酸酯(PGMEA)  溶劑-2：3-甲氧基-1-丁醇(MB)Solvent-1: Propylene glycol monomethyl ether acetate (PGMEA) Solvent-2: 3-methoxy-1-butanol (MB)

＜顏料分散液1之製備＞  以成為表1中所記載之質量比之方式混合顏料、分散劑、鹼可溶性樹脂、及溶劑。利用塗料振盪器將該溶液於25～45℃之溫度範圍內進行3小時分散處理。珠粒使用0.5 mm

Figure 02_image079
之氧化鋯珠，並添加分散液之2.5倍之質量。分散結束後，利用過濾器將珠粒與分散液分離，而製備顏料分散液1。 <Preparation of Pigment Dispersion Liquid 1> A pigment, a dispersant, an alkali-soluble resin, and a solvent were mixed so as to have the mass ratio described in Table 1. This solution was subjected to dispersion treatment at a temperature range of 25 to 45° C. for 3 hours using a paint shaker. Beads use 0.5 mm
Figure 02_image079
Zirconia beads, and add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid 1 .

[表1]    顏料分散液 1 調配比率(質量份) 顏料 C.I.顏料藍60 50 C.I.顏料紫29 49 C.I.顏料橙64 1 分散劑 (固形物成分換算) 分散劑-1 20 鹼可溶性樹脂 (固形物成分換算) 鹼可溶性樹脂(b-1) 33 溶劑 溶劑-1 357 溶劑-2 89 [Table 1] Pigment dispersion 1 Blending ratio (parts by mass) pigment CI Pigment Blue 60 50 CI Pigment Violet 29 49 CI Pigment Orange 64 1 Dispersant (solid content conversion) Dispersant-1 20 Alkali-soluble resin (solid content conversion) Alkali-soluble resin (b-1) 33 solvent Solvent-1 357 Solvent-2 89

[實施例1]  使用顏料分散液1，以感光性樹脂組合物之全部固形物成分中之各成分之固形物成分的比率成為表2之調配比率之方式添加各成分，進而以全部固形物成分之含有比率成為34質量%之方式添加溶劑-1，進行攪拌使其溶解，而製備感光性樹脂組合物1。表2中之顏料分散液、鹼可溶性樹脂、共聚物之調配比率為固形物成分換算值。  藉由以下所記載之方法對感光性樹脂組合物1進行評價。[Example 1] Using Pigment Dispersion Liquid 1, each component was added so that the ratio of the solid content of each component in the total solid content of the photosensitive resin composition became the formulation ratio in Table 2, and then the total solid content Solvent-1 was added so that the content rate might become 34 mass %, it stirred and melt|dissolved, and the photosensitive resin composition 1 was prepared. The blending ratios of pigment dispersion liquid, alkali-soluble resin, and copolymer in Table 2 are converted values of solid content. The photosensitive resin composition 1 was evaluated by the method described below.

(水及二碘甲烷之接觸角之測定)  使用旋轉塗佈機，於玻璃基板上以加熱硬化後成為10.0 μm之厚度之方式塗佈感光性樹脂組合物1。其後，不使用光罩，使用大日本科研公司製造之曝光機MA-1100，對在100℃下於加熱板上加熱乾燥2分鐘所獲得之塗膜，以曝光量50 mJ/cm 2對整個面進行曝光。此時之波長365 nm下之強度為40 mW/cm 2。繼而，利用24℃之0.033質量%KOH(氫氧化鉀)水溶液進行70秒鐘噴霧顯影，其後利用純水進行10秒鐘洗淨。將該基板於烘箱中於230℃下進行30分鐘加熱硬化，獲得附有硬化物之接觸角測定用基板。 (Measurement of Contact Angle of Water and Diiodomethane) Using a spin coater, the photosensitive resin composition 1 was applied on a glass substrate so as to have a thickness of 10.0 μm after heat curing. Afterwards, without using a photomask, use the exposure machine MA-1100 manufactured by Dainippon Scientific Research Co., Ltd. to heat and dry the coating film obtained by heating on a heating plate at 100°C for 2 minutes. surface for exposure. The intensity at this time at a wavelength of 365 nm was 40 mW/cm 2 . Next, spray image development was performed for 70 seconds with 24 degreeC 0.033 mass % KOH (potassium hydroxide) aqueous solution, and it rinsed with pure water for 10 seconds after that. This substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for measuring contact angle with a cured product.

