TW201905593A - Resin composition, cured film, color filter, and method for producing cured film - Google Patents

Resin composition, cured film, color filter, and method for producing cured film

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Publication number
TW201905593A
TW201905593A TW107112842A TW107112842A TW201905593A TW 201905593 A TW201905593 A TW 201905593A TW 107112842 A TW107112842 A TW 107112842A TW 107112842 A TW107112842 A TW 107112842A TW 201905593 A TW201905593 A TW 201905593A
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group
resin composition
carbon atoms
substituent
formula
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TW107112842A
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Chinese (zh)
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松本直純
石川達郎
三隅浩一
塩田大
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日商東京應化工業股份有限公司
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Publication of TW201905593A publication Critical patent/TW201905593A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/20—Exposure; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Graft Or Block Polymers (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention provides a resin composition capable of forming a pattern having good adherence to a substrate and capable of inhibiting generation of a developing residue on a unexposed portion, a method for producing a hardened film using the resin composition, a hardened film formed by hardening the resin composition and a color filter provided with the hardened film. A compound represented by formula (e1) is blended in a resin composition to serve as a silane coupling agent (E). The resin composition comprises an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a pigment (D). In the formula (R e1 O)a(R e2 )3-aSi-R e3 -NH-CO-R e4 -R e5 ……(e1), R e1and R e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, wherein a is 2 or 3, R e3 is an alkylene group with 1 to 10 carbon atoms, R e4 is a bivalent organic group, and R e5 is a bronsted acid group, an alcoholic hydroxyl group, an amino group or an amino formyl group.

Description

樹脂組成物、硬化膜、色彩濾波器及硬化膜之製造方法Resin composition, cured film, color filter and method for producing cured film

本發明係關於樹脂組成物、使該樹脂組成物硬化而形成之硬化膜、具備該硬化膜之色彩濾波器與使用了前述之樹脂組成物之硬化膜之製造方法。The present invention relates to a resin composition, a cured film formed by curing the resin composition, a color filter including the cured film, and a method for producing a cured film using the aforementioned resin composition.

液晶顯示器等顯示體形成為下述構造：在形成有相互對置的成對的電極的2片基板之間夾持有液晶層的構造。而且，在一方之基板的內側形成有具有由紅色(R)、綠色(G)、藍色(B)等各種顏色形成的畫素的色彩濾波器(color filter)。而且，為了防止各畫素中的不同的顏色之混色，或者隱藏電極的圖案，通常在該色彩濾波器中形成有被配置成矩陣狀的黑色矩陣，以使得對R、G、B的各種顏色的畫素進行劃分。A display body such as a liquid crystal display has a structure having a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes facing each other is formed. A color filter having pixels formed of various colors, such as red (R), green (G), and blue (B), is formed inside one of the substrates. In addition, in order to prevent different colors in each pixel from being mixed, or to hide the electrode pattern, a black matrix arranged in a matrix is usually formed in the color filter so that various colors of R, G, and B can be used. Pixels.

通常，色彩濾波器可利用光刻法形成。具體而言，首先，在基板上塗佈黑色之感光性組成物，進行曝光、顯影，形成黑色矩陣。然後，接下來針對紅(R)、綠(G)、藍(B)各種顏色之感光性組成物，分別藉由重複進行塗佈、曝光、顯影，由此在特定位置形成各種顏色的圖案，從而形成色彩濾波器。Generally, a color filter can be formed using a photolithography method. Specifically, first, a black photosensitive composition is coated on a substrate, and exposed and developed to form a black matrix. Then, the photosensitive composition of each color of red (R), green (G), and blue (B) is repeatedly coated, exposed, and developed to form a pattern of each color at a specific position. Thereby, a color filter is formed.

關於構成色彩濾波器之著色膜的形成方法，例如黑色矩陣的形成方法，提出了使用負型感光性樹脂組成物之方法。 　　例如，專利文獻1中，關於用作低成本、且可同時實現高遮光性與低反射率的黑色矩陣的原料的黑色感光性樹脂組成物，示出了摻合有碳黑與疏水性二氧化矽微粒等之負型感光性樹脂組成物。 [現有技術文獻] [專利文獻]As a method for forming a coloring film constituting a color filter, for example, a method for forming a black matrix, a method using a negative photosensitive resin composition has been proposed. For example, Patent Document 1 shows a black photosensitive resin composition that is used as a raw material for a black matrix that can achieve both high light-shielding properties and low reflectance at a low cost. Carbon black and hydrophobic dioxide are blended. A negative photosensitive resin composition such as silicon particles. [Prior Art Literature] [Patent Literature]

[專利文獻1] 日本特開2015-161815號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-161815

[發明所欲解決之課題][Problems to be Solved by the Invention]

然而，本申請的發明人進行了研究，結果發現，在使用專利文獻1中記載之組成物等以往的感光性樹脂組成物時，存在下述問題：難以形成良好地密著於基板的圖案；或者，容易在未曝光部中產生殘渣。However, the inventors of the present application conducted research and found that when using a conventional photosensitive resin composition such as the composition described in Patent Document 1, there is a problem that it is difficult to form a pattern that adheres well to a substrate; Alternatively, residues are likely to be generated in the unexposed portions.

本發明是鑒於上述課題而作出的，目的在於提供可形成對基板的密著性良好的圖案且可抑制在未曝光部產生顯影殘渣的樹脂組成物、使用了該樹脂組成物之硬化膜之製造方法、使該樹脂組成物硬化而形成的硬化膜，與具備該硬化膜的色彩濾波器。 [用於解決課題的之手段]The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a resin composition capable of forming a pattern having good adhesion to a substrate and suppressing development residues in an unexposed portion, and production of a cured film using the resin composition. A method, a cured film formed by curing the resin composition, and a color filter including the cured film. [Means for solving problems]

本申請的發明人發現，經由在包含鹼可溶性樹脂(A)、光聚合性化合物(B)、光聚合引發劑(C)，與顏料(D)之樹脂組成物中摻合後述特定構造之化合物作為矽烷偶合劑(E)，可解決上述課題，從而完成了本發明。具體而言，本發明提供以下的方案。The inventors of the present application have discovered that a compound having a specific structure described later is blended with a resin composition containing a base-soluble resin (A), a photopolymerizable compound (B), and a photopolymerization initiator (C) and a pigment (D). As the silane coupling agent (E), the above-mentioned problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following solutions.

本發明的第1方式係樹脂組成物，其特徵為包含： 　　鹼可溶性樹脂(A)、 　　光聚合性化合物(B)、 　　光聚合引發劑(C)、 　　顏料(D)，與 　　矽烷偶合劑(E)； 　　矽烷偶合劑(E)包含下述式(e1)表示之烷氧基矽烷化合物。 　　(Re1 O)a (Re2 )3-a Si-Re3 -NH-CO-Re4 -Re5 ……(e1) 　　(式(e1)中，Re1 及Re2 各自獨立地為碳原子數1～6之烴基，a為2或3，Re3 為碳原子數1～10之亞烷基，Re4 為2價之有機基，Re5 為布朗斯特酸性基、醇式羥基、胺基或胺基甲醯基。)A first aspect of the present invention is a resin composition, comprising: an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D), and a silane coupling agent (E ); The silane coupling agent (E) contains an alkoxysilane compound represented by the following formula (e1). (R e1 O) a (R e2 ) 3-a Si-R e3 -NH-CO-R e4 -R e5 ... (e1) (In the formula (e1), R e1 and R e2 are each independently a carbon atom A hydrocarbon group of 1 to 6, a is 2 or 3, R e3 is an alkylene group having 1 to 10 carbon atoms, R e4 is a divalent organic group, and R e5 is a Bronsted acid group, an alcoholic hydroxyl group, and an amine Or amino formamyl.)

本發明之第2方式係硬化膜，其係將如第1方式相關之樹脂組成物硬化而形成的。A second aspect of the present invention is a cured film formed by curing a resin composition according to the first aspect.

本發明之第3方式係色彩濾波器，其係具備如第2方式相關之硬化膜。A third aspect of the present invention is a color filter including a cured film according to the second aspect.

本發明之第4方式係硬化膜之製造方法，所述製造方法包含下述步驟： 　　藉由塗佈如第1方式相關之樹脂組成物，從而形成塗佈膜之步驟， 　　位置選擇性地將塗佈膜曝光之步驟， 　　將經曝光之塗佈膜顯影，形成經圖案化的硬化膜之步驟，與 　　對經圖案化的硬化膜進行烘烤之步驟。 [發明之效果]The fourth aspect of the present invention is a method for manufacturing a cured film, which includes the following steps: The step of forming a coating film by applying the resin composition according to the first aspect, selectively applying the coating at a position The step of exposing the cloth film: (1) the step of developing the exposed coating film to form a patterned cured film, and the step of baking the patterned cured film. [Effect of the invention]

依據本發明，可提供可形成對基板之密著性良好的圖案且可抑制在未曝光部產生顯影殘渣之樹脂組成物、使用了該樹脂組成物之硬化膜之製造方法、使該樹脂組成物硬化而形成之硬化膜，與具備該硬化膜之色彩濾波器。According to the present invention, it is possible to provide a resin composition capable of forming a pattern with good adhesion to a substrate and suppressing development residues in unexposed areas, a method for producing a cured film using the resin composition, and the resin composition. A cured film formed by curing and a color filter including the cured film.

以下，基於較佳的實施方式對本發明進行說明。尚，對於本說明書中的「～」而言，只要沒有特別說明，則表示從以上(下限值)至以下(上限值)。Hereinafter, the present invention will be described based on preferred embodiments. In addition, "-" in this specification means from the above (lower limit value) to the following (upper limit value) unless there is particular notice.

