TW202323307A - Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, and image display device - Google Patents

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

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TW202323307A
TW202323307A TW111137059A TW111137059A TW202323307A TW 202323307 A TW202323307 A TW 202323307A TW 111137059 A TW111137059 A TW 111137059A TW 111137059 A TW111137059 A TW 111137059A TW 202323307 A TW202323307 A TW 202323307A
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group
mass
ring
monomer
resin composition
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利光恵理子
木村明日香
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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    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/09—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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • 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
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a photosensitive resin composition which is capable of achieving both sufficient liquid repellency and inkjet coat ability. A photosensitive resin composition according to the present invention contains (A) a copolymer, (B) an alkali-soluble resin and (C) a photo polymerizable compound; and the copolymer (A) contains, as constituent monomers, a monomer (a1) which has an active group that generates radicals when irradiated with an active energy ray, a monomer (a2) which has a fluorine atom, and a monomer (a3) which has a cyclic ether group having 2 to 4 carbon atoms.

Description

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

本發明係關於一種感光性樹脂組合物、使感光性樹脂組合物硬化所得之硬化物、包含硬化物之阻隔壁、具備阻隔壁之有機電致發光元件、及包括有機電致發光元件之圖像顯示裝置。  本案係基於2021年10月1日於日本提出申請之特願2021-162453號而主張優先權，將其內容引用於本文。The present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, a barrier rib including the cured product, an organic electroluminescent element with a barrier wall, and an image including the organic electroluminescent element display device. This case claims priority based on Japanese Patent Application No. 2021-162453 filed in Japan on October 1, 2021, the contents of which are incorporated herein.

先前，有機電致顯示器等中所含之有機電致發光元件係以如下方式製造：於基板上形成阻隔壁(障壁)後，於被阻隔壁包圍之區域內積層各種功能層。作為容易地形成此種阻隔壁之方法，已知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 electroluminescent elements included in organic electroluminescent displays and the like are produced by forming barrier ribs (barrier ribs) on a substrate and then laminating various functional layers in regions surrounded by the barrier ribs. As a method of easily forming such a barrier rib, a method of forming by photolithography using a photosensitive resin composition is known.

又，作為於被阻隔壁包圍之區域內積層各種功能層之方法，已知如下方法：首先製備含有構成功能層之材料之油墨，繼而，將製備之油墨注入被阻隔壁包圍之區域內。該方法中，就易於將特定量之油墨準確地注入特定部位之方面而言，較多採用噴墨(以下有時記為IJ)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 region surrounded by barrier ribs. Among these methods, the inkjet (hereinafter sometimes referred to as IJ) method is often used in terms of making it easy to accurately inject 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，為了預防油墨附著於阻隔壁、或防止於鄰接之區域間注入之油墨彼此混合等，有時要求對阻隔壁賦予撥油墨性(撥液性)。Furthermore, when ink is used to form a functional layer, it may be required to impart ink repellency (liquid repellency) to the barrier ribs in order to prevent ink from adhering to the barrier ribs or prevent inks injected between adjacent regions from mixing with each other.

於以噴墨法形成有機發光層之情形時，被阻隔壁包圍之區域(以下，亦稱為開口部)為了防止有機發光元件之空心、或積層平坦之有機發光層，需要使油墨具有易於潤濕擴散之性質。In the case of forming the organic light-emitting layer by the inkjet method, the area surrounded by the barrier ribs (hereinafter, also referred to as the opening) needs to have an ink that is easy to wet in order to prevent the hollow of the organic light-emitting element or to build up a flat organic light-emitting layer. The nature of moisture diffusion.

於專利文獻1中記載有於用於保護膜之塗佈材之紫外線硬化型硬塗材用途中，具有防污性效果之具有聚(全氟伸烷基醚鏈)及光聚合起始能力之含氟硬化性樹脂及組合物。In Patent Document 1, it is described that a poly(perfluoroalkylene ether chain) and a photopolymerization initiation ability have an antifouling effect in the application of an ultraviolet curable hard coating material for a coating material of a protective film. Fluorine-containing curable resin and composition.

於專利文獻2中記載有藉由使用含有具有多環式飽和烴骨架及乙烯性雙鍵之丙烯酸樹脂之感光性組合物，即使於UV洗淨處理後，撥油墨性亦良好。  [先前技術文獻]  [專利文獻]In Patent Document 2, it is described that by using a photosensitive composition containing an acrylic resin having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond, ink repellency is good even after UV cleaning treatment. [Prior technical literature] [Patent literature]

[專利文獻1]日本專利特開2011-089052號公報  [專利文獻2]國際公開第2019/146680號[Patent Document 1] Japanese Patent Laid-Open No. 2011-089052 [Patent Document 2] International Publication No. 2019/146680

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

本發明者等人經過研究而瞭解：於使用專利文獻1、2中記載之組合物形成阻隔壁，以噴墨法於被阻隔壁包圍之區域塗佈油墨之情形時，油墨不易潤濕擴散，噴墨塗佈性較差。The inventors of the present invention have learned through studies that when the barrier walls are formed using the compositions described in Patent Documents 1 and 2, and the ink is applied to the area surrounded by the barrier walls by the inkjet method, the ink is not easy to wet and spread. Inkjet coatability is poor.

因此本發明之目的在於提供一種具有充分之撥液性且可兼顧噴墨塗佈性之感光性樹脂組合物，尤其是阻隔壁形成用感光性樹脂組合物。  又，本發明提供一種使感光性樹脂組合物硬化所得之硬化物、包含硬化物之阻隔壁、具備阻隔壁之有機電致發光元件、包括有機電致發光元件之圖像顯示裝置。 [解決問題之技術手段] Therefore, the object of the present invention is to provide a photosensitive resin composition having sufficient liquid repellency and inkjet coating properties, especially a photosensitive resin composition for barrier rib formation. Also, the present invention provides a cured product obtained by curing the photosensitive resin composition, a barrier rib comprising the cured product, an organic electroluminescent element having the barrier rib, and an image display device including the organic electroluminescent element. [Technical means to solve the problem]

本發明者等人進行潛心研究，結果發現藉由組合使用特定之共聚物、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(C)光聚合性化合物者，並且  上述(A)共聚物含有下述單體(a1)、下述單體(a2)及下述單體(a3)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的單體。  單體(a2)：具有氟原子之單體。  單體(a3)：具有碳數2～4之環狀醚基之單體。  [2]如[1]之感光性樹脂組合物，其中上述單體(a2)具有氟烷基。  [3]如[2]之感光性樹脂組合物，其中上述單體(a2)具有下述式(1)所表示之基。  -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20以下之氟烷基或氟原子)  [4]如[1]至[3]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、烷基苯酮基、α-羥基酮基、α-胺基酮基、α-二酮基及α-二酮二烷基縮酮基所組成之群中之一種以上。  [5]如[1]至[4]中任一項之感光性樹脂組合物，其中上述單體(a3)中之碳數2～4之環狀醚基為環氧基。  [6]如[1]至[5]中任一項之感光性樹脂組合物，其中上述(A)共聚物進而含有下述單體(a4)作為構成單體。  單體(a4)：具有羥基之單體。  [7]如[1]至[6]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5～60質量%。  [8]如[1]至[7]中任一項之感光性樹脂組合物，其進而含有(D)光聚合起始劑。  [9]如[1]至[8]中任一項之感光性樹脂組合物，其進而含有(E)著色劑。  [10]如[1]至[9]中任一項之感光性樹脂組合物，其係阻隔壁形成用感光性樹脂組合物。  [11]一種硬化物，其係使如[1]至[10]中任一項之感光性樹脂組合物硬化所得者。  [12]一種阻隔壁，其包含如[11]之硬化物。  [13]一種有機電致發光元件，其具備如[12]之阻隔壁。  [14]一種圖像顯示裝置，其包括如[13]之有機電致發光元件。 [發明之效果] [1] A photosensitive resin composition comprising (A) a copolymer, (B) an alkali-soluble resin, and (C) a photopolymerizable compound, wherein the (A) copolymer contains the following monomer (a1) , The following monomer (a2) and the following monomer (a3) are used as constituent monomers. Monomer (a1): A monomer having an active group that generates radicals by irradiation with active energy rays. Monomer (a2): A monomer having a fluorine atom. Monomer (a3): a monomer having a cyclic ether group having 2 to 4 carbon atoms. [2] The photosensitive resin composition according to [1], wherein the monomer (a2) has a fluoroalkyl group. [3] The photosensitive resin composition according to [2], wherein the monomer (a2) has 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 fluoroalkyl group or a fluorine atom with a carbon number of 1 to 20 that may have an etheric oxygen atom) [4 ] The photosensitive resin composition according to any one of [1] to [3], wherein the active group in the above-mentioned monomer (a1) is selected from the group consisting of benzophenone group, alkylphenone group, α-hydroxy ketone One or more of the group consisting of α-aminoketone group, α-diketone group and α-diketone dialkyl ketal group. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the cyclic ether group having 2 to 4 carbon atoms in the monomer (a3) is an epoxy group. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the above-mentioned (A) copolymer further contains the following monomer (a4) as a constituent monomer. Monomer (a4): A monomer having a hydroxyl group. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the fluorine atom content in the above-mentioned (A) copolymer is 5 to 60% by mass. [8] The photosensitive resin composition according to any one of [1] to [7], which further contains (D) a photopolymerization initiator. [9] The photosensitive resin composition according to any one of [1] to [8], which further contains (E) a colorant. [10] The photosensitive resin composition according to any one of [1] to [9], which is a photosensitive resin composition for barrier rib formation. [11] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [10]. [12] A barrier rib comprising the cured product according to [11]. [13] An organic electroluminescent device comprising the barrier rib according to [12]. [14] An image display device comprising the organic electroluminescent element according to [13]. [Effect of Invention]

藉由本發明，可提供一種具有充分之撥液性且可兼顧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 that has sufficient liquid repellency and inkjet coating properties.

以下，詳細說明本發明。以下之記載係本發明之實施方式之一例，本發明只要不超出其主旨，則不特定於該等。  於本發明中，所謂「(甲基)丙烯醯基」係指「丙烯醯基及/或甲基丙烯醯基」。  於本發明中，所謂「全部固形物成分」係指感光性樹脂組合物中之溶劑以外之全部成分，即使溶劑以外之成分於常溫下為液體，該成分亦不包含於溶劑中而包含於全部固形物成分中。  於本發明中，使用「～」而表示之數值範圍係包含「～」之前後記載之數值作為下限值及上限值之範圍。  於本發明中，所謂「A及/或B」係指A及B之一者或兩者，具體而言係指A、B或者A及B。  於本發明中，所謂「(共)聚合物」係指包含均聚物(homopolymer)與共聚物(copolymer)之兩者，又，所謂「多元酸(酐)」係指「多元酸及/或多元酸酐」。  於本發明中，所謂重量平均分子量係指藉由GPC(凝膠滲透層析法)測定之聚苯乙烯換算之重量平均分子量(Mw)。  於本發明中，所謂酸值係表示有效固形物成分換算之酸值，係藉由中和滴定而算出。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 thereto unless the gist is exceeded. In the present invention, the so-called "(meth)acryl" refers to "acryl and/or methacryl". In the present invention, the so-called "total solid content" refers to all components other than the solvent in the photosensitive resin composition. Even if the components other than the solvent are liquid at normal temperature, these components are not included in the solvent but included in all in the solid content. In the present invention, the numerical range represented by "~" is a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present invention, the so-called "A and/or B" refers to one or both of A and B, specifically refers to A, B or A and B. In the present invention, the so-called "(co)polymer" refers to both homopolymer (homopolymer) and copolymer (copolymer), and the so-called "polyacid (anhydride)" refers to "polyacid and/or polyanhydrides". In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). In the present invention, the so-called acid value refers to the acid value in terms of effective solid content, which is calculated by neutralization titration.

於本發明中，所謂阻隔壁材係指障壁(bank)材、壁材、牆壁(wall)材，同樣地，所謂阻隔壁係指障壁、壁、牆壁。  於本發明中，所謂發光部(像素部)係指於提供電能之情形時發出光之部分。In the present invention, the so-called barrier wall material refers to barrier wall (bank) material, wall material, wall (wall) material, similarly, the so-called barrier wall refers to barrier wall, wall, wall. In the present invention, the so-called light-emitting portion (pixel portion) refers to a portion that emits light when electric energy is supplied.

[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(C)光聚合性化合物，(A)共聚物含有下述之特定單體(a1)、特定單體(a2)及特定單體(a3)作為構成單體。本發明之感光性樹脂組合物視需要可進而含有其他成分，例如可含有(D)光聚合起始劑、(E)著色劑、(F)鏈轉移劑。[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) copolymer, (B) alkali-soluble resin, and (C) photopolymerizable compound, (A) copolymer contains the following specific monomer The body (a1), the specific monomer (a2), and the specific monomer (a3) serve as constituent monomers. The photosensitive resin composition of this invention can further contain other components as needed, for example, (D) photoinitiator, (E) coloring agent, (F) chain transfer agent can be contained.

於本發明中，所謂阻隔壁，例如係用以劃分主動驅動型有機電致發光元件中之功能層(有機層、發光部)者，例如係以如下目的而使用者：藉由於劃分之區域(像素區域)內噴出作為用以構成功能層之材料之油墨並加以乾燥，而形成包含功能層及阻隔壁之像素。In the present invention, the so-called barrier rib is, for example, used to divide the functional layer (organic layer, light-emitting part) in the active-driven organic electroluminescent element, for example, it is used for the following purpose: by dividing the region ( The ink used as the material for constituting the functional layer is sprayed into the pixel area) and dried to form a pixel including the functional layer and the barrier ribs.

[1-1]感光性樹脂組合物之成分及組成  對構成本發明之感光性樹脂組合物之成分及其組成進行說明。  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(C)光聚合性化合物。[1-1] Components and Composition of Photosensitive Resin Composition The components constituting the photosensitive resin composition of the present invention and their composition will be described. The photosensitive resin composition of the present invention contains (A) copolymer, (B) alkali-soluble resin and (C) photopolymerizable compound.

[1-1-1](A)共聚物  於本發明之感光性樹脂組合物中，(A)共聚物含有單體(a1)、單體(a2)、及單體(a3)作為構成單體。即，(A)共聚物具有基於單體(a1)之單元、基於單體(a2)之單元、及基於單體(a3)之單元作為其結構單元。  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)：具有氟原子之單體。  單體(a3)：具有碳數2～4之環狀醚基之單體。  於使用本發明之感光性樹脂組合物形成阻隔壁之情形時，若對塗佈感光性樹脂組合物而形成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，以產生之自由基為起點，與(C)光聚合性化合物進行聚合反應，故而認為易於使(A)共聚物固定化於塗膜之表面附近。其結果，即使經過對曝光後之塗膜進行顯影之步驟，亦可維持阻隔壁上表面之撥液性。進而，於後烘烤時，因(A)共聚物之碳數2～4之環狀醚基之反應而使(A)共聚物固定化，可抑制(A)共聚物或其熱分解產物向像素部移動。故而，認為使用噴墨法，於被阻隔壁包圍之區域，例如像素部塗佈油墨時，可兼顧對鄰接之像素部間之混色之產生之抑制、及像素部之良好之噴墨塗佈性。[1-1-1] (A) Copolymer In the photosensitive resin composition of the present invention, (A) copolymer contains monomer (a1), monomer (a2), and monomer (a3) as constituent units body. That is, (A) copolymer has the unit based on a monomer (a1), the unit based on a monomer (a2), and the unit based on a monomer (a3) as its structural unit. Monomer (a1): A monomer having active radicals that generate free radicals by irradiating active energy rays. Monomer (a2): a monomer having a fluorine atom. Monomer (a3): A monomer having a cyclic ether group with 2 to 4 carbon atoms. When the barrier rib is formed using the photosensitive resin composition of the present invention, when the coating film formed by coating the photosensitive resin composition is irradiated with active energy rays, free radicals are generated from the active radicals of the (A) copolymer, The polymerization reaction with the (C) photopolymerizable compound proceeds from the generated radical as a starting point, so 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 rib can be maintained. Furthermore, during post-baking, the (A) copolymer is immobilized due to the reaction of the cyclic ether group with 2 to 4 carbon atoms in the (A) copolymer, which can inhibit the (A) copolymer or its thermal decomposition products from Pixels move. Therefore, it is considered that when inkjet method is used to apply ink to the area surrounded by the barrier ribs, such as the pixel portion, it can take into account the suppression of color mixing between adjacent pixel portions and the good inkjet coating property of the pixel portion. .

以下，對(A)共聚物之構成單體進行說明。Hereinafter, the constituent monomers of the (A) copolymer will be described.

[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的單體。  作為單體(a1)，可例舉：具有活性基與自由基聚合性基之化合物。[Monomer (a1)] The monomer (a1) is a monomer having active radicals that generate radicals by irradiation with active energy rays. The monomer (a1) may, for example, be a compound having an active group and a radically polymerizable group.

作為單體(a1)之活性基，只要為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。  作為活性基之具體例，可例舉：二苯甲酮基、烷基苯酮基、安息香基、安息香醚基、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」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、α-二酮二烷基縮酮基、蒽醌基、9-氧硫𠮿

Figure 111137059-001
基、酮香豆素基、苯甲醯甲酸烷基酯基、氧化膦基、肟酯基。  該等之中，就自由基產生效率較高之方面而言，較佳為二苯甲酮基、烷基苯酮基、α-羥基酮基、α-胺基酮基、α-二酮基、α-二酮二烷基縮酮基，更佳為二苯甲酮基、烷基苯酮基、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. Specific examples of active groups include: benzophenone groups, alkylphenone groups, benzoin groups, benzoin ether groups, α-hydroxyketone groups (for example, from 1-[4-(2-hydroxyethoxy base) phenyl]-2-hydroxy-2-methyl-1-propanone (the base obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy group"), α-aminoketone group, α-di Keto group, α-diketone dialkyl acetal group, α-diketone dialkyl ketal group, anthraquinone group, 9-oxythiol
Figure 111137059-001
 group, ketocoumarin group, alkyl benzoyl carboxylate group, phosphine oxide group, oxime ester group. Among these, benzophenone group, alkylphenone group, α-hydroxy ketone group, α-amino ketone group, α-diketone group are preferable in terms of high radical generation efficiency. , α-diketone dialkyl ketal group, more preferably benzophenone group, alkyl phenone group, α-hydroxy ketone group, especially α-hydroxy ketone group.

作為單體(a1)之自由基聚合性基，可例舉：含有自由基聚合性不飽和鍵(碳-碳雙鍵等)之官能基，作為具體例，可例舉：(甲基)丙烯醯基、乙烯基。The radically polymerizable group of the monomer (a1) may, for example, be a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), and a specific example may include (meth)acrylic Acyl, vinyl.

作為單體(a1)，就易於合成(A)共聚物、易於調整活性基之導入量之觀點而言，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：甲基丙烯酸2-[4-(2-羥基-2-甲基-1-側氧基丙基)苯氧基]乙酯、4-甲基丙烯醯氧基二苯甲酮、4-[(4-甲基丙烯醯胺)苯硫基]二苯甲酮、1-[(2-丙烯醯氧基)乙氧基羰基]-9-氧硫

Figure 111137059-001
、1-[4-(2-丙烯醯氧基乙硫基)苯基]-2-甲基-2-𠰌啉基丙烷-1-酮。其中，就撥液性、噴墨塗佈性之觀點而言，更佳為甲基丙烯酸2-[4-(2-羥基-2-甲基-1-側氧基丙基)苯氧基]乙酯。  該等具有活性基之單體可單獨使用，亦可併用兩種以上。 The monomer (a1) is preferably a (meth)acrylate having an active group from the viewpoint of ease of synthesizing the (A) copolymer and adjusting the amount of active group introduced. Examples of the monomer (a1) include: 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methylpropene Acyloxybenzophenone, 4-[(4-methacrylamide)phenylthio]benzophenone, 1-[(2-acryloxy)ethoxycarbonyl]-9-oxosulfur
Figure 111137059-001
 , 1-[4-(2-acryloyloxyethylthio)phenyl]-2-methyl-2-?olinylpropan-1-one. Among them, 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy] methacrylate is more preferable from the viewpoint of liquid repellency and inkjet coating property. ethyl ester. These active group-containing monomers may be used alone or in combination of two or more.

[單體(a2)]  單體(a2)係具有氟原子之單體。  作為單體(a2)，例如可例舉：具有氟原子與自由基聚合性基之化合物。自由基聚合性基與上述相同。  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者，有助於硬化物之撥液性。  又，只要(A)共聚物具有該單元，則形成感光性樹脂組合物之塗膜時，(A)共聚物易於偏析至塗膜之表面側。  若(A)共聚物偏析至塗膜之表面側，則塗膜表面側之基於單體(a2)之單元之濃度變高，可高效率地對硬化物之表面賦予撥液性。[Monomer (a2)] The monomer (a2) is a monomer having a fluorine atom. Examples of the monomer (a2) include compounds having a fluorine atom and a radically polymerizable group. The radically polymerizable group is the same as above. 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. Also, as long as the (A) copolymer has this unit, the (A) copolymer tends to segregate to the surface side of the coating film when forming a coating film of the photosensitive resin composition. When the (A) copolymer is segregated to the surface side of the coating film, the concentration of units based on the monomer (a2) on the surface side of the coating film becomes high, and liquid repellency can be efficiently imparted to the surface of the cured product.

又，藉由使(A)共聚物偏析至塗膜之表面側，塗膜表面側之活性基之濃度變高，照射活性能量線時，自(A)共聚物之活性基產生自由基，以產生之自由基為起點，與(C)光聚合性化合物進行聚合反應，故而認為(A)共聚物易於固定化於塗膜之表面附近。其結果，即使經過對曝光後之塗膜進行顯影之步驟，亦可維持阻隔壁上表面之撥液性。故而，認為使用噴墨法，於被阻隔壁包圍之區域，例如像素部塗佈油墨時，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之量及活性基之量，即，(A)共聚物及(D)光聚合起始劑之量或製版時之曝光量等而調整。  作為單體(a2)，較佳為具有氟烷基之單體，更佳為具有氟烷基與自由基聚合性基之單體。In addition, by segregating the (A) copolymer to the surface side of the coating film, the concentration of active groups on the surface side of the coating film becomes high, and when irradiated with active energy rays, radicals are generated from the active radicals of the (A) copolymer, and The generated radicals act as a starting point and undergo a polymerization reaction with the (C) photopolymerizable compound, so 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 rib can be maintained. Therefore, it is considered that when an inkjet method is used to apply ink to a region surrounded by barrier ribs, such as a pixel portion, the occurrence of color mixture between adjacent pixel portions can be suppressed. The hardening degree 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 (D) photopolymerization initiator or the amount of Adjust the exposure, etc. The monomer (a2) is preferably a monomer having a fluoroalkyl group, more preferably a monomer having a fluoroalkyl group and a radical polymerizable group.

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 fluoroalkyl group with 1 to 20 carbon atoms that may have an etheric oxygen atom or fluorine atom)

式(1)中之R f之碳數較佳為1以上，更佳為2以上，進而較佳為3以上，尤佳為5以上，又，較佳為20以下，更佳為10以下，進而較佳為6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2～20，進而較佳為3～10，尤佳為5～6。藉由設為下限值以上，存在表現撥液性之傾向。又，藉由設為上限值以下，存在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。 The carbon number of R f in formula (1) is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, especially preferably 5 or more, and preferably 20 or less, more preferably 10 or less, Furthermore, it is preferably 6 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-20 is preferable, 2-20 is more preferable, 3-10 is still more preferable, 5-6 is especially preferable. By making it more than the lower limit, there exists a tendency for a liquid-repellent property to express. 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.

作為具有氟烷基與自由基聚合性基之化合物，較佳為具有氟烷基之(甲基)丙烯酸酯。As a compound which has a fluoroalkyl group and a radically polymerizable group, (meth)acrylate which has a fluoroalkyl group is preferable.

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。  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(大阪有機化學工業股份有限公司製造之Viscoat 3F)、丙烯酸2,2,3,3-四氟丙酯(大阪有機化學工業股份有限公司製造之Viscoat 4F)、甲基丙烯酸2,2,3,3-四氟丙酯(大金工業股份有限公司製造之DK-4F、Unimatec股份有限公司製造之CHEMINOX FAMAC-6)、甲基丙烯酸2,2,3,3,3-五氟丙酯(大金工業股份有限公司製造之DK-5F)、甲基丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯(大金工業股份有限公司製造之C6SFMA MONOMER)、丙烯酸1H,1H,5H-八氟戊酯(大阪有機化學工業股份有限公司製造之Viscoat 8F)、甲基丙烯酸1H,1H,5H-八氟戊酯(大阪有機化學工業股份有限公司製造之Viscoat 8FM)、丙烯酸1H,1H,2H,2H-十三氟辛酯(大阪有機化學工業股份有限公司製造之Viscoat 13F、Unimatec股份有限公司製造之CHEMINOX FAAC-6)、丙烯酸1H,1H,2H,2H-九氟己酯(Unimatec股份有限公司製造之CHEMINOX FAAC-4)、甲基丙烯酸1H,1H,2H,2H-九氟己酯(Unimatec股份有限公司製造之CHEMINOX FAMAC-4)、甲基丙烯酸1H,1H,2H,2H-十三氟辛酯(Unimatec股份有限公司製造之CHEMINOX FAMAC-6)。As the (meth)acrylate which has a fluoroalkyl group, the (meth)acrylate which has a perfluoroalkyl group is more preferable. Examples of fluoroalkyl-containing (meth)acrylates include 2,2,2-trifluoroethyl acrylate (Viscoat 3F manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2,2,3, 3-Tetrafluoropropyl ester (Viscoat 4F manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2,2,3,3-tetrafluoropropyl methacrylate (DK-4F manufactured by Daikin Industries, Ltd., Unimatec Co., Ltd. CHEMINOX FAMAC-6 manufactured by Co., Ltd.), 2,2,3,3,3-pentafluoropropyl methacrylate (DK-5F manufactured by Daikin Industries Co., Ltd.), 3,3,4, 4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl (C6SFMA MONOMER manufactured by Daikin Industries Co., Ltd.), 1H,1H,5H-octafluoropentyl acrylate ( Viscoat 8F manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1H,1H,5H-octafluoropentyl methacrylate (Viscoat 8FM manufactured by Osaka Organic Chemical Industry Co., Ltd.), acrylic acid 1H,1H,2H,2H-10 Trifluorooctyl (Viscoat 13F manufactured by Osaka Organic Chemical Industry Co., Ltd., CHEMINOX FAAC-6 manufactured by Unimatec Co., Ltd.), 1H,1H,2H,2H-nonafluorohexyl acrylate (CHEMINOX manufactured by Unimatec Co., Ltd.) FAAC-4), 1H,1H,2H,2H-nonafluorohexyl methacrylate (CHEMINOX FAMAC-4 manufactured by Unimatec Co., Ltd.), 1H,1H,2H,2H-tridecafluorooctyl methacrylate ( CHEMINOX FAMAC-6 manufactured by Unimatec Co., Ltd.).

單體(a2)亦可為具有氟伸烷基與自由基聚合性基之化合物，作為氟伸烷基，並無特別限定，較佳為具有全氟伸烷基醚鏈。作為具體例，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2價基。  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 monomer (a2) may also be a compound having a fluoroalkylene group and a radical polymerizable group. The fluoroalkylene group is not particularly limited, but preferably has a perfluoroalkylene ether chain. As specific examples, -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. As a compound which has a fluoroalkylene group and a radical polymerizable group, the following monomers are mentioned, for example.

[化1]

Figure 02_image001
[chemical 1]
Figure 02_image001

上述式中，PFPE表示全氟伸烷基醚鏈。In the above formula, PFPE represents a perfluoroalkylene ether chain.