接觸角之測定係使用協和界面科學公司製造之Drop Master 500接觸角測定裝置，於23℃濕度50%之條件下進行。向接觸角測定用基板之硬化物上滴加水、或二碘甲烷0.7 μL，並測定1秒後之接觸角。The measurement of the contact angle was carried out under the conditions of 23°C and 50% humidity using the Drop Master 500 contact angle measurement device manufactured by Kyowa Interface Science Co., Ltd. 0.7 μL of water or diiodomethane was dropped onto the cured product of the substrate for contact angle measurement, and the contact angle after 1 second was measured.

(撥液性揮發成分之測定)  使用旋轉塗佈機，於玻璃基板上以加熱硬化後成為10.0 μm之厚度之方式塗佈感光性樹脂組合物1。其後，不使用光罩，使用大日本科研公司製造之曝光機MA-1100，對在100℃下於加熱板上加熱乾燥2分鐘所獲得之塗膜，以曝光量50 mJ/cm 2對整個面進行曝光，而獲得基板1。於該基板1之對面使用間隔件隔開100 μm之間隙，以與基板1之塗膜相對之方式設置玻璃基板2，準備試片。將該試片於烘箱中於230℃下進行30分鐘加熱硬化，其後取出玻璃基板2，將該玻璃基板2設為撥液性揮發成分測定用之基板。 (Measurement of Liquid Repellent Volatile Component) Using a spin coater, the photosensitive resin composition 1 was applied on a glass substrate so as to have a thickness of 10.0 μm after heat curing. Afterwards, without using a photomask, use the exposure machine MA-1100 manufactured by Dainippon Research Co., Ltd. to heat and dry the coating film obtained by heating and drying on a heating plate at 100°C for 2 minutes. The surface is exposed to obtain a substrate 1 . On the opposite side of the substrate 1, a gap of 100 μm was separated using a spacer, and the glass substrate 2 was set so as to face the coating film of the substrate 1, and a test piece was prepared. The test piece was heated and hardened in an oven at 230° C. for 30 minutes, and then the glass substrate 2 was taken out, and the glass substrate 2 was used as a substrate for measuring liquid-repellent volatile components.

來自塗膜之撥液性揮發成分向玻璃基板2之附著係測定設置於塗膜之對面之玻璃基板2表面之接觸角(表2中，以「接觸角A」表示)進行確認。  接觸角之測定係使用協和界面科學公司製造之Drop Master 500接觸角測定裝置，於23℃濕度50%之條件下進行。向設置於塗膜之對面之玻璃基板2表面滴加水0.7 μL，並測定1秒後之接觸角。Adhesion of the liquid-repellent volatile component from the coating film to the glass substrate 2 was confirmed by measuring the contact angle (indicated by "contact angle A" in Table 2) of the surface of the glass substrate 2 provided on the opposite side of the coating film. The measurement of the contact angle was carried out at 23°C and 50% humidity using the Drop Master 500 contact angle measurement device manufactured by Kyowa Interface Science. 0.7 μL of water was dropped on the surface of the glass substrate 2 provided on the opposite side of the coating film, and the contact angle after 1 second was measured.