≪樹脂組成物≫ 　　樹脂組成物包含鹼可溶性樹脂(A)、光聚合性化合物(B)、光聚合引發劑(C)、顏料(D)，與矽烷偶合劑(E)。 　　矽烷偶合劑(E)包含下述式(e1)表示之烷氧基矽烷化合物。 　　(Re1 O)a (Re2 )3-a Si-Re3 -NH-CO-Re4 -Re5 ……(e1) 　　(式(e1)中，Re1 及Re2 各自獨立地為碳原子數1～6之烴基，a為2或3，Re3 為碳原子數1～10的亞烷基，Re4 為2價之有機基，Re5 為布朗斯特酸性基、醇式羥基、胺基或胺基甲醯基。) 　　本實施方式中，經由使樹脂組成物包含上述的矽烷偶合劑(E)，從而可得到可形成對基板的密著性良好的圖案且可抑制在未曝光部產生顯影殘渣的樹脂組成物。≪Resin Composition≫ The resin composition contains an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D), and a silane coupling agent (E). The silane coupling agent (E) includes an alkoxysilane compound represented by the following formula (e1). (R e1 O) a (R e2 ) 3-a Si-R e3 -NH-CO-R e4 -R e5 ... (e1) (In the formula (e1), R e1 and R e2 are each independently a carbon atom A hydrocarbon group of 1 to 6, a is 2 or 3, R e3 is an alkylene group having 1 to 10 carbon atoms, R e4 is a divalent organic group, and R e5 is a Bronsted acid group, an alcoholic hydroxyl group, and an amine Or aminomethylamino group.) In the present embodiment, the resin composition contains the silane coupling agent (E) as described above, so that a pattern having good adhesion to the substrate can be obtained and can be suppressed in the unexposed portion. A resin composition that generates a development residue.

以下，對樹脂組成物中包含之必需或任選的成分與樹脂組成物之調製方法進行說明。Hereinafter, the necessary or optional components included in the resin composition and the method for preparing the resin composition will be described.

＜鹼可溶性樹脂(A)＞ 　　樹脂組成物包含鹼可溶性樹脂(A)(本說明書中，亦記為「(A)成分」)。作為鹼可溶性樹脂(A)，沒有特別限制，可從一直以來在各種感光性的樹脂組成物中摻合的鹼可溶性樹脂中適當選擇。 　　於此，本說明書中，所謂鹼可溶性樹脂(A)，係指在分子內含有使其具有鹼可溶性的官能基(例如，酚性羥基、羧基、磺酸基等)之樹脂。<Alkali-soluble resin (A)> The resin composition contains an alkali-soluble resin (A) (also referred to as "(A) component" in this specification). The alkali-soluble resin (A) is not particularly limited, and can be appropriately selected from alkali-soluble resins which have been conventionally blended into various photosensitive resin compositions. In this context, the alkali-soluble resin (A) in the present specification refers to a resin containing a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) that makes it alkali-soluble in the molecule.

關於較佳作為鹼可溶性樹脂之樹脂，可舉出具有卡多(Cardo)構造之樹脂(A1)(以下，亦記為「卡多(Cardo)樹脂(A1)」)。 　　使用具有卡多(Cardo)構造之樹脂(A1)作為鹼可溶性樹脂時，容易得到分辨力優異之樹脂組成物，使用樹脂組成物容易形成不易因加熱而過度流動之硬化膜。Examples of the resin that is preferably used as the alkali-soluble resin include a resin (A1) having a Cardo structure (hereinafter, also referred to as "Cardo resin (A1)"). When a resin (A1) having a Cardo structure is used as the alkali-soluble resin, a resin composition having excellent resolution is easily obtained, and a hardened film that is hard to flow excessively by heating is easily formed using the resin composition.

[具有卡多(Cardo)構造之樹脂(A1)] 　　作為具有卡多(Cardo)構造之樹脂(A1)，可使用在其構造中具有卡多(Cardo)骨架，且具有特定的鹼可溶性之樹脂。所謂卡多(Cardo)骨架，係指第2環狀構造與第3環狀構造鍵結於構成第1環狀構造的1個環碳原子而成的骨架。尚，第2環狀構造與第3環狀構造可為相同的構造，亦可為不同的構造。 　　作為卡多(Cardo)骨架的代表例，可舉出2個芳香環(例如苯環)鍵結於芴環的9位的碳原子而成的骨架。[Resin (C1) with Cardo structure] As the resin (A1) with Cardo structure, a resin having a Cardo skeleton in its structure and having a specific alkali solubility can be used . The Cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. The second ring structure and the third ring structure may be the same structure or different structures. As a representative example of the Cardo skeleton, fluorene includes a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to a carbon atom at the 9-position of the fluorene ring.

作為(A1)卡多(Cardo)構造樹脂，沒有特別限制，可使用現有已知的樹脂。其中，較佳為下述式(a-1)表示之樹脂。There are no particular restrictions on the (A1) Cardo structural resin, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferred.

[化1] [Chemical 1]

式(a-1)中，Xa 表示下述式(a-2)表示之基。m1表示0~20之整數。In the formula (a-1), X a represents a group represented by the following formula (a-2). m1 represents an integer from 0 to 20.

[化2] [Chemical 2]

上述式(a-2)中，Ra1 各自獨立地表示氫原子、碳原子數1～6之烴基或鹵素原子，Ra2 各自獨立地表示氫原子或甲基，Ra3 各自獨立地表示直鏈或支鏈之亞烷基，m2表示0或1，Wa 表示下述式(a-3)表示之基。In the formula (a-2), R a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R a2 each independently represents a hydrogen atom or a methyl group, and R a3 each independently represents a straight chain Or a branched alkylene group, m2 represents 0 or 1, and W a represents a group represented by the following formula (a-3).

[化3] [Chemical 3]

式(a-2)中，作為Ra3 ，較佳為碳原子數1～20之亞烷基，更佳為碳原子數1～10的亞烷基，特別佳為碳原子數1～6之亞烷基，最佳為乙烷-1,2-二基、丙烷-1,2-二基及丙烷-1,3-二基。In the formula (a-2), R a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 6 carbon atoms. Alkylene is preferably ethane-1,2-diyl, propane-1,2-diyl and propane-1,3-diyl.

式(a-3)中的環A表示可與芳香族環縮合，且可具有取代基之脂肪族環。脂肪族環可為脂肪族烴環，亦可為脂肪族雜環。 　　作為脂肪族環，可舉出單環烷烴、雙環烷烴、三環烷烴、四環烷烴等。 　　具體而言，可舉出環戊烷、環己烷、環庚烷、環辛烷等單環烷烴、金剛烷、降冰片烷、異冰片烷、三環癸烷、四環十二烷。 　　可與脂肪族環縮合之芳香族環可為芳香族烴環，亦可為芳香族雜環，較佳為芳香族烴環。具體而言，較佳為苯環及萘環。The ring A in the formula (a-3) represents an aliphatic ring which can be condensed with an aromatic ring and which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring. As the aliphatic ring, monocycloalkanes, bicycloalkanes, tricycloalkanes, tetracycloalkanes, and the like can be mentioned. Specifically, monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned. The aromatic ring which can be condensed with an aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

作為式(a-3)表示的2價基之較佳例，可舉出下述之基。 　　[化4] Preferred examples of the divalent group represented by the formula (a-3) include the following groups. [Chemical 4]

式(a-1)中之2價基Xa 可經由使提供殘基Za 之四羧酸二酐與下式(a-2a)表示的二醇化合物反應從而被導入至(A1)卡多(Cardo)樹脂中。 　　[化5] The divalent group X a in formula (a-1) can be introduced into (A1) Cardo by reacting a tetracarboxylic dianhydride providing a residue Z a with a diol compound represented by the following formula (a-2a) (Cardo) in resin. [Chemical 5]

式(a-2a)中，Ra1 、Ra2 、Ra3 、及m2與針對式(a-2)而進行的說明相同。關於式(a-2a)中之環A，與針對式(a-3)而進行的說明相同。In the formula (a-2a), R a1 , R a2 , R a3 , and m2 are the same as those described for the formula (a-2). The ring A in the formula (a-2a) is the same as that described for the formula (a-3).

式(a-2a)表示的二醇化合物例如可利用以下的方法製造。 　　首先，根據需要，按照常規方法，將下述式(a-2b)表示之二醇化合物所具有的酚性羥基中的氫原子取代成 -Ra3 -OH所表示之基，然後使用表氯醇等進行縮水甘油基化，得到下述式(a-2c)表示之環氧化合物。 　　接下來，經由使式(a-2c)表示之環氧化合物與丙烯酸或甲基丙烯酸反應，從而可得到式(a-2a)表示之二醇化合物。 　　式(a-2b)及式(a-2c)中，Ra1 、Ra3 、及m2與針對式(a-2)而進行的說明相同。關於式(a-2b)及式(a-2c)中的環A，與針對式(a-3)而進行的說明相同。 　　尚，式(a-2a)表示之二醇化合物之製造方法不限於上述的方法。 　　[化6] The diol compound represented by the formula (a-2a) can be produced, for example, by the following method. First, if necessary, a hydrogen atom in a phenolic hydroxyl group of a diol compound represented by the following formula (a-2b) is substituted with a group represented by -R a3 -OH according to a conventional method, and then epichlorohydrin is used. The glycidylation was performed to obtain an epoxy compound represented by the following formula (a-2c). Next, by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid, a diol compound represented by the formula (a-2a) can be obtained. In the formulae (a-2b) and (a-2c), R a1 , R a3 , and m2 are the same as those described for the formula (a-2). The ring A in the formula (a-2b) and the formula (a-2c) is the same as that described for the formula (a-3). The method for producing the diol compound represented by the formula (a-2a) is not limited to the method described above. [Chemical 6]

作為式(a-2b)表示之二醇化合物的較佳例，可舉出以下的二醇化合物。 　　[化7] Preferred examples of the diol compound represented by the formula (a-2b) include the following diol compounds. [Chemical 7]

上述式(a-1)中，Ra0 為氫原子或 -CO-Ya -COOH表示之基。於此，Ya 表示從二羧酸酐中除去酸酐基(-CO-O-CO-)而得到的殘基。作為二羧酸酐的例子，可舉出馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯菌酸酐(Chlorendic Anhydride)、甲基四氫鄰苯二甲酸酐、戊二酸酐等。In the formula (a-1), R a0 is a hydrogen atom or a group represented by -CO-Y a -COOH. Here, Y a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylmethylenetetrahydrogen. Phthalic anhydride, Chlorendic Anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

另外，上述式(a-1)中，Za 表示從四羧酸二酐中除去2個酸酐基而得到的殘基。作為四羧酸二酐的例子，可舉出下述式(a-4)表示之四羧酸二酐、均苯四甲酸二酐、二苯甲酮四甲酸二酐、聯苯四甲酸二酐、二苯基醚四甲酸二酐等。 　　另外，上述式(a-1)中，m表示0～20之整數。In the formula (a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride represented by the following formula (a-4). , Diphenyl ether tetracarboxylic dianhydride, etc. In the formula (a-1), m represents an integer of 0 to 20.