該等之中，就撥液性、噴墨塗佈性之觀點而言，較佳為具有氟烷基之單體，更佳為具有全氟烷基之單體，進而較佳為甲基丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯基之單體。  該等具有氟原子之單體可單獨使用，亦可併用兩種以上。Among these, monomers having a fluoroalkyl group are preferred from the viewpoint of liquid repellency and inkjet coating properties, monomers having a perfluoroalkyl group are more preferred, and methacrylic acid is further preferred. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl monomer. These monomers having fluorine atoms may be used alone or in combination of two or more.

[單體(a3)]  單體(a3)係具有碳數2～4之環狀醚基之單體。作為環狀醚基，例如可例舉：環氧基、氧雜環丁基或四氫呋喃基。  作為單體(a3)，可例舉：具有碳數2～4之環狀醚基與自由基聚合性基之化合物。作為碳數2～4之環狀醚基，較佳為環氧基。自由基聚合性基與上述相同。[Monomer (a3)] Monomer (a3) is a monomer having a cyclic ether group with 2 to 4 carbon atoms. As a cyclic ether group, an epoxy group, an oxetanyl group, or a tetrahydrofuryl group is mentioned, for example. The monomer (a3) may, for example, be a compound having a cyclic ether group having 2 to 4 carbon atoms and a radically polymerizable group. The cyclic ether group having 2 to 4 carbon atoms is preferably an epoxy group. The radically polymerizable group is the same as above.

作為具有環氧基之單體，例如可例舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯、(甲基)丙烯酸2-乙基縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯、(甲基)丙烯酸3,4-環氧環己酯、(甲基)丙烯酸3,4-環氧環己基甲酯、縮水甘油基乙烯醚、1,2-環氧-4-乙烯基環己烷、2-乙烯基苄基縮水甘油醚、3-乙烯基苄基縮水甘油醚、4-乙烯基苄基縮水甘油醚、α-甲基-2-乙烯基苄基縮水甘油醚、α-甲基-3-乙烯基苄基縮水甘油醚、α-甲基-4-乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯。As a monomer having an epoxy group, for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, ( 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4 (meth)acrylate - Epoxycyclohexyl methyl ester, glycidyl vinyl ether, 1,2-epoxy-4-vinylcyclohexane, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4 -Vinylbenzyl glycidyl ether, α-methyl-2-vinylbenzyl glycidyl ether, α-methyl-3-vinylbenzyl glycidyl ether, α-methyl-4-vinylbenzyl glycidyl ether Glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)benzene Ethylene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl) ) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyl Oxymethyl) styrene.

作為具有氧雜環丁基之單體，例如可例舉：3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷。As a monomer having an oxetanyl group, for example, 3-methyl-3-(meth)acryloxymethyloxetane, 3-ethyl-3-(methyl) Acryloxymethyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 3-ethyl-3-(methyl)acryloxy Ethyl oxetane.

作為具有四氫呋喃基之單體，例如可例舉：(甲基)丙烯酸四氫糠酯、2-甲基丙烯醯氧基-丙酸四氫糠酯、(甲基)丙烯酸四氫呋喃-3-基酯。Examples of monomers having a tetrahydrofuryl group include tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl 2-methacryloxy-propionate, and tetrahydrofuran-3-yl (meth)acrylate. .

該等之中，作為單體(a3)，就易於合成(A)共聚物、易於調整環狀醚基之導入量之觀點而言，較佳為(甲基)丙烯酸縮水甘油酯。該等具有環狀醚基之單體可單獨使用，亦可併用兩種以上。Among them, glycidyl (meth)acrylate is preferred as the monomer (a3) from the viewpoints of easiness in synthesizing the (A) copolymer and easiness in adjusting the amount of introduced cyclic ether groups. These monomers having a cyclic ether group may be used alone or in combination of two or more.

[單體(a4)]  就提高(A)共聚物與(B)鹼可溶性樹脂及(C)光聚合性化合物之相溶性之觀點而言，(A)共聚物可進而含有具有羥基之單體(a4)(以下，亦稱為單體(a4))作為構成單體。[Monomer (a4)] From the viewpoint of improving the compatibility of (A) copolymer with (B) alkali-soluble resin and (C) photopolymerizable compound, (A) copolymer may further contain a monomer having a hydroxyl group (a4) (hereinafter also referred to as a monomer (a4)) is a constituent monomer.

作為單體(a4)，例如可例舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(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、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、甘油(甲基)丙烯酸酯或環己烷二甲醇單(甲基)丙烯酸酯等(甲基)丙烯酸羥基烷基酯類；丙烯酸乙基-α-(羥基甲基)酯、(甲基)丙烯酸對羥基苯基乙酯。該等可單獨使用，亦可併用兩種以上。就易於合成(A)共聚物、易於調整羥基之導入量之觀點而言，較佳為(甲基)丙烯酸2-羥基乙酯。Examples of the monomer (a4) include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2-Hydroxybutyl, 3-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 6-Hydroxyhexyl (meth)acrylate, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol (meth)acrylate or cyclohexane Hydroxyalkyl (meth)acrylates such as dimethanol mono(meth)acrylate; ethyl-α-(hydroxymethyl)acrylate, p-hydroxyphenylethyl (meth)acrylate. These may be used alone or in combination of two or more. 2-Hydroxyethyl (meth)acrylate is preferred from the viewpoints of easiness of synthesizing the (A) copolymer and easiness of adjusting the amount of hydroxyl groups introduced.

[單體(a5)]  (A)共聚物視需要可進而含有具有氫供與性官能基之單體(a5)(以下，亦稱為單體(a5))作為構成單體。  尤其，於單體(a1)具有奪氫型之活性基之情形時，較佳為含有基於單體(a5)之單元。若(A)共聚物具有基於單體(a5)之單元，則存在如下傾向：可抑制來自感光性樹脂組合物之塗膜表面之氧所導致之聚合阻礙，有效地進行塗膜之硬化，可容易地表現撥液性。[Monomer (a5)] (A) The copolymer may further contain a monomer (a5) having a hydrogen-donating functional group (hereinafter also referred to as monomer (a5)) as a constituent monomer if necessary. In particular, when the monomer (a1) has a hydrogen-abstracting active group, it is preferred to contain a unit based on the monomer (a5). If the (A) copolymer has a unit based on the monomer (a5), there is a tendency that polymerization inhibition caused by oxygen from the surface of the coating film of the photosensitive resin composition can be suppressed, and the hardening of the coating film can be effectively performed. Easily express liquid repellency.

作為氫供與性官能基，例如可例舉：烷基胺基、巰基、醯胺基、烷基醚基。該等之中，尤其就有效率地進行硬化反應，與氧自由基之反應性較高之觀點而言，較佳為巰基、烷基胺基、醯胺基。As a hydrogen-donating functional group, an alkylamine group, a mercapto group, an amido group, and an alkylether group are mentioned, for example. Among these, mercapto groups, alkylamine groups, and amide groups are particularly preferred from the viewpoint of efficient hardening reaction and high reactivity with oxygen radicals.

作為單體(a5)，可例舉：具有氫供與性官能基與自由基聚合性基之化合物，就易於合成化合物及易於調整氫供與性官能基之導入量之觀點而言，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。  作為單體(a5)，例如可例舉：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-二甲胺基乙酯、(甲基)丙烯酸2-[(丁胺基)羰基]氧基]乙酯、N,N-二甲胺基丙基(甲基)丙烯醯胺、N,N-二乙胺基丙基(甲基)丙烯醯胺、(甲基)丙烯酸N,N-二乙胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯、(甲基)丙烯酸N,N-二乙胺基丙酯、N,N-二甲胺基乙基(甲基)丙烯醯胺、N,N-二乙胺基乙基(甲基)丙烯醯胺、(甲基)丙烯醯基𠰌啉、乙烯基乙醯胺等含胺基或醯胺基之單體。該等之中，就與活性基併用時，硬化促進效果優異之方面而言，較佳為N,N-二甲基丙烯醯胺、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二乙胺基乙酯，就可抑制氧所導致之聚合阻礙，有效地進行硬化，可容易地表現撥液性之觀點而言，更佳為(甲基)丙烯酸N,N-二乙胺基乙酯。  該等化合物可單獨使用一種，亦可併用兩種以上。The monomer (a5) may, for example, be a compound having a hydrogen donating functional group and a radical polymerizable group, and is preferable from the viewpoint of ease of compound synthesis and adjustment of the amount of introduction of the hydrogen donating functional group. It is a (meth)acrylate or (meth)acrylamide having a hydrogen-donating functional group. Examples of the monomer (a5) include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-vinylcaprolactam , N-vinylpyrrolidone, N-isopropyl(meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, 2-[(butylamino)(meth)acrylate )carbonyl]oxy]ethyl ester, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, (meth)acrylic acid N,N-diethylaminoethyl ester, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylamine Ethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acrylyl methacrylamide, vinyl acetamide, etc. Amino monomer. Among these, N,N-dimethylacrylamide and N,N-dimethylaminoethyl (meth)acrylate are preferable in terms of excellent hardening acceleration effect when used in combination with an active group. N,N-diethylaminoethyl (meth)acrylate is more preferably (methyl)acrylic acid in view of inhibiting polymerization inhibition caused by oxygen, effectively hardening, and easily expressing liquid repellency. ) N,N-diethylaminoethyl acrylate. These compounds may be used alone or in combination of two or more.

[單體(a6)]  就更有效地使(A)共聚物偏析至塗膜之表面之觀點而言，(A)共聚物可進而含有一種以上之基於具有碳數4以上之烷基之單體(a6)(以下，亦稱為單體(a6))之單元作為構成單體。[Monomer (a6)] From the viewpoint of more effectively segregating the (A) copolymer to the surface of the coating film, the (A) copolymer may further contain one or more monomers based on an alkyl group having 4 or more carbon atoms. A unit of the body (a6) (hereinafter, also referred to as a monomer (a6)) serves as a constituent monomer.

單體(a6)中之碳數4以上之烷基可為直鏈狀、支鏈狀、環狀之任一者。環狀之烷基可為單環式，亦可為多環式。就更有效地使(A)共聚物偏析至塗膜之表面之觀點而言，烷基較佳為直鏈狀。  作為碳數4以上之烷基之碳數，就更有效地使(A)共聚物偏析至塗膜之表面之觀點而言，較佳為4～30，更佳為6～20，進而較佳為12～18。The alkyl group having 4 or more carbon atoms in the monomer (a6) may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the (A) copolymer to the surface of the coating film, the alkyl group is preferably linear. The carbon number of the alkyl group having 4 or more carbon atoms is preferably from 4 to 30, more preferably from 6 to 20, and still more preferably from the viewpoint of efficiently segregating the (A) copolymer to the surface of the coating film 12 to 18.

作為單體(a6)，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，就易於合成化合物及易於調整碳數4以上之烷基之導入量之觀點而言，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(a6)，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)丙烯酸異𦯉基酯、(甲基)丙烯酸金剛烷基酯。  該等之中，較佳為具有直鏈狀之碳數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，較佳為烷基之碳數為上述較佳範圍內者，若亦考慮製造之容易性等，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。  該等(甲基)丙烯酸酯可單獨使用一種，亦可併用兩種以上。The monomer (a6) 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 synthesis of the compound and adjustment of the introduction amount of the alkyl group having 4 or more carbon atoms, It is preferably an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms. Examples of the monomer (a6) 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, iso(meth)acrylate, adamantyl (meth)acrylate. Among them, an alkyl (meth)acrylate having a straight-chain alkyl group having 4 or more carbon atoms is preferable. As an alkyl (meth)acrylate having a straight-chain alkyl group having 4 or more carbon atoms, it is preferable that the carbon number of the alkyl group is within the above-mentioned preferable range, and if the ease of production, etc. are also taken into consideration, it is more preferable Preferred are 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, especially (meth)acrylic acid stearyl esters. These (meth)acrylates may be used alone or in combination of two or more.

對單體(a1)～(a6)之區分進行記載。  若為具有藉由照射活性能量線而產生自由基之活性基的單體，則即使具有作為其他單體(a2)～(a6)之特徵之氟原子或官能基，亦視為單體(a1)。  若為具有氟原子之單體，則即使具有作為其他單體(a3)～(a6)之特徵之官能基，亦視為單體(a2)。  若為具有碳數2～4之環狀醚基之單體，則即使具有作為其他單體(a4)～(a6)之特徵之官能基，亦視為單體(a3)。  若為具有羥基之單體，則即使具有作為其他單體(a5)～(a6)之特徵之官能基，亦視為單體(a4)。  若為具有氫供與性官能基之單體，則即使具有作為單體(a6)之特徵之碳數4以上之烷基，亦視為單體(a5)。The classification of monomers (a1) to (a6) is described. If it is a monomer having active radicals that generate radicals by irradiating active energy rays, even if it has a fluorine atom or a functional group that is characteristic of other monomers (a2) to (a6), it is also regarded as a monomer (a1 ). In the case of a monomer having a fluorine atom, even if it has a functional group characteristic of other monomers (a3) to (a6), it is also regarded as a monomer (a2). In the case of a monomer having a cyclic ether group with 2 to 4 carbon atoms, even if it has a functional group characteristic of other monomers (a4) to (a6), it is also considered as a monomer (a3). In the case of a monomer having a hydroxyl group, even if it has a functional group characteristic of other monomers (a5) to (a6), it is also regarded as a monomer (a4). In the case of a monomer having a hydrogen-donating functional group, even if it has an alkyl group having 4 or more carbon atoms that is characteristic of the monomer (a6), it is also regarded as the monomer (a5).

(A)共聚物視需要可進而具有基於上述以外之其他單體之單元。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2～4之環狀醚基、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、甲基順丁烯二酸等含羧基之單體及該等之鹽；(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)丙烯腈等含氮之單體；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；含磷之乙烯系單體；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 based on other monomers other than the above, if necessary. Examples of other monomers include radically polymerizable groups and no active groups, cyclic ether groups having 2 to 4 carbon atoms, alkyl groups having 4 or more carbon atoms, fluorine atoms, and hydrogen-donating functional groups compound. Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, methylmaleic acid, and These salts; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; benzene Styrenic compounds such as ethylene, α-methylstyrene, divinylbenzene, vinyltoluene, etc., vinyl esters such as vinyl propionate and vinyl acetate; vinyl monomers containing phosphorus; vinyl chloride, vinylidene chloride, etc. Vinyl halides; conjugated dienes such as butadiene.

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，存在可使塗膜表面附近之活性基之濃度變高之傾向。  (A)共聚物每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。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。若活性基之含量為上述範圍之下限值以上，則存在硬化性更優異，可表現較高之撥液性之傾向。又，若為上限值以下，則存在感光性樹脂組合物之儲存穩定性更優異之傾向。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 which comprises (A) copolymer. (A) The copolymer preferably has a plurality of active groups in the molecule. Thereby, there exists a tendency for the density|concentration of the active group near the surface of a coating film to become high. (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 Below, more preferably below 2.0 mmol/g. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 0.1 to 2.5 mmol/g, more preferably 0.5 to 2.5 mmol/g, and still more preferably 0.8 to 2.0 mmol/g. When the content of the active group is more than the lower limit of the above-mentioned range, the curability is more excellent, and there is a tendency that a higher liquid repellency can be expressed. 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.

於本發明之感光性樹脂組合物中之(A)共聚物中，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(100質量%)之比率較佳為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90質量%以下，更佳為80質量%以下，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1～90質量%，更佳為10～80質量%，進而較佳為20～70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，則存在硬化性更優異，可表現較高之撥液性之傾向。若為上限值以下，則存在感光性樹脂組合物之儲存穩定性更優異之傾向。In the (A) copolymer in the photosensitive resin composition of the present invention, the ratio of the unit based on the monomer (a1) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably 1 mass % or more, more preferably 10 mass % or more, further preferably 20 mass % or more, especially preferably 30 mass % or more, and more preferably 90 mass % or less, more preferably 80 mass % or less, and more preferably It is preferably at most 70% by mass, more preferably at most 60% by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-90 mass % is preferable, 10-80 mass % is more preferable, 20-70 mass % is still more preferable, and 30-60 mass % is especially preferable. 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 sclerosis, and it exists in the tendency which can 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(100質量%)之比率較佳為5質量%以上，更佳為15質量%以上，進而較佳為25質量%以上，進而更佳為35質量%以上，尤佳為40質量%以上，尤其進而較佳為45質量%以上。又，較佳為70質量%以下，更佳為65質量%以下，進而較佳為60質量%以下，進而更佳為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5～70質量%，更佳為15～70質量%，進而較佳為25～65質量%，進而更佳為35～60質量%，尤佳為40～55質量%，尤其進而較佳為45～50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，則存在更有效地提高撥液性之傾向。若為上限值以下，則存在噴墨塗佈性優異之傾向。The ratio of the unit based on the monomer (a2) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably at least 5% by mass, more preferably at least 15% by mass, still more preferably 25% by mass % by mass or more, more preferably at least 35% by mass, even more preferably at least 40% by mass, especially more preferably at least 45% by mass. Moreover, it is preferably 70 mass % or less, more preferably 65 mass % or less, still more preferably 60 mass % or less, still more preferably 55 mass % or less, especially preferably 50 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 5 to 70% by mass, more preferably 15 to 70% by mass, further preferably 25 to 65% by mass, even more preferably 35 to 60% by mass, especially preferably 40 to 55% by mass, especially Furthermore, it is more preferable that it is 45-50 mass %. When the ratio of the unit based on a monomer (a2) is more than the lower limit of the said range, there exists a tendency for liquid repellency to be improved more effectively. There exists a tendency for inkjet coatability to be excellent as it is below an upper limit.

於本發明之感光性樹脂組合物中之(A)共聚物中，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(100質量)之比率較佳為1質量%以上，更佳為2質量%以上，進而較佳為3質量%以上。又，較佳為50質量%以下，更佳為40質量%以下，進而較佳為30質量%以下，尤佳為20質量%以下。上述上限及下限可任意地組合。例如，較佳為1～50質量%，更佳為1～40質量%，進而較佳為2～30質量%，尤佳為3～20質量%。若基於單體(a3)之單元之比率為上述範圍內，則存在可更有效地表現撥液性之傾向。In the (A) copolymer in the photosensitive resin composition of the present invention, the ratio of the unit based on the monomer (a3) to the total mass (100 mass) of all units constituting the (A) copolymer is preferably 1 % by mass or more, more preferably at least 2 mass %, still more preferably at least 3 mass %. Moreover, it is preferably at most 50 mass %, more preferably at most 40 mass %, still more preferably at most 30 mass %, particularly preferably at most 20 mass %. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-50 mass % is preferable, 1-40 mass % is more preferable, 2-30 mass % is still more preferable, 3-20 mass % is especially preferable. 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(100質量%)之比率較佳為1質量%以上，更佳為5質量%以上，進而較佳為8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1～70質量%，進而較佳為5～60質量%，尤佳為8～50質量%。若基於單體(a4)之單元之比率為上述範圍內，則存在可更有效地表現撥液性之傾向。When the (A) copolymer contains the monomer (a4) as a constituent monomer, the ratio based on the unit of the monomer (a4) relative to the total mass (100% by mass) of all units constituting the (A) copolymer is compared Preferably at least 1% by mass, more preferably at least 5% by mass, more preferably at least 8% by mass, more preferably at most 80% by mass, more preferably at most 70% by mass, further preferably at most 60% by mass , preferably 50% by mass or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-80 mass % is preferable, 1-70 mass % is more preferable, 5-60 mass % is still more preferable, 8-50 mass % is especially preferable. When the ratio of the unit based on a monomer (a4) exists in the said range, it exists in the tendency which can express a liquid repellency more effectively.

於(A)共聚物含有單體(a5)作為構成單體之情形時，基於單體(a5)之單元相對於構成(A)共聚物之全部單元之合計質量(100質量%)之比率較佳為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60質量%以下，更佳為30質量%以下，進而較佳為10質量%以下。上述上限及下限可任意地組合。例如，較佳為1～60質量%，更佳為1～30質量%，進而較佳為3～30質量%，尤佳為1～10質量%。若基於單體(a5)之單元之比率為上述範圍內，則存在可更有效地表現撥液性之傾向。When the (A) copolymer contains the monomer (a5) as a constituent monomer, the ratio based on the unit of the monomer (a5) relative to the total mass (100% by mass) of all units constituting the (A) copolymer is compared Preferably at least 1% by mass, more preferably at least 3% by mass, more preferably at least 5% by mass, more preferably at most 60% by mass, more preferably at most 30% by mass, further preferably at most 10% by mass . The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-60 mass % is preferable, 1-30 mass % is more preferable, 3-30 mass % is still more preferable, and 1-10 mass % is especially preferable. When the ratio of the unit based on a monomer (a5) 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(a6)作為構成單體之情形時，基於單體(a6)之單元相對於構成(A)共聚物之全部單元之合計質量(100質量%)之比率較佳為1質量%以上，更佳為5質量%以上，進而較佳為10質量%以上，又，較佳為60質量%以下，更佳為30質量%以下，進而較佳為10質量%以下。上述上限及下限可任意地組合。例如，較佳為1～60質量%，更佳為1～30質量%，進而較佳為1～10質量%。若基於單體(a6)之單元之比率為上述範圍內，則存在可更有效地表現撥液性之傾向。When the (A) copolymer contains the monomer (a6) as a constituent monomer, the ratio based on the unit of the monomer (a6) relative to the total mass (100% by mass) of all units constituting the (A) copolymer is compared Preferably at least 1% by mass, more preferably at least 5% by mass, more preferably at least 10% by mass, more preferably at most 60% by mass, more preferably at most 30% by mass, further preferably at most 10% by mass . The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 1 to 60% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 10% by mass. When the ratio of the unit based on a monomer (a6) exists in the said range, it exists in the tendency which can express a liquid repellency more effectively.

於(A)共聚物含有單體(a1)～單體(a6)以外之單體作為構成單體之情形時，其他單體之單元相對於構成(A)共聚物之全部單元之合計質量(100質量%)之比率較佳為1質量%以上，更佳為5質量%以上，又，較佳為40質量%以下，更佳為20質量%以下，進而較佳為10質量%以下。上述上限及下限可任意地組合。例如，較佳為1～40質量%，更佳為1～20質量%，進而較佳為5～10質量%。When the (A) copolymer contains monomers other than monomers (a1) to (a6) as constituent monomers, the units of other monomers are relative to the total mass of all units constituting the (A) copolymer ( 100% by mass) is preferably at least 1% by mass, more preferably at least 5% by mass, more preferably at most 40% by mass, more preferably at most 20% by mass, further preferably at most 10% by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, 1-40 mass % is preferable, 1-20 mass % is more preferable, and 5-10 mass % is still more preferable.

(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15質量%以上，進而更佳為20質量%以上，尤佳為24質量%以上。又，較佳為60質量%以下，更佳為50質量%以下，進而較佳為40質量%以下，進而更佳為30質量%以下。上述上限及下限可任意地組合。例如，較佳為5～60質量%，更佳為10～60質量%，進而較佳為15～50質量%，進而更佳為20～40質量%，尤佳為24～30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，則存在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，則存在與其材料之相溶性變得良好之傾向。(A) The fluorine atom content in the copolymer is preferably at least 5% by mass, more preferably at least 10% by mass, further preferably at least 15% by mass, still more preferably at least 20% by mass, particularly preferably at least 24% by mass above. Moreover, it is preferably 60 mass % or less, more preferably 50 mass % or less, still more preferably 40 mass % or less, still more preferably 30 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 5-60 mass %, more preferably 10-60 mass %, still more preferably 15-50 mass %, still more preferably 20-40 mass %, especially preferably 24-30 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 the material 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10000以上，更佳為30000以上，進而較佳為50000以上，進而更佳為70000以上，尤佳為80000以上。又，較佳為500000以下，更佳為300000以下，進而較佳為200000以下，進而更佳為150000以下。上述上限及下限可任意地組合。例如，較佳為10000～500000，更佳為30000～500000，進而較佳為50000～300000，進而更佳為70000～200000，尤佳為80000～150000。若Mw為上述範圍之下限值以上，則存在噴墨塗佈性變得良好之傾向。又，若為上限值以下，則存在撥液性變良好，又，與鹼可溶性樹脂之相溶性變佳，故而塗佈性變得良好之傾向。  (A)共聚物之Mw係藉由凝膠滲透層析法(GPC)而測定之標準聚苯乙烯換算之值。詳細之測定條件如下述實施例中所記載。(A) The weight average molecular weight (Mw) of the copolymer is preferably at least 10,000, more preferably at least 30,000, still more preferably at least 50,000, still more preferably at least 70,000, particularly preferably at least 80,000. Moreover, it is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, still more preferably 150,000 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 10,000 to 500,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 300,000, still more preferably 70,000 to 200,000, and most preferably 80,000 to 150,000. There exists a tendency for inkjet coating property to become favorable that Mw is more than the lower limit of the said range. Moreover, since liquid repellency becomes favorable and the compatibility with alkali-soluble resin becomes favorable as it is below an upper limit, it exists in the tendency for applicability to become favorable. (A) The 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)共聚物係藉由使含有必需之單體之單體成分聚合而獲得。例如，藉由使含有單體(a1)、單體(a2)、單體(a3)之單體成分聚合而獲得。單體成分視需要可進而含有單體(a4)、單體(a5)、單體(a6)及其他單體之任一種以上。(A) Copolymers are obtained by polymerizing monomer components containing necessary monomers. For example, it can be obtained by polymerizing a monomer component containing a monomer (a1), a monomer (a2), and a monomer (a3). The monomer component may further contain any one or more of a monomer (a4), a monomer (a5), a monomer (a6) and other monomers as necessary.

(A)共聚物之聚合典型而言係於聚合起始劑之存在下進行。聚合時，視需要可併用鏈轉移劑。  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，就操作簡便，生產性較高之方面而言，較佳為溶液聚合。(A) Polymerization of the copolymer is typically carried out in the presence of a polymerization initiator. During polymerization, a chain transfer agent may be used in combination if necessary. The polymerization method may, for example, be a known method such as solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. Among them, solution polymerization is preferred in terms of ease of operation and high 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(100質量%)中，較佳為0.01質量%以上，更佳為0.05質量%以上，進而較佳為0.07質量%以上，進而更佳為0.1質量%以上，又，較佳為50質量%以下，更佳為30質量%以下，進而較佳為20質量%以下，進而更佳為10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0.07～10質量%，尤佳為0.1～5質量%。藉由設為上述下限值以上，存在撥油墨性提高之傾向。藉由設為上述上限值以下，存在與其他成分之相溶性提高之傾向。The content ratio of the (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 in the total solid content (100% by mass) of the photosensitive resin composition, more preferably Preferably at least 0.05% by mass, more preferably at least 0.07% by mass, still more preferably at least 0.1% by mass, more preferably at most 50% by mass, more preferably at most 30% by mass, further preferably at most 20% by mass or less, more preferably 10% by mass or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, further preferably 0.07 to 10% by mass, and particularly preferably 0.1 to 5% by 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)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，只要為能夠以鹼性顯影液進行顯影之樹脂，則無特別限定。於本發明中，(B)鹼可溶性樹脂係與(A)共聚物不同之成分，於存在屬於(A)共聚物之鹼可溶性樹脂之情形時，將其作為(A)共聚物處理。作為(B)鹼可溶性樹脂，可例舉：含有羧基及/或羥基之各種樹脂。其中，就獲得適度之傾斜角之阻隔壁，可抑制顯影後之殘渣等觀點而言，較佳為具有羧基之樹脂。[1-1-2] (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 there is an alkali-soluble resin belonging to the (A) copolymer, it is handled as the (A) copolymer. As (B) alkali-soluble resin, the various resin containing a carboxyl group and/or a hydroxyl group is mentioned. Among them, a resin having a carboxyl group is preferable from the viewpoint of obtaining a barrier rib having an appropriate inclination angle and suppressing residue after development.