[表2]    實施例1 感光性組合物 1 調配比率(質量份) (A)共聚物 共聚物(a-1) 1.0 (B)鹼可溶性樹脂 鹼可溶性樹脂(b-1) 64.8 (C)光聚合性化合物 光聚合性化合物(c-1) 22.1 (D)光聚合起始劑 光聚合起始劑(d-1) 4.0 (F)鏈轉移劑 鏈轉移劑(f-1) 1.0 添加劑 添加劑-1 0.5 顏料分散液 顏料分散液1 6.6 評價結果 接觸角(°/水) 110 接觸角(°/二碘甲烷) 90 接觸角A(°/水) 74 [Table 2] Example 1 photosensitive composition 1 Blending ratio (parts by mass) (A) Copolymer Copolymer (a-1) 1.0 (B) Alkali-soluble resin Alkali-soluble resin (b-1) 64.8 (C) Photopolymerizable compound Photopolymerizable compound (c-1) 22.1 (D) Photopolymerization initiator Photopolymerization initiator (d-1) 4.0 (F) Chain transfer agent Chain transfer agent (f-1) 1.0 additive Additive-1 0.5 Pigment dispersion Pigment dispersion 1 6.6 Evaluation results Contact angle (°/water) 110 Contact angle (°/diiodomethane) 90 Contact angle A(°/water) 74

實施例1中，確認到本發明之感光性樹脂組合物之塗膜表現出較高之撥液性。認為其原因在於：藉由單體(a1)與單體(a2)作為構成單體存在於同一樹脂中，單體(a2)單元固定化於塗膜之上表面，撥液成分於顯影時向顯影液之流出得以抑制。  另一方面，關於實施例1之撥液性揮發成分之評價，確認到撥液性揮發成分測定用之基板表面之水之接觸角為74°，撥液性較低。撥液性揮發成分附著前之玻璃基板表面之水之接觸角為62°，由撥液性揮發成分之附著所引起之撥液性之增大較低，故提示藉由對實施例1之感光性樹脂組合物進行加熱所產生之撥液性之揮發成分較少。藉此，於使用實施例1之感光性樹脂組合物形成阻隔壁之情形時，因熱分解產生撥液性之揮發成分，並附著於由阻隔壁所圍成之區域之情況得以抑制，故藉由噴墨法將油墨塗佈於由阻隔壁所圍成之區域之情形時，表現出良好之噴墨塗佈性。In Example 1, it was confirmed that the coating film of the photosensitive resin composition of the present invention showed high liquid repellency. The reason for this is considered to be that the monomer (a1) and the monomer (a2) exist in the same resin as constituent monomers, the monomer (a2) unit is fixed on the upper surface of the coating film, and the liquid-repellent component is released to the surface during development. The outflow of the developer is suppressed. On the other hand, regarding the evaluation of the liquid-repellent volatile component in Example 1, it was confirmed that the contact angle of water on the surface of the substrate used for the measurement of the liquid-repellent volatile component was 74°, and the liquid-repellent property was low. The contact angle of water on the surface of the glass substrate before the liquid-repellent volatile component was attached was 62°, and the increase in the liquid-repellent property caused by the attachment of the liquid-repellent volatile component was relatively low. The liquid-repellent volatile components produced by heating the resin composition are less. In this way, when the barrier rib is formed using the photosensitive resin composition of Example 1, the liquid-repellent volatile components generated by thermal decomposition and attached to the area surrounded by the barrier rib are suppressed. When the ink is applied to the region surrounded by the barrier ribs by the inkjet method, good inkjet applicability is exhibited.

1:綠色發光性奈米晶粒 2:紅色發光性奈米晶粒 10:基板 20:阻隔壁 30:紅色像素 40:綠色像素 50:藍色像素 100:彩色濾光器1: Green Luminescent Nanocrystals 2: Red Luminescent Nanocrystals 10: Substrate 20: Barrier Wall 30: Red Pixels 40: Green Pixels 50: Blue Pixels 100: Color Filters

圖1係具備本發明之阻隔壁之彩色濾光器之一例的模式剖視圖。FIG. 1 is a schematic cross-sectional view of an example of a color filter provided with a barrier rib of the present invention.