[化8](式(a-4)中，Ra4 、Ra5 及Ra6 各自獨立地表示選自由氫原子、碳原子數1～10之烷基及氟原子所成之群中之1種，m3表示0～12之整數。)[Chemical 8] (In formula (a-4), R a4 , R a5, and R a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 represents 0. An integer of ~ 12.)

可作為式(a-4)中之Ra4 而被選擇的烷基為碳原子數為1～10的烷基。藉由將烷基所具備的碳原子數設定為上述範圍，可進一步提高得到之羧酸酯的耐熱性。Ra4 為烷基時，從容易得到耐熱性優異之卡多(Cardo)樹脂方面考慮，其碳原子數較佳為1~6，更佳為1～5，進一步較佳為1~4，特別佳為1～3。 　　Ra4 為烷基時，該烷基可為直鏈狀，亦可為支鏈狀。The alkyl group which can be selected as R a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group to the above range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R a4 is an alkyl group, the number of carbon atoms is preferably from 1 to 6, more preferably from 1 to 5, and even more preferably from 1 to 4, from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance. It is preferably 1 to 3. When R a4 is an alkyl group, the alkyl group may be linear or branched.

作為式(a-4)中的Ra4 ，從容易得到耐熱性優異之卡多(Cardo)樹脂方面考慮，各自獨立地更佳為氫原子或碳原子數1～10之烷基。式(a-4)中的Ra4 更佳為氫原子、甲基、乙基、正丙基或異丙基，特別佳為氫原子或甲基。 　　從容易調製高純度的四羧酸二酐方面考慮，式(a-4)中的多個Ra4 較佳為相同的基。As R a4 in formula (a-4), from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance, each is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R a4 in formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group. From the viewpoint of easily preparing a high-purity tetracarboxylic dianhydride, a plurality of R a4 in the formula (a-4) are preferably the same group.

式(a-4)中的m3表示0～12之整數。經由使m3的值為12以下，可使四羧酸二酐的純化容易進行。 　　從容易進行四羧酸二酐之純化方面考慮，m3的上限較佳為5，更佳為3。 　　從四羧酸二酐的化學穩定性方面考慮，m3的下限較佳為1，更佳為2。 　　式(a-4)中的m3特別較佳為2或3。M3 in formula (a-4) represents an integer of 0-12. By setting the value of m3 to 12 or less, the purification of tetracarboxylic dianhydride can be easily performed.考虑 From the viewpoint of easily purifying tetracarboxylic dianhydride, the upper limit of m3 is preferably 5 and more preferably 3.考虑 From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1 and more preferably 2. M3 in formula (a-4) is particularly preferably 2 or 3.

可作為式(a-4)中之Ra5 及Ra6 而被選擇的碳原子數1～10的烷基與可作為Ra4 而被選擇之碳原子數1～10之烷基同樣。 　　從容易進行四羧酸二酐的純化方面考慮，Ra5 及Ra6 較佳為氫原子或碳原子數1～10(較佳為1～6、更佳為1～5、進一步較佳為1～4、特別佳為1～3)之烷基，特別佳為氫原子或甲基。The alkyl group having 1 to 10 carbon atoms that can be selected as R a5 and R a6 in formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R a4 . From the viewpoint of facilitating the purification of tetracarboxylic dianhydride, R a5 and R a6 are preferably hydrogen atoms or carbon atoms of 1 to 10 (preferably 1 to 6, more preferably 1 to 5, and even more preferably 1). An alkyl group of ∼4, particularly preferably 1-3), particularly preferably a hydrogen atom or a methyl group.

作為式(a-4)表示之四羧酸二酐，可舉出例如降冰片烷-2-螺-α-環戊酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐(別名「降冰片烷-2-螺-2’-環戊酮-5’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐」)、甲基降冰片烷-2-螺-α-環戊酮-α’-螺-2”-(甲基降冰片烷)-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環己酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐(別名「降冰片烷-2-螺-2’-環己酮-6’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐」)、甲基降冰片烷-2-螺-α-環己酮-α’-螺-2”-(甲基降冰片烷)-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環丙酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環丁酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環庚酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環辛酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環壬酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環癸酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十一烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十二烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環三癸酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十四烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-環十五烷酮-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-(甲基環戊酮)-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐、降冰片烷-2-螺-α-(甲基環己酮)-α’-螺-2”-降冰片烷-5,5”,6,6”-四甲酸二酐等。Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include, for example, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride (alias" norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2 "-norbornane-5,5", 6,6 "-tetra Formic acid dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane) -5,5 ", 6,6" -tetracarboxylic acid Dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride (alias" norbornane- 2-spiro-2'-cyclohexanone-6'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride"), methylnorbornane-2-spiro- α-Cyclohexanone-α'-spiro-2 "-(methylnorbornane) -5,5", 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloacetone- α'-spiro-2 ”-norbornane-5,5”, 6,6 ”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2” -nor Bornane-5,5 ”, 6,6” -tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2 ”-norbornane-5,5”, 6 , 6 ”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2” -norbornane-5,5 , 6,6 ”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononone-α'-spiro-2” -norbornane-5,5 ”, 6,6” -tetracarboxylic acid di Anhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2 ”-norbornane-5,5”, 6,6 ”-tetracarboxylic dianhydride, norbornane-2-spiro -α-cycloundecone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecane Ketone-α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotridecone-α'-spiro-2 ”-Norbornane-5,5”, 6,6 ”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2” -norbornane-5 , 5 ”, 6,6” -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2 ”-norbornane-5,5”, 6,6 ”-Tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2” -norbornane-5,5 ”, 6,6” -tetracarboxylic acid di Anhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride and the like.

(A1)卡多(Cardo)樹脂之重量平均分子量較佳為1000～40000，更佳為1500～30000，進一步較佳為2000～10000。經由成為上述的範圍，從而不僅可得到良好的顯影性，而且可得到充分的耐熱性、膜強度。The weight average molecular weight of (A1) Cardo resin is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 10,000. By being in the above range, not only good developability can be obtained, but also sufficient heat resistance and film strength can be obtained.

[丙烯酸系樹脂(A2)] 　　鹼可溶性樹脂(A)可包含卡多(Cardo)樹脂(A1)以外的鹼可溶性樹脂。作為所述鹼可溶性樹脂，可舉出丙烯酸系樹脂(A2)。[Acrylic resin (A2)] The alkali-soluble resin (A) may include an alkali-soluble resin other than Cardo resin (A1). Examples of the alkali-soluble resin include an acrylic resin (A2).

作為丙烯酸系樹脂(A2)，可使用包含來自(甲基)丙烯酸之構成單元及/或來自(甲基)丙烯酸酯等其他單體的構成單元之丙烯酸系樹脂。(甲基)丙烯酸為丙烯酸或甲基丙烯酸。(甲基)丙烯酸酯為下述式(a-5)表示之者，只要不妨礙本發明的目的，就沒有特別限制。As the acrylic resin (A2), an acrylic resin containing a structural unit derived from (meth) acrylic acid and / or a structural unit derived from other monomers such as (meth) acrylate can be used. (Meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylate is one represented by the following formula (a-5), and is not particularly limited as long as it does not hinder the object of the present invention.

[化9] [Chemical 9]

上述式(a-5)中，Ra7 為氫原子或甲基，Ra8 為1價之有機基。對於該有機基而言，可在該有機基中包含雜原子等烴基以外之鍵或取代基。另外，該有機基可為直鏈狀、支鏈狀、環狀中之任一者。In the formula (a-5), R a7 is a hydrogen atom or a methyl group, and R a8 is a monovalent organic group. The organic group may include a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched, and cyclic.

作為Ra8 之有機基中的烴基以外的取代基，沒有特別限制，只要不損害本發明的效果即可，可舉出鹵素原子、羥基、巰基、硫醚基、氰基、異氰基、氰酸酯基、異氰酸酯基、硫氰酸酯基、異硫氰酸酯基、甲矽烷基、矽烷醇基、烷氧基、烷氧基羰基、胺基甲醯基、硫代胺基甲醯基、硝基、亞硝基、羧基、羧酸鹽/酯基(carboxylate group)、醯基、醯基氧基、亞磺基、磺基、磺酸鹽/酯基(sulfonato group)、膦基(phosphino group)、氧膦基(phosphinyl group)、膦醯基、膦酸鹽/酯基(phosphonato group)、羥基亞胺基、烷基醚基、烷基硫醚基、芳基醚基、芳基硫醚基、胺基(-NH2 、-NHR、-NRR’：R及 R’各自獨立地表示烴基)等。上述取代基中包含的氫原子可被烴基取代。另外，上述取代基中包含的烴基可為直鏈狀、支鏈狀、及環狀中的任何。The substituent other than the hydrocarbon group in the organic group of R a8 is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, and a cyanide group. Ester group, isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, aminoformyl group, thioaminoformyl group , Nitro, nitroso, carboxyl, carboxylate group, fluorenyl, fluorenyloxy, sulfinyl, sulfo, sulfonato group, phosphine ( phosphino group), phosphinyl group, phosphino group, phosphonato group, hydroxyimide group, alkyl ether group, alkyl sulfide group, aryl ether group, aryl group A thioether group, an amine group (-NH 2 , -NHR, -NRR ': R and R' each independently represent a hydrocarbon group), and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group included in the substituent may be any of linear, branched, and cyclic.

作為Ra8 ，較佳為烷基、芳基、芳烷基、或雜環基，此等基可被鹵素原子、羥基、烷基、或雜環基取代。另外，此等基包含亞烷基部分時，亞烷基部分可被醚鍵、硫醚鍵、酯鍵中斷。As R a8 , an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group is preferable, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. In addition, when these groups include an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

烷基為直鏈狀或支鏈狀的烷基時，其碳原子數較佳為1～20，更佳為1~15，特別佳為1~10。作為較佳之烷基的例子，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、異癸基等。When the alkyl group is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and sec Amyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl and the like.