[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含有具有乙烯性雙鍵之鹼可溶性樹脂(b)(以下，有時簡記為「鹼可溶性樹脂(b)」)。藉由含有具有乙烯性雙鍵之鹼可溶性樹脂(b)，存在如下傾向：硬化性變高，抑制顯影時之(A)共聚物及/或撥液劑之流出，藉此使所獲得之阻隔壁之撥油墨性變高。[Alkali-soluble resin (b) having an ethylenic double bond] In the photosensitive resin composition of the present invention, the (B) alkali-soluble resin preferably contains an alkali-soluble resin (b) having an ethylenic double bond (hereinafter, Sometimes abbreviated as "alkali-soluble resin (b)"). By containing the alkali-soluble resin (b) having an ethylenic double bond, there is a tendency that the curability becomes high, and the outflow of the (A) copolymer and/or the liquid-repelling agent during development is inhibited, thereby making the obtained barrier The ink removal property of the wall becomes higher.

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，就顯影溶解性之觀點而言，較佳為環氧(甲基)丙烯酸酯樹脂(b1)、丙烯酸系共聚樹脂(b2)，就減少釋氣之觀點而言，較佳為環氧(甲基)丙烯酸酯樹脂(b1)。  以下，詳細敍述環氧(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), acrylic copolymer resin ( b2), from the viewpoint of reducing outgassing, epoxy (meth)acrylate resin (b1) is preferred. Hereinafter, the epoxy (meth)acrylate resin (b1) will be described in detail.

[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酐所得的樹脂。例如可例舉：於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，藉此，經由酯鍵(-COO-)而於環氧樹脂上加成乙烯性不飽和鍵，並且於此時生成之羥基上加成多元酸酐之一個羧基所得者。又，亦可例舉：於加成多元酸酐時，同時添加多元醇並使之加成所得者。進而，使具有可反應之官能基之化合物進而與上述反應中獲得之樹脂之羧基進行反應所得的樹脂亦包含於環氧(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不具有環氧基，且不限定於「(甲基)丙烯酸酯」，但環氧化合物(環氧樹脂)為原料，且「(甲基)丙烯酸酯」為代表例，故而依據慣用而如此命名。  又，作為環氧(甲基)丙烯酸酯樹脂(b1)，就阻隔壁下部之形狀變佳，顯影密接性變得良好之觀點而言，可更佳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 the resin. For example, it can be exemplified: the carboxyl group of an acid having an ethylenically unsaturated bond is added to the epoxy group of the epoxy resin through ring-opening, thereby adding ethylenic acid to the epoxy resin through the ester bond (-COO-). It is obtained by adding a carboxyl group of polybasic acid anhydride to the hydroxyl group formed at this time. Moreover, when adding polybasic acid anhydride, the thing which added polyhydric alcohol simultaneously and added it can also be mentioned. Furthermore, 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 is contained also in epoxy (meth)acrylate resin (b1). In this way, epoxy (meth)acrylate resin does not have epoxy group substantially in chemical structure, and is not limited to "(meth)acrylate", but epoxy compound (epoxy resin) is a raw material, and "( "Meth)acrylate" is a representative example, so it is named according to customary practice. Also, as the epoxy (meth)acrylate resin (b1), those having an aromatic ring in the main chain can be more preferably used from the viewpoint of improving the shape of the lower portion of the barrier ribs and improving the development adhesion.

此處所謂環氧樹脂，亦包含藉由熱硬化而形成樹脂之前之原料化合物，作為該環氧樹脂，可自公知之環氧樹脂中適宜選擇使用。又，環氧樹脂可使用使酚性化合物與表鹵醇反應而獲得之化合物。作為酚性化合物，較佳為具有2元或2元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，可較佳地使用於主鏈具有芳香族環者。Here, the epoxy resin also includes raw material compounds before forming a resin by thermosetting, and the epoxy resin 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, diglycidyl etherate of 1,1-bis(4'-hydroxyphenyl)adamantane, which can be preferably used in the main chain with aromatic Clan rings.

其中，就硬化膜強度之觀點而言，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 novolak epoxy resin, epoxy resin of polymer of phenol and dicyclopentadiene are preferable from the viewpoint of the strength of the cured film. Compound, epoxide of 9,9-bis(4'-hydroxyphenyl) fluorine, more preferably bisphenol A type 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、甲基順丁烯二酸、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，就感度之觀點而言，較佳為(甲基)丙烯酸。As the acid having an ethylenically unsaturated bond, for example, (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, methylmaleic acid, pentaerythritol tri(methyl) ) acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(methyl) Acrylate phthalic 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(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、及該等之酐。該等可單獨使用一種，亦可併用兩種以上。該等之中，就減少顯影後之像素部之殘渣之觀點而言，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 (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 development.

藉由使用多元醇，存在如下傾向：增大環氧(甲基)丙烯酸酯樹脂(b1)之分子量，可於分子中導入支鏈，可獲得分子量與黏度之平衡。又，存在如下傾向：可增加酸基於分子中之導入率，易於獲得感度與密接性等之平衡。  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 polyhydric alcohol, there is a tendency that the molecular weight of the epoxy (meth)acrylate resin (b1) is increased, a branched chain can be introduced into the molecule, and a balance between the molecular weight and the viscosity can be obtained. In addition, there is a tendency that the rate of introduction of acid into the molecule can be increased, and the balance between sensitivity and adhesiveness can be easily obtained. 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，進而更佳為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，進而更佳為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，進而更佳為40～120 mgKOH/g，尤佳為60～100 mgKOH/g。藉由設為上述下限值以上，存在顯影後之殘渣減少之傾向。又，藉由設為上述上限值以下，存在顯影時膜不易被鹼溶解，膜強度提高之傾向。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 Preferably at least 60 mgKOH/g, more preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, further preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, especially preferably It is below 100 mgKOH/g. 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, further preferably 40-120 mgKOH /g, preferably 60-100 mgKOH/g. There exists a tendency for the residue after image development to reduce by making it more than the said lower limit. Moreover, by making it below the said upper limit, there exists a tendency for a film to become difficult to be dissolved by alkali at the time of image development, and film strength improves.

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，進而更佳為4000以上，進一步較佳為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，進而更佳為4000～20000，進一步較佳為5000～15000，尤佳為6000～15000，最佳為7000～10000。藉由設為上述下限值以上，存在顯影時膜不易被鹼溶解，膜強度提高之傾向。又，藉由設為上述上限值以下，存在顯影後之殘渣減少之傾向。The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably at least 1,000, more preferably at least 2,000, further preferably at least 3,000, and even more preferably at least 4,000. More preferably, it is 5,000 or more, especially preferably 6,000 or more, most preferably 7,000 or more, and is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, especially preferably 10,000 or less. The above upper and lower limits can be combined arbitrarily, preferably 1000-30000, more preferably 2000-30000, further preferably 3000-20000, further preferably 4000-20000, further preferably 5000-15000, especially preferably 6000-15000, preferably 7000-10000. By setting it as more than the said lower limit, it exists in the tendency for a film to be hard to be dissolved by alkali at the time of image development, and film strength improves. Moreover, there exists a tendency for the residue after image development to reduce by making it below the said upper limit.

環氧(甲基)丙烯酸酯樹脂(b1)可藉由先前公知之方法而合成。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，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並使之進行加成反應，進而添加多元酸或其酐並持續反應。Epoxy (meth)acrylate resin (b1) can be synthesize|combined by a conventionally well-known method. Specifically, the method of 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 perform addition reaction, further adding polybasic acid or its anhydride and continuing the reaction.

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：三乙胺、二甲苄胺、三苄胺等三級胺類；四甲基氯化銨、甲基三乙基氯化銨、四乙基氯化銨、四丁基氯化銨、三甲基苄基氯化銨等四級銨鹽類；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, dimethylbenzylamine, and tribenzylamine; tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, Quaternary ammonium salts such as 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.

具有乙烯性不飽和鍵之酸或酯化合物可使用相對於環氧樹脂之環氧基之1化學當量，較佳為0.7～1.3化學當量，更佳為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℃。多元酸(酐)可使用相對於加成反應中生成之羥基之1化學當量，較佳為0.1～1.2化學當量，更佳為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 1 chemical equivalent relative to the epoxy group of the epoxy resin, preferably 0.7-1.3 chemical equivalents, more preferably 0.9-1.1 chemical equivalents. The temperature during the addition reaction is preferably from 60 to 150°C, more preferably from 80 to 120°C. The polybasic acid (anhydride) can be used in an amount of 1 chemical equivalent relative to the hydroxyl group formed in the addition reaction, preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents.

作為環氧(甲基)丙烯酸酯樹脂(b1)，就減少釋氣，易於獲得垂直之傾斜形狀之觀點而言，較佳為包含選自由含有下述通式(i)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-1)(以下，有時稱為「環氧(甲基)丙烯酸酯樹脂(b1-1)」)、含有下述通式(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)」)、及含有下述通式(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。The epoxy (meth)acrylate resin (b1) preferably contains one selected from a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing and making it easier to obtain a vertical inclined shape. Epoxy (meth)acrylate resin (b1-1) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b1-1)"), containing Epoxy (meth)acrylate resin (b1-2) of partial structure (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b1-2)"), and the following general formula (iii ) in the group consisting of epoxy (meth)acrylate resin (b1-3) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-3)") having a partial structure represented by at least one of them.

作為環氧(甲基)丙烯酸酯樹脂(b1)，該等之中，就減少釋氣，阻隔壁下部之形狀變佳之觀點而言，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)。作為理由之一，推測如下等原因：藉由具有剛直之主骨架，不易對熱分解，又，減少顯影時顯影液向曝光部之滲透。Among them, as the epoxy (meth)acrylate resin (b1), it is preferable to include a compound represented by the following general formula (i) from the viewpoint of reducing outgassing and improving the shape of the lower part of the barrier rib. The epoxy (meth)acrylate resin (b1-1) of partial structure is more preferably the epoxy (meth)acrylate resin (b1-1) containing the partial structure represented by following general formula (i). As one of the reasons, it is presumed that the rigid main frame makes it difficult to decompose against heat, and also reduces the penetration of the developing solution into the exposed part during development.

[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2價之烴基。式(i)中之苯環可進而經任意之取代基取代。*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)  於上述式(i)中，R b表示可具有取代基之2價之烴基。作為2價之烴基，可例舉：2價之脂肪族基、2價之芳香族環基、1個以上之2價之脂肪族基與1個以上之2價之芳香族環基連結而成之基。 (R b ) In the above formula (i), R b represents a divalent hydrocarbon group which may have a substituent. Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and combinations of one or more divalent aliphatic groups and one or more divalent aromatic ring groups. foundation.

2價之脂肪族基可例舉：直鏈狀、支鏈狀、環狀者。該等之中，就顯影溶解性之觀點而言，較佳為直鏈狀者，另一方面，就減少顯影液向曝光部之滲透之觀點而言，較佳為環狀者。其碳數較佳為1以上，更佳為3以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The divalent aliphatic group may, for example, be linear, branched or cyclic. Among them, a linear one is preferable from the viewpoint of image development solubility, and a cyclic one is preferable from the viewpoint of reducing the permeation of the developing solution to the exposed portion on the other hand. The carbon number is preferably at least 1, more preferably at least 3, still more preferably at least 6, and is preferably at most 20, more preferably at most 15, and still more preferably at most 10. 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. There exists a tendency for image development adhesiveness 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2價之直鏈狀脂肪族基，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，就殘渣減少之觀點而言，較佳為亞甲基。  作為2價之支鏈狀脂肪族基，例如可例舉：於上述2價之直鏈狀脂肪族基上具有甲基、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。  2價之環狀之脂肪族基所具有之環數並無特別限定，較佳為1以上，更佳為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，存在殘膜率提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。作為2價之環狀之脂肪族基，例如可例舉：自環己烷環、環庚烷環、環癸烷環、環十二烷環、二環戊烷環、降𦯉烷環、異𦯉烷環、金剛烷環之環去除2個氫原子所得之基。該等之中，就顯影密接性之觀點而言，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 these, methylene is preferable from the viewpoint of residue reduction. Examples of the divalent branched aliphatic group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups on the above-mentioned divalent straight-chain aliphatic group. , Second butyl, third butyl as the structure of the side chain. The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for a residual film rate to improve 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. As a divalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a northane ring, an iso The group obtained by removing 2 hydrogen atoms from the ring of 𦯉alkane ring and adamantane 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2價之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，就合成容易性之觀點而言，較佳為未經取代。As a substituent that a divalent aliphatic 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; a carboxyl group, is easy to synthesize From this point of view, it is preferably unsubstituted.

作為2價之芳香族環基，可例舉：2價之芳香族烴環基及2價之芳香族雜環基。其碳數較佳為4以上，更佳為5以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The divalent aromatic ring group may, for example, be a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group. The carbon number is preferably at least 4, more preferably at least 5, still more preferably at least 6, and is preferably at most 20, more preferably at most 15, even more preferably at most 10. 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. There exists a tendency for image development adhesiveness 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2價之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2價之芳香族烴環基，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 111137059-002
環、聯三伸苯環、苊環、螢蒽環、茀環。  作為2價之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2價之芳香族雜環基，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，就光硬化性之觀點而言，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 111137059-002
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 di Azole 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, three sulfonium ring, quinoline ring, isoquinoline ring, phenoline ring , quinoline ring, phenanthridine ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, 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2價之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，就硬化性之觀點而言，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 hardenability.

作為1個以上之2價之脂肪族基與1個以上之2價之芳香族環基連結而成之基，可例舉：1個以上之上述2價之脂肪族基與1個以上之上述2價之芳香族環基連結而成之基。 2價之脂肪族基之數量並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  2價之芳香族環基之數量並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include: one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned A group formed by linking divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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 preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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1個以上之2價之脂肪族基與1個以上之2價之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，就骨架之剛直性與膜之疏水化之觀點而言，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 in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked together, for example, groups represented by the following formulas (i-A) to (i-F) may be mentioned. Among them, 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

如上所述，式(i)中之苯環可進而經任意之取代基取代。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。取代基之數量亦無特別限定，只要化學上容許，可為1個，亦可為2個以上。  就硬化性之觀點而言，較佳為未經取代。As mentioned above, 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.

就顯影溶解性之觀點而言，上述式(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 the above 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與上述式(i)之R a及R b含義相同。R 1表示可具有取代基之碳數1～4之2價之烴基。*表示鍵結鍵。式(i-1)中之苯環可進而經任意之取代基取代。 In formula (i-1), R a and R b have the same meaning as R a and R b of formula (i) above. 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)  於上述通式(i-1)中，R 1表示可具有取代基之碳數1～4之2價之烴基。作為2價之烴基，可例舉：伸烷基、伸烯基。 (R 1 ) In the above general 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，就顯影溶解性之觀點而言，較佳為直鏈。其碳數並無特別限定，較佳為1以上，更佳為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，存在殘膜率變高之傾向。又，藉由設為上述上限值以下，存在釋氣產生量變少之傾向。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 preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for a residual film rate to become high by setting it as more than the said lower limit. Moreover, there exists a tendency for the amount of outgassing generation to become small by making it below the said upper limit.

作為伸烷基之具體例，可例舉：亞甲基、伸乙基、伸丙基、伸丁基，就釋氣減少之觀點而言，較佳為亞甲基、伸乙基，更佳為伸乙基。Specific examples of alkylene groups include: methylene, ethylidene, propylidene, and butylene. From the viewpoint of reducing outgassing, methylene and ethylidene are preferred, and more preferably For ethylidene.

伸烯基可為直鏈，亦可為支鏈，就顯影溶解性之觀點而言，較佳為直鏈。其碳數並無特別限定，較佳為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，存在殘膜率變高之傾向。又，藉由設為上述上限值以下，存在釋氣產生量變少之傾向。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 preferably 2 or more, and is preferably 4 or less, more preferably 3 or less. For example, 2-4 are preferable, and 2-3 are more preferable. There exists a tendency for a residual film rate to become high by setting it as more than the said lower limit. Moreover, there exists a tendency for the amount of outgassing generation to become small by making it below the said upper limit.

作為伸烯基之具體例，可例舉：伸乙烯基、伸丙烯基、伸丁烯基，就釋氣之觀點而言，較佳為伸乙烯基。Specific examples of the alkenylene group include vinylene groups, propenylene groups, and butylene groups, and vinylene groups are preferred from the viewpoint of outgassing.

碳數1～4之2價之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，就合成之容易性之觀點而言，較佳為未經取代。The substituents that a divalent hydrocarbon group having 1 to 4 carbon atoms may have are not particularly limited, for example, halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups are preferred. Preferably unsubstituted.

該等之中，就釋氣減少之觀點而言，R 1較佳為碳數1～4之2價之伸烷基，更佳為亞甲基、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 ethylene group, and still more preferably an ethylene group .

環氧(甲基)丙烯酸酯樹脂(b1-1)1分子中所含之上述式(i-1)所表示之部分結構可為一種，亦可為兩種以上。The partial structure represented by the said 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分子中所含之上述式(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，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The number of partial structures represented by the above formula (i) contained in one molecule of epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further Preferably, it is 3 or more, and it is more preferable that it is 10 or less, and it is still more preferable that it is 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. There exists a tendency for image development adhesiveness 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分子中所含之上述式(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，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The number of partial structures represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more , and more preferably 3 or more, and more preferably 10 or less, further 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. There exists a tendency for image development adhesiveness 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

作為另外之態樣，就顯影密接性之觀點而言，環氧(甲基)丙烯酸酯樹脂(b1)較佳為含有下述式(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) Ester resin (b1-2).

[化12]

Figure 02_image023
[chemical 12]
Figure 02_image023

式(ii)中，R c各自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2價之烴基。*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)  於上述式(ii)中，R d表示具有環狀烴基作為側鏈之2價之烴基。  作為環狀烴基，可例舉：脂肪族環基或芳香族環基。 (R d ) In the above 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數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  脂肪族環基之碳數較佳為4以上，更佳為6以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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、異𦯉烷環、金剛烷環。該等之中，就顯影密接性之觀點而言，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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 carbon atoms in the aliphatic ring group is preferably at least 4, more preferably at least 6, still more preferably at least 8, and preferably at most 40, more preferably at most 30, further preferably at most 20, especially preferably at most 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. There exists a tendency for image development adhesiveness 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, noraleane ring, isoalne 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數並無特別限定，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，存在殘渣減少之傾向。又，藉由設為上述上限值以下，存在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。芳香族環基之碳數較佳為4以上，更佳為6以上，進而較佳為8以上，進而更佳為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，進而更佳為10～20，尤佳為12～15。藉由設為上述下限值以上，存在殘渣減少之傾向。又，藉由設為上述上限值以下，存在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 111137059-002
環、聯三伸苯環、苊環、螢蒽環、茀環。該等之中，就圖案化特性之觀點而言，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is 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 number of carbon atoms in the aromatic ring group is preferably at least 4, more preferably at least 6, further preferably at least 8, still more preferably at least 10, especially preferably at least 12, and is preferably at most 40, more preferably at least 40. 30 or less, more preferably 20 or less, particularly preferably 15 or less. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 4-40, more preferably 6-40, still more 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 111137059-002
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2價之烴基中之2價之烴基並無特別限定，例如可例舉：2價之脂肪族基、2價之芳香族環基、1個以上之2價之脂肪族基與1個以上之2價之芳香族環基連結而成之基。Among the divalent hydrocarbon groups having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, and examples thereof include: a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. A group formed by linking an aliphatic group with one or more divalent aromatic ring groups.

2價之脂肪族基可例舉：直鏈狀、支鏈狀、環狀之脂肪族基。該等之中，就顯影溶解性之觀點而言，較佳為直鏈狀之脂肪族基，另一方面，就減少顯影液向曝光部之滲透之觀點而言，較佳為環狀之脂肪族基。其碳數較佳為1以上，更佳為3以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The divalent aliphatic group may, for example, be a linear, branched or cyclic aliphatic group. Among them, a straight-chain aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developing solution to the exposed portion. group base. The carbon number is preferably at least 1, more preferably at least 3, still more preferably at least 6, and is preferably at most 25, more preferably at most 20, even more preferably at most 15. 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. There exists a tendency for image development adhesiveness 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2價之直鏈狀脂肪族基，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，就殘渣之觀點而言，較佳為亞甲基。  作為2價之支鏈狀脂肪族基，例如可例舉：於上述2價之直鏈狀脂肪族基上具有甲基、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。  2價之環狀之脂肪族基所具有之環數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  作為2價之環狀之脂肪族基，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、異𦯉烷環、金剛烷環去除2個氫原子所得之基。該等之中，就顯影密接性之觀點而言，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 these, methylene is preferable from the viewpoint of residue. Examples of the divalent branched aliphatic group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups on the above-mentioned divalent straight-chain aliphatic group. , Second butyl, third butyl as the structure of the side chain. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 3 the following. 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. There exists a tendency for image development adhesiveness 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 divalent cyclic aliphatic group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, nor-alkane ring, iso-alkane ring, adamantane 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2價之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，就合成容易性之觀點而言，較佳為未經取代。As a substituent that a divalent aliphatic 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; a carboxyl group, is easy to synthesize From this point of view, it is preferably unsubstituted.

作為2價之芳香族環基，可例舉：2價之芳香族烴環基及2價之芳香族雜環基。其碳數較佳為4以上，更佳為5以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The divalent aromatic ring group may, for example, be a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group. The carbon number is preferably at least 4, more preferably at least 5, still more preferably at least 6, and is preferably at most 30, more preferably at most 20, and still more preferably at most 15. 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. There exists a tendency for image development adhesiveness 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2價之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2價之芳香族烴環基，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 111137059-002
環、聯三伸苯環、苊環、螢蒽環、茀環。  作為2價之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2價之芳香族雜環基，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，就光硬化性之觀點而言，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 111137059-002
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 di Azole 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, three sulfonium ring, quinoline ring, isoquinoline ring, phenoline ring , quinoline ring, phenanthridine ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, 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2價之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，就硬化性之觀點而言，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 hardenability.

作為1個以上之2價之脂肪族基與1個以上之2價之芳香族環基連結而成之基，可例舉：1個以上之上述2價之脂肪族基與1個以上之上述2價之芳香族環基連結而成之基。 2價之脂肪族基之數量並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  2價之芳香族環基之數量並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include: one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned A group formed by linking divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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 preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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1個以上之2價之脂肪族基與1個以上之2價之芳香族環基連結而成之基，例如可例舉：上述式(i-A)～(i-F)所表示之基。該等之中，就殘渣減少之觀點而言，較佳為上述式(i-C)所表示之基。As a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, for example, groups represented by the above formulas (i-A) to (i-F) may be mentioned. Among them, the group represented by the above formula (i-C) is preferable from the viewpoint of residue reduction.

作為側鏈之環狀烴基對該等2價之烴基之鍵結態樣並無特別限定，例如可例舉：以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。The cyclic hydrocarbon group as a side chain is not particularly limited to the bonding state of these bivalent hydrocarbon groups, for example, a side chain is substituted for one hydrogen atom of an aliphatic group or an aromatic ring group, Or a form in which one carbon atom of an aliphatic group constitutes a cyclic hydrocarbon group as a side chain.

就顯影密接性之觀點而言，上述式(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 the above 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與上述式(ii)含義相同。R α表示可具有取代基之1價之環狀烴基。n為1以上之整數。式(ii-1)中之苯環可進而經任意之取代基取代。*表示鍵結鍵。 In the formula (ii-1), R c has the same meaning as in the above formula (ii). R α represents a monovalent 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)  於上述式(ii-1)中，R α表示可具有取代基之1價之環狀烴基。  作為環狀烴基，可例舉：脂肪族環基或芳香族環基。 (R α ) In the above formula (ii-1), R α represents a monovalent 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數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  又，脂肪族環基之碳數較佳為4以上，更佳為6以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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、異𦯉烷環、金剛烷環。該等之中，就顯影密接性之觀點而言，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, 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. There exists a tendency for image development adhesiveness 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 preferably at least 4, more preferably at least 6, further preferably at least 8, and is preferably at most 40, more preferably at most 30, further preferably at most 20, especially Preferably under 15. 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. There exists a tendency for image development adhesiveness 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, noraleane ring, isoalne 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數並無特別限定，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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  作為芳香族環基，可例舉：芳香族烴環基、芳香族雜環基。又，芳香族環基之數量較佳為4以上，更佳為5以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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，就顯影密接性之觀點而言，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is 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. There exists a tendency for image development adhesiveness 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. Also, the number of aromatic ring groups is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, 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. There exists a tendency for image development adhesiveness 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，就合成之容易性之觀點而言，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 having 1 to 5 carbon atoms; an alkoxy group having 1 to 5 carbon atoms such as methoxy or ethoxy; a hydroxyl group; a nitro group; a cyano group; Not replaced.

n表示1以上之整數，較佳為2以上，又，較佳為3以下。例如，較佳為1～3，更佳為1～2。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1-3 are preferable, and 1-2 are more preferable. There exists a tendency for image development adhesiveness 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，就堅固之膜硬化度與電特性之觀點而言，R α較佳為1價之脂肪族環基，更佳為金剛烷基。 Among them, R α is preferably a monovalent aliphatic ring group, more preferably an adamantyl group, from the viewpoint of strong film hardening degree and electrical characteristics.

如上所述，式(ii-1)中之苯環可進而經任意之取代基取代。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。取代基之數量亦無特別限定，可為1個，亦可為2個以上。就硬化性之觀點而言，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.

以下例舉上述式(ii-1)所表示之部分結構之具體例。Specific examples of the partial structure represented by the above 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] [chemical 17]

[化18]

Figure 02_image035
[chemical 18]
Figure 02_image035

就顯影密接性之觀點而言，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與上述式(ii)相同。R β表示可具有取代基之2價之環狀烴基。式(ii-2)中之苯環可進而經任意之取代基取代。*表示鍵結鍵。 In the formula (ii-2), R c is the same as the above 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)  於上述式(ii-2)中，R β表示可具有取代基之2價之環狀烴基。  作為環狀烴基，可例舉：脂肪族環基或芳香族環基。 (R β ) In the above 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數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  又，脂肪族環基之碳數較佳為4以上，更佳為6以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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、異𦯉烷環、金剛烷環。該等之中，就顯影密接性之觀點而言，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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. Also, the carbon number of the aliphatic ring group is preferably at least 4, more preferably at least 6, still more preferably at least 8, and is preferably at most 40, more preferably at most 35, even more preferably at most 30. 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. There exists a tendency for image development adhesiveness 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 a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a noralane ring, an isoalkane ring, and 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數並無特別限定，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，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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  作為芳香族環基，可例舉：芳香族烴環基、芳香族雜環基。又，芳香族環基之碳數較佳為4以上，更佳為6以上，進而較佳為8以上，尤佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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，就顯影密接性之觀點而言，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is 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. There exists a tendency for image development adhesiveness 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. Also, the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, especially preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and more preferably Preferably below 20, especially 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. There exists a tendency for image development adhesiveness 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，就合成之簡易性之觀點而言，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，就硬化性之觀點而言，R β較佳為2價之脂肪族環基，更佳為2價之金剛烷環基。  作為另外之態樣，就顯影密接性之觀點而言，R β較佳為2價之芳香族環基，更佳為2價之茀環基。 Among these, Rβ 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.

如上所述，式(ii-2)中之苯環可進而經任意之取代基取代。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。取代基之數量亦無特別限定，可為1個，亦可為2個以上。就硬化性之觀點而言，較佳為未經取代。As mentioned above, 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.

以下例舉上述式(ii-2)所表示之部分結構之具體例。Specific examples of the partial structure represented by the above 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

就硬化性之觀點而言，上述式(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 the above 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與上述式(ii)含義相同。R 1與上述式(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 in formula (ii) above. R 1 has the same meaning as in the above formula (i-1). * Indicates a bonded bond.