Claims (15)

一種感光性樹脂組合物，其係含有(A)共聚物、(B)鹼可溶性樹脂及(D)光聚合性化合物者，且  上述(A)共聚物含有下述單體(a1)及下述單體(a2)作為構成單體，  單體(a1)：具有藉由照射活性能量線而產生自由基之活性基之單體  單體(a2)：具有氟原子及/或矽原子之單體。A photosensitive resin composition comprising (A) a copolymer, (B) an alkali-soluble resin, and (D) a photopolymerizable compound, and the above-mentioned (A) copolymer contains the following monomer (a1) and the following Monomer (a2) as a constituent monomer, Monomer (a1): a monomer having an active group that generates free radicals by irradiating active energy rays Monomer (a2): a monomer having a fluorine atom and/or a silicon atom . 如請求項1之感光性樹脂組合物，其中上述單體(a2)係具有氟原子之單體。The photosensitive resin composition according to claim 1, wherein the above-mentioned monomer (a2) is a monomer having a fluorine atom. 如請求項2之感光性樹脂組合物，其中上述單體(a2)係具有氟烷基之單體。The photosensitive resin composition according to claim 2, wherein the above-mentioned monomer (a2) is a monomer having a fluoroalkyl group. 如請求項3之感光性樹脂組合物，其中上述單體(a2)係具有下述式(1)所表示之基之單體，  -CFXR f・・・式(1)  (式(1)中，X為氫原子、氟原子或三氟甲基，R f為可具有醚性氧原子之碳數1以上且20以下之氟烷基、或氟原子)。 Such as the photosensitive resin composition of claim 3, wherein the above-mentioned monomer (a2) is a monomer having a group represented by the following formula (1), -CFXR f ... formula (1) (in formula (1) , X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or a fluorine atom). 如請求項1至4中任一項之感光性樹脂組合物，其中上述(A)共聚物中之氟原子含量為5～40質量%。The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of fluorine atoms in the above-mentioned (A) copolymer is 5 to 40% by mass. 如請求項1至5中任一項之感光性樹脂組合物，其中上述單體(a1)中之活性基為選自由二苯甲酮基、苯乙酮基、α-羥基酮基、α-胺基酮基、α-二酮基及α-二酮二烷基縮醛基所組成之群中之一種以上。The photosensitive resin composition according to any one of claims 1 to 5, wherein the active group in the above-mentioned monomer (a1) is selected from benzophenone group, acetophenone group, α-hydroxyketone group, α- One or more of the group consisting of aminoketone group, α-diketone group and α-diketone dialkyl acetal group. 如請求項1至6中任一項之感光性樹脂組合物，其進而含有(C)光聚合起始劑。The photosensitive resin composition according to any one of claims 1 to 6, further comprising (C) a photopolymerization initiator. 如請求項1至7中任一項之感光性樹脂組合物，其進而含有(E)著色劑。The photosensitive resin composition according to any one of claims 1 to 7, further comprising (E) a colorant. 如請求項1至8中任一項之感光性樹脂組合物，其用於形成阻隔壁。The photosensitive resin composition according to any one of Claims 1 to 8, which is used to form a barrier wall. 一種硬化物，其係使如請求項1至9中任一項之感光性樹脂組合物硬化而成。A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 9. 一種阻隔壁，其包含如請求項10之硬化物。A barrier wall comprising the cured product according to claim 10. 一種有機電致發光元件，其具備如請求項11之阻隔壁。An organic electroluminescent element, which is provided with the barrier wall as claimed in claim 11. 一種彩色濾光器，其包含發光性奈米晶粒，且具備如請求項11之阻隔壁。A color filter, which includes luminescent nanocrystal grains, and has the barrier wall as claimed in claim 11. 一種圖像顯示裝置，其包含如請求項12之有機電致發光元件。An image display device comprising the organic electroluminescence element as claimed in claim 12. 一種圖像顯示裝置，其包含如請求項13之彩色濾光器。An image display device comprising the color filter according to claim 13.
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