烷基為脂環式基或包含脂環式基的基時，作為烷基中包含的較佳之脂環式基，可舉出環戊基及環己基等單環的脂環式基、金剛烷基、降冰片基、異冰片基、三環壬基、三環癸基、及四環十二烷基等多環的脂環式基。When the alkyl group is an alicyclic group or a group containing an alicyclic group, examples of the preferable alicyclic group included in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and adamantane. Polycyclic cycloaliphatic radicals, such as methyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

另外，(A2)丙烯酸系樹脂可為聚合有(甲基)丙烯酸酯以外之單體的樹脂。作為這樣的單體，可舉出(甲基)丙烯醯胺類、不飽和羧酸類、烯丙基化合物、乙烯基醚類、乙烯基酯類、苯乙烯類等。此等單體可單獨使用，或者可組合2種以上而使用。The (A2) acrylic resin may be a resin in which a monomer other than (meth) acrylate is polymerized. Examples of such monomers include (meth) acrylamide, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used alone or in combination of two or more kinds.

作為(甲基)丙烯醯胺類，可舉出(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N-芳基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺、N,N-芳基(甲基)丙烯醯胺、N-甲基-N-苯基(甲基)丙烯醯胺、N-羥基乙基-N-甲基(甲基)丙烯醯胺等。Examples of (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-diamine Alkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-formyl (Meth) acrylamide and the like.

作為不飽和羧酸類，可舉出丁烯酸等單羧酸；馬來酸、富馬酸、檸康酸、中康酸、衣康酸等二羧酸；此等二羧酸之酐；等。Examples of unsaturated carboxylic acids include monocarboxylic acids such as butenoic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; etc. .

作為烯丙基化合物，可舉出乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、棕櫚酸烯丙酯、硬脂酸烯丙酯、苯甲酸烯丙酯、乙醯乙酸烯丙酯、乳酸烯丙酯等烯丙基酯類；烯丙基氧基乙醇；等。Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Allyl esters such as allyl acetate, allyl lactate; allyloxyethanol; etc.

作為乙烯基醚類，可舉出己基乙烯基醚、辛基乙烯基醚、癸基乙烯基醚、乙基己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、氯乙基乙烯基醚、1-甲基-2,2-二甲基丙基乙烯基醚、2-乙基丁基乙烯基醚、羥基乙基乙烯基醚、二乙二醇乙烯基醚、二甲基胺基乙基乙烯基醚、二乙基胺基乙基乙烯基醚、丁基胺基乙基乙烯基醚、苄基乙烯基醚、四氫糠基乙烯基醚等烷基乙烯基醚；乙烯基苯基醚、乙烯基甲苯基醚、乙烯基氯苯基醚、乙烯基-2,4-二氯苯基醚、乙烯基萘基醚、乙烯基蒽基醚等乙烯基芳基醚；等。Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether , Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether Alkyl ethylene such as dimethylaminoethyl vinyl ether, diethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthracene Ether; etc.

作為乙烯基酯類，可舉出丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、二乙基乙酸乙烯酯、戊酸乙烯酯(vinyl valerate)、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、乙烯基苯基乙酸酯、乙醯乙酸乙烯酯、乳酸乙烯酯、β-苯基丁酸乙烯酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯、萘甲酸乙烯酯等。Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, and chloroacetic acid. Vinyl ester, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenylacetate, vinylacetate, vinyl lactate, beta-phenylbutyrate, Vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.

作為苯乙烯類，可舉出苯乙烯；甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙烯等烷基苯乙烯；甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等烷氧基苯乙烯；氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、4-氟-3-三氟甲基苯乙烯等鹵代苯乙烯；等。Examples of the styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, Alkyl such as hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxymethylstyrene, etc. Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 -Halogenated styrenes such as trifluoromethylstyrene; etc.

丙烯酸系樹脂(A2)中之來自(甲基)丙烯酸之構成單元的量與來自其他單體之構成單元的量在不妨礙本發明的目的的範圍內沒有特別限制。丙烯酸系樹脂(A2)中之來自(甲基)丙烯酸的構成單元的量相對於丙烯酸系樹脂的質量而言較佳為5～50質量%，更佳為10～30質量%。The amount of the constituent units derived from (meth) acrylic acid and the amount of constituent units derived from other monomers in the acrylic resin (A2) are not particularly limited as long as they do not hinder the object of the present invention. The amount of the constituent units derived from (meth) acrylic acid in the acrylic resin (A2) is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass based on the mass of the acrylic resin.

丙烯酸系樹脂(A2)之重量平均分子量較佳為2000～50000，更佳為5000～30000。經由成為上述的範圍，從而存在下述傾向：容易獲得樹脂組成物之成膜能力、曝光後的顯影性的平衡。The weight average molecular weight of the acrylic resin (A2) is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By setting it as the said range, there exists a tendency which becomes easy to obtain the balance of the film-forming ability of a resin composition, and the developability after exposure.

[酚醛清漆樹脂(A3)] 　　對於鹼可溶性樹脂而言，從抑制因後烘烤時之加熱而導致的硬化膜的過度熱流動之觀點考慮，包含酚醛清漆樹脂(A3)亦為較佳的。 　　作為酚醛清漆樹脂(A3)，可使用一直以來在感光性的樹脂組成物中摻合的各種酚醛清漆樹脂。作為酚醛清漆樹脂(A3)，較佳經由在酸催化劑下使具有酚性羥基的芳香族化合物(以下，簡稱為「 酚類 」。)與醛類進行加成縮合而得到。[Novolak Resin (A3)] For alkali-soluble resins, from the viewpoint of suppressing excessive heat flow of the cured film due to heating during post-baking, it is also preferable to include novolak resin (A3). As the novolak resin (A3), various novolak resins which have been conventionally blended in a photosensitive resin composition can be used. The novolak resin (A3) is preferably obtained by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") to addition condensation with an aldehyde under an acid catalyst.

(酚類) 　　作為製作酚醛清漆樹脂(A3)時使用之酚類，可舉出例如苯酚；鄰甲酚、間甲酚、對甲酚等甲酚類；2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚等二甲苯酚類；鄰乙基苯酚、間乙基苯酚、對乙基苯酚等乙基酚類；2-異丙基苯酚、3-異丙基苯酚、4-異丙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、以及對叔丁基苯酚等烷基酚類；2,3,5-三甲基苯酚、及3,4,5-三甲基苯酚等三烷基酚類；間苯二酚、鄰苯二酚、對苯二酚、對苯二酚單甲基醚、連苯三酚、及間苯三酚等多元酚類；烷基間苯二酚、烷基鄰苯二酚、及烷基對苯二酚等烷基多元酚類(所有烷基之碳原子數均為1以上4以下。)；α-萘酚；β-萘酚；羥基聯苯(hydroxydiphenyl)；以及雙酚A等。此等酚類可單獨使用，亦可組合使用2種以上。(Phenols) Examples of phenols used in the production of novolac resin (A3) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2, Dimethylphenols such as 4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; o-ethylphenol, m-ethyl Ethyl phenols such as p-phenol, p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and Alkylphenols such as p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Resorcinol, catechol, Polyphenols such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and resorcinol; alkylresorcinol, alkylcatechol, and alkylhydroquinone Iso-alkyl polyphenols (the number of carbon atoms of all alkyl groups is 1 or more and 4 or less.); Α-naphthol; β-naphthol; hydroxydiphenyl; These phenols may be used alone or in combination of two or more.

此等酚類中，較佳為間甲酚及對甲酚，更佳併用間甲酚與對甲酚。此種情況下，可經由調整兩者的摻合比例，從而對使用樹脂組成物形成的硬化膜的耐熱性等各種特性進行調節。 　　間甲酚與對甲酚的摻合比例沒有特別限制，以間甲酚/對甲酚的莫耳比計，較佳為3/7以上8/2以下。藉由以上述範圍的比率使用間甲酚及對甲酚，從而容易得到可形成耐熱性優異的硬化膜之樹脂組成物。Of these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are used in combination. In this case, various characteristics such as heat resistance of the cured film formed using the resin composition can be adjusted by adjusting the blending ratio of the two. The blending ratio of p-cresol and p-cresol is not particularly limited, and it is preferably 3/7 or more and 8/2 or less based on the molar ratio of m-cresol / p-cresol. By using m-cresol and p-cresol at a ratio in the above range, a resin composition capable of forming a cured film excellent in heat resistance is easily obtained.

另外，併用間甲酚與2,3,5-三甲基苯酚而製造的酚醛清漆樹脂亦為較佳的。使用上述的酚醛清漆樹脂時，特別容易得到可形成不易由於後烘烤時的加熱而過度流動的硬化膜之樹脂組成物。 　　間甲酚與2,3,5-三甲基苯酚之摻合比例沒有特別限制，以間甲酚/2,3,5-三甲基苯酚的莫耳比計，較佳為70/30以上95/5以下。In addition, a novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferred. When the above-mentioned novolak resin is used, it is particularly easy to obtain a resin composition that can form a cured film that is less likely to flow excessively due to heating during post-baking. The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited. Based on the molar ratio of m-cresol / 2,3,5-trimethylphenol, it is preferably 70/30 or more. Below 95/5.

(醛類) 　　作為製作酚醛清漆樹脂(A3)時使用之醛類，可舉出例如甲醛、低聚甲醛(paraformaldehyde)、糠醛、苯甲醛、硝基苯甲醛、及乙醛等。此等醛類可單獨使用亦可組合使用2種以上。(Aldehydes) Examples of aldehydes used in the production of novolak resin (A3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

(酸催化劑) 　　作為製作酚醛清漆樹脂(A3)時可使用之酸催化劑，可舉出例如鹽酸、硫酸、硝酸、磷酸、及亞磷酸等無機酸類；甲酸、草酸、乙酸、硫酸二乙基酯、及對甲苯磺酸等有機酸類；以及乙酸鋅等金屬鹽類等。此等酸催化劑可單獨使用亦可組合使用2種以上。(Acid catalyst) As acid catalysts usable in the production of novolak resin (A3), for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfate, And organic acids such as p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(分子量) 　　對於酚醛清漆樹脂(A3)之按照聚苯乙烯換算的重量平均分子量(Mw；以下，亦簡稱為「重量平均分子量」)而言，從使用樹脂組成物形成的硬化膜對於因加熱而導致的流動之抗性的觀點考慮，作為下限值，較佳為2000，更佳為5000，特別較佳為10000，進一步較佳為15000，最佳為20000，作為上限值，較佳為50000，更佳為45000，進一步較佳為40000，最佳為35000。(Molecular Weight) For a polystyrene-equivalent weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the novolak resin (A3), a cured film formed by using a resin composition is effective against From the viewpoint of the resistance of the resulting flow, the lower limit value is preferably 2000, more preferably 5000, particularly preferably 10,000, even more preferably 15,000, most preferably 20,000, and as the upper limit, more preferably 50000, more preferably 45,000, still more preferably 40,000, and most preferably 35,000.