環氧(甲基)丙烯酸酯樹脂(b1-2)1分子中所含之上述式(ii-3)所表示之部分結構可為一種，亦可為兩種以上。The partial structure represented by the said 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分子中所含之上述式(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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The number of partial structures represented by the above 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 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 1-15, still more preferably 3-10. There exists a tendency for image development adhesiveness 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.

進而作為另外之態樣，就易於減少釋氣之觀點而言，環氧(甲基)丙烯酸酯樹脂(b1)較佳為含有下述通式(iii)所表示之部分結構之環氧(甲基)丙烯酸酯樹脂(b1-3)。Furthermore, as another aspect, the epoxy (meth)acrylate resin (b1) is preferably epoxy (meth)acrylate resin (b1) containing a partial structure represented by the following general formula (iii) from the viewpoint of easy reduction of outgassing. base) 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2價之環狀烴基。式(iii)中之苯環可進而經任意之取代基取代。*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)  於上述式(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2價之環狀烴基。(γ) In the above 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，就顯影溶解性之觀點而言，較佳為直鏈狀，就顯影密接性之觀點而言，較佳為支鏈狀。其碳數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。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 preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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，就兼顧顯影密接性與顯影溶解性之觀點而言，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, and are preferably 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，就兼顧顯影密接性與顯影溶解性之觀點而言，較佳為未經取代。As substituents that the alkylene group may have, for example: alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; From the viewpoint of solubility, it is preferably unsubstituted.

作為2價之環狀烴基，可例舉：2價之脂肪族環基或2價之芳香族環基。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數並無特別限定，較佳為1以上，更佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  又，脂肪族環基之碳數較佳為4以上，更佳為6以上，進而較佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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、異𦯉烷環、金剛烷環。該等之中，就顯影密接性之觀點而言，較佳為金剛烷環。The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is 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. There exists a tendency for image development adhesiveness 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. Also, the carbon number of the aliphatic ring group is preferably at least 4, more preferably at least 6, still more preferably at least 8, and is preferably at most 40, more preferably at most 35, even more preferably at most 30. 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. There exists a tendency for image development adhesiveness 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, noraleane ring, isoalne 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數並無特別限定，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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  作為芳香族環基，可例舉：芳香族烴環基、芳香族雜環基。芳香族環基之碳數較佳為4以上，更佳為6以上，進而較佳為8以上，尤佳為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，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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，就顯影密接性之觀點而言，較佳為茀環。The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is 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. There exists a tendency for image development adhesiveness 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 preferably at least 4, more preferably at least 6, still more preferably at least 8, especially preferably at least 10, and is preferably at most 40, more preferably at most 30, and still more preferably at least 30. Below 20, 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. There exists a tendency for image development adhesiveness 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，就合成之簡易性之觀點而言，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 having 1 to 5 carbons; an alkoxy group having 1 to 5 carbons such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; Not replaced.

該等之中，就殘渣減少之觀點而言，γ較佳為可具有取代基之伸烷基，更佳為二甲基亞甲基。Among these, γ is preferably an alkylene group which may have a substituent, more preferably a dimethylmethylene group, from the viewpoint of residue reduction.

如上所述，式(iii)中之苯環可進而經任意之取代基取代。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。取代基之數量亦無特別限定，可為1個，亦可為2個以上。就硬化性之觀點而言，較佳為未經取代。As mentioned above, 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.

就顯影溶解性之觀點而言，上述式(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 above 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與上述式(iii)含義相同。R 1與上述式(i-1)之R 1含義相同。*表示鍵結鍵。式(iii-1)中之苯環可進而經任意之取代基取代。 In formula (iii-1), R e and γ have the same meanings as in formula (iii) above. R 1 has the same meaning as R 1 in the above formula (i-1). * Indicates a bonded bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

環氧(甲基)丙烯酸酯樹脂(b1-3)1分子中所含之上述式(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，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1～18，更佳為5～18，進而較佳為10～15。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The number of partial structures represented by the above formula (iii) contained in one molecule of epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and further Preferably, it is 10 or more, and it is more preferable that it is 18 or less, and it is still more preferable that it is 15 or less. 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. There exists a tendency for image development adhesiveness 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分子中所含之上述式(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，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1～18，更佳為3～18，進而較佳為5～15。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The number of partial structures represented by the above formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more , and more preferably 5 or more, and more preferably 18 or less, further 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. There exists a tendency for image development adhesiveness 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

[丙烯酸系共聚樹脂(b2)]  就硬化性之觀點而言，丙烯酸系共聚樹脂(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.

丙烯酸系共聚樹脂(b2)中，就顯影溶解性、撥液性之觀點而言，較佳為含有下述通式(I)所表示之部分結構之丙烯酸系共聚樹脂(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 and liquid repellency.

[化30] [chem 30]

式(I)中，R A及R B各自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.

就顯影性之觀點而言，上述式(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 above 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與上述式(I)之R A及R B含義相同。R 1與上述式(i-1)之R 1含義相同。 In formula (I-1), R A and R B have the same meanings as R A and R B in formula (I) above. R 1 has the same meaning as R 1 in the above formula (i-1).

就感度之觀點而言，上述式(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 above 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與上述式(I)之R A及R B含義相同。 In formula (I-2), R A and R B have the same meaning as R A and R B of formula (I).

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I)所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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，進而更佳為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%，進而更佳為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，存在殘渣減少之傾向。又，藉由設為上述上限值以下，存在顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), the partial structure represented by the above general formula (I) contained in the acrylic copolymer resin (b2-1) The content is not particularly limited, preferably at least 5 mol%, more preferably at least 20 mol%, further preferably at least 30 mol%, even more preferably at least 50 mol%, especially preferably 70 mol% mol% or more, more preferably 80 mol% or more, and more preferably 99 mol% or less, more preferably 97 mol% or less, further preferably 95 mol% or less. The upper and lower limits above can be combined arbitrarily, for example, preferably 5-99 mol%, more preferably 20-99 mol%, further preferably 30-97 mol%, and even more preferably 50-97 mol% ear%, 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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I-1)所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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，進而更佳為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，進而更佳為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%，進而更佳為8～30莫耳%，尤佳為10～20莫耳%。藉由設為上述下限值以上，存在感度變高，殘渣減少之傾向。又，藉由設為上述上限值以下，存在顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-1), the acrylic copolymer resin (b2-1) contained in the above general formula (I-1) The content of the partial structure represented is not particularly limited, but is preferably at least 1 mol%, more preferably at least 5 mol%, further preferably at least 8 mol%, even more preferably at least 10 mol%. , preferably less than 99 mol%, more preferably less than 60 mol%, further preferably less than 40 mol%, further preferably less than 30 mol%, especially preferably less than 20 mol%. 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%, further preferably 8-30 mol% ear%, 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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I-2)所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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，進而更佳為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%，進而更佳為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，存在感度變高之傾向。又，藉由設為上述上限值以下，存在顯影性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-2), the acrylic copolymer resin (b2-1) contained in the above general formula (I-2) The content of the partial structure represented is not particularly limited, but is preferably at least 10 mol%, more preferably at least 20 mol%, further preferably at least 30 mol%, even more preferably at least 40 mol%, especially Preferably at least 50 mol%, more preferably at least 70 mol%, and preferably less than 99 mol%, more preferably less than 95 mol%, further preferably less than 90 mol%, especially preferably less than 90 mol%. Below 85 mole%. 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%, and even more preferably 40-95 mol% ear%, 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, there exists a tendency for developability to improve by making it below the said upper limit.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I)所表示之部分結構之情形時，其他可含有之部分結構並無特別限定，就顯影密接性之觀點而言，例如，較佳為含有下述通式(I')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains a partial structure represented by the above-mentioned general formula (I), other partial structures that may be contained are not particularly limited, but from the viewpoint of developing adhesiveness, for example, preferably It contains a partial structure represented by the following general formula (I').

[化33]

Figure 02_image065
[chem 33]
Figure 02_image065

上述式(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 the above formula (I'), R D represents a hydrogen atom or a methyl group, RE represents an alkyl group that may have a substituent, an aryl group (aromatic ring group) that may have a substituent, or an alkenyl group that may have a substituent .

(R E)  於上述式(I')中，R E表示可具有取代基之烷基、可具有取代基之芳基(芳香族環基)、或可具有取代基之烯基。  作為R E之烷基，可例舉：直鏈狀、支鏈狀或環狀之烷基。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，進而更佳為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，進而更佳為3～14，尤佳為5～12。藉由設為上述下限值以上，存在膜強度變高，顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 (R E ) In the above formula (I'), RE represents an alkyl group which may have a substituent, an aryl group (aromatic ring group) which may have a substituent, or an alkenyl group which may have a substituent. The alkyl group of R E may, for example, be a linear, branched or cyclic alkyl group. The carbon number is preferably at least 1, more preferably at least 3, more preferably at least 5, and preferably at most 20, more preferably at most 18, further preferably at most 16, and even more preferably at most 14, Preferably under 12. The above 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 there exists a tendency for image development adhesiveness 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，就膜強度之觀點而言，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，就顯影性之觀點而言，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, A carboxyl group, an acryl group, and a methacryl group are preferably a hydroxyl group and an oligoglycol group from the viewpoint of developability.

作為R E之芳基(芳香族環基)，可例舉：1價之芳香族烴環基、1價之芳香族雜環基。其碳數較佳為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。例如，較佳為6～24，更佳為6～22，進而較佳為6～20，尤佳為6～18。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。  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 111137059-002
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，就硬化性之觀點而言，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，就顯影性之觀點而言，較佳為羥基、低聚乙二醇基。 Examples of the aryl group (aromatic ring group) of RE include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably at least 6, and is preferably at most 24, more preferably at most 22, further preferably at most 20, particularly preferably at most 18. For example, it is preferably 6-24, more preferably 6-22, still more preferably 6-20, and especially preferably 6-18. There exists a tendency for image development adhesiveness 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 111137059-002
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, a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable. 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之烯基，可例舉：直鏈狀、支鏈狀或環狀之烯基。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，進而更佳為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，進而更佳為2～16，尤佳為2～14。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 The alkenyl group of R E may, for example, be a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably at least 2, preferably at most 22, more preferably at most 20, further preferably at most 18, even more preferably at most 16, particularly preferably at most 14. For example, it is preferably 2-22, more preferably 2-20, still more preferably 2-18, still more preferably 2-16, and especially preferably 2-14. There exists a tendency for image development adhesiveness 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，就硬化性之觀點而言，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，就顯影性之觀點而言，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 these, vinyl and acryl are preferred from the viewpoint of curability, 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，就顯影性之觀點而言，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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I')所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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%，進而更佳為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%，進而更佳為1.5～30莫耳%，尤佳為2～10莫耳%。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。When the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I'), the acrylic copolymer resin (b2-1) represented by the above general formula (I') The content of the partial structure is not particularly limited, preferably at least 0.5 mol %, more preferably at least 1 mol %, further preferably at least 1.5 mol %, especially preferably at least 2 mol %, and more preferably It is 90 mol% or less, more preferably 70 mol% or less, still more preferably 50% mol%, still more preferably 30 mol% or less, especially preferably 10 mol% or less. 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%, and even more preferably 1.5-30 mol% , preferably 2 to 10 mol%. There exists a tendency for image development adhesiveness 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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I)所表示之部分結構之情形時，就耐熱性、膜強度之觀點而言，較佳為進而含有下述通式(I'')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above-mentioned general formula (I), it is preferable to further contain the following general formula (I'') from the viewpoint of heat resistance and film strength ) represents the partial structure.

[化34]

Figure 02_image067
[chem 34]
Figure 02_image067

上述式(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、或可具有取代基之硫化烷基。t表示0～5之整數。 In the above formula (I''), R F represents a hydrogen atom or a methyl group, and R G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, or an optionally substituted alkyl group. An oxy group, a thiol group, or a sulfide alkyl group which may have a substituent. t represents an integer of 0-5.

(R G)  於上述式(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、或可具有取代基之硫化烷基。  作為R G之烷基，可例舉：直鏈狀、支鏈狀或環狀之烷基。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，進而更佳為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，進而更佳為3～14，尤佳為5～12。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 (R G ) In the above 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, sulfur Alcohol group, or sulfide alkyl group which may have a substituent. The alkyl group of R G may, for example, be a linear, branched or cyclic alkyl group. The carbon number is preferably at least 1, more preferably at least 3, more preferably at least 5, and preferably at most 20, more preferably at most 18, further preferably at most 16, and even more preferably at most 14, Preferably under 12. The above 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. There exists a tendency for image development adhesiveness 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，就顯影密接性之觀點而言，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，就顯影性之觀點而言，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 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, A carboxyl group, an acryl group, and a methacryl group are preferably a hydroxyl group and an oligoglycol group from the viewpoint of developability.

作為R G之烯基，可例舉：直鏈狀、支鏈狀或環狀之烯基。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，進而更佳為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，進而更佳為2～16，尤佳為2～14。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 The alkenyl group of R G may, for example, be a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably at least 2, preferably at most 22, more preferably at most 20, further preferably at most 18, even more preferably at most 16, particularly preferably at most 14. For example, it is preferably 2-22, more preferably 2-20, still more preferably 2-18, still more preferably 2-16, and especially preferably 2-14. There exists a tendency for image development adhesiveness 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，就硬化性之觀點而言，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，就顯影性之觀點而言，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 these, vinyl and acryl are preferred from the viewpoint of curability, 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之鹵素原子，可例舉：氟原子、氯原子、溴原子、碘原子，該等之中，就撥油墨性之觀點而言，較佳為氟原子。 The halogen atom of RG may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a fluorine atom is preferred from the viewpoint of ink repellency.

作為R G之烷氧基，可例舉：直鏈狀、支鏈狀或環狀之烷氧基。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，進而更佳為14以下，尤佳為12以下。例如，較佳為1～20，更佳為1～18，進而較佳為1～16，進而更佳為1～14，尤佳為1～12。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 The alkoxy group of R G may, for example, be a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, even more preferably at most 14, particularly preferably at most 12. For example, 1-20 is preferable, 1-18 is more preferable, 1-16 is still more preferable, 1-14 is still more preferable, 1-12 is especially preferable. There exists a tendency for image development adhesiveness 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，就顯影性之觀點而言，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, acryl, and methacryl, and from the viewpoint of developability, preferably hydroxyl and oligoethylene glycol.

作為R G之硫化烷基，可例舉：直鏈狀、支鏈狀或環狀之硫化烷基。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，進而更佳為14以下，尤佳為12以下。例如，較佳為1～20，更佳為1～18，進而較佳為1～16，進而更佳為1～14，尤佳為1～12。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。 The sulfurized alkyl group of R G may, for example, be a linear, branched or cyclic sulfurized alkyl group. The number of carbon atoms is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, even more preferably at most 14, particularly preferably at most 12. For example, 1-20 is preferable, 1-18 is more preferable, 1-16 is still more preferable, 1-14 is still more preferable, 1-12 is especially preferable. There exists a tendency for image development adhesiveness 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.

作為硫化烷基，例如可例舉：甲硫醚基、乙硫醚基、丙硫醚基、丁硫醚基。該等之中，就顯影性之觀點而言，較佳為甲硫醚基、乙硫醚基。  作為硫化烷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，就顯影性之觀點而言，較佳為羥基、低聚乙二醇基。As a sulfurized alkyl group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group are mentioned, for example. Among these, a methylsulfide group and an ethylsulfide group are preferred from the viewpoint of developability. As the substituent that the alkyl group in the sulfurized alkyl group may have, for example, methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amine group, epoxy group, oligoethylene glycol A phenyl group, a carboxyl group, an acryl group, a methacryl group, and a hydroxyl group and an oligoglycol group are preferable from the viewpoint of developability.

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

(t)  於上述式(I'')中，t表示0～5之整數。就顯影性之觀點而言，較佳為0～2，更佳為0～1，進而較佳為0。(t) In the above formula (I''), t represents an integer of 0-5. From the viewpoint of developability, it is preferably 0-2, more preferably 0-1, and still more preferably 0.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I'')所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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4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，進而更佳為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%，進而更佳為2～30莫耳%，尤佳為3～20莫耳%，最佳為4～10莫耳%。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I''), the acrylic copolymer resin (b2-1) contained in the above general formula (I'') The content of the partial structure represented is not particularly limited, but is preferably at least 1 mol%, more preferably at least 2 mol%, further preferably at least 3 mol%, and most preferably at least 4 mol%. It is preferably less than 90 mol%, more preferably less than 70 mol%, further preferably less than 50 mol%, further preferably less than 30 mol%, especially preferably less than 20 mol%, most preferably less than 20 mol%. Below 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 %, further preferably 2-30 mol % ear%, preferably 3-20 mole%, most preferably 4-10 mole%. There exists a tendency for image development adhesiveness 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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I)所表示之部分結構之情形時，就顯影性之觀點而言，較佳為進而含有下述通式(I''')所表示之部分結構。When the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I), it is preferable to further contain the following general formula (I''') from the viewpoint of developability Represents a partial structure.

[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.

於丙烯酸系共聚樹脂(b2-1)含有上述通式(I''')所表示之部分結構之情形時，丙烯酸系共聚樹脂(b2-1)中所含之上述通式(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，存在殘渣減少之傾向。又，藉由設為上述上限值以下，存在顯影密接性提高之傾向。When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above-mentioned general formula (I'''), the above-mentioned general formula (I''' contained in the acrylic copolymer resin (b2-1) ) is not particularly limited, but is preferably at least 5 mol%, more preferably at least 10 mol%, further preferably at least 30 mol%, and more preferably at least 90 mol% or less, more preferably less than 80 mol%, further preferably less than 70 mol%, especially preferably less than 50 mol%. 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.

丙烯酸系共聚樹脂(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，進而更佳為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，進而更佳為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，進而更佳為25～40 mgKOH/g。藉由設為上述下限值以上，存在殘渣減少之傾向。又，藉由設為上述上限值以下，存在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, even 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, further 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.

丙烯酸系共聚樹脂(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，進而更佳為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，進而更佳為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，進而更佳為4000～10000，尤佳為5000～8000。藉由設為上述下限值以上，存在顯影密接性提高之傾向。又，藉由設為上述上限值以下，存在殘渣減少之傾向。The weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, but is preferably at least 1,000, more preferably at least 2,000, further preferably at least 3,000, still more preferably at least 4,000, and especially preferably at least 5,000 , and, preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, still more preferably 10,000 or less. Preferably it is below 8000. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1000-30000, more preferably 2000-20000, further preferably 3000-15000, further preferably 4000-10000, especially preferably 5000-8000. There exists a tendency for image development adhesiveness 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.

(B)鹼可溶性樹脂中可單獨含有環氧(甲基)丙烯酸酯樹脂(b1)及丙烯酸系共聚樹脂(b2)之任一者，亦可含有兩者。進而，(B)鹼可溶性樹脂中可含有鹼可溶性樹脂(b)以外之鹼可溶性樹脂。  例如可例舉：國際公開2016/194619號公報、國際公開2017/154439號公報中記載之樹脂。(B) Either one of an epoxy (meth)acrylate resin (b1) and an acrylic copolymer resin (b2) may be contained independently, or both may be contained in alkali-soluble resin. Furthermore, alkali-soluble resins other than the alkali-soluble resin (b) may be contained in (B) alkali-soluble resin. For example, the resins described in International Publication No. 2016/194619 and International Publication No. 2017/154439 can be cited.

本發明之感光性樹脂組合物中之(B)鹼可溶性樹脂之含量於感光性樹脂組合物之全部固形物成分(100質量%)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，進而更佳為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%，進而更佳為30～70質量%。藉由設為上述下限值以上，存在顯影性提高之傾向。又，藉由設為上述上限值以下，存在易於確保較高之撥液性之傾向。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 10% by mass, in the total solid content (100% by mass) of the photosensitive resin composition more than 20% by mass, more preferably at least 30% by mass, particularly preferably at least 40% by mass, and more preferably at most 90% by mass, more preferably at most 80% by mass, and still more preferably at least 90% by mass. 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 %, still more 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 securing high liquid repellency easily by making it below the said upper limit.

於本發明之感光性樹脂組合物含有環氧(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(100質量%)，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，進而更佳為20質量%以上，尤佳為25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10～70質量%，進而更佳為15～60質量%，尤佳為20～50質量%。藉由設為上述下限值以上，存在顯影性提高，阻隔壁下部之形狀變佳之傾向。又，藉由設為上述上限值以下，存在撥液性變得良好之傾向。When the photosensitive resin composition of the present invention contains 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 (100% by mass), it is preferably at least 5% by mass, more preferably at least 10% by mass, further preferably at least 15% by mass, still more preferably at least 20% by mass, especially preferably at least 20% by mass 25% by mass or more, and preferably at most 90% by mass, more preferably at most 70% by mass, further preferably at most 60% by mass, particularly preferably at most 50% by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily, for example, preferably 5-90 mass %, more preferably 10-90 mass %, further preferably 10-70 mass %, still more preferably 15-60 mass %, especially Preferably, it is 20 to 50% by mass. There exists a tendency for developability to improve and the shape of a barrier rib lower part to become favorable by making it more than the said lower limit. Moreover, there exists a tendency for liquid repellency to become favorable by making it below the said upper limit.

又，於本發明之感光性樹脂組合物含有丙烯酸系共聚樹脂(b2)之情形時，丙烯酸系共聚樹脂(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(100質量%)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，進而更佳為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%，進而更佳為30～70質量%。藉由設為上述下限值以上，存在顯影性提高，撥液性變佳之傾向。又，藉由設為上述上限值以下，存在阻隔壁下部之形狀變佳之傾向。Also, 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, and the total solid content of the photosensitive resin composition (100 mass %), preferably at least 5 mass %, more preferably at least 10 mass %, further preferably at least 20 mass %, further preferably at least 30 mass %, especially preferably at least 40 mass %, and more preferably Preferably, it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 70 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 %, still more preferably 20-80 mass %, still more preferably 30-70 mass %. There exists a tendency for developability to improve and liquid repellency to improve by making it more than the said lower limit. Moreover, there exists a tendency for the shape of the barrier rib lower part to become favorable by making it below the said upper limit.

於(B)鹼可溶性樹脂含有環氧(甲基)丙烯酸酯樹脂(b1)之情形時，環氧(甲基)丙烯酸酯樹脂(b1)之含量相對於(B)鹼可溶性樹脂(100質量%)並無特別限定，較佳為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上，進而更佳為35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50質量%以下。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20～90質量%，進而較佳為20～70質量%，進而更佳為20～50質量%，尤佳為30～50質量%。藉由設為上述下限值以上，存在阻隔壁下部之形狀變佳之傾向。又，藉由設為上限值以下，存在撥液性變得良好之傾向。When (B) alkali-soluble resin contains epoxy (meth)acrylate resin (b1), content of epoxy (meth)acrylate resin (b1) is relative to (B) alkali-soluble resin (100 mass % ) is not particularly limited, and is preferably at least 10% by mass, more preferably at least 20% by mass, further preferably at least 30% by mass, and even more preferably at least 35% by mass. Moreover, it is preferably at most 90% by mass, more preferably at most 70% by mass, and still more preferably at most 50% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10-90% by mass, more preferably 20-90% by mass, further preferably 20-70% by mass, still more preferably 20-50% by mass, especially Preferably, it is 30 to 50% by mass. There exists a tendency for the shape of the barrier rib lower part to become favorable by making it more than the said lower limit. Moreover, there exists a tendency for liquid repellency to become favorable by making it below an upper limit.

於(B)鹼可溶性樹脂含有丙烯酸系共聚樹脂(b2)之情形時，丙烯酸系共聚樹脂(b2)之含量相對於(B)鹼可溶性樹脂(100質量%)並無特別限定，較佳為20質量%以上，更佳為40質量%以上，進而較佳為50質量%以上，進而更佳為60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20～90質量%，更佳為40～90質量%，進而較佳為40～80質量%，進而更佳為50～80質量%，尤佳為50～70質量%。藉由設為上述下限值以上，存在撥液性變得良好之傾向。又，藉由設為上限值以下，存在阻隔壁下部之形狀變佳之傾向。When (B) alkali-soluble resin contains acrylic copolymer resin (b2), the content of acrylic copolymer resin (b2) is not specifically limited with respect to (B) alkali-soluble resin (100 mass %), Preferably it is 20 % by mass or more, more preferably at least 40 mass %, further preferably at least 50 mass %, further preferably at least 60 mass %. Also, it is preferably at most 90% by mass, more preferably at most 80% by mass, and still more preferably at most 70% by mass. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 20-90% by mass, more preferably 40-90% by mass, further preferably 40-80% by mass, still more preferably 50-80% by mass, especially Preferably, it is 50 to 70% by mass. There exists a tendency for liquid repellency to become favorable by making it more than the said lower limit. Moreover, there exists a tendency for the shape of the barrier rib lower part to become favorable by making it below an upper limit.

又，感光性樹脂組合物之全部固形物成分(100質量%)中之(B)鹼可溶性樹脂及(C)光聚合性化合物之含量之合計較佳為5質量%以上，更佳為10質量%以上，進而較佳為30質量%以上，進而更佳為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%，進而更佳為50～97質量%，進一步較佳為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，存在硬化性、撥液性提高之傾向。又，藉由設為上述上限值以下，存在藉由增加著色劑量而使遮光性變得良好之傾向。In addition, the total content of the (B) alkali-soluble resin and (C) photopolymerizable compound in the total solid content (100% by mass) of the photosensitive resin composition is preferably at least 5% by mass, more preferably 10% by mass. % or more, more preferably more than 30% by mass, more preferably more than 50% by mass, more preferably more than 70% by mass, more preferably more than 80% by mass, most preferably more than 90% by mass, and more preferably It is 99 mass % or less, More preferably, it is 97 mass % or less, More preferably, it is 95 mass % or less. 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, further preferably 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 and liquid repellency to improve by setting it as more than the said lower limit. Moreover, there exists a tendency for light-shielding property to become favorable by increasing a coloring quantity by making it below the said upper limit.

作為(B)鹼可溶性樹脂相對於感光性樹脂組合物中之(C)光聚合性化合物之調配比，相對於(C)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50～400質量份，更佳為60～300質量份。藉由設為上述下限值以上，存在傾斜形狀變高之傾向。又，藉由設為上述上限值以下，存在硬化性、撥液性提高之傾向。The compounding ratio of the (B) alkali-soluble resin to the (C) photopolymerizable compound in the photosensitive resin composition is preferably at least 50 parts by mass, more preferably at least 100 parts by mass of the photopolymerizable compound (C). 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, 50-400 mass parts are preferable, and 60-300 mass parts are more preferable. There exists a tendency for an inclination shape to become high by making it more than the said lower limit. Moreover, there exists a tendency for curability and liquid repellency to improve by making it below the said upper limit.

[1-1-3](C)光聚合性化合物  本發明之感光性樹脂組合物含有(C)光聚合性化合物。認為藉由含有(C)光聚合性化合物，可成為高感度。  於本發明中，(C)光聚合性化合物係與(A)共聚物不同之成分，於存在屬於(A)共聚物之光聚合性化合物之情形時，將其作為(A)共聚物處理。  作為此處所使用之(C)光聚合性化合物，係指於分子內具有1個以上之乙烯性不飽和鍵(乙烯性雙鍵)之化合物，就聚合性、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而言，較佳為於分子內具有2個以上之乙烯性不飽和鍵之化合物。又，進而較佳為該不飽和鍵源自(甲基)丙烯醯氧基，即為(甲基)丙烯酸酯化合物。[1-1-3] (C) Photopolymerizable compound The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that high sensitivity can be achieved by containing (C) a photopolymerizable compound. In the present invention, the (C) photopolymerizable compound is a component different from the (A) copolymer, and when there is a photopolymerizable compound belonging to the (A) copolymer, it is treated as the (A) copolymer. The (C) photopolymerizable compound used here refers to a compound having one or more ethylenically unsaturated bonds (ethylenically double bonds) in the molecule. From the viewpoint of the difference in developer solubility between the exposed part and the non-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, it is a (meth)acrylate compound.