作為酚醛清漆樹脂(A3)，可將至少2種按照聚苯乙烯換算之重量平均分子量不同的酚醛清漆樹脂組合使用。經由將重量平均分子量不同的酚醛清漆樹脂進行大小組合併使用，從而可取得樹脂組成物的顯影性與使用樹脂組成物形成的硬化膜的耐熱性的平衡。As the novolak resin (A3), at least two kinds of novolak resins having different weight average molecular weights in terms of polystyrene can be used in combination. By combining and using novolak resins having different weight average molecular weights, it is possible to achieve a balance between the developability of the resin composition and the heat resistance of the cured film formed using the resin composition.

關於鹼可溶性樹脂(A)的含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為10～65質量%，更佳為15～50質量%。經由成為上述的範圍，從而容易得到顯影性優異之樹脂組成物。The content of the alkali-soluble resin (A) is preferably 10 to 65% by mass, and more preferably 15 to 50% by mass, with respect to the mass of the entire solid content of the resin composition. By setting it as the said range, it becomes easy to obtain the resin composition excellent in developability.

使用卡多(Cardo)樹脂(A1)時，關於其含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為5～40質量%，更佳為10～35質量%，進一步較佳為15～30質量%。經由成為上述的範圍，更能形成不易由於後烘烤時的加熱而發生過度流動的硬化膜，容易得到顯影性優異之樹脂組成物。When Cardo resin (A1) is used, its content is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and more preferably 10 to 35% by mass relative to the mass of the solid content of the resin composition as a whole. It is preferably 15 to 30% by mass. By setting it as the said range, the hardened film which does not flow easily by the heating at the time of a post-baking can be formed more, and it is easy to obtain the resin composition excellent in developability.

使用丙烯酸系樹脂(A2)時，關於其含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為2～55質量%，更佳為4～50質量%，進一步較佳為8～45質量%。經由成為上述的範圍，可形成不易由於後烘烤時的加熱而發生過度流動的硬化膜，容易得到顯影性優異之樹脂組成物。When an acrylic resin (A2) is used, its content is preferably 2 to 55% by mass, more preferably 4 to 50% by mass, and still more preferably 8 to the mass of the solid content of the resin composition as a whole. ～ 45% by mass. By setting it as the said range, the hardened film which is hard to generate | occur | produce excessive flow by the heating at the time of post-baking can be formed, and it is easy to obtain the resin composition excellent in developability.

使用酚醛清漆樹脂(A3)時，關於其含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為0.2～15質量%，更佳為0.5～10質量%，進一步較佳為0.8～5質量%。經由成為上述的範圍，可形成不易由於後烘烤時的加熱而發生過度流動的硬化膜，容易得到顯影性優異之樹脂組成物。When a novolak resin (A3) is used, its content is preferably 0.2 to 15% by mass, more preferably 0.5 to 10% by mass, and still more preferably 0.8 to the mass of the solid content of the resin composition as a whole. ~ 5 mass%. By setting it as the said range, the hardened film which is hard to generate | occur | produce excessive flow by the heating at the time of post-baking can be formed, and it is easy to obtain the resin composition excellent in developability.

＜光聚合性化合物(B)＞ 　　樹脂組成物包含光聚合性化合物(B)。作為光聚合性化合物(B)，較佳具有乙烯性不飽和基的單體。所述單體包含單官能單體與多官能單體。<Photopolymerizable compound (B)> The fluorene resin composition contains a photopolymerizable compound (B). The photopolymerizable compound (B) is preferably a monomer having an ethylenically unsaturated group. The monomer includes a monofunctional monomer and a polyfunctional monomer.

作為單官能單體，可舉出(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、富馬酸、馬來酸、馬來酸酐、衣康酸、衣康酸酐、檸康酸、檸康酸酐、丁烯酸、2-丙烯醯胺基-2-甲基丙磺酸、叔丁基丙烯醯胺基磺酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(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2-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、2-(甲基)丙烯醯基氧基-2-羥基丙基鄰苯二甲酸酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、鄰苯二甲酸衍生物的(甲基)丙烯酸半酯等。此等單官能單體可單獨使用，或者可組合2種以上而使用。Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, butenoic acid, 2-propene Amido-2-methylpropanesulfonic acid, tert-butylpropeneamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) propenyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, shrinking (meth) acrylate Glyceryl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid halves of phthalic acid derivatives Esters, etc. These monofunctional monomers may be used alone or in combination of two or more kinds.

另一方面，作為多官能單體，可舉出乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基多乙氧基苯基)丙烷、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯基氧基丙基酯、乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚縮水甘油基醚聚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯(即，甲苯二異氰酸酯、三甲基-1,6-己二異氰酸酯、或1,6-己二異氰酸酯等與(甲基)丙烯酸2-羥基乙酯的反應物)、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺的縮合物等多官能單體或1,3,5-三丙烯醯基六氫-1,3,5-三嗪(triacrylformal)等。此等多官能單體可單獨使用，或者可組合2種以上而使用。On the other hand, examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Base) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2- Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, (methyl) 2-hydroxy-3- (meth) acrylfluorenyloxypropyl acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol Glycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, aminomethyl (Meth) acrylate (that is, a reactant of toluene diisocyanate, trimethyl-1,6-hexanediisocyanate, or 1,6-hexanediisocyanate, etc. with 2-hydroxyethyl (meth) acrylate ), Polyfunctional monomers such as methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polycondensates of polyhydric alcohols and N-methylol (meth) acrylamide, or 1,3,5-tripropenylhexahydro-1,3,5-triazine (triacrylformal) and the like. These polyfunctional monomers may be used alone or in combination of two or more kinds.

此等具有乙烯性不飽和基的單體中，從存在提高樹脂組成物對基板的密著性、樹脂組成物之硬化後的強度的傾向方面考慮，較佳為3官能以上的多官能單體，更佳為4官能以上的多官能單體，進一步較佳為5官能以上的多官能單體。 　　具體而言，較佳為使用5官能以上的多官能單體，更佳為使用二季戊四醇五(甲基)丙烯酸酯、及/或二季戊四醇六(甲基)丙烯酸酯。Among these monomers having an ethylenically unsaturated group, a trifunctional or higher-functional polyfunctional monomer is preferred because of its tendency to improve the adhesion of the resin composition to the substrate and the strength after curing of the resin composition. , More preferably a polyfunctional monomer having 4 or more functions, and still more preferably a polyfunctional monomer having 5 or more functions. Specifically, it is preferable to use a polyfunctional monomer having 5 or more functions, and it is more preferable to use dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

關於光聚合性化合物(B)在樹脂組成物中的含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為1～50質量%，更佳為5～40質量%。經由成為上述的範圍，存在容易取得敏感度、顯影性、分辨力的平衡的傾向。The content of the photopolymerizable compound (B) in the resin composition is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass based on the mass of the solid content of the resin composition as a whole. By being in the above-mentioned range, there is a tendency that it is easy to achieve a balance between sensitivity, developability, and resolution.

＜光聚合引發劑(C)＞ 　　作為光聚合引發劑(C)，沒有特別限制，可使用現有已知的光聚合引發劑。<Photopolymerization Initiator (C)> As the photopolymerization initiator (C), there is no particular limitation, and conventionally known photopolymerization initiators can be used.

作為光聚合引發劑(C)，具體而言，可舉出1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(4-二甲基胺基苯基)酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉代(morpholino)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁烷-1-酮、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-哢唑-3-基]乙酮肟、(9-乙基-6-硝基-9H-哢唑-3-基)[4-(2-甲氧基-1-甲基乙氧基)-2-甲基苯基]甲酮O-乙醯基肟、2-(苯甲醯基氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、4-苯甲醯基-4’-甲基二甲基硫醚、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基-2-乙基己基苯甲酸、4-二甲基胺基-2-異戊基苯甲酸、苯偶醯-β-甲氧基乙基縮醛、苯偶醯二甲基縮酮、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、鄰苯甲醯基苯甲酸甲酯、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、1-氯-4-丙氧基噻噸酮、噻噸、2-氯噻噸、2,4-二乙基噻噸、2-甲基噻噸、2-異丙基噻噸、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、過氧化氫異丙苯、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)-咪唑基二聚體、二苯甲酮、2-氯二苯甲酮、4,4’-雙二甲基胺基二苯甲酮、4,4’-雙二乙基胺基二苯甲酮、4,4’-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苯偶醯、苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、苯偶姻丁基醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對叔丁基苯乙酮、對二甲基胺基苯乙酮、對叔丁基三氯苯乙酮、對叔丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、二苯并環庚酮(dibenzosuberone)、4-二甲基胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三嗪、2,4,6-三(三氯甲基)均三嗪、2-甲基-4,6-雙(三氯甲基)均三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)均三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)均三嗪、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)均三嗪、2,4-雙三氯甲基-6-(3-溴-4-甲氧基)苯基均三嗪、2,4-雙三氯甲基-6-(2-溴-4-甲氧基)苯基均三嗪、2,4-雙三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基均三嗪、2,4-雙三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基均三嗪等。此等光聚合引發劑可單獨使用，或者可組合2種以上而使用。Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- ( 2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane- 1-ketone, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-1- Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, O-acetamidin-1- [6- (2-methyl Benzamidine) -9-ethyl-9H-oxazol-3-yl] ethanone oxime, (9-ethyl-6-nitro-9H-oxazol-3-yl) [4- (2- Methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetamidooxime, 2- (benzylideneoxyimino) -1- [4- (benzene Methylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzylidenediphenylphosphine oxide, 4-benzylidene-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzoin-β-methoxyethyl acetal, benzoin Methyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone , 2-methylthioxan, 2-isopropylthioxan, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azo Bisisobutyronitrile, benzamidine peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4 , 5-bis (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4, 4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl Ether, acetoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminophenylacetone, dichloroacetophenone, trichloride Acetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4 -Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, amyl 4-dimethylaminobenzoate , 9-phenylacridine, 1,7-bis- (9-acridyl) heptane, 1,5-bis- (9-acridyl) pentane, 1,3-bis- (9-acryl (Pyridyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) mesatriazine, 2-methyl-4,6-bis (trichloromethyl) mesatriazine, 2 -[2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) himetriazine, 2- [2- (furan-2-yl) vinyl]- 4,6-bis (trichloromethyl) mesatriazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl ) Mesatriazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) mesatriazine, 2- (4-methoxybenzene Phenyl) -4,6-bis (trichloromethyl) mesatriazine, 2- (4-ethoxy Styryl) -4,6-bis (trichloromethyl) mesazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) mesazine, 2, 4-bistrichloromethyl-6- (3-bromo-4-methoxy) phenyl mesazine, 2,4-bistrichloromethyl-6- (2-bromo-4-methoxy) Phenyl-s-triazine, 2,4-bistrichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bistrichloromethyl-6- (2-Bromo-4-methoxy) styrylphenylmethanetriazine and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds.