於本發明之感光性樹脂組合物中，尤其理想的為使用於1分子中具有2個以上之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，存在聚合性提高，成為高感度之傾向。藉由設為上述上限值以下，存在顯影性變得更良好之傾向。  作為(C)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而獲得之酯。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. 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, polymerizability improves and there exists a tendency for it to become high sensitivity. There exists a tendency for developability to become more favorable by making it below the said upper limit. As (C) 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之伊康酸酯；將該等化合物之丙烯酸酯替換為丁烯酸酯之丁烯酸酯；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; Substitution of acrylates of these compounds for methacrylates of methacrylates; substitution of acrylates of these compounds for itaconates of itaconates; substitution of acrylates of these compounds for crotonates crotonate esters; replace acrylate esters of these compounds with maleic esters of maleic acid esters.

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而獲得之酯，並非必須為單一物質，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. For example, acrylic acid, ortho Condensates of phthalic 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 and glycerol condensation products.

作為本發明之感光性樹脂組合物中所使用之(C)光聚合性化合物之上述以外之例，例如有用的為：使多異氰酸酯化合物與含羥基之(甲基)丙烯酸酯或使多異氰酸酯化合物與多元醇及含羥基之(甲基)丙烯酸酯反應而獲得之胺基甲酸酯(甲基)丙烯酸酯類；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類的環氧丙烯酸酯類；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。As an example of the (C) 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 Urethane (meth)acrylates obtained by reacting with polyols and hydroxyl-containing (meth)acrylates; polyvalent epoxy compounds and hydroxyl-containing (meth)acrylates or (meth)acrylic acid Epoxy acrylates such as addition reactants; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; divinyl phthalate, etc. Vinyl compounds.

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(共榮社化學公司製造)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(日本合成化學工業公司製造)。As 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 company), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

於本發明之感光性樹脂組合物中，(C)光聚合性化合物之分子量並無特別限定，就感度、撥油墨性、傾斜角之觀點而言，較佳為100以上，更佳為150以上，進而較佳為200以上，進而更佳為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，進而更佳為300～700，尤佳為400～700，最佳為500～700。In the photosensitive resin composition of the present invention, the molecular weight of the (C) photopolymerizable compound is not particularly limited, but it is preferably 100 or more, more preferably 150 or more from the viewpoint of sensitivity, ink repellency, and tilt angle , and more preferably at least 200, still more preferably at least 300, especially preferably at least 400, most preferably at least 500, and more preferably at most 1000, more preferably at most 700. The upper and lower limits above can be combined arbitrarily, for example, preferably 100-1000, more preferably 150-1000, further preferably 200-1000, further preferably 300-700, especially preferably 400-700, most preferably 500-700.

(C)光聚合性化合物之碳數並無特別限定，就感度、撥油墨性、傾斜角之觀點而言，較佳為7以上，更佳為10以上，進而較佳為15以上，進而更佳為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，進而更佳為20～35，尤佳為25～30。(C) 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 tilt angle. Preferably at least 20, especially preferably at least 25, more preferably at most 50, more preferably at most 40, further 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.

就感度、撥油墨性、傾斜角之觀點而言，較佳為脂肪族多羥基化合物與不飽和羧酸之酯類、環氧(甲基)丙烯酸酯類、及胺基甲酸酯(甲基)丙烯酸酯類，其中，進而較佳為三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等三官能以上之酯(甲基)丙烯酸酯類、2,2,2-三(甲基)丙烯醯氧基甲基乙基鄰苯二甲酸、二季戊四醇五(甲基)丙烯酸酯之二元酸酐加成物等對三官能以上之酯(甲基)丙烯酸酯類之酸酐之加成物。  該等可單獨使用一種，亦可併用兩種以上。In terms of sensitivity, ink repellency, and tilt angle, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, epoxy (meth)acrylates, and urethane (methyl) ) acrylates, wherein, further preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Esters, dipentaerythritol penta(meth)acrylates and other trifunctional esters (meth)acrylates, 2,2,2-tri(meth)acryloxymethylethylphthalic acid, di Addition of dibasic acid anhydrides such as pentaerythritol penta(meth)acrylate to anhydrides of trifunctional or higher ester (meth)acrylates. One of these can be used alone, or two or more can be used in combination.

本發明之感光性樹脂組合物中之(C)光聚合性化合物之含量於感光性樹脂組合物之全部固形物成分(100質量%)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，進而更佳為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，進而更佳為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%，進而更佳為30～55質量%，尤佳為40～50質量%。藉由設為上述下限值以上，存在成為適宜之內部硬化性之傾向。藉由設為上述上限值以下，存在顯影性變得良好之傾向。The content of the (C) photopolymerizable compound in the photosensitive resin composition of the present invention is preferably at least 5% by mass, more preferably 10% by mass in the total solid content (100% by mass) of the photosensitive resin composition. % or more, more preferably at least 20 mass %, more preferably at least 30 mass %, particularly preferably at least 40 mass %, and more preferably at most 80 mass %, more preferably at most 70 mass %, and more preferably at least 70 mass % It is 60 mass % or less, More preferably, it is 55 mass % or less, Especially preferably, it is 50 mass % or less. The above-mentioned 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 %, especially Preferably, it is 40 to 50% by mass. There exists a tendency which becomes suitable internal hardening property by setting it as more than the said lower limit. There exists a tendency for developability to become favorable by making it below the said upper limit.

[1-1-4](D)光聚合起始劑  本發明之感光性樹脂組合物除(A)共聚物外，可進而含有(D)光聚合起始劑。(D)光聚合起始劑只要為藉由活性光線而使(C)光聚合性化合物聚合，例如使(C)光聚合性化合物所具有之乙烯性不飽和鍵聚合的化合物，則並無特別限定。[1-1-4] (D) Photopolymerization initiator The photosensitive resin composition of the present invention may further contain (D) a photopolymerization initiator in addition to the (A) copolymer. (D) The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the (C) photopolymerizable compound by active rays, for example, polymerizes the ethylenically unsaturated bond of the (C) photopolymerizable compound. limited.

本發明之感光性樹脂組合物可使用該領域中通常所使用之光聚合起始劑作為(D)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號公報中記載之鹵甲基化㗁二唑衍生物類、鹵甲基對稱三𠯤衍生物類、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-胺基烷基苯酮衍生物類；日本專利特開2000-80068號公報、日本專利特開2006-36750號公報等中記載之肟酯系化合物。The photosensitive resin composition of this invention can use the photoinitiator normally used in this field as (D) photoinitiator. 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 Application Laid-Open No. 2000-56118; Halomethylated oxadiazole derivatives and halomethyl symmetrical trioxazole derivatives described in Japanese Patent Application Laid-Open No. 10-39503 free radical activity such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc. Agents, α-aminoalkylphenone derivatives; oxime ester compounds described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, etc.

具體而言，例如，作為茂金屬化合物，可例舉：二環戊二烯基二氯化鈦、二環戊二烯基雙苯基鈦、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。Specifically, for example, as the metallocene compound, dicyclopentadienyl titanium dichloride, dicyclopentadienyl biphenyl titanium, dicyclopentadienyl bis(2,3,4 ,5,6-pentafluorophenyl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienylbis(2,4,6-tri Fluorophenyl)titanium, dicyclopentadienylbis(2,6-difluorophenyl)titanium, dicyclopentadienylbis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl)titanium Dienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, dicyclopentadiene Alkenyl[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.

作為鹵甲基對稱三𠯤衍生物類，例如可例舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)對稱三𠯤、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)對稱三𠯤。As the halomethyl symmetrical trioxetine derivatives, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)symmetric trioxetine, 2-(4-methoxyphenyl) Nylnaphthyl)-4,6-bis(trichloromethyl)symmetric trisulfone, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)symmetric trisulfite, 2-( 4-Ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)symmetric trisulfone.

作為α-胺基烷基苯酮衍生物類，例如可例舉：2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-𠰌啉基苯基)丁烷-1-酮、2-二甲胺基-2-(4-甲基苄基)-1-(4-𠰌啉基苯基)丁烷-1-酮、3,6-雙(2-甲基-2-𠰌啉基丙醯基)-9-辛基咔唑。Examples of α-aminoalkylphenone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-alphalinylpropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-alcolinylphenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4 - 𠰌linylphenyl) butan-1-one, 3,6-bis(2-methyl-2-𠰌linylpropionyl)-9-octylcarbazole.

作為(D)光聚合起始劑，尤其就感度或製版性之方面而言，有效的為肟酯系化合物，例如於使用含有酚性羥基之鹼可溶性樹脂之情形時，就感度之方面而言不利，故而尤其有用的為此種感度優異之肟酯系化合物。肟酯系化合物之光反應之量子產率較高，生成之自由基之活性較高，故而感度較高且對熱反應穩定，以少量即可獲得高感度之感光性樹脂組合物。As (D) the photopolymerization initiator, especially in terms of sensitivity and plate-making properties, oxime ester compounds are effective, for example, in the case of using an alkali-soluble resin containing a phenolic hydroxyl group, in terms of sensitivity Oxime ester compounds with excellent sensitivity are especially useful. The quantum yield of the photoreaction of the oxime ester compound is high, and the activity of the free radicals generated is high, so the sensitivity is high and the reaction to heat is stable, and a high-sensitivity photosensitive resin composition 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 compound, the compound represented by following general formula (IV) is mentioned, for example.

[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表示含有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 containing 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之烷基之碳數並無特別限定，就對溶劑之溶解性、感度、噴墨塗佈性之觀點而言，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。作為烷基之具體例，例如可例舉：甲基、乙基、丙基、丁基、戊基、己基、環戊基甲基、環戊基乙基、環己基甲基、環己基乙基。 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-乙醯基-N-乙醯氧基胺基。作為烷基，就合成容易性之觀點而言，較佳為未經取代。 The number of carbon atoms in the alkyl group of R 21a is not particularly limited, but it 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. Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl . 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-acetyloxyamine. The alkyl group is preferably unsubstituted from the viewpoint of ease of synthesis.

作為R 21a之芳香族環基，可例舉：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，就對感光性樹脂組合物之溶解性之觀點而言，較佳為5以上。又，就顯影性之觀點而言，較佳為30以下，更佳為20以下，進而較佳為12以下。例如，較佳為5～30，更佳為5～20，進而較佳為5～12。 The aromatic ring group of R 21a may, for example, be an aromatic hydrocarbon ring group or 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. For example, it is preferably 5-30, more preferably 5-20, and still more preferably 5-12.

作為芳香族環基之具體例，例如可例舉：苯基、萘基、吡啶基、呋喃基，該等之中，就顯影性之觀點而言，較佳為苯基或萘基，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，就顯影性之觀點而言，較佳為烷基、烷氧基、該等連結而成之基，更佳為連結而成之烷氧基。  該等之中，就噴墨塗佈性之觀點而言，R 21a較佳為可具有取代基之烷基。 Specific examples of the aromatic ring group include, for example, phenyl, naphthyl, pyridyl, and furyl. Among these, phenyl or naphthyl is preferred from the viewpoint of developability, and more preferred For phenyl. The substituents that the aromatic ring group may have include, for example: hydroxyl group, carboxyl group, halogen atom, amino group, amido group, alkyl group, alkoxy group, and a group formed by linking these substituents. From the standpoint, it is preferably an alkyl group, an alkoxy group, or a group in which these are linked, and an alkoxy group in which they are linked is more preferred. Among them, R 21a is preferably an alkyl group which may have a substituent from the viewpoint of inkjet coatability.

作為R 21b，較佳可例舉：可經取代之咔唑基、可經取代之9-氧硫𠮿

Figure 111137059-001
基、可經取代之二苯硫醚基、可經取代之茀基或可經取代之吲哚基。該等之中，就噴墨塗佈性之觀點而言，較佳為可經取代之二苯硫醚基。 As R 21b , preferably, there may be exemplified: carbazolyl which may be substituted, 9-oxothiol which may be substituted
Figure 111137059-001
 group, diphenylsulfide group which may be substituted, fenyl group which may be substituted or indolyl group which may be substituted. Among these, diphenylsulfide groups which may be substituted are preferred from the viewpoint of inkjet coatability.

R 22a之烷醯基之碳數並無特別限定，就對溶劑之溶解性或感度之觀點而言，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，進而更佳為5以下。作為烷醯基之具體例，例如可例舉：乙醯基(aceyl)、乙醯基(ethyloyl)、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，就合成容易性之觀點而言，較佳為未經取代。 The number of carbon atoms in the alkyl group of R 22a is not particularly limited, but it is preferably at least 2, preferably at most 20, more preferably at most 15, and even more preferably from the viewpoint of solubility or sensitivity to solvents. 10 or less, more preferably 5 or less. Specific examples of the alkyl group include, for example, an acetyl group (aceyl), an acetyl group (ethyloyl), a propionyl group, and a butyryl group. 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 ease of synthesis.

R 22a之芳醯基之碳數並無特別限定，就對溶劑之溶解性或感度之觀點而言，較佳為7以上，又，較佳為20以下，更佳為15以下，進而較佳為10以下。作為芳醯基之具體例，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，就合成容易性之觀點而言，較佳為未經取代。 該等之中，就感度之觀點而言，R 22a較佳為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 number of carbon atoms in the aryl group of R 22a is not particularly limited, but it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, and still more preferably from the viewpoint of solubility or sensitivity to solvents. 10 or less. Specific examples of the aryl group include, for example, a benzoyl group and a naphthyl group. 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 alkylyl group which may have a substituent, more preferably an unsubstituted alkylyl group, and still more preferably an acetyl group.

例如可使用：日本專利第4454067號公報、國際公開第2002/100903號、國際公開第2012/45736號、國際公開第2015/36910號、國際公開第2006/18973號、國際公開第2008/78678號、日本專利第4818458號公報、國際公開第2005/80338號、國際公開第2008/75564號、國際公開第2009/131189號、國際公開第2009/131189號、國際公開第2010/133077號、國際公開第2010/102502號、國際公開第2012/68879號中記載之光聚合起始劑等。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, and International Publication No. 2008/78678 can be used. , Japanese Patent No. 4818458, 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. Photopolymerization initiators and the like described in No. 2010/102502 and International Publication No. 2012/68879.

(D)光聚合起始劑可單獨使用一種，亦可組合兩種以上使用。視需要，以提高感度為目的，可於(D)光聚合起始劑中調配應對圖像曝光光源之波長之增感色素、聚合促進劑。(D) The photoinitiator may be used individually by 1 type, and may use it in combination of 2 or more types. If necessary, for the purpose of increasing the sensitivity, a sensitizing pigment and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be formulated in the (D) photopolymerization initiator.

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號公報中記載之𠮿

Figure 111137059-001
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號公報中記載之3-酮香豆素化合物、日本專利特開平6-19240號公報中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號公報中記載之具有二烷基胺基苯骨架之色素。 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 111137059-001
 Pigment, Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, coumarin pigment having a heterocycle, Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335 The 3-ketocoumarin compound described in the Publication No. 1, the pyrromethene pigment described in the Japanese Patent Laid-Open Publication No. 6-19240, the Japanese Patent Laid-Open Publication No. 47-2528, and the Japanese Patent Laid-Open Publication No. 54-155292 Publication No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, and Japanese Patent Laid-Open No. 58-15503 Show No. 60-88005 communique, Japanese Patent Laid-Open No. 59-56403 communique, Japanese Patent Laid-Open No. 2-69 communique, Japanese Patent Laid-Open No. 57-168088 communique, Japanese Patent Laid-Open No. 5-107761 communique, Japan Pigment having a dialkylaminobenzene skeleton described in JP-A-5-210240 and JP-A-4-288818.

該等增感色素中，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'-二甲胺基二苯甲酮、4,4'-二乙胺基二苯甲酮、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-(對二甲胺基苯基)苯并㗁唑、2-(對二乙胺基苯基)苯并㗁唑、2-(對二甲胺基苯基)苯并[4,5]苯并㗁唑、2-(對二甲胺基苯基)苯并[6,7]苯并㗁唑、2,5-雙(對二乙胺基苯基)-1,3,4-㗁唑、2-(對二甲胺基苯基)苯并噻唑、2-(對二乙胺基苯基)苯并噻唑、2-(對二甲胺基苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2,5-雙(對二乙胺基苯基)-1,3,4-噻二唑、(對二甲胺基苯基)吡啶、(對二乙胺基苯基)吡啶、(對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二甲胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等含對二烷基胺基苯基之化合物。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, more preferably 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone Ketone, 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 oxazole, 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-diethyl Aminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylamine phenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) Pyrimidine and other compounds containing p-dialkylaminophenyl groups. 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：4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸2-乙基己酯、4-二甲胺基苯乙酮、4-二甲胺基苯丙酮等芳香族胺、正丁胺、N-甲基二乙醇胺、苯甲酸2-二甲胺基乙酯等脂肪族胺。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, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, 4-dimethylamine Aromatic amines such as propiophenone, aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate. 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中含有(D)光聚合起始劑之情形時，(D)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(100質量%)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，進而更佳為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，進而更佳為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%，進而更佳為1～10質量%，進一步較佳為2～7質量%，尤佳為3～5質量%。藉由設為上述下限值以上，存在撥油墨性提高之傾向。藉由設為上述上限值以下，存在殘渣減少之傾向。In the case where (D) photopolymerization initiator is contained in the photosensitive resin composition of the present invention, the content ratio of (D) photopolymerization initiator is not particularly limited, and the total solid content of the photosensitive resin composition (100% by mass), preferably at least 0.01% by mass, more preferably at least 0.1% by mass, more preferably at least 1% by mass, still more preferably at least 2% by mass, particularly preferably at least 3% by mass, and , preferably less than 25% by mass, more preferably less than 20% by mass, more preferably less than 15% by mass, more preferably less than 10% by mass, especially preferably less than 7% by mass, most preferably less than 5% by mass . The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, still more preferably 0.1 to 15% by mass, still more preferably 1 to 10% by mass, further preferably 2 to 7% by mass, Most 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.

於本發明之感光性樹脂組合物中含有(D)光聚合起始劑之情形時，作為(D)光聚合起始劑相對於感光性樹脂組合物中之(C)光聚合性化合物之調配比，相對於(C)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，進而更佳為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，進而更佳為15～50質量份，尤佳為20～30質量份。藉由設為上述下限值以上，存在撥油墨性提高之傾向。藉由設為上述上限值以下，存在殘渣減少之傾向。When the photosensitive resin composition of the present invention contains the (D) photopolymerization initiator, as the formulation of the (D) photopolymerization initiator with respect to the (C) photopolymerizable compound in the photosensitive resin composition The ratio 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 still more preferably at least 15 parts by mass, with respect to 100 parts by mass of the (C) photopolymerizable compound, especially It is preferably at least 20 parts by mass, more preferably at most 200 parts by mass, more preferably at most 100 parts by mass, further preferably at most 50 parts by mass, and particularly preferably at most 30 parts by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 1-200 parts by mass, more preferably 5-200 parts by mass, still more preferably 10-100 parts by mass, still more preferably 15-50 parts by mass, particularly preferably 20-30 parts by 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.

[1-1-5](E)著色劑  本發明之感光性樹脂組合物可以使阻隔壁著色為目的而含有(E)著色劑。作為(E)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，就耐久性之觀點而言，較佳為使用顏料。[1-1-5] (E) Colorant The photosensitive resin composition of the present invention may contain the (E) colorant for the purpose of coloring the barrier ribs. As (E) 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一種，亦可為兩種以上。尤其就於可見光區域內均勻地遮光之觀點而言，較佳為兩種以上。  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，就控制感光性樹脂組合物之透過波長，有效率地使之硬化之觀點而言，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，所謂有機著色顏料係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 the colorant may be one kind, or two or more kinds. In particular, two or more are preferable from the viewpoint of uniformly shielding light in the visible light region. The type of pigment that can be used as (E) colorant 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. Examples of organic pigments include organic colored pigments and organic black pigments. Here, the organic colored pigment refers to 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.

有機顏料中，就紫外線吸收性之觀點而言，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，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 organic colored pigments from the viewpoint of ultraviolet absorbing properties. One type of organic coloring pigment can be used alone, or two or more types can be used in combination. In particular, when 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、喹吖啶酮系、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」等用語係指染料索引(C.I.)。The chemical structures of these organic pigments are not particularly limited, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxin-based, anion-based Danthrelin series, perylene series. 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，就遮光性、分散性之觀點而言，較佳可例舉：C.I.顏料紅48：1、122、149、168、177、179、194、202、206、207、209、224、242、254，進而較佳可例舉：C.I.顏料紅177、209、224、254。  再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料紅177、254、272，於以紫外線使感光性樹脂組合物硬化之情形時，作為紅色顏料，較佳為使用紫外線吸收率較低者，就該觀點而言，更佳為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 light-shielding properties and dispersibility, preferred examples include: C.I. 254, and more preferably: C.I. Pigment Red 177, 209, 224, 254. Furthermore, it is preferable to use C.I. Pigment Red 177, 254, and 272 in terms of dispersibility or light-shielding properties. When the photosensitive resin composition is cured by ultraviolet rays, it is preferable to use ultraviolet rays as a red pigment. Those with lower absorption rate are more preferably C.I. Pigment Red 254 and 272 from this point of view.

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，就分散性或遮光性之觀點而言，較佳為使用C.I.顏料橙13、43、64、72，於以紫外線使感光性樹脂組合物硬化之情形時，作為橙色顏料，較佳為紫外線吸收率較低者，就該觀點而言，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. When the photosensitive resin composition is cured by ultraviolet rays, ultraviolet rays are preferable as orange pigments. Those with lower absorption rate are more preferably 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，就遮光性之觀點而言，較佳可例舉：C.I.顏料藍15、15：1、15：2、15：3、15：4、15：6、60，進而較佳可例舉：C.I.顏料藍15：6。  再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料藍15：6、16、60，於以紫外線使感光性樹脂組合物硬化之情形時，作為藍色顏料，較佳為使用紫外線吸收率較低者，就該觀點而言，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, preferred examples include: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60, and more preferred examples include: 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 the photosensitive resin composition is hardened by ultraviolet rays, it is preferable as a blue pigment. From this point of view, it is more preferable to use C.I. Pigment Blue 60 in order to use one with a lower ultraviolet absorption rate.

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，就遮光性之觀點而言，較佳可例舉：C.I.顏料紫19、23，進而較佳可例舉C.I.顏料紫23。  再者，就分散性或遮光性之方面而言，較佳為使用C.I.顏料紫23、29，於以紫外線使感光性樹脂組合物硬化之情形時，作為紫色顏料，較佳為使用紫外線吸收率較低者，就該觀點而言，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, from the viewpoint of light-shielding properties, C.I. Pigment Violet 19 and 23 are preferable, and C.I. Pigment Violet 23 is more preferable. Furthermore, it is preferable to use C.I. Pigment Violet 23 and 29 in terms of dispersibility or light-shielding properties, and when the photosensitive resin composition is hardened with ultraviolet rays, it is preferable to use ultraviolet absorption rate The lower one, from this point of view, it is more preferable to use C.I. Pigment Violet 29.

作為除紅色顏料、橙色顏料、藍色顏料、紫色顏料外可使用之有機著色顏料，例如可例舉：綠色顏料、黃色顏料。  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，較佳可例舉：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，較佳可例舉：C.I.顏料黃83、117、129、138、139、150、154、155、180、185，進而較佳可例舉：C.I.顏料黃83、138、139、150、180。Examples of usable organic coloring pigments other than red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments. 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, preferred examples include: C.I. Pigment Green 7, 36. 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, preferred examples include: C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, and more preferred examples include: C.I. Pigment Yellow 83, 138, 139, 150, and 180 .

該等之中，就遮光性或撥油墨性之觀點而言，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，就硬化性或撥油墨性之觀點而言，較佳為含有以下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、29 Among 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 Violet Pigments: C.I. Pigment Violet 23, 29

又，就遮光性之觀點而言，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、苝黑或下述通式(2)所表示之有機黑色顏料。其中，就遮光性、分散性之觀點而言，更佳為下述通式(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 organic black pigments include aniline black, perylene black, or organic black pigments represented by the following general formula (2). Among them, an organic black pigment represented by the following general 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。該等之中，就遮光性、分散性之觀點而言，可較佳地使用碳黑。In addition, inorganic pigments can also be used. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among them, carbon black can be preferably used from the viewpoint of light-shielding properties and dispersibility.

又，亦可使用白色顏料。作為白色顏料，例如可例舉：氧化鈦、鈦酸鍶、鈦酸鋇、氧化鋅、氧化鎂、氧化鋯、氧化鋁、硫酸鋇、二氧化矽、滑石、雲母、氫氧化鋁、矽酸鈣、矽酸鋁。該等之中，就散射性之觀點而言，較佳為氧化鈦。Moreover, a white pigment can also be used. Examples of white pigments include: titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate , Aluminum silicate. Among them, titanium oxide is preferable from the viewpoint of scattering properties.

使用顏料時，可併用公知之分散劑或分散助劑，以使該顏料不凝集而可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 be used together so that this pigment can exist stably in a photosensitive resin composition, without aggregating.

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(E)著色劑之含量，就製版性與色特性之觀點而言，於感光性樹脂組合物之全部固形物成分(100質量%)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。例如，較佳為0.01～60質量%，更佳為0.01～40質量%。  作為另一態樣，若於感光性樹脂組合物中含有(E)著色劑，則存在阻隔壁之硬化性下降，阻隔壁之撥液性下降，釋氣亦易於產生之傾向。故而，較理想的為感光性樹脂組合物中之(E)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。例如較佳為0.01～20質量%，更佳為0.01～10質量%。In the case where the photosensitive resin composition of the present invention contains (E) colorant, the content of (E) colorant is equal to the total solid content of the photosensitive resin composition from the viewpoint of plate making property and color characteristics. (100% by mass), preferably at most 60% by mass, more preferably at most 40% by mass. The lower limit is not particularly limited, but is preferably 0.01% by mass or more. For example, it is preferably 0.01 to 60% by mass, more preferably 0.01 to 40% by mass. As another aspect, if the (E) colorant is contained in the photosensitive resin composition, the curability of the barrier wall decreases, the liquid repellency of the barrier wall decreases, and outgassing tends to occur. Therefore, it is desirable that the content of the (E) coloring agent in the photosensitive resin composition be lower, for example, preferably less than 20% by mass, more preferably 10% by mass relative to the total solid content of the photosensitive resin composition %the following. For example, it is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass.

[1-1-7](F)鏈轉移劑  本發明之感光性樹脂組合物可含有(F)鏈轉移劑。藉由含有(F)鏈轉移劑，存在表面附近之氧阻礙等所導致之自由基失活得以改善，可提高表面硬化性，傾斜角變高之傾向。又，藉由提高表面硬化性，存在可抑制(A)共聚物及/或撥液劑之流出，易於將(A)共聚物及/或撥液劑固定於阻隔壁之表面附近，接觸角變高之傾向。  作為(F)鏈轉移劑，例如可例舉：含巰基之化合物或四氯化碳，就存在鏈轉移效果較高之傾向之方面而言，更佳為含巰基之化合物。對含巰基之化合物而言，S-H鍵結能較小，藉此易於產生斷鍵，易於產生鏈轉移反應，故而存在可提高表面硬化性之傾向。[1-1-7] (F) Chain transfer agent The photosensitive resin composition of the present invention may contain (F) a chain transfer agent. By containing the (F) chain transfer agent, there is a tendency to improve the free radical deactivation caused by the oxygen barrier near the surface, improve the surface hardening property, and increase the inclination angle. In addition, by improving the surface hardening property, it is possible to suppress the outflow of (A) copolymer and/or liquid-repelling agent, and it is easy to fix (A) copolymer and/or liquid-repelling agent near the surface of the barrier wall, and the contact angle becomes smaller. high tendency. As the (F) chain transfer agent, for example, a mercapto group-containing compound or carbon tetrachloride may be mentioned, and a mercapto group-containing compound is more preferable in terms of a tendency to have a higher chain transfer effect. For compounds containing mercapto groups, the S-H bonding energy is small, so bond breaking and chain transfer reactions are easy to occur, so there is a tendency to improve surface hardening.