此等中，從敏感度方面考慮，特別較佳為使用肟系的光聚合引發劑。肟系的光聚合引發劑中，作為特別較佳之肟系的光聚合引發劑，可舉出O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-哢唑-3-基]乙酮肟、1-[9-乙基-6-(吡咯-2-基羰基)-9H-哢唑-3-基]乙酮1-(O-乙醯基肟)、及2-(苯甲醯基氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮。Among these, in view of sensitivity, it is particularly preferable to use an oxime-based photopolymerization initiator. Among the oxime-based photopolymerization initiators, as a particularly preferred oxime-based photopolymerization initiator, O-ethylfluorenyl-1- [6- (2-methylbenzylidene) -9-ethyl is mentioned. -9H-oxazol-3-yl] ethanone oxime, 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-oxazol-3-yl] ethanone 1- (O-ethyl Fluorenyl oxime), and 2- (benzylideneoxyimino) -1- [4- (phenylthio) phenyl] -1-octanone.

作為光聚合引發劑，另外還較佳為使用下述式(c1)表示的肟系化合物。 　　[化10](Rc1 為選自由1價之有機基、胺基、鹵素、硝基、及氰基組成之組中的基， 　　n1為0～4的整數， 　　n2為0或1， 　　Rc2 為可具有取代基之苯基或可具有取代基的哢唑基， 　　Rc3 為氫原子或碳原子數1～6之烷基)。As the photopolymerization initiator, it is also preferable to use an oxime-based compound represented by the following formula (c1). [Chemical 10] (R c1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, n1 is an integer of 0 to 4, n2 is 0 or 1, and R c2 is a substituent The phenyl group may be an oxazolyl group which may have a substituent, and R c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

式(c1)中，對於Rc1 而言，在不妨礙本發明的目的的範圍內沒有特別限制，可從各種有機基中適當選擇。作為Rc1 為有機基時的較佳例，可舉出烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯基氧基、烷氧基羰基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、胺基、被1或2個有機基取代的胺基、嗎啉-1-基、及呱嗪-1-基、鹵素、硝基、及氰基等。n1為2～4之整數時，Rc1 可相同亦可不同。另外，取代基之碳原子數不包含取代基進一步所具有的取代基的碳原子數。In formula (c1), R c1 is not particularly limited as long as it does not hinder the object of the present invention, and may be appropriately selected from various organic groups. Preferable examples when R c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, a saturated aliphatic fluorenyloxy group, an alkoxycarbonyl group, A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzamyloxy group which may have a substituent, may A phenylalkyl group having a substituent, a naphthyl group having a substituent, a naphthyloxy group having a substituent, a naphthylmethyl group having a substituent, a naphthyloxycarbonyl group having a substituent, and a substituent Naphthylmethyloxy, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, amino group, amino group substituted with 1 or 2 organic groups, morpholin-1-yl, and Fluorazin-1-yl, halogen, nitro, and cyano. When n1 is an integer of 2 to 4, R c1 may be the same or different. In addition, the carbon number of a substituent does not include the carbon number of the substituent which the substituent further has.

Rc1 為烷基時，碳原子數較佳為1～20，碳原子數更佳為1～6。另外，Rc1 為烷基時，可為直鏈，亦可為支鏈。作為Rc1 為烷基時的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、及異癸基等。另外，Rc1 為烷基時，烷基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷基的例子，可舉出甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。When R c1 is an alkyl group, the number of carbon atoms is preferably 1 to 20, and the number of carbon atoms is more preferably 1 to 6. When R c1 is an alkyl group, it may be a straight chain or a branched chain. As specific examples when R c1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl Base, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, t-octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. . When R c1 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxy. Ethoxyethyl, and methoxypropyl.

Rc1 為烷氧基時，碳原子數較佳為1～20，碳原子數更佳為1～6。另外，Rc1 為烷氧基時，可為直鏈，也可為支鏈。作為Rc1 為烷氧基時之具體例，可舉出甲氧基、乙氧基、正丙基氧基、異丙基氧基、正丁基氧基、異丁基氧基、仲丁基氧基、叔丁基氧基、正戊基氧基、異戊基氧基、仲戊基氧基、叔戊基氧基、正己基氧基、正庚基氧基、正辛基氧基、異辛基氧基、仲辛基氧基、叔辛基氧基、正壬基氧基、異壬基氧基、正癸基氧基、及異癸基氧基等。另外，Rc1 為烷氧基時，烷氧基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷氧基的例子，可舉出甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙基氧基乙氧基乙氧基、及甲氧基丙基氧基等。When R c1 is an alkoxy group, the number of carbon atoms is preferably 1 to 20, and the number of carbon atoms is more preferably 1 to 6. When R c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R c1 is alkoxy include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyl Oxy, t-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, t-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, Isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. When R c1 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Groups, propyloxyethoxyethoxy, and methoxypropyloxy.

Rc1 為環烷基或環烷氧基時，碳原子數較佳為3～10，碳原子數更佳為3～6。作為Rc1 為環烷基時之具體例，可舉出環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Rc1 為環烷氧基時之具體例，可舉出環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、及環辛基氧基等。When R c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and the number of carbon atoms is more preferably 3 to 6. Specific examples when R c1 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R c1 is a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy Base etc.

Rc1 為飽和脂肪族醯基或飽和脂肪族醯基氧基時，碳原子數較佳為2～20，碳原子數更佳為2～7。作為Rc1 為飽和脂肪族醯基時的具體例，可舉出乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一烷醯基、正十二烷醯基、正十三烷醯基、正十四烷醯基、正十五烷醯基、及正十六烷醯基等。作為Rc1 為飽和脂肪族醯基氧基時的具體例，可舉出乙醯基氧基、丙醯基氧基、正丁醯基氧基、2-甲基丙醯基氧基、正戊醯基氧基、2,2-二甲基丙醯基氧基、正己醯基氧基、正庚醯基氧基、正辛醯基氧基、正壬醯基氧基、正癸醯基氧基、正十一烷醯基氧基、正十二烷醯基氧基、正十三烷醯基氧基、正十四烷醯基氧基、正十五烷醯基氧基、及正十六烷醯基氧基等。When R c1 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms is preferably 2 to 20, and the number of carbon atoms is more preferably 2 to 7. Specific examples when R c1 is a saturated aliphatic fluorenyl group include ethyl fluorenyl, propyl fluorenyl, n-butyl fluorenyl, 2-methylpropyl fluorenyl, n-pentyl fluorenyl, and 2,2-dimethylpropanyl N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecanyl N-pentadecanyl, and n-hexadecylfluorenyl. Specific examples when R c1 is a saturated aliphatic fluorenyloxy group include ethynyloxy, propionyloxy, n-butylfluorenyloxy, 2-methylpropanyloxy, and n-pentamyloxy. Oxy, 2,2-dimethylpropionyloxy, n-hexylfluorenyloxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonylfluorenyloxy, n-decylfluorenyloxy, n-decyl Monoalkylfluorenyloxy, n-dodecylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecanylfluorenyloxy, n-pentadecanylfluorenyloxy, and n-hexadecylfluorenyl Oxygen, etc.

Rc1 為烷氧基羰基時，碳原子數較佳為2～20，碳原子數更佳為2～7。作為Rc1 為烷氧基羰基時的之具體例，可舉出甲氧基羰基、乙氧基羰基、正丙基氧基羰基、異丙基氧基羰基、正丁基氧基羰基、異丁基氧基羰基、仲丁基氧基羰基、叔丁基氧基羰基、正戊基氧基羰基、異戊基氧基羰基、仲戊基氧基羰基、叔戊基氧基羰基、正己基氧基羰基、正庚基氧基羰基、正辛基氧基羰基、異辛基氧基羰基、仲辛基氧基羰基、叔辛基氧基羰基、正壬基氧基羰基、異壬基氧基羰基、正癸基氧基羰基、及異癸基氧基羰基等。When R c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and the number of carbon atoms is more preferably 2 to 7. Specific examples when R c1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, and isobutyl Oxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxy Carbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxy Carbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

Rc1 為苯基烷基時，碳原子數較佳為7～20，碳原子數更佳為7～10。另外，Rc1 為萘基烷基時，碳原子數較佳為11～20，碳原子數更佳為11～14。作為Rc1 為苯基烷基時的具體例，可舉出苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Rc1 為萘基烷基時的具體例，可舉出α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。Rc1 為苯基烷基或萘基烷基時，Rc1 可在苯基、或萘基上進一步具有取代基。When R c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and the number of carbon atoms is more preferably 7 to 10. When R c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and the number of carbon atoms is more preferably 11 to 14. Specific examples when R c1 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R c1 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) Ethyl. When R c1 is phenylalkyl or naphthylalkyl, R c1 may further have a substituent on phenyl or naphthyl.

Rc1 為雜環基時，雜環基為包含1個以上之N、S、O的五元或六元的單環、或者為所述單環彼此縮合、或所述單環與苯環縮合而成的雜環基。雜環基為縮合環時，環數為3以下。作為構成所述雜環基的雜環，可舉出呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚嗪、苯并咪唑、苯并***、苯并噁唑、苯并噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、肉啉、及喹喔啉等。Rc1 為雜環基時，雜環基可進一步具有取代基。When R c1 is a heterocyclic group, the heterocyclic group is a five- or six-membered monocyclic ring containing one or more N, S, and O, or the monocyclic rings are condensed with each other, or the monocyclic ring and a benzene ring are condensed. And formed into a heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, iso Quinoline, quinazoline, phthalazine, carboline, and quinoxaline. When R c1 is a heterocyclic group, the heterocyclic group may further have a substituent.

Rc1 為被1或2個有機基取代的胺基時，關於有機基的較佳例，可舉出碳原子數1～20的烷基、碳原子數3～10的環烷基、碳原子數2～20的飽和脂肪族醯基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的碳原子數7～20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的碳原子數11～20的萘基烷基、及雜環基等。此等較佳的有機基的具體例與Rc1 同樣。作為被1或2個有機基取代的胺基的具體例，可舉出甲基胺基、乙基胺基、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。When R c1 is an amine group substituted with one or two organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. 2 to 20 saturated aliphatic fluorenyl groups, phenyl groups which may have a substituent, benzamidine groups which may have a substituent, phenylalkyl groups which have 7 to 20 carbon atoms, which may have a substituent A naphthyl group, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group, and the like. Specific examples of these preferable organic groups are the same as those of R c1 . Specific examples of the amino group substituted by one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, and isopropyl Amino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamine Group, phenylamino group, naphthylamino group, ethylamino group, propionylamino group, n-butylmethylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, Octylamino, n-decanoylamino, benzamidoamino, α-naphthylmethylamino, β-naphthylamino, and the like.

作為Rc1 中包含的苯基、萘基、及雜環基進一步具有取代基時的取代基，可舉出碳原子數1～6的烷基、碳原子數1～6的烷氧基、碳原子數2～7的飽和脂肪族醯基、碳原子數2～7的烷氧基羰基、碳原子數2～7的飽和脂肪族醯基氧基、具有碳原子數1～6的烷基的單烷基胺基、具有碳原子數1～6的烷基的二烷基胺基、嗎啉-1-基、呱嗪-1-基、鹵素、硝基、及氰基等。Rc1 中包含的苯基、萘基、及雜環基進一步具有取代基時，對於其取代基的個數而言，在不妨礙本發明的目的的範圍內沒有限制，較佳為1～4。Rc1 中包含的苯基、萘基、及雜環基具有多個取代基時，多個取代基可相同亦可不同。Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon A saturated aliphatic fluorenyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms A monoalkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyrazin-1-yl group, a halogen group, a nitro group, and a cyano group. When the phenyl, naphthyl, and heterocyclic group contained in R c1 further has a substituent, the number of the substituents is not limited as long as it does not hinder the object of the present invention, and is preferably 1 to 4 . When a phenyl group, a naphthyl group, and a heterocyclic group included in R c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Rc1 中，從化學穩定、空間位阻小、容易合成肟酯化合物等方面考慮，較佳為選自由碳原子數1～6之烷基、碳原子數1～6之烷氧基、及碳原子數2～7的飽和脂肪族醯基所組成之群中之基，更佳為碳原子數1～6的烷基，特別佳為甲基。R c1 is preferably selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon in view of chemical stability, small steric hindrance, and easy synthesis of an oxime ester compound. The group in the group consisting of a saturated aliphatic fluorenyl group having 2 to 7 atoms is more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

針對Rc1 所鍵結之苯基，在將苯基與肟酯化合物的主骨架的鍵結鍵的位置作為1位，將甲基的位置作為2位時，Rc1 在苯基上鍵結的位置較佳為4位或5位，更佳為5位。另外，n1較佳為0～3的整數，更佳為0～2的整數，特別佳為0或1。Regarding the phenyl group to which R c1 is bonded, when the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is taken as the first position and the position of the methyl group is taken as the second position, R c1 is bonded to the phenyl group. The position is preferably 4 or 5 positions, and more preferably 5 positions. In addition, n1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

Rc2 為可具有取代基的苯基、或可具有取代基的哢唑基。另外，Rc2 為可具有取代基的哢唑基時，哢唑基上的氮原子可被碳原子數1～6的烷基取代。R c2 is a phenyl group which may have a substituent, or an oxazolyl group which may have a substituent. When R c2 is an oxazolyl group which may have a substituent, the nitrogen atom on the oxazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

Rc2 中，苯基、或哢唑基所具有的取代基在不妨礙本發明的目的的範圍內沒有特別限制。作為苯基、或哢唑基可在碳原子上具有的較佳的取代基的例子，可舉出碳原子數1～20的烷基、碳原子數1～20的烷氧基、碳原子數3～10的環烷基、碳原子數3～10的環烷氧基、碳原子數2～20的飽和脂肪族醯基、碳原子數2～20的烷氧基羰基、碳原子數2～20的飽和脂肪族醯基氧基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯基硫基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的碳原子數7～20的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的碳原子數11～20的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環基羰基、胺基、被1個或2個有機基取代的胺基、嗎啉-1-基、及呱嗪-1-基、鹵素、硝基、及氰基等。In R c2 , the substituent of the phenyl group or the oxazolyl group is not particularly limited as long as it does not hinder the object of the present invention. Examples of preferred substituents which the phenyl or oxazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon number. 3 to 10 cycloalkyl, 3 to 10 carbon alkoxy, 2 to 20 saturated aliphatic fluorenyl, 2 to 20 carbon alkoxycarbonyl, 2 to 2 carbon atoms 20 saturated aliphatic fluorenyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, phenylthio which may have a substituent, benzamidine which may have a substituent, may have a substituent Phenoxycarbonyl group, benzamyloxy group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthalene which may have a substituent Oxy group, naphthylmethyl group which may have a substituent, naphthyloxycarbonyl group which may have a substituent, naphthylmethyloxy group which may have a substituent, and naphthylalkane having 11 to 20 carbon atoms which may have a substituent Group, a heterocyclic group which may have a substituent, a heterocyclic group which may have a substituent, a carbonyl group, an amino group, an amino group substituted with one or two organic groups, morpholine- 1-yl, and pyrazin-1-yl, halogen, nitro, and cyano.

Rc2 為哢唑基時，作為哢唑基可在氮原子上具有的較佳的取代基的例子，可舉出碳原子數1～20的烷基、碳原子數3～10的環烷基、碳原子數2～20的飽和脂肪族醯基、碳原子數2～20的烷氧基羰基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的碳原子數7～20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的碳原子數11～20的萘基烷基、可具有取代基的雜環基、及可具有取代基的雜環基羰基等。此等取代基中，較佳為碳原子數1～20的烷基，更佳為碳原子數1～6的烷基，特別較佳為乙基。When R c2 is an oxazolyl group, examples of preferred substituents which the oxazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, benzamidine group which may have a substituent, benzene which may have a substituent An oxycarbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, A naphthylalkyl group having 11 to 20 carbon atoms which has a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

對於苯基、或哢唑基可具有的取代基的具體例而言，關於烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基烷基、可具有取代基的雜環基、及被1個或2個有機基取代的胺基，與Rc1 同樣。Specific examples of the substituent which the phenyl group or the oxazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, and a saturated aliphatic group. A fluorenyloxy group, a phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with one or two organic groups, and R c1 is the same.

Rc2 中，作為苯基、或哢唑基所具有的取代基中包含的苯基、萘基、及雜環基進一步具有取代基時的取代基的例子，可舉出碳原子數1～6的烷基；碳原子數1～6的烷氧基；碳原子數2～7的飽和脂肪族醯基；碳原子數2～7的烷氧基羰基；碳原子數2～7的飽和脂肪族醯基氧基；苯基；萘基；苯甲醯基；萘甲醯基；被選自由碳原子數1～6的烷基、嗎啉-1-基、呱嗪-1-基、及苯基組成的組中的基取代的苯甲醯基；具有碳原子數1～6的烷基的單烷基胺基；具有碳原子數1～6的烷基的二烷基胺基；嗎啉-1-基；呱嗪-1-基；鹵素；硝基；氰基。苯基、或哢唑基所具有的取代基中包含的苯基、萘基、及雜環基進一步具有取代基時，其取代基的個數在不妨礙本發明的目的的範圍內沒有限制，較佳為1～4。苯基、萘基、及雜環基具有多個取代基時，多個取代基可相同亦可不同。Examples of the substituent when R c2 further includes a phenyl group, a naphthyl group, and a heterocyclic group included in the substituent included in the oxazolyl group include carbon atoms of 1 to 6 Alkyl groups; alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic fluorenyl groups having 2 to 7 carbon atoms; alkoxycarbonyl groups having 2 to 7 carbon atoms; saturated aliphatic groups having 2 to 7 carbon atoms Fluorenyloxy; phenyl; naphthyl; benzamyl; naphthylmethyl; selected from alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl, pyrazin-1-yl, and benzene A benzamidine group substituted with a group in the group consisting of a base; a monoalkylamine group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine -1-yl; pyrazin-1-yl; halogen; nitro; cyano. When the phenyl, naphthyl, and heterocyclic group contained in the phenyl or oxazolyl substituent further has a substituent, the number of substituents is not limited as long as it does not prevent the object of the present invention. It is preferably 1 to 4. When a phenyl group, a naphthyl group, and a heterocyclic group have multiple substituents, the multiple substituents may be the same or different.

Rc2 中，從容易得到敏感度優異的光聚合引發劑方面考慮，較佳為下述式(c2)或(c3)表示的基，更佳為下述式(c2)表示的基，特別較佳A為S的下述式(c2)表示的基。In R c2 , a group represented by the following formula (c2) or (c3) is preferred, and a group represented by the following formula (c2) is more preferred from the standpoint of easily obtaining a photopolymerization initiator having excellent sensitivity. Preferably, A is a group represented by the following formula (c2) of S.

[化11](Rc4 為選自由1價的有機基、胺基、鹵素、硝基、及氰基組成的組中的基，A為S或O，n3為0～4的整數。)[Chemical 11] (R c4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 to 4.)

[化12](Rc5 及Rc6 分別為1價的有機基。)[Chemical 12] (R c5 and R c6 are each a monovalent organic group.)