鏈轉移劑中，就傾斜角、表面硬化性之觀點而言，較佳為具有芳香族環之含巰基之化合物、脂肪族系之含巰基之化合物。  作為脂肪族系之含巰基之化合物，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, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are preferable from the viewpoint of an inclination angle and surface hardening properties. Examples of aliphatic mercapto-containing compounds include butanediol bis(3-mercaptopropionate), butanediol bis(3-mercaptopropionate), butanediol bis(3-mercaptopropionate), Ethylene glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis(3- mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri( 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)。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), pentaerythritol tetrakis(3-mercaptobutyrate).

該等可單獨使用一種，亦可併用兩種以上。These may be used alone or in combination of two or more.

該等之中，就提高撥油墨性之觀點而言，較佳為組合選自由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，作為光聚合起始劑系統而使用，更佳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，就表面硬化性之觀點而言，較佳為季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)。Among them, from the viewpoint of improving the ink repellency, it is preferable to combine one or more kinds selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole. It is used as a photopolymerization initiator system with a photopolymerization initiator, more preferably in combination 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 properties, pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are preferable.

於本發明之感光性樹脂組合物含有(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(100質量%)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，進而更佳為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%，進而更佳為0.1～4質量%，尤佳為1～3質量%。藉由設為上述下限值以上，存在表面硬化性變高，撥液性變高之傾向。又，藉由設為上述上限值以下，存在易於形成所期望之圖案之傾向。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 in the total solid content (100% by mass) of the photosensitive resin composition % or more, more preferably at least 0.025% by mass, more preferably at least 0.05% by mass, even more preferably at least 0.1% by mass, especially preferably at least 1% by mass, more preferably at least 5% by mass, more preferably at least 5% by mass 4% by mass or less, 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 to 3% by 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, there exists a tendency to form a desired pattern easily by making it below the said upper limit.

作為(F)鏈轉移劑，作為併用具有芳香族環之含巰基之化合物與脂肪族系之含巰基之化合物時之其含量，相對於具有芳香族環之含巰基之化合物100質量份，脂肪族系之含巰基之化合物較佳為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，存在撥油墨性變高之傾向。又，藉由設為上述上限值以下，存在感度變高之傾向。(F) As the chain transfer agent, the content when the mercapto-group-containing compound having an aromatic ring and the mercapto-group-containing compound having an aliphatic system are used in combination is relative to 100 parts by mass of the mercapto-group-containing compound having an aromatic ring, and the aliphatic The mercapto group-containing compound is preferably at least 10 parts by mass, more preferably at least 50 parts by mass, more preferably at least 80 parts by mass, and preferably at most 400 parts by mass, more preferably at most 300 parts by mass, and further preferably at least 400 parts by mass. It is preferably at most 200 parts by mass, particularly preferably at most 150 parts by mass. 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含有(F)鏈轉移劑及(D)光聚合起始劑之情形時，作為(F)鏈轉移劑相對於感光性樹脂組合物中之(D)光聚合起始劑之調配比，相對於(D)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，進而更佳為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，進而更佳為20～200質量份，尤佳為20～150質量份。藉由設為上述下限值以上，存在表面硬化性變高，撥液性變高之傾向。又，藉由設為上述上限值以下，存在易於形成所期望之圖案之傾向。When the photosensitive resin composition of the present invention contains (F) chain transfer agent and (D) photopolymerization initiator, as (F) chain transfer agent relative to (D) photopolymerization in the photosensitive resin composition 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 (D) 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, particularly 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, even more preferably 20-200 parts by mass, especially 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, there exists a tendency to form a desired pattern easily by making it below the said upper limit.

[1-1-7](G)撥液劑  本發明之感光性樹脂組合物除(A)共聚物外，可進而含有(G)撥液劑。作為(G)撥液劑，較佳為具有交聯基之含氟原子之樹脂。認為藉由含有具有交聯基之含氟原子之樹脂，可對所獲得之阻隔壁之表面賦予撥油墨性，因此可使所得獲得之阻隔壁成為防止每個像素之混色者。[1-1-7] (G) Liquid-repellent agent The photosensitive resin composition of the present invention may further contain (G) liquid-repellent agent in addition to (A) copolymer. As (G) the liquid repellent, a fluorine atom-containing resin having a crosslinking group is preferred. It is considered that the resin containing a fluorine atom having a crosslinking group can impart ink repellency to the surface of the obtained barrier rib, 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，就抑制撥液劑向顯影液流出之觀點而言，較佳為乙烯性不飽和基。  認為藉由使用具有交聯基之撥液劑，對形成之塗佈膜曝光時，可加速其表面之交聯反應，撥液劑不易因顯影處理而流出，其結果，可使所獲得之阻隔壁成為顯示較高之撥油墨性者。As a crosslinking group, an epoxy group or an ethylenically unsaturated group is mentioned, for example, and an ethylenically unsaturated group is preferable from a viewpoint of suppressing the outflow of a liquid-repellent agent to a developing solution. It is believed that by using a liquid-repelling agent with a cross-linking group, when the formed coating film is exposed to light, the cross-linking reaction on the surface can be accelerated, and the liquid-repelling agent is not easy to flow out due to the development treatment. As a result, the obtained barrier The wall becomes the one that exhibits higher ink repellency.

又，作為含氟原子之樹脂之(G)撥液劑存在如下傾向：於阻隔壁之表面配向，發揮防止油墨之滲入或混色之作用。進而詳細而言，存在如下傾向：具有氟原子之基彈開油墨，發揮防止油墨越過阻隔壁而進入鄰接之區域從而導致油墨之滲入或混色之作用。In addition, the (G) liquid-repelling agent, which is a resin containing fluorine atoms, tends to be aligned on the surface of the barrier wall to prevent ink penetration or color mixing. More specifically, there is a tendency that the base having a fluorine atom bounces off the ink, and prevents the ink from entering the adjacent area beyond the barrier wall, thereby causing ink bleeding or color mixing.

具有交聯基之含氟原子之樹脂較佳為具有全氟烷基及全氟伸烷基醚鏈之任一者或兩者。藉由含有全氟烷基及全氟伸烷基醚鏈之任一者或兩者，存在如下傾向：含氟原子之樹脂更容易於阻隔壁之表面配向，顯示更高之撥油墨性，進一步防止油墨之滲入或混色。The fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By containing any one or both of perfluoroalkyl and perfluoroalkylene ether chains, there is a tendency that the resin containing fluorine atoms is more likely to be aligned on the surface of the barrier rib, showing higher ink repellency, and further Prevent ink seepage or color mixing.

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2價之基。 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之樹脂之具體例，例如可例舉：具有環氧基及全氟烷基之丙烯酸系共聚樹脂、具有環氧基及全氟伸烷基醚鏈之丙烯酸系共聚樹脂、具有乙烯性不飽和基及全氟烷基之丙烯酸系共聚樹脂、具有乙烯性不飽和基及全氟伸烷基醚鏈之丙烯酸系共聚樹脂、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，就撥油墨性之觀點而言，較佳為具有乙烯性不飽和基及全氟烷基之丙烯酸系共聚樹脂、具有乙烯性不飽和基及全氟伸烷基醚鏈之丙烯酸系共聚樹脂，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系共聚樹脂。Specific examples of fluorine-containing resins having crosslinking groups include, for example, acrylic copolymer resins having epoxy groups and perfluoroalkyl groups, acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains, Copolymer resin, acrylic copolymer resin with ethylenically unsaturated group and perfluoroalkyl group, acrylic copolymer resin with ethylenically unsaturated group and perfluoroalkyl ether chain, epoxy group and perfluoroalkyl group Epoxy (meth)acrylate resin, epoxy (meth)acrylate resin with epoxy group and perfluoroalkylene ether chain, epoxy (meth)acrylate resin with ethylenically unsaturated group and perfluoroalkyl group ) acrylate resins, epoxy (meth)acrylate resins with ethylenically unsaturated groups and perfluoroalkylene ether chains. Among them, from the viewpoint of ink repellency, acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkyl group, acrylic acid having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable. It is a copolymer resin, preferably an acrylic copolymer resin with ethylenically unsaturated groups and perfluoroalkylene ether chains.

作為該等具有交聯基之含氟原子之樹脂之市售品，可使用以DIC公司製造之「MEGAFAC(註冊商標，以下相同)F116」、「MEGAFAC F120」、「MEGAFAC F142D」、「MEGAFAC F144D」、「MEGAFAC F150」、「MEGAFAC F160」、「MEGAFAC F171」、「MEGAFAC F172」、「MEGAFAC F173」、「MEGAFAC F177」、「MEGAFAC F178A」、「MEGAFAC F178K」、「MEGAFAC F179」、「MEGAFAC F183」、「MEGAFAC F184」、「MEGAFAC F191」、「MEGAFAC F812」、「MEGAFAC F815」、「MEGAFAC F824」、「MEGAFAC F833」、「MEGAFAC RS101」、「MEGAFAC RS102」「MEGAFAC RS105」、「MEGAFAC RS201」、「MEGAFAC RS202」、「MEGAFAC RS301」、「MEGAFAC RS303」「MEGAFAC RS304」、「MEGAFAC RS401」、「MEGAFAC RS402」、「MEGAFAC RS501」、「MEGAFAC RS502」、「MEGAFAC RS-72-K」、「MEGAFAC RS-78」、「MEGAFAC RS-90」、「DEFENSA(註冊商標，以下相同)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，以下相同)S-382」、「Surflon SC-101」、「Surflon SC-102」、「Surflon SC-103」、「Surflon SC-104」、「Surflon SC-105」、「Surflon SC-106」等商品名市售之含氟有機化合物。  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系共聚樹脂，可較佳地使用「MEGAFAC RS-72-K」、「MEGAFAC RS-78」、「MEGAFAC RS-90」。As commercial products of such fluorine atom-containing resins having crosslinking groups, "MEGAFAC (registered trademark, the same hereinafter) F116", "MEGAFAC F120", "MEGAFAC F142D", "MEGAFAC F144D" manufactured by DIC Corporation can be used. ", "MEGAFAC F150", "MEGAFAC F160", "MEGAFAC F171", "MEGAFAC F172", "MEGAFAC F173", "MEGAFAC F177", "MEGAFAC F178A", "MEGAFAC F178K", "MEGAFAC F179", "MEGAFAC F183 ", "MEGAFAC F184", "MEGAFAC F191", "MEGAFAC F812", "MEGAFAC F815", "MEGAFAC F824", "MEGAFAC F833", "MEGAFAC RS101", "MEGAFAC RS102", "MEGAFAC RS105", "MEGAFAC RS201" , "MEGAFAC RS202", "MEGAFAC RS301", "MEGAFAC RS303", "MEGAFAC RS304", "MEGAFAC RS401", "MEGAFAC RS402", "MEGAFAC RS501", "MEGAFAC RS502", "MEGAFAC RS-72-K", " MEGAFAC RS-78", "MEGAFAC RS-90", "DEFENSA (registered trademark, the same below) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Fluorad FC430" manufactured by 3M Japan, "Fluorad FC431", "FC-4430", "FC4432", "AsahiGuard (registered trademark) AG710" manufactured by AGC Corporation, "Surflon (registered trademark, the same below) S-382", "Surflon SC-101", " Fluorine-containing organic compounds commercially available under trade names such as Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, and Surflon SC-106. Among them, "MEGAFAC RS-72-K", "MEGAFAC RS-78", "MEGAFAC RS-90 ".

具有交聯基之含氟原子之樹脂中之氟原子含有比率並無特別限制，於具有交聯基之含氟原子之樹脂(100質量%)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，進而更佳為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，存在可抑制向像素部之流出之傾向。藉由設為上述上限值以下，存在顯示較高之接觸角之傾向。The fluorine atom content ratio in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but it is preferably at least 5% by mass, more preferably 10% by mass, in the fluorine atom-containing resin having a crosslinking group (100% by mass). % by mass or more, more preferably at least 20% by mass, even 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-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, further preferably 20 to 35% by mass, and particularly preferably 25 to 35% by mass. There exists a tendency for the outflow to a pixel part to be suppressed by setting it as more than the said lower limit. There exists a tendency for a high contact angle to be shown by being below the said upper limit.

具有交聯基之含氟原子之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。就可抑制後烘烤所引起之流動性，抑制自阻隔壁之流出之方面而言，較佳為高分子量體。於為具有交聯基之含氟原子之樹脂高分子量體之情形時，具有交聯基之含氟原子之樹脂之數量平均分子量較佳為100以上，更佳為500以上，又，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-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 substance is preferable in terms of suppressing fluidity caused by post-baking and suppressing outflow from barrier ribs. 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 100 or more, more preferably 500 or more, and is preferably Less than 100000, more preferably less than 10000. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 100 to 100,000, more preferably 500 to 10,000.

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(100質量%)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，存在撥油墨性提高之傾向。藉由設為上述上限值以下，存在阻隔壁形成後將油墨塗佈於像素部時易於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. The total solid content (100% by mass) 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 3% by mass. mass % or less, and more preferably 2 mass % or less. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by 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, there exists a tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

於本發明之感光性樹脂組合物除(A)共聚物外亦含有具有交聯基之含氟原子之樹脂之情形時，本發明之感光性樹脂組合物中之具有交聯基之含氟原子之樹脂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(100質量%)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，存在撥油墨性提高之傾向。藉由設為上述上限值以下，存在阻隔壁形成後將油墨塗佈於像素部時易於獲得均勻之塗膜之傾向。In the case where the photosensitive resin composition of the present invention contains a fluorine-containing resin having a crosslinking group in addition to the (A) copolymer, the fluorine-containing atom having a crosslinking group in the photosensitive resin composition of the present invention The content ratio of the resin is not particularly limited, but it is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, and still more preferably 0.5% by mass in the total solid content (100% by mass) of the photosensitive resin composition The above, and more preferably at most 5% by mass, more preferably at most 3% by mass, further preferably at most 2% by mass. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by 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, there exists a tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

[1-1-8]塗佈性提昇劑、顯影改良劑  本發明之感光性樹脂組合物為提高塗佈性或顯影溶解性，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。  界面活性劑可以感光性樹脂組合物之作為塗佈液之塗佈性、及塗佈膜之顯影性之提昇等為目的而使用，其中，較佳為氟系界面活性劑或聚矽氧系界面活性劑。  尤其，就顯影時存在自未曝光部去除感光性樹脂組合物之殘渣之作用，又，具有表現潤濕性之功能的方面而言，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 The photosensitive resin composition of the present invention may contain a coatability enhancer or a development improver in order to improve coatability or development solubility. 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 photosensitive resin composition as a coating solution and the development of the coating film, among which fluorine-based surfactants or polysiloxane-based surfactants are preferred. active agent. In particular, silicone-based surfactants are preferred because they have the effect of removing residues of the photosensitive resin composition from unexposed areas during development and also have the function of expressing wettability, and more preferably Polyether modified polysiloxane surfactant.

作為氟系界面活性劑，適合的為於末端、主鏈及側鏈之至少任一部位具有氟烷基或氟伸烷基之化合物。具體可例舉：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基醚、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「MEGAFAC F470」、「MEGAFAC F475」、「MEGAFAC F554」、「MEGAFAC F559」、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 a terminal, a main chain, and a side chain is suitable. Specific examples include: 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethyl Glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis(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-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Examples of such commercially available products include "BM-1000" and "BM-1100" manufactured by BM Chemie, "MEGAFAC F470", "MEGAFAC F475", "MEGAFAC F554" and "MEGAFAC F554" manufactured by DIC Corporation. MEGAFAC F559", "FC430" manufactured by 3M Japan Corporation, and "DFX-18" manufactured by NEOS Corporation.

作為聚矽氧系界面活性劑，例如可例舉：Dow Corning Toray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，以下相同)323」、「BYK330」。  作為界面活性劑，可含有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-based surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032 Additive", "SH8400 ", "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 surfactants. active agent.

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、山梨糖醇脂肪酸酯類、聚氧乙烯山梨糖醇脂肪酸酯類。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，以下相同)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 Sugar alcohol fatty acid esters, polyoxyethylene sorbitol fatty acid esters. Examples of such commercially available products include polyoxyethylene-based surfactants such as "Emulgen (registered trademark, the same hereinafter) 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，進而較佳為特殊聚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，作為烷基硫酸酯鹽類，可例舉：花王公司製造之「Emal(註冊商標)10」等，作為烷基萘磺酸鹽類，可例舉：花王公司製造之「Pelex(註冊商標)NB-L」等，作為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，以下相同)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, as an alkyl sulfate ester salt, "Emal (registered trademark) 10" manufactured by Kao Corporation, etc., as an alkyl naphthalene sulfonate, for example: Kao Corporation "Pelex (registered trademark) NB-L" manufactured by Kao Corporation, "Homogenol (registered trademark, the same below) L-18", "Homogenol L-100 "wait.

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兩性界面活性劑，例如，作為烷胺鹽類，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，以下相同)24P」、「Quartamin 86W」。  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。作為該聚矽氧系界面活性劑/氟系界面活性劑之組合，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」之組合、BYK-Chemie公司製造之「BYK-300」或「BYK-330」/AGC SEIMI CHEMICAL公司製造之「S-393」之組合、BYK-Chemie公司製造之「BYK-300」或「BYK-330」/DIC公司製造之「F-554」或「F-559」之組合、Shin-Etsu Silicones公司製造之「KP340」/DIC公司製造之「F-478」或「F-475」之組合、Dow Corning Toray公司製造之「SH7PA」/Daikin公司製造之「DS-401」之組合、NUC公司製造之「L-77」/3M Japan公司製造之「FC4430」之組合。  作為顯影改良劑，例如亦可使用含有有機羧酸或其酐之公知之顯影改良劑。  於本發明之感光性樹脂組合物含有塗佈性提昇劑或顯影改良劑之情形時，塗佈性提昇劑或顯影改良劑之含量就感度之觀點而言，於感光性樹脂組合物之全部固形物成分(100質量%)中，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 cationic surfactant or amphoteric surfactant, for example, as alkylamine salt, "Acetamin (registered trademark) 24" manufactured by Kao Corporation, as quaternary ammonium salt, may be mentioned: Kao Corporation Manufactured "Quartamin (registered trademark, the same below) 24P" and "Quartamin 86W". 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. As a combination of the polysiloxane-based surfactant/fluorine-based surfactant, for example, "BYK-300" or "BYK-330" manufactured by BYK-Chemie/"DFX-18" manufactured by NEOS Combination of "BYK-300" or "BYK-330" manufactured by BYK-Chemie / "S-393" manufactured by AGC SEIMI CHEMICAL, "BYK-300" or "BYK- 330"/"F-554" or "F-559" manufactured by DIC Corporation, "KP340" manufactured by Shin-Etsu Silicones/"F-478" or "F-475" manufactured by DIC Corporation, A combination of "SH7PA" manufactured by Dow Corning Toray Co., Ltd./"DS-401" manufactured by Daikin Corporation, and a combination of "L-77" manufactured by NUC Corporation/"FC4430" manufactured by 3M Japan Co., Ltd. As the development improving agent, for example, a known development improving agent containing an organic carboxylic acid or an anhydride thereof can be used. When the photosensitive resin composition of the present invention contains a coatability enhancer or a development improver, the content of the coatability enhancer or developm Among the material components (100% by mass), each is 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可含有紫外線吸收劑。紫外線吸收劑係以如下目的而添加者：藉由利用紫外線吸收劑吸收曝光中所使用之光源之特定之波長，而控制光硬化分佈。藉由含有紫外線吸收劑，存在如下傾向：獲得改善顯影後之傾斜角形狀、或減少顯影後非曝光部剩餘之殘渣等效果。作為紫外線吸收劑，就阻礙光聚合起始劑所引起之光吸收之觀點而言，例如可使用於波長250 nm至400 nm之間具有吸收極大之化合物。  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、肉桂酸衍生物、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。[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 the distribution of photohardening by absorbing the specific wavelength of the light source used for exposure by the ultraviolet absorber. By containing an ultraviolet absorber, there exists a tendency to acquire effects, such as improvement of the off-angle shape after image development, and reduction of the residue remaining in the non-exposed part after image development. As the ultraviolet absorber, from the viewpoint of inhibiting light absorption by the photopolymerization initiator, for example, a compound having a maximum absorption 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.

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-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯與3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸2-乙基己酯之混合物、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，就傾斜角與曝光感度之觀點而言，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。Examples of benzotriazole-based compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H -Benzotriazole, 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]octyl propionate and 3-[3- A mixture of 2-ethylhexyl tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propanoate, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro Benzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl) benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl) benzo Triazole, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] heptyl propionate, 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, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H- Benzotriazol-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] is preferable from the viewpoint of inclination angle and exposure sensitivity Heptyl propionate, 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，以下相同)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，以下相同)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，以下相同)100、Tomisorb600(API Corporation公司製造)、SEESORB(註冊商標，以下相同)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, SUMISORB 250, SUMISORB 300, SUMISORB 340, SUMISORB 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( Seonghoku Chemical Industry Co., Ltd.), TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF Corporation), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EV ERSORB74, 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)-1,3,5-三𠯤與縮水甘油酸(2-乙基己基)酯之反應產物、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，就傾斜角與曝光感度之觀點而言，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-trisalpine and glycidyl acid (2 -Ethylhexyl) ester reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5- Three 𠯤. Among them, a hydroxyphenyl trisulfone compound is preferable from the viewpoint of an inclination 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(API Corporation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；肉桂酸2-乙基己酯、對甲氧基肉桂酸2-乙基己酯、甲氧基肉桂酸異丙酯、甲氧基肉桂酸異戊酯等肉桂酸衍生物；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、氰基丙烯酸二苯酯系染料、三𠯤系染料、對胺基苯甲酸系染料等染料。該等之中，就曝光感度之觀點而言，較佳為使用肉桂酸衍生物、萘衍生物，尤佳為使用肉桂酸衍生物。Examples of other ultraviolet absorbers include: 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 , SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Shipro Kasei) and other benzophenone compounds; SUMISORB400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamate, Cinnamic acid derivatives such as 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthol, β-naphthol, α-naphthol Methyl 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 hydroxyanthracene; azo-based dyes, benzophenone-based dyes, aminoketone-based dyes, quinoline-based dyes, anthraquinone-based dyes, diphenyl cyanoacrylate-based dyes, and trioxane-based dyes , p-aminobenzoic acid dyes and other dyes. Among them, it is preferable to use a cinnamic acid derivative and a naphthalene derivative, and it is particularly preferable to use a cinnamic acid derivative from the viewpoint of exposure sensitivity.

於本發明之感光性樹脂組合物含有紫外線吸收劑之情形時，感光性樹脂組合物中之紫外線吸收劑之含量於感光性樹脂組合物之全部固形物成分(100質量%)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，進而更佳為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%，進而更佳為0.5～5質量%，尤佳為1～3質量%。藉由設為上述下限值以上，存在傾斜角變大之傾向。又，藉由設為上述上限值以下，存在成為高感度之傾向。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 in the total solid content (100% by mass) of the photosensitive resin composition. 0.01 mass % or more, more preferably 0.05 mass % or more, more preferably 0.1 mass % or more, still more preferably 0.5 mass % or more, especially preferably 1 mass % or more, and more preferably 15 mass % or less, more preferably Preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less, Most preferably, it is 3 mass % or less. The above-mentioned 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 %, especially Preferably, it is 1 to 3% by mass. There exists a tendency for an inclination angle to become large by setting it as more than the said lower limit. 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含有(D)光聚合起始劑及紫外線吸收劑之情形時，作為紫外線吸收劑相對於(D)光聚合起始劑之調配比，相對於(D)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，進而更佳為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，存在傾斜角變大之傾向。又，藉由設為上述上限值以下，存在成為高感度之傾向。In the case where the photosensitive resin composition of the present invention contains (D) photopolymerization initiator and ultraviolet absorber, as the compounding ratio of ultraviolet absorber to (D) photopolymerization initiator, relative to (D) light 100 parts by mass of a polymerization initiator, preferably more than 1 part by mass, more preferably 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, Moreover, it is preferably at most 500 parts by mass, more preferably at most 300 parts by mass, still more preferably at most 200 parts by mass, particularly preferably at most 150 parts by mass. 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. There exists a tendency for an inclination angle to become large by setting it as more than the said lower limit. 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可含有聚合抑制劑。認為藉由含有聚合抑制劑，可阻礙自由基聚合，因此可使所獲得之阻隔壁之傾斜角變大。  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，就聚合抑制能力之觀點而言，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 can be inhibited by containing a polymerization inhibitor, so that the inclination angle of the obtained barrier ribs can be increased. Examples of polymerization inhibitors include: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, 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，製造(B)鹼可溶性樹脂時，有時於樹脂中含有聚合抑制劑，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添加除樹脂中所含之聚合抑制劑之外的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 producing (B) alkali-soluble resin, a polymerization inhibitor is sometimes contained in the resin, which can be used as the polymerization inhibitor contained in the photosensitive resin composition of the present invention, and can also be used in the photosensitive resin composition The same or different polymerization inhibitors other than those contained in the resin are added during production.

於本發明之感光性樹脂組合物含有聚合抑制劑之情形時，感光性樹脂組合物中之聚合抑制劑之含量於感光性樹脂組合物之全部固形物成分(100質量%)中，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，存在可使傾斜角變高之傾向。又，藉由設為上述上限值以下，存在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 in the total solid content (100% by mass) of the photosensitive resin composition. 0.0005 mass % or more, more preferably 0.001 mass % or more, more preferably 0.01 mass % or more, and preferably 0.3 mass % or less, more preferably 0.2 mass % or less, further preferably 0.1 mass % or less. 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 an inclination angle to become 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改善與基板之密接性，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。就提高密接性之觀點而言，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含有矽烷偶合劑之情形時，矽烷偶合劑之含量就密接性之觀點而言，於感光性樹脂組合物之全部固形物成分(100質量%)中，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 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, the content of the silane coupling agent is preferably in the total solid content (100% by mass) of the photosensitive resin composition from the viewpoint of adhesion. It is 20 mass % or less, More preferably, it is 15 mass % or less.

[1-1-12]磷酸系密接提昇劑  本發明之感光性樹脂組合物為改善與基板之密接性，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 The photosensitive resin composition of the present invention may contain a phosphoric acid-based adhesion enhancer in order to improve the adhesion with the substrate. 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

於上述通式(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 above general 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(100質量%)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，存在與基板之密接性提高之傾向。又，藉由設為上述上限值以下，存在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 (100% by mass) of the photosensitive resin composition , more preferably at least 0.2% by mass, more preferably at least 0.3% by mass, and more preferably at most 5% by mass, more preferably at most 3% by mass, further preferably at most 1% by mass. 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, there exists a tendency for surface hardening property 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，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；環己醇乙酸酯等乙酸烷基酯類；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、雙戊烯、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 acid esters and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, diisopropyl ether, Butyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diiso Propyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentyl ketone Ketones such as ketones; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl Amyl 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; Alicyclic hydrocarbons such as hexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, Ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, Methyl Isobutyrate, Ethyl Octanoate, Butyl Stearate, Ethyl Benzoate, Methyl 3-Ethoxypropionate, Ethyl 3-Ethoxypropionate, Methyl 3-Methoxypropionate , 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3-methoxy butyl propionate, γ-butyrolactone and other chain or cyclic esters; 3-methoxy Alkoxycarboxylic acids such as propionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile : Tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc.

作為屬於上述之市售之溶劑，例如可使用：礦油精(mineral sprit)、Varsol#2、Apco#18 Solvent、Apco稀釋劑、Socal Solvent No.1及No.2、Solvesso#150、Shell TS28 Solvent、卡必醇(Carbitol)、乙基卡必醇(Ethyl Carbitol)、丁基卡必醇(Butyl Carbitol)、甲基賽路蘇(Methyl Cellosolve)、乙基賽路蘇(Ethyl Cellosolve)、乙酸乙基賽路蘇(Ethyl Cellosolve Acetate)、乙酸甲基賽路蘇(Methyl Cellosolve Acetate)、二乙二醇二甲醚(diglyme)(均為商品名)。As the above-mentioned commercially available solvents, for example, mineral spirits (mineral sprit), Varsol#2, Apco#18 Solvent, Apco thinner, Socal Solvent No.1 and No.2, Solvesso#150, Shell TS28 can be used Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Acetic Acid Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, diglyme (all trade names).

溶劑可溶解或分散感光性樹脂組合物中之各成分，根據本發明之感光性樹脂組合物之使用方法而選擇，就塗佈性之觀點而言，較佳為大氣壓下(1013.25 hPa)下之沸點為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 it is selected according to the usage method of the photosensitive resin composition of the present invention. From the viewpoint of coatability, it is preferably under atmospheric pressure (1013.25 hPa) Those with a boiling point of 60 to 280°C, more preferably 70 to 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成為較佳為10質量%以上，更佳為15質量%以上，進而較佳為18質量%以上，又，較佳為90質量%以下，更佳為50質量%以下，進而較佳為40質量%以下，尤佳為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，存在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，存在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% by mass of the total solid content in the photosensitive resin composition. or less, more preferably 50% by mass or less, further preferably 40% by mass or less, particularly preferably 30% by mass or less. 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 also 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以攪拌機混合上述各成分而製備。再者，可以製備之感光性樹脂組合物成為均勻者之方式，例如使用膜濾器進行過濾。[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, the photosensitive resin composition that can be prepared can be made uniform, for example, by filtering using a membrane filter.

[2]硬化物、阻隔壁及其形成方法  本發明之感光性樹脂組合物可較佳地用於形成阻隔壁，尤其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所得之硬化物、或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而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：包括將感光性樹脂組合物塗佈於基板上從而形成感光性樹脂組合物層之塗佈步驟、及將感光性樹脂組合物層曝光之曝光步驟的方法。作為此種阻隔壁之形成方法之具體例，可例舉：光微影法。[2] Cured product, barrier rib and method for forming the same The photosensitive resin composition of the present invention can be preferably used to form barrier ribs, especially barrier ribs for dividing the organic layer (light-emitting portion) of an organic electroluminescent device. The barrier rib of the present invention includes a cured product obtained by curing the photosensitive resin composition of the present invention, or a cured product obtained by curing the photosensitive resin composition of the present invention. The method for forming barrier ribs using the photosensitive resin composition of the present invention is not particularly limited, and a previously known method can be used. As a method for forming a barrier rib, for example, a method including a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer to light may be mentioned. method. As a specific example of the formation method of such a barrier rib, the photolithography method is mentioned.

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區域之整個面，形成感光性樹脂組合物層。將所形成之感光性樹脂組合物層根據特定之阻隔壁之圖案進行曝光後，對經曝光之感光性樹脂組合物層進行顯影，從而於基板上形成阻隔壁。In the photolithography method, the photosensitive resin composition is applied to the entire surface of the region where the barrier ribs are to be formed on the substrate to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer according to a specific pattern of barrier ribs, the exposed photosensitive resin composition layer is developed to form barrier ribs on the substrate.

阻隔壁之形成中所使用之基板並無特別限定，可根據使用形成阻隔壁之基板而製造之有機電致發光元件之種類而適宜選擇。作為適宜之基板之材料，可例舉：玻璃或各種樹脂材料。作為樹脂材料之具體例，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)丙烯酸樹脂；聚碸；聚醯亞胺。  該等基板之材料之中，就耐熱性優異之方面而言，較佳為玻璃及聚醯亞胺。又，根據所製造之有機電致發光元件之種類，可於形成阻隔壁之基板之表面預先設置ITO(Indium Tin Oxides，氧化銦錫)或ZnO等透明電極層。The substrate used for the formation of the barrier ribs is not particularly limited, and can be appropriately selected according to the type of organic electroluminescent element manufactured using the substrate on which the barrier ribs are formed. As a material of a suitable board|substrate, glass and various resin materials are mentioned, for example. Specific examples of resin materials include 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. In addition, according to the type of organic electroluminescent element to be manufactured, a transparent electrode layer such as ITO (Indium Tin Oxides, indium tin oxide) or ZnO can be pre-set on the surface of the substrate forming the barrier rib.

於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，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，於欲形成阻隔壁之基板上塗佈感光性樹脂組合物，視需要，藉由乾燥而去除溶劑，從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, contact transfer coating devices such as roll coaters, reverse coaters, and bar coaters are used Or a non-contact coating device such as a spin coater (rotary coating device), a curtain type flat coater, etc., to coat the photosensitive resin composition on the substrate to form the barrier wall, 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，以乾燥膜厚成為較佳為0.5 μm～30 μm，更佳為1 μm～15 μm，進而較佳為1 μm～5 μm之方式進行塗佈。重要的是乾燥膜厚或最終形成之阻隔壁之高度於基板全域內均勻。不均越小，越可抑制顯示裝置所產生之不均缺陷。The amount of coating varies depending on the application. For example, in the case of a barrier wall, the dry film thickness is preferably 0.5 μm to 30 μm, more preferably 1 μm to 15 μm, and more preferably 1 μm to 5 μm way of coating. It is important that the dry film thickness or the final height of the barrier ribs be uniform over the entire area of the substrate. The smaller the unevenness, the more the unevenness defects generated in the display device can be suppressed.

將感光性樹脂組合物供給至基板上後之乾燥較佳為利用使用有加熱板、IR(Infrared，紅外)烘箱、對流烘箱之乾燥方法。可組合不提高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, infrared) oven, or a convection oven. It can be combined with the reduced-pressure drying method of drying in a reduced-pressure chamber without raising the temperature.

乾燥之條件可根據溶劑成分之種類、所使用之乾燥機之性能等而適宜選擇。乾燥時間係根據溶劑成分之種類、所使用之乾燥機之性能等，較佳為於40℃～130℃之溫度下、15秒～5分鐘之範圍內選擇，更佳為於50℃～110℃之溫度下、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 is based on the type of solvent components, the performance of the dryer used, etc., preferably at a temperature of 40°C to 130°C, within the range of 15 seconds to 5 minutes, more preferably at 50°C to 110°C Under the temperature, choose within the range of 30 seconds to 3 minutes.

繼而，於曝光步驟中，利用負型之遮罩，對感光性樹脂組合物照射紫外線、準分子光等活性能量線，將感光性樹脂組合物層根據阻隔壁之圖案而進行部分曝光。曝光中可使用高壓水銀燈、超高壓水銀燈、氙氣燈、碳弧燈等發出紫外線之光源。曝光量亦根據感光性樹脂組合物之組成而有所不同，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 light using a negative mask to partially expose the photosensitive resin composition layer according to the pattern of the barrier ribs. Light sources emitting ultraviolet rays such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps can be used for exposure. The exposure amount also varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 400 mJ/cm 2 , for example.

繼而，於顯影步驟中，以顯影液對根據阻隔壁之圖案而曝光之感光性樹脂組合物層進行顯影，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。作為顯影液之具體例，可例舉：二甲基苄胺、單乙醇胺、二乙醇胺、三乙醇胺等有機系之顯影液或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、四級銨鹽等之水溶液。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 according 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. Specific examples of developers include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. of aqueous solution. Moreover, you may add an antifoaming agent or surfactant to a developer.

其後，對顯影後之阻隔壁圖案實施後烘烤(熱硬化處理)而進行加熱硬化，藉此獲得阻隔壁。後烘烤較佳為於100～250℃下、15～60分鐘內進行。Thereafter, the barrier rib pattern was obtained by performing post-baking (thermosetting treatment) on the developed barrier rib pattern to heat-harden it. The post-baking is preferably performed at 100-250° C. within 15-60 minutes.

阻隔壁形成後，可進行以洗淨未曝光部為目的之洗淨處理。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。準分子光照射或UV照射中，藉由光照射，活性氧將附著於像素部之有機物分解而去除。After the barrier ribs are formed, a cleaning treatment for cleaning the unexposed portion may be performed. 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。  使用具備藉由以上說明之方法而製造之阻隔壁圖案之基板，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，較佳為藉由如下方式製造有機電致發光元件：藉由上述方法而於基板上形成阻隔壁之圖案後，於基板上之被阻隔壁包圍之區域內注入油墨而形成像素等有機層。  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。  作為底部發光型，例如以如下方式製作：於積層有透明電極之玻璃基板上形成阻隔壁，於被阻隔壁包圍之開口部積層電洞傳輸層、發光層、電子傳輸層、金屬電極層。作為頂部發光型，例如以如下方式製作：於積層有金屬電極層之玻璃基板上形成阻隔壁，於被阻隔壁包圍之開口部積層電子傳輸層、發光層、電洞傳輸層、透明電極層。[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 for forming the organic electroluminescent element is not particularly limited, and it is preferable to manufacture the organic electroluminescent element by the following method: after forming a pattern of barrier ribs on the substrate by the above method, the area on the substrate surrounded by barrier ribs Ink is injected into the area to form organic layers such as pixels. As the type of organic electroluminescent element, it can be exemplified: bottom emission type or top emission type. As a bottom emission type, for example, a barrier wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the barrier wall. As a top emission type, for example, a barrier rib is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the barrier rib.

於阻隔壁為裙狀底部形狀之情形時，有機層形成用之油墨於阻隔壁之下擺部分被彈開，故而存在被阻隔壁包圍之區域內未被有機層形成用之油墨充分覆蓋之情形。相對於此，藉由製為無裙狀底部之良好形狀，可使被阻隔壁包圍之區域內被有機層形成用之油墨充分覆蓋。藉此，例如可消除有機EL顯示元件中之暈光問題。When the barrier rib has a skirt-like bottom shape, the ink for forming the organic layer is bounced off at the hem portion of the barrier rib, so the area surrounded by the barrier rib may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by making it into a favorable shape without a skirt-like bottom, the area surrounded by a barrier rib can be fully covered with the ink for organic layer formation. Thereby, for example, the problem of halation in an organic EL display element can be eliminated.

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。有機溶劑只要可於油墨注入後自所形成之皮膜去除，則並無特別限定。作為有機溶劑，例如可例舉：甲苯、二甲苯、苯甲醚、對稱三甲苯、萘滿、環己苯、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，可於油墨中添加界面活性劑、抗氧化劑、黏度調整劑、紫外線吸收劑等。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 ink injection. Examples of organic solvents include toluene, xylene, anisole, trimethylbenzene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Ethanol, Isopropanol, Ethyl Acetate, Butyl Acetate, 3-Phenoxytoluene. In addition, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, and the like can be added to the ink.

作為於被阻隔壁包圍之區域內注入油墨之方法，就可容易地將少量之油墨注入特定之部位之方面而言，較佳為噴墨法。有機層之形成中所使用之油墨係根據所製造之有機電致發光元件之種類而適宜選擇。於藉由噴墨法注入油墨之情形時，作為油墨之黏度，只要可將油墨自噴墨頭良好地噴出，則並無特別限定，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而調整。As a method of injecting ink into a region surrounded by barrier walls, an inkjet method is preferable in that a small amount of ink can be easily injected into a specific portion. The ink used for the formation of the organic layer is appropriately selected according to the type of organic electroluminescent device 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, and more preferably 5 to 20 mPa·s. 10 mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content of the ink, changing the solvent, adding a viscosity modifier, etc.

再者，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。又，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。Furthermore, 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 . Also, quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101 may be used.

[4]含有發光性奈米結晶粒子之彩色濾光片  本發明之含有發光性奈米結晶粒子之彩色濾光片只要具備本發明之阻隔壁，則並無特別限定，可例舉：於被阻隔壁劃分之區域中形成有像素者。[4] Color filter containing luminescent nanocrystalline particles The color filter containing luminescent nanocrystalline particles of the present invention is not particularly limited as long as it has the barrier wall of the present invention. Examples include: Pixels are formed in the regions divided by the barrier ribs.

圖2係具備本發明之阻隔壁之彩色濾光片之一例之模式剖視圖。如圖2所示，彩色濾光片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以依據該順序重複之方式排列為格子狀。阻隔壁20設置於該等相鄰之像素間。換言之，該等相鄰之像素彼此被阻隔壁20劃分。Fig. 2 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. 2 , the color filter 100 includes a substrate 10 , barrier ribs 20 provided 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 grid pattern so as to repeat in this order. The barrier wall 20 is disposed between the adjacent pixels. In other words, the adjacent pixels are divided by the barrier ribs 20 .

紅色像素30中含有紅色發光性之奈米結晶粒子12，並且綠色像素40中含有綠色發光性之奈米結晶粒子11。藍色像素50係使來自光源之藍光透過之像素。The red pixel 30 contains red luminescent nano crystal particles 12 , and the green pixel 40 contains green luminescent nano crystal particles 11 . The blue pixel 50 is a pixel that transmits blue light from a light source.

該等奈米結晶粒子係吸收激發光而發出螢光或磷光之奈米尺寸之結晶體，例如係藉由穿透式電子顯微鏡或掃描式電子顯微鏡而測定之最大粒徑為100 nm以下之結晶體。These nanocrystalline particles 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.

發光性奈米結晶粒子係可藉由吸收特定波長之光而發出與所吸收之波長不同之波長之光(螢光或磷光)者，例如，紅色發光性之奈米結晶粒子12係發出於605～665 nm之範圍內具有發光峰值波長之光(紅光)者，綠色發光性之奈米結晶粒子11係發出於500～560 nm之範圍內具有發光峰值波長之光(綠光)者。Luminescent nano crystal particles 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 nano crystal particles 12 are emitted at 605 Those having light emission peak wavelengths (red light) in the range of ~665 nm, the green luminescent nano crystal particles 11 are those that have light emission peak wavelengths in the range of 500~560 nm (green light).

根據井型電位模型之薛定諤波動方程式之解，發光性奈米結晶粒子發出之光之波長(發光色)取決於發光性奈米結晶粒子之尺寸(例如粒徑)，但亦取決於發光性奈米結晶粒子所具有之能隙。故而，藉由變更所使用之發光性奈米結晶粒子之構成材料及尺寸，可選擇發光色。作為發光性奈米結晶粒子，可例舉量子點等。According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength (luminescent color) of the light emitted by the luminescent nanocrystalline particles depends on the size (such as particle diameter) of the luminescent nanocrystalline particles, but also depends on the luminescent nanocrystalline particles. The energy gap of rice crystal particles. Therefore, by changing the constituent material and size of the luminescent nano crystal particles used, the color of luminescence can be selected. As the luminescent nanocrystalline particles, quantum dots and the like may, for example, be mentioned.

含有發光性奈米結晶粒子之彩色濾光片之製造方法並無特別限定，可例舉如下方法：準備具備包含本發明之硬化物之阻隔壁之基板，於被阻隔壁劃分之區域中形成含有發光性奈米結晶粒子之層。形成含有發光性奈米結晶粒子之層之方法並無特別限定，例如可藉由如下方法而製造：藉由噴墨方式而使含有發光性奈米結晶粒子之油墨組合物選擇性地附著，藉由活性能量線之照射或加熱而使油墨組合物硬化。The method of manufacturing a color filter containing luminescent nanocrystalline particles is not particularly limited, and the following method is exemplified: preparing a substrate having a barrier rib containing the hardened product of the present invention, forming a substrate containing a barrier rib in a region divided by the barrier rib A layer of luminescent nanocrystalline particles. The method of forming the layer containing the luminescent nano crystal particles is not particularly limited, for example, it can be produced by the following method: the ink composition containing the luminescent nano crystal particles is selectively attached by an inkjet method, and by The ink composition is cured by irradiation with active energy rays or heating.

[5]圖像顯示裝置  本發明之圖像顯示裝置具備本發明之阻隔壁。  作為本發明之圖像顯示裝置，例如可例舉：包括本發明之有機電致發光元件之圖像顯示裝置。只要為包括有機電致發光元件者，則關於圖像顯示裝置之型式或結構並無特別限制，例如可使用主動驅動型有機電致發光元件並依據常法而組裝。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)中所記載之方法而形成本發明之圖像顯示裝置。例如，可組合發出白光之有機電致發光元件與彩色濾光片而使圖像顯示，亦可組合RGB等發光色不同之有機電致發光元件而使圖像顯示。[5] Image display device The image display device of the present invention includes the barrier rib of the present invention. As the image display device of the present invention, for example, an image display device including the organic electroluminescent element of the present invention can be cited. There are no particular limitations on the type or structure of the image display device as long as it includes an organic electroluminescent element. For example, an actively driven organic electroluminescent element can be used and assembled according to a conventional 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, written by Seishi Oma, Chihaya Adachi, and Hideyuki Murata at the time). For example, an organic electroluminescent element emitting white light and a color filter can be combined to display an image, or an organic electroluminescent element with different luminescent colors such as RGB can be combined to display an image.

又，作為本發明之圖像顯示裝置，例如可例舉：具備本發明之含有發光性奈米結晶粒子之彩色濾光片之圖像顯示裝置。  作為圖像顯示裝置之種類，可例舉：液晶顯示裝置或包括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、及具備於每個像素部控制自光源發出之藍光之電極之液晶層者。  另一方面，作為包括有機電致發光元件之圖像顯示裝置，可例舉：於與上述彩色濾光片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。具體可例舉：日本專利特開2019-87746號公報中記載之方式。  [實施例]Moreover, as the image display device of the present invention, for example, an image display device provided with the color filter containing the luminescent nanocrystal particles of the present invention may be mentioned. 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. On the other hand, as an image display device including an organic electroluminescent element, an organic electroluminescent element that emits blue light is arranged at a position corresponding to each pixel portion of the above-mentioned color filter. Specifically, for example: the method described in Japanese Patent Laid-Open No. 2019-87746. [Example]

以下，例舉具體之實施例說明本發明之感光性樹脂組合物，但本發明只要不超出其主旨，則不限定於以下之實施例。  以下之實施例及比較例中所使用之感光性樹脂組合物之構成成分如下所述。Hereinafter, the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless the gist is exceeded. The components of the photosensitive resin composition used in the following examples and comparative examples are as follows.

＜鹼可溶性樹脂-1＞  於以甲基丙烯酸二環戊酯/苯乙烯/甲基丙烯酸縮水甘油酯(莫耳比：0.30/0.10/0.60)為構成單體之共聚樹脂上，以相對於上述甲基丙烯酸縮水甘油酯為等量之量加成丙烯酸，進而以相對於上述共聚樹脂1莫耳為0.39莫耳之方式加成四氫鄰苯二甲酸酐，從而獲得鹼可溶性之丙烯酸系共聚樹脂。以GPC測定之聚苯乙烯換算之重量平均分子量(Mw)為9000，酸值為80 mgKOH/g，雙鍵當量為470 g/mol。<Alkali-soluble resin-1> On a copolymer resin composed of dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.30/0.10/0.60) Glycidyl methacrylate is the addition of acrylic acid in an equal amount, and then added tetrahydrophthalic anhydride in such a way that 0.39 mol is added to 1 mol of the above-mentioned copolymer resin, thereby obtaining an alkali-soluble acrylic copolymer resin . The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 9000, the acid value was 80 mgKOH/g, and the double bond equivalent was 470 g/mol.

＜鹼可溶性樹脂-2＞  於以甲基丙烯酸二環戊酯/苯乙烯/甲基丙烯酸縮水甘油酯(莫耳比：0.02/0.05/0.93)為構成單體之共聚樹脂上以相對於上述甲基丙烯酸縮水甘油酯為等量之量加成丙烯酸，進而以相對於上述共聚樹脂1莫耳為0.10莫耳之方式加成四氫鄰苯二甲酸酐，從而獲得鹼可溶性之丙烯酸系共聚樹脂。以GPC測定之聚苯乙烯換算之重量平均分子量(Mw)為7700，酸值為28.5 mgKOH/g，雙鍵當量為260 g/mol。＜Alkali-soluble resin-2＞ On a copolymer resin composed of dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) Acrylic acid was added to glycidyl acrylate in an equivalent amount, and tetrahydrophthalic anhydride was added in an amount of 0.10 mol to 1 mol of the above-mentioned copolymer resin to obtain an alkali-soluble acrylic copolymer resin. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 7700, the acid value was 28.5 mgKOH/g, and the double bond equivalent was 260 g/mol.

＜鹼可溶性樹脂-3＞  日本化藥公司製造之「ZCR-1642H」(重量平均分子量Mw＝6500，酸值＝98 mgKOH/g)。具有下述式(C2)所表示之部分結構。<Alkali-soluble resin-3> "ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 6500, acid value = 98 mgKOH/g). It has a partial structure represented by the following formula (C2).

[化39]

Figure 02_image077
[chem 39]
Figure 02_image077

式(C2)中，*表示鍵結鍵。In the formula (C2), * represents a bonding bond.

＜分散劑-1＞  BYK-Chemie公司製造之BYK-LPN21116<Dispersant-1> BYK-LPN21116 manufactured by BYK-Chemie

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

＜光聚合性化合物-1＞  DPHA：日本化藥公司製造之二季戊四醇六丙烯酸酯  ＜光聚合性化合物-2＞  TMP-A：共榮公司製造之三羥甲基丙烷三丙烯酸酯＜Photopolymerizable compound-1＞ DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. ＜Photopolymerizable compound-2＞ TMP-A: Trimethylolpropane triacrylate manufactured by Kyoei Co., Ltd.

＜光聚合起始劑-1＞  使用具有以下化學結構之化合物。<Photopolymerization Initiator-1> A compound having the following chemical structure was used.

[化40]

Figure 02_image079
[chemical 40]
Figure 02_image079

＜光聚合起始劑-2＞  使用具有以下化學結構之化合物。<Photopolymerization Initiator-2> A compound with the following chemical structure was used.

[化41]

Figure 02_image081
[chem 41]
Figure 02_image081

＜共聚物-1～7＞  (1)重量平均分子量(Mw)  依據下述條件之GPC測定共聚物之重量平均分子量。  機器：Tosoh公司製造之HLC-8320GPC，  管柱：Tosoh股份有限公司製造之「TSKgel SuperHZM-M＋HZM-M＋HZ2000」，  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/分鐘，  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。<Copolymer-1~7> (1) Weight average molecular weight (Mw) The weight average molecular weight of the copolymer was measured by GPC under the following conditions. Machine: HLC-8320GPC manufactured by Tosoh Corporation, Column: "TSKgel SuperHZM-M+HZM-M+HZ2000" manufactured by Tosoh Corporation, 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.

(2)構成單體、聚合起始劑、溶劑  HHMPMA：甲基丙烯酸2-[4-(2-羥基-2-甲基-1-側氧基丙基)苯氧基]乙酯  FMA：甲基丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯(大金工業股份有限公司製造之C6SFMA MONOMER)  GMA：甲基丙烯酸縮水甘油酯  HEMA：甲基丙烯酸2-羥基乙酯  MIBK：甲基異丁基酮  AMBN：2,2'-偶氮雙(2-甲基丁腈)(2) Constituent monomers, polymerization initiators, solvents HHMPMA: 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate FMA: methyl 3,3,4,4,5,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl acrylate (C6SFMA MONOMER manufactured by Daikin Industries, Ltd.) GMA: Methacrylic acid Glycidyl ester HEMA: 2-hydroxyethyl methacrylate MIBK: methyl isobutyl ketone AMBN: 2,2'-azobis(2-methylbutyronitrile)

(合成例1：甲基丙烯酸2-[4-(2-羥基-2-甲基-1-側氧基丙基)苯氧基]乙酯(HHMPMA)之合成)  減壓蒸餾甲基丙烯酸酐(東京化成工業股份有限公司製造)，將純度成為99.8%以上之餾份進行回收，獲得甲基丙烯酸酐之蒸餾物。減壓蒸餾係以於壓力30 pa下自室溫緩慢升溫至90℃之方法實施。  另外，將1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基丙酮(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。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)，攪拌12小時。  將所獲得之反應液以離子交換水500 mL洗淨3次後，濃縮有機相，蒸餾去除溶劑。將殘留物以管柱層析法(乙酸乙酯/己烷＝10/90(體積比))精製，獲得目標之化合物21.6 g(產率74%)。  藉由 1H-NMR分析，確認所獲得之化合物為HHMPMA。 1H 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)。 (Synthesis Example 1: Synthesis of 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate (HHMPMA)) Vacuum distillation of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), the fraction with a purity of 99.8% or more was recovered to obtain a distillate of methacrylic anhydride. The vacuum distillation was carried out by slowly raising the temperature from room temperature to 90°C under a pressure of 30 Pa. Separately, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) and triethylamine (Tokyo Kasei Kogyo Co., Ltd.) 30.4 g (0.3 mol) was dissolved in methylene chloride (Tokyo Kasei Kogyo Co., Ltd.) 500 mL. 23.1 g (0.15 mol) of the distillate of the above-mentioned methacrylic anhydride was added dropwise thereto at room temperature, and stirred for 12 hours. The obtained reaction solution was washed three times with 500 mL of ion-exchanged water, 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 analysis, it was confirmed that the obtained compound was HHMPMA. 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1-1：共聚物-1之製造)  於具備攪拌機、滴液漏斗、冷凝管及溫度計之燒瓶中加入PGMEA 28.55質量份、HHMPMA 5.70質量份、FMA 6.75質量份、HEMA 1.50質量份、GMA 1.05質量份，一邊攪拌一邊將內溫升溫至90℃。繼而，自滴液漏斗以4小時滴加PGMEA 44.53質量份、HHMPMA 13.30質量份、FMA 15.75質量份、HEMA 3.50質量份、GMA 2.45質量份、作為聚合起始劑之AMBN 0.20質量份之混合溶液。滴加結束後，每30分鐘投入AMBN 0.18質量份3次，進而於30分鐘後將內溫升溫至110℃，保持1.5小時。其後，將反應液冷卻至40℃，添加PGMEA 45.27質量份，獲得精製前之共聚物-1之PGMEA溶液。  精製前之共聚物-1之PGMEA溶液之固形物成分(不揮發分)為30質量%。(Manufacturing Example 1-1: Manufacture of Copolymer-1) Add 28.55 parts by mass of PGMEA, 5.70 parts by mass of HHMPMA, 6.75 parts by mass of FMA, 1.50 parts by mass of HEMA, 1.05 parts by mass of GMA was added, and the internal temperature was raised to 90° C. while stirring. Then, a mixed solution of 44.53 parts by mass of PGMEA, 13.30 parts by mass of HHMPMA, 15.75 parts by mass of FMA, 3.50 parts by mass of HEMA, 2.45 parts by mass of GMA, and 0.20 parts by mass of AMBN as a polymerization initiator was added dropwise from the dropping funnel over 4 hours. After completion of the dropwise addition, 0.18 parts by mass of AMBN was injected three times every 30 minutes, and the internal temperature was raised to 110° C. after 30 minutes, and maintained for 1.5 hours. Then, the reaction liquid was cooled to 40 degreeC, 45.27 mass parts of PGMEA were added, and the PGMEA solution of the copolymer-1 before purification was obtained. The solid content (non-volatile matter) of the PGMEA solution of the copolymer-1 before purification was 30% by mass.

(製造例1-2：共聚物-1之精製)  於具備攪拌機、滴液漏斗、冷凝管及溫度計之燒瓶中投入己烷300質量份，一邊攪拌一邊將內溫調整為25℃。繼而，於滴液漏斗中投入製造例1中製造之共聚物-1之PGMEA溶液30質量份、MIBK 30質量份，進行攪拌直至均勻，以30分鐘滴加。滴加結束後，進而進行2小時攪拌後停止。攪拌停止後，確認於燒杯之底面存在共聚物-1之沈澱物。使用濾紙將共聚物-1之沈澱物回收，於40℃下減壓乾燥6小時後，以PGMEA將固形物成分(不揮發分)製備為15質量%，獲得重量平均分子量102600之精製後之共聚物-1之PGMEA溶液。共聚物-1之每1 g之活性基之含量為1.28(mmol/g)。(Manufacturing Example 1-2: Purification of Copolymer-1) 300 parts by mass of hexane were put into a flask equipped with a stirrer, dropping funnel, condenser and thermometer, and the internal temperature was adjusted to 25°C while stirring. Then, 30 parts by mass of the PGMEA solution of the copolymer-1 produced in Production Example 1 and 30 parts by mass of MIBK were put into the dropping funnel, stirred until uniform, and added dropwise over 30 minutes. After completion of the dropwise addition, stirring was further performed for 2 hours, and then stopped. After the stirring was stopped, it was confirmed that there was a precipitate of copolymer-1 on the bottom surface of the beaker. The precipitate of Copolymer-1 was collected using filter paper, dried under reduced pressure at 40°C for 6 hours, and the solid content (non-volatile matter) was prepared to 15% by mass with PGMEA to obtain a purified copolymer with a weight average molecular weight of 102,600. PGMEA solution of substance-1. The active group content per 1 g of copolymer-1 was 1.28 (mmol/g).

(共聚物-2～5之製造、精製)  進行與共聚物-1相同之操作，以成為表1所記載之構成單體質量比之方式進行製造、精製，獲得共聚物-2～5之PGMEA溶液。(Manufacture and purification of copolymers-2 to 5) The same operation as that of copolymer-1 was carried out to obtain the PGMEA of copolymers-2 to 5 in such a manner that the mass ratio of the constituent monomers was recorded in Table 1. solution.

(比較製造例1-1：共聚物-6之製造)  於具備攪拌機、滴液漏斗、冷凝管及溫度計之燒瓶中加入PGMEA 28.45質量份、HHMPMA 6.53質量份、FMA 6.75質量份、HEMA 1.73質量份，一邊攪拌一邊將內溫升溫至90℃。繼而，自滴液漏斗以4小時滴加PGMEA 44.63質量份、HHMPMA 15.23質量份、FMA 15.75質量份、HEMA 4.03質量份、作為聚合起始劑之AMBN 0.20質量份之混合溶液。滴加結束後，每30分鐘投入AMBN 0.18質量份3次，進而於30分鐘後將內溫升溫至110℃，保持1.5小時。其後，將反應液冷卻至40℃，添加PGMEA 45.27質量份，獲得精製前之共聚物-6之PGMEA溶液。  精製前之共聚物-6之PGMEA溶液之固形物成分(不揮發分)為30質量%。(Comparative Manufacturing Example 1-1: Manufacture of Copolymer-6) Add 28.45 parts by mass of PGMEA, 6.53 parts by mass of HHMPMA, 6.75 parts by mass of FMA, and 1.73 parts by mass of HEMA into a flask equipped with a stirrer, dropping funnel, condenser and thermometer , while stirring, the internal temperature was raised to 90°C. Then, a mixed solution of 44.63 parts by mass of PGMEA, 15.23 parts by mass of HHMPMA, 15.75 parts by mass of FMA, 4.03 parts by mass of HEMA, and 0.20 parts by mass of AMBN as a polymerization initiator was added dropwise from the dropping funnel over 4 hours. After completion of the dropwise addition, 0.18 parts by mass of AMBN was injected three times every 30 minutes, and the internal temperature was raised to 110° C. after 30 minutes, and maintained for 1.5 hours. Thereafter, the reaction liquid was cooled to 40° C., and 45.27 parts by mass of PGMEA was added to obtain a PGMEA solution of Copolymer-6 before purification. The solid content (non-volatile matter) of the PGMEA solution of the copolymer-6 before refining was 30% by mass.

(比較製造例1-2：共聚物-6之精製)  除將所使用之聚合溶液設為共聚物-6之PGMEA溶液以外，以與製造例1-2相同之方式，獲得重量平均分子量94800之精製後之共聚物-6之PGMEA溶液聚合物溶液。共聚物-6之每1 g之活性基之含量為1.47(mmol/g)。(Comparative Manufacturing Example 1-2: Purification of Copolymer-6) Except that the polymerization solution used is set as the PGMEA solution of Copolymer-6, in the same manner as in Manufacturing Example 1-2, a compound with a weight average molecular weight of 94800 was obtained. PGMEA solution polymer solution of the refined copolymer-6. The active group content per 1 g of copolymer-6 was 1.47 (mmol/g).

(比較製造例2-1：共聚物-7之製造)  於具備攪拌機、滴液漏斗、冷凝管及溫度計之燒瓶中加入PGMEA 29.24質量份、FMA 6.75質量份、HEMA 4.86質量份、GMA 3.39質量份，一邊攪拌一邊將內溫升溫至90℃。繼而，自滴液漏斗以4小時滴加PGMEA 43.85質量份、FMA 15.75質量份、HEMA 11.34質量份、GMA 7.91質量份、作為聚合起始劑之AMBN 0.20質量份之混合溶液。滴加結束後，每30分鐘投入AMBN 0.18質量份3次，進而於30分鐘後將內溫升溫至110℃，保持1.5小時。其後，將反應液冷卻至40℃，添加PGMEA 45.27質量份，獲得精製前之共聚物-7之PGMEA溶液。  共聚物-7之PGMEA溶液之固形物成分(不揮發分)為30質量%。(Comparative Manufacturing Example 2-1: Manufacture of Copolymer-7) Add 29.24 parts by mass of PGMEA, 6.75 parts by mass of FMA, 4.86 parts by mass of HEMA, and 3.39 parts by mass of GMA into a flask equipped with a stirrer, dropping funnel, condenser and thermometer , while stirring, the internal temperature was raised to 90°C. Then, a mixed solution of 43.85 parts by mass of PGMEA, 15.75 parts by mass of FMA, 11.34 parts by mass of HEMA, 7.91 parts by mass of GMA, and 0.20 parts by mass of AMBN as a polymerization initiator was added dropwise from the dropping funnel over 4 hours. After completion of the dropwise addition, 0.18 parts by mass of AMBN was injected three times every 30 minutes, and the internal temperature was raised to 110° C. after 30 minutes, and maintained for 1.5 hours. Thereafter, the reaction liquid was cooled to 40° C., and 45.27 parts by mass of PGMEA was added to obtain a PGMEA solution of Copolymer-7 before purification. The solid content (non-volatile matter) of the PGMEA solution of copolymer-7 was 30% by mass.

(製造例2-2：共聚物-7之精製)  除將所使用之聚合溶液設為精製前之共聚物-7之PGMEA溶液以外，以與製造例1-2相同之方式，獲得重量平均分子量103900之精製後之共聚物-7之PGMEA溶液。共聚物-7之每1 g之活性基之含量為0(mmol/g)。(Manufacturing Example 2-2: Purification of Copolymer-7) Except that the polymerization solution used was set as the PGMEA solution of Copolymer-7 before purification, the weight average molecular weight was obtained in the same manner as in Production Example 1-2 103900 PGMEA solution of refined copolymer-7. The active group content per 1 g of copolymer-7 was 0 (mmol/g).

[表1]    共聚物 1 2 3 4 5 6 7 構成單體質量比 FMA 45 45 45 40 35 45 45 GMA 7 7 7 10 10    22.6 HEMA 10 10 10 10 15 11.5 32.4 HHMPMA 38 38 38 40 40 43.5    共聚物中之氟量 (質量%) 25.7 25.7 25.7 22.9 20.0 25.7 25.7 重量平均分子量 102600 60000 165000 91000 97000 94800 103900 [Table 1] Copolymer 1 2 3 4 5 6 7 Constituent monomer mass ratio FMA 45 45 45 40 35 45 45 GMA 7 7 7 10 10 22.6 HEMA 10 10 10 10 15 11.5 32.4 HHMPMA 38 38 38 40 40 43.5 Amount of fluorine in copolymer (mass%) 25.7 25.7 25.7 22.9 20.0 25.7 25.7 Weight average molecular weight 102600 60000 165000 91000 97000 94800 103900

＜添加劑-1＞  昭和電工公司製造之Karenz MT PE1(季戊四醇四(3-巰基丁酸酯)  ＜添加劑-2＞  Dow Corning Toray公司製造之SH6040(3-縮水甘油氧基丙基三甲氧基矽烷)  ＜添加劑-3＞  日本化藥公司製造之KAYAMER PM-21(含甲基丙烯醯基之磷酸酯)<Additive-1> Showa Denko Karenz MT PE1 (pentaerythritol tetrakis(3-mercaptobutyrate) <Additive-2> SH6040 (3-glycidoxypropyltrimethoxysilane) manufactured by Dow Corning Toray <Additive-3> KAYAMER PM-21 (phosphate ester containing methacryl group) manufactured by Nippon Kayaku Co., Ltd.

＜顏料分散液-1之製備＞  以成為表2中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。藉由塗料振盪機對該溶液於25～45℃之溫度範圍內進行3小時分散處理。珠粒係使用0.5 mm

Figure 02_image083
之氧化鋯珠，添加分散液之2.5倍之質量。分散結束後，藉由過濾器將珠粒與分散液分離，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 2. The solution was subjected to dispersion treatment at a temperature range of 25 to 45° C. for 3 hours by means of a paint shaker. The bead system uses 0.5 mm
Figure 02_image083
For zirconia beads, add 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare Pigment Dispersion-1.

[表2]    顏料分散液-1 比率 (質量份) 顏料 C.I.顏料紫29 49 C.I.顏料藍60 50 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-1 33 溶劑 溶劑-1 367 溶劑-2 92 [Table 2] Pigment dispersion-1 Ratio (parts by mass) pigment CI Pigment Violet 29 49 CI Pigment Blue 60 50 CI Pigment Orange 64 1 Dispersant (solid content conversion) Dispersant-1 20 Alkali-soluble resin (solid content conversion) Alkali soluble resin-1 33 solvent Solvent-1 367 Solvent-2 92

[實施例1～7及比較例1～2]  以表3中記載之調配比率混合顏料分散液-1以外之各成分，加以攪拌而使之充分溶解後，添加顏料分散液-1並混合後，使用超音波洗淨機攪拌10分鐘，製備感光性樹脂組合物。使用所獲得之各感光性樹脂組合物，根據下述方法進行評價。  再者，表3中之顏料分散液、鹼可溶性樹脂、共聚物之調配比率係固形物成分換算值。[Examples 1 to 7 and Comparative Examples 1 to 2] Mix the components other than Pigment Dispersion-1 at the mixing ratio shown in Table 3, stir and dissolve them sufficiently, add Pigment Dispersion-1 and mix , and stirred for 10 minutes using an ultrasonic cleaner to prepare a photosensitive resin composition. Using each obtained photosensitive resin composition, it evaluated by the following method. Furthermore, the blending ratios of the pigment dispersion liquid, alkali-soluble resin, and copolymer in Table 3 are conversion values of solid components.

[表3]    實施例 比較例 1 2 3 4 5 6 7 1 2 調配比率 (質量份) 顏料分散液-1 (固形物成分換算) 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 鹼可溶性樹脂-1 (固形物成分換算) 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 鹼可溶性樹脂-2 (固形物成分換算) 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 鹼可溶性樹脂-3 (固形物成分換算) 7.81 7.81 7.81 7.81 7.81 7.81 7.81 7.81 7.81 光聚合性化合物-1 5.59 5.59 5.59 5.59 5.59 5.59 5.59 5.59 5.59 光聚合性化合物-2 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 光聚合起始劑-1 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 光聚合起始劑-2 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 共聚物-1 (固形物成分換算) 0.06                         共聚物-2 (固形物成分換算)    0.06                      共聚物-3 (固形物成分換算)       0.06                   共聚物-4 (固形物成分換算)          0.06    0.07          共聚物-5 (固形物成分換算)             0.06    0.08       共聚物-6 (固形物成分換算)                      0.06    共聚物-7 (固形物成分換算)                         0.06 添加劑-1 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 添加劑-2 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 添加劑-3 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 溶劑-1 55.20 55.20 55.20 55.20 55.20 55.20 55.20 55.20 55.20 溶劑-2 13.80 13.80 13.80 13.80 13.80 13.80 13.80 13.80 13.80 評價 噴墨時之潤濕性 B C B B A B A E E PGMEA接觸角(°) 56 55 53 51 44 52 45 52 56 [table 3] Example comparative example 1 2 3 4 5 6 7 1 2 Blending ratio (parts by mass) Pigment dispersion-1 (calculated as solid content) 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 Alkali-soluble resin-1 (calculated as solid content) 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 Alkali-soluble resin-2 (calculated as solid content) 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 5.85 Alkali-soluble resin-3 (calculated as solid content) 7.81 7.81 7.81 7.81 7.81 7.81 7.81 7.81 7.81 Photopolymerizable compound-1 5.59 5.59 5.59 5.59 5.59 5.59 5.59 5.59 5.59 Photopolymerizable compound-2 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 Photopolymerization initiator-1 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 Photopolymerization initiator-2 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 Copolymer-1 (solid content conversion) 0.06 Copolymer-2 (solid content conversion) 0.06 Copolymer-3 (solid content conversion) 0.06 Copolymer-4 (solid content conversion) 0.06 0.07 Copolymer-5 (Converted to solid content) 0.06 0.08 Copolymer-6 (solid content conversion) 0.06 Copolymer-7 (solid content conversion) 0.06 Additive-1 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 Additive-2 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 Additive-3 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 Solvent-1 55.20 55.20 55.20 55.20 55.20 55.20 55.20 55.20 55.20 Solvent-2 13.80 13.80 13.80 13.80 13.80 13.80 13.80 13.80 13.80 evaluate Wettability during inkjet B C B B A B A E. E. PGMEA contact angle (°) 56 55 53 51 44 52 45 52 56

以下說明性能評價之方法。The method of performance evaluation will be described below.

＜PGMEA接觸角之測定＞  使用旋轉塗佈機，以後烘烤後成為10 μm之厚度之方式將上述感光性樹脂組合物塗佈於玻璃基板上。將該塗佈基板進行1分鐘之真空乾燥，進而於100℃下，於加熱板上加熱乾燥120秒。使用CANON公司製造之鏡面投影型之曝光機(MPA-600FA)，以曝光量80 mJ/cm 2對所獲得之塗膜進行整面曝光。此時之波長365 nm下之光強度為500 mW/cm 2。其次，將溶解有0.04質量%之KOH及0.07質量%之Emulgen A-60(花王公司製造之界面活性劑)之水溶液作為顯影液，對該基板於24℃下進行70秒之噴霧顯影後，以純水洗淨10秒。最後，將該基板於烘箱中於230℃下進行30分鐘之後烘烤，獲得接觸角測定用基板。 <Measurement of PGMEA contact angle> Using a spin coater, the said photosensitive resin composition was apply|coated on the glass substrate so that it might become 10 micrometers thickness after post-baking. The coated substrate was vacuum-dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 120 seconds. The entire surface of the obtained coating film was exposed at an exposure amount of 80 mJ/cm 2 using a mirror projection type exposure machine (MPA-600FA) manufactured by CANON. At this time, the light intensity at a wavelength of 365 nm was 500 mW/cm 2 . Next, an aqueous solution of 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) was dissolved as a developing solution, and the substrate was subjected to spray development at 24° C. for 70 seconds. Rinse with pure water for 10 seconds. Finally, the substrate was baked in an oven at 230° C. for 30 minutes to obtain a substrate for contact angle measurement.

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%RH之條件下測定滴加PGMEA 0.7 μL之1秒後之上述接觸角測定用基板之接觸角，根據以下基準評價撥油墨性。其結果示於表3。於接觸角較大之情形時表示撥油墨性較高。Using the Drop Master 500 (contact angle measurement device) manufactured by Kyowa Interface Science Co., Ltd., the contact angle of the above-mentioned substrate for contact angle measurement was measured under the conditions of 23°C and humidity 50%RH for 1 second after dropping 0.7 μL of PGMEA, according to Ink repellency was evaluated on the following criteria. The results are shown in Table 3. When the contact angle is larger, it means higher ink repellency.

＜噴墨(IJ)塗佈性之評價＞  使用旋轉塗佈機，以後烘烤後成為10 μm之厚度之方式將上述感光性樹脂組合物塗佈於玻璃基板上。將該塗佈基板進行1分鐘之真空乾燥，進而於100℃下，於加熱板上加熱乾燥120秒。其次，使用光罩，藉由MPA曝光機，以曝光量80 mJ/cm 2對所獲得之塗膜基板進行曝光。此時之波長365 nm下之光強度為500 mW/cm 2。光罩係使用寬15 μm之開口以縱置100 μm、橫置200 μm被設置為格子狀之光罩。繼而，於與接觸角測定用基板之製作時相同之條件下進行顯影處理，於烘箱中於230℃下進行30分鐘之後烘烤，製作具有IJ用阻隔壁圖案之IJ用基板。 <Evaluation of Inkjet (IJ) Coatability> Using a spin coater, the above-mentioned photosensitive resin composition was applied on a glass substrate so as to have a thickness of 10 μm after post-baking. The coated substrate was vacuum-dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 120 seconds. Next, using a photomask, the obtained coated film substrate was exposed with an exposure dose of 80 mJ/cm 2 by an MPA exposure machine. At this time, the light intensity at a wavelength of 365 nm was 500 mW/cm 2 . The mask is a mask with a width of 15 μm and an opening of 100 μm vertically and 200 μm horizontally. Next, development treatment was carried out under the same conditions as in the preparation of the substrate for contact angle measurement, followed by baking in an oven at 230° C. for 30 minutes to prepare a substrate for IJ having a barrier rib pattern for IJ.

於FUJIFILM公司製造之噴墨裝置DMP-2831上，安裝填充有Mitsubishi Chemical公司製造之YED216D(1,6-己二醇二縮水甘油醚)作為噴出用油墨之對應10 pL之噴嘴之匣，於上述IJ用基板之像素部(四方被阻隔壁包圍之開口部分)噴出1滴(相當於10 pL)。根據噴出之液滴之潤濕擴散之尺寸，依據以下評價基準對IJ塗佈性進行評價。On the inkjet device DMP-2831 manufactured by FUJIFILM, a nozzle cartridge corresponding to 10 pL filled with YED216D (1,6-hexanediol diglycidyl ether) manufactured by Mitsubishi Chemical Co., Ltd. as the ink for ejection was installed. One drop (equivalent to 10 pL) was discharged from the pixel portion of the substrate for IJ (opening portion surrounded by barrier walls on all sides). From the size of the wetting spread of the ejected liquid droplets, the IJ coating property was evaluated according to the following evaluation criteria.

＜IJ塗佈性評價基準＞  依據圖1之影像，以目視評價於像素部2(阻隔壁部1內)潤濕擴散之噴墨滴下部3之面積。圖1表示自左開始IJ塗佈性依序變得更優異，A最佳，B、C、D之潤濕擴散不如A，但實用上無問題，E幾乎未潤濕擴散，於實用上存在問題。<IJ Coatability Evaluation Criteria> Based on the image in FIG. 1 , the area of the inkjet dropping part 3 that wets and diffuses in the pixel part 2 (inside the barrier wall part 1 ) was visually evaluated. Figure 1 shows that from the left, IJ coating properties become more excellent in order, A is the best, B, C, and D are not as good as A in wetting and spreading, but there is no problem in practical use, and E has almost no wetting and spreading, which exists in practice question.

自實施例1～7與比較例1之比較可知：(A)共聚物藉由具有環氧基，於像素內以IJ噴出之液滴之潤濕擴散變得良好。認為其係後烘烤時環氧基發生開環反應從而固定於障壁中之效果，認為於不具有環氧基之比較例1中，後烘烤中障壁軟化時(A)共聚物滲出至像素內，故而使潤濕擴散變差。From the comparison of Examples 1 to 7 and Comparative Example 1, it can be seen that (A) the copolymer has an epoxy group, so that the wetting and spreading of the liquid droplets ejected by IJ in the pixel becomes good. It is considered that the epoxy group undergoes a ring-opening reaction during post-baking and is fixed in the barrier rib. It is believed that in Comparative Example 1 without epoxy group, the (A) copolymer oozes out to the pixel when the barrier rib softens during post-baking Therefore, the wetting and spreading are deteriorated.

自實施例1～7與比較例2之比較可知：(A)共聚物藉由具有藉由照射活性能量線而產生自由基之活性基，於像素內以IJ噴出之液滴之潤濕擴散變得良好。認為其原因在於：曝光時(A)共聚物產生自由基，有助於感光性樹脂組合物之自由基聚合，故而(A)共聚物固定於障壁，顯影時不易滲出。於(A)共聚物未固定而滲出之情形時，(A)共聚物將像素內污染，IJ之油墨之潤濕擴散變差。From the comparison of Examples 1 to 7 and Comparative Example 2, it can be seen that: (A) The copolymer has active radicals that generate free radicals by irradiating active energy rays, and the wetting and diffusion of liquid droplets ejected as IJ in the pixel become changed. well. The reason for this is considered to be that the (A) copolymer generates free radicals during exposure, which contributes to the radical polymerization of the photosensitive resin composition, so the (A) copolymer is fixed on the barrier and is less likely to bleed out during development. When the (A) copolymer is not fixed and bleeds out, the (A) copolymer contaminates the inside of the pixel, and the wetting and spreading of the ink of IJ becomes poor.

自實施例1～3之比較可判斷：若本發明之(A)共聚物之分子量變大，則存在噴墨塗佈性稍稍變佳之傾向。認為其原因在於：於分子量較高之情形時，顯影或後烘烤時不易軟化，不易發生滲出，不易污染像素。From the comparison of Examples 1 to 3, it can be judged that if the molecular weight of the (A) copolymer of the present invention is increased, the inkjet coating property tends to be slightly improved. The reason is considered to be that when the molecular weight is high, it is not easy to soften during development or post-baking, it is not easy to bleed out, and it is not easy to contaminate pixels.

自實施例1、4～7之比較可知：於本發明之(A)共聚物之具有氟原子之單體單元較多之情形時，存在撥液性變高之傾向。又，即使相應地增加(A)共聚物量而將氟量設為同程度，存在撥液性變高之傾向的亦為具有氟原子之單體單元。由此認為：為表現本發明之(A)共聚物之撥液性，較佳為(A)共聚物之1分子中之含有氟原子之單體單元較多。From the comparison of Examples 1 and 4 to 7, it can be seen that when there are many monomer units having fluorine atoms in the (A) copolymer of the present invention, the liquid repellency tends to increase. Moreover, even if the amount of (A) copolymer is increased correspondingly and the amount of fluorine is set to the same level, it is a monomer unit having a fluorine atom that tends to increase the liquid repellency. From this, it is considered that in order to express the liquid repellency of the (A) copolymer of the present invention, it is preferable that there are more monomer units containing fluorine atoms in one molecule of the (A) copolymer.

1:阻隔壁部 2:像素部(非圖像部) 3:噴墨滴下部 10:基板 11:綠色發光性之奈米結晶粒子 12:紅色發光性之奈米結晶粒子 20:阻隔壁 30:紅色像素 40:綠色像素 50:藍色像素 100:彩色濾光片1: Barrier wall part 2: Pixel part (non-image part) 3: Inkjet dropping part 10: Substrate 11: Green luminescent nano crystal particles 12: Red luminescent nano crystal particles 20: Barrier wall 30: Red pixel 40: Green pixel 50: Blue pixel 100: Color filter

圖1係表示噴墨塗佈性之評價基準之模式圖。  圖2係具備本發明之阻隔壁之彩色濾光片之一例之模式剖視圖。Fig. 1 is a schematic diagram showing evaluation criteria of inkjet coating properties. Fig. 2 is a schematic cross-sectional view of an example of a color filter having a barrier rib of the present invention.

Claims (14)

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(C)光聚合性化合物者，並且  上述(A)共聚物含有下述單體(a1)、下述單體(a2)及下述單體(a3)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的單體；  單體(a2)：具有氟原子之單體；  單體(a3)：具有碳數2～4之環狀醚基之單體。A photosensitive resin composition comprising (A) a copolymer, (B) an alkali-soluble resin, and (C) a photopolymerizable compound, and the above-mentioned (A) copolymer contains the following monomer (a1), the following Monomer (a2) and the following monomer (a3) are used as constituent monomers; Monomer (a1): a monomer having an active group that generates free radicals by irradiation with active energy rays; Monomer (a2): having fluorine Atom monomers; Monomer (a3): A monomer having a cyclic ether group with 2 to 4 carbon atoms. 如請求項1之感光性樹脂組合物，其中上述單體(a2)具有氟烷基。The photosensitive resin composition according to claim 1, wherein the above-mentioned monomer (a2) has a fluoroalkyl group. 如請求項2之感光性樹脂組合物，其中上述單體(a2)具有下述式(1)所表示之基；  -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20以下之氟烷基或氟原子)。 The photosensitive resin composition as claimed in item 2, wherein the above-mentioned monomer (a2) has 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 fluoroalkyl group having 1 to 20 carbon atoms or a fluorine atom which may have an etheric oxygen atom). 如請求項1至3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、烷基苯酮基、α-羥基酮基、α-胺基酮基、α-二酮基及α-二酮二烷基縮酮基所組成之群中之一種以上。The photosensitive resin composition according to any one of claims 1 to 3, wherein the active group in the above-mentioned monomer (a1) is selected from benzophenone group, alkylphenone group, α-hydroxy ketone group, α -One or more of the group consisting of aminoketo group, α-diketone group and α-diketone dialkyl ketal group. 如請求項1至4中任一項之感光性樹脂組合物，其中上述單體(a3)中之碳數2～4之環狀醚基為環氧基。The photosensitive resin composition according to any one of claims 1 to 4, wherein the cyclic ether group having 2 to 4 carbon atoms in the monomer (a3) is an epoxy group. 如請求項1至5中任一項之感光性樹脂組合物，其中上述(A)共聚物進而含有下述單體(a4)作為構成單體； 單體(a4)：具有羥基之單體。 The photosensitive resin composition according to any one of claims 1 to 5, wherein the (A) copolymer further contains the following monomer (a4) as a constituent monomer; Monomer (a4): A monomer having a hydroxyl group. 如請求項1至6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5～60質量%。The photosensitive resin composition according to any one of Claims 1 to 6, wherein the content of fluorine atoms in the above-mentioned (A) copolymer is 5 to 60% by mass. 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(D)光聚合起始劑。The photosensitive resin composition according to any one of claims 1 to 7, further comprising (D) a photopolymerization initiator. 如請求項1至8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 8, further comprising (E) a colorant. 如請求項1至9中任一項之感光性樹脂組合物，其係阻隔壁形成用感光性樹脂組合物。The photosensitive resin composition according to any one of claims 1 to 9, which is a photosensitive resin composition for barrier rib formation. 一種硬化物，其係使如請求項1至10中任一項之感光性樹脂組合物硬化所得者。A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. 一種阻隔壁，其包含如請求項11之硬化物。A barrier wall comprising the cured product according to claim 11. 一種有機電致發光元件，其具備如請求項12之阻隔壁。An organic electroluminescent element, which is provided with the barrier wall as claimed in claim 12. 一種圖像顯示裝置，其包括如請求項13之有機電致發光元件。An image display device comprising the organic electroluminescent element as claimed in claim 13.
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