式(c2)中的Rc4 為有機基時，可在不妨礙本發明的目的的範圍內從各種有機基中選擇。作為式(c2)中Rc4 為有機基時的較佳例，可舉出碳原子數1～6的烷基；碳原子數1～6的烷氧基；碳原子數2～7的飽和脂肪族醯基；碳原子數2～7的烷氧基羰基；碳原子數2～7的飽和脂肪族醯基氧基；苯基；萘基；苯甲醯基；萘甲醯基；被選自由碳原子數1～6的烷基、嗎啉-1-基、呱嗪-1-基、及苯基所組成之群中之基取代的苯甲醯基；具有碳原子數1～6的烷基的單烷基胺基；具有碳原子數1～6的烷基的二烷基胺基；嗎啉-1-基；呱嗪-1-基；鹵素；硝基；氰基。When R c4 in the formula (c2) is an organic group, it can be selected from various organic groups within a range not hindering the object of the present invention. Preferred examples when R c4 is an organic group in formula (c2) include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated fat having 2 to 7 carbon atoms. Group fluorenyl groups; alkoxycarbonyl groups with 2 to 7 carbon atoms; saturated aliphatic fluorenyloxy groups with 2 to 7 carbon atoms; phenyl; naphthyl; benzamyl; naphthylmethyl; A benzamidine group substituted with a group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyrazine-1-yl group, and a phenyl group; an alkane group having 1 to 6 carbon atoms A monoalkylamino group of a radical; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a hydrazine-1-yl group; a halogen group; a nitro group; and a cyano group.

Rc4 中，較佳為苯甲醯基；萘甲醯基；被選自由碳原子數1～6的烷基、嗎啉-1-基、呱嗪-1-基、及苯基所組成之群中的基取代的苯甲醯基；硝基，更佳為苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(呱嗪-1-基)苯基羰基；4-(苯基)苯基羰基。R c4 is preferably benzamyl; naphthylmethyl; is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, pyrazin-1-yl, and phenyl A benzamyl group substituted by a group in the group; a nitro group, more preferably a benzamyl group; a naphthylmethane group; a 2-methylphenylcarbonyl group; a 4- (fluorazin-1-yl) phenylcarbonyl group; 4 -(Phenyl) phenylcarbonyl.

另外，式(c2)中，n3較佳為0～3的整數，更佳為0～2的整數，特別佳為0或1。n3為1時，Rc4 的鍵結位置較佳相對於Rc4 所鍵結的苯基與氧原子或硫原子相鍵結的鍵結鍵而言為對位。In formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. n3 is 1, R c4 bonding position with respect to preferred R c4 are bonded a phenyl group or a sulfur atom and an oxygen atom bonded to the bonding position for the key terms.

式(c3)中的Rc5 可在不妨礙本發明的目的的範圍內從各種有機基中選擇。作為Rc5 的較佳例，可舉出碳原子數1～20的烷基、碳原子數3～10的環烷基、碳原子數2～20的飽和脂肪族醯基、碳原子數2～20的烷氧基羰基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的碳原子數7～20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的碳原子數11～20的萘基烷基、可具有取代基的雜環基、及可具有取代基的雜環基羰基等。R c5 in formula (c3) can be selected from various organic groups within a range that does not prevent the object of the present invention. Preferable examples of R c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and 2 to 2 carbon atoms. Alkoxycarbonyl group of 20, phenyl group which may have a substituent, benzamidine group which may have a substituent, phenoxycarbonyl group which may have a substituent, and phenylalkane having 7 to 20 carbon atoms which may have a substituent Group, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, may have a substituent Heterocyclyl, and heterocyclylcarbonyl which may have a substituent.

Rc5 中，較佳為碳原子數1～20的烷基，更佳為碳原子數1～6的烷基，特別佳為乙基。R c5 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

式(c3)中的Rc6 在不妨礙本發明的目的的範圍內沒有特別限制，可從各種有機基中選擇。關於作為Rc6 的較佳基的具體例，可舉出碳原子數1～20的烷基、可具有取代基的苯基、可具有取代基的萘基、及可具有取代基的雜環基。作為Rc6 ，在此等基中，更佳為可具有取代基的苯基，特別較佳為2-甲基苯基。R c6 in formula (c3) is not particularly limited as long as it does not hinder the object of the present invention, and may be selected from various organic groups. Specific examples of the preferable group as R c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. . Of these groups, R c6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

作為Rc4 、Rc5 、或Rc6 中包含的苯基、萘基、及雜環基進一步具有取代基時的取代基，可舉出碳原子數1～6的烷基、碳原子數1～6的烷氧基、碳原子數2～7的飽和脂肪族醯基、碳原子數2～7的烷氧基羰基、碳原子數2～7的飽和脂肪族醯基氧基、具有碳原子數1～6的烷基的單烷基胺基、具有碳原子數1～6的烷基的二烷基胺基、嗎啉-1-基、呱嗪-1-基、鹵素、硝基、及氰基等。Rc4 、Rc5 、或Rc6 中包含的苯基、萘基、及雜環基進一步具有取代基時，其取代基的個數在不妨礙本發明的目的的範圍內沒有限制，較佳為1～4。Rc4 、Rc5 、或Rc6 中包含的苯基、萘基、及雜環基具有多個取代基時，多個取代基可相同亦可不同。 Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R c4 , R c5 , or R c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. 6 alkoxy group, saturated aliphatic fluorenyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic fluorenyl group with 2 to 7 carbon atoms, and has carbon number Monoalkylamino groups of 1 to 6 alkyl groups, dialkylamino groups of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl, oxazin-1-yl, halogen, nitro, and Cyano, etc. When the phenyl, naphthyl, and heterocyclic group contained in R c4 , R c5 , or R c6 further has a substituent, the number of substituents is not limited as long as it does not prevent the object of the present invention, and is preferably 1 to 4. When the phenyl, naphthyl, and heterocyclic group contained in R c4 , R c5 , or R c6 has a plurality of substituents, the plurality of substituents may be the same or different.

式(c1)中之Rc3 為氫原子或碳原子數1～6的烷基。作為Rc3 ，較佳為甲基或乙基，更佳為甲基。R c3 in formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R c3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

式(c1)表示的肟酯化合物中，作為特別較佳的化合物，可舉出下述的PI-1～PI-42。 　　[化13] Among the oxime ester compounds represented by the formula (c1), particularly preferred compounds include PI-1 to PI-42 described below. [Chemical 13]

[化14] [Chemical 14]

[化15] [Chemical 15]

[化16] [Chemical 16]

[化17] [Chemical 17]

[化18] [Chemical 18]

另外，下述式(c4)表示之肟酯化合物亦較佳作為光聚合引發劑。The oxime ester compound represented by the following formula (c4) is also preferably used as a photopolymerization initiator.

[化19](Rc7 為氫原子、硝基或1價之有機基，Rc8 及Rc9 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基、或氫原子，Rc8 與Rc9 可相互鍵結而形成環，Rc10 為1價之有機基，Rc11 為氫原子、可具有取代基的碳原子數1～11的烷基、或可具有取代基的芳基，n4為0～4的整數，n5為0或1。)[Chemical 19] (R c7 is a hydrogen atom, a nitro group, or a monovalent organic group, R c8 and R c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R c8 and R c9 may be bonded to each other to form a ring, R c10 is a monovalent organic group of, R c11 is a hydrogen atom, an alkyl group may have a substituent group having a carbon number of 1 to 11, an aryl group, or may have a substituent group, n4 (It is an integer from 0 to 4. n5 is 0 or 1.)

於此，作為用於製造式(c4)的肟酯化合物之肟化合物，較佳為下式(c5)表示的化合物。Here, as the oxime compound for producing the oxime ester compound of the formula (c4), a compound represented by the following formula (c5) is preferred.

[化20](Rc7 、Rc8 、Rc9 、Rc10 、n4、及n5與式(c4)同樣)。[Chemical 20] (R c7 , R c8 , R c9 , R c10 , n4, and n5 are the same as the formula (c4)).

式(c4)及(c5)中，Rc7 為氫原子、硝基或1價之有機基。Rc7 在式(c4)中的芴環上鍵結於與-(CO)n5 -表示之基所鍵結之六元芳香環不同的六元芳香環上。式(c4)中，Rc7 相對於芴環而言之鍵結位置沒有特別限制。式(c4)表示的化合物具有1個以上Rc7 時，從容易合成式(c4)表示的化合物等方面考慮，較佳為1個以上的Rc7 中之1個鍵結於芴環中的2位。Rc7 為多個時，多個Rc7 可相同亦可不同。In the formulae (c4) and (c5), R c7 is a hydrogen atom, a nitro group, or a monovalent organic group. R c7 is bonded to the fluorene ring in formula (c4) to a six-membered aromatic ring different from the six-membered aromatic ring bonded to the group represented by- (CO) n5- . In formula (c4), the bonding position of R c7 with respect to the fluorene ring is not particularly limited. When the compound represented by formula (c4) has one or more R c7 , from the viewpoint of easy synthesis of the compound represented by formula (c4), it is preferred that one of one or more R c7 is bonded to 2 in the fluorene ring. Bit. R c7 is a plurality, the plurality of R c7 may be identical or different.

Rc7 為有機基時，Rc7 在不妨礙本發明的目的的範圍內沒有特別限制，可從各種有機基中適當選擇。作為Rc7 為有機基時的較佳例，可舉出烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯基氧基、烷氧基羰基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環基羰基、被1個或2個有機基取代的胺基、嗎啉-1-基、及呱嗪-1-基等。When R c7 is an organic group, R c7 is not particularly limited as long as it does not hinder the object of the present invention, and may be appropriately selected from various organic groups. Preferable examples when R c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, a saturated aliphatic fluorenyloxy group, an alkoxycarbonyl group, A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzamyloxy group which may have a substituent, may A phenylalkyl group having a substituent, a naphthyl group having a substituent, a naphthyloxy group having a substituent, a naphthylmethyl group having a substituent, a naphthyloxycarbonyl group having a substituent, and a substituent Naphthylmethyloxy, naphthylalkyl which may have substituents, heterocyclyl which may have substituents, heterocyclylcarbonyl which may have substituents, amino groups substituted with one or two organic groups, Morpholin-1-yl, and pyrazin-1-yl and the like.

Rc7 為烷基時，烷基的碳原子數較佳為1～20，更佳為1～6。另外，Rc7 為烷基時，可為直鏈，亦可為支鏈。作為Rc7 為烷基時的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、及異癸基等。另外，Rc7 為烷基時，烷基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷基的例子，可舉出甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。When R c7 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 6. When R c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R c7 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and isopentyl. Base, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, t-octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. . When R c7 is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxy. Ethoxyethyl, and methoxypropyl.

Rc7 為烷氧基時，烷氧基的碳原子數較佳為1～20，更佳為1～6。另外，Rc7 為烷氧基時，可為直鏈，也可為支鏈。作為Rc7 為烷氧基時之具體例，可舉出甲氧基、乙氧基、正丙基氧基、異丙基氧基、正丁基氧基、異丁基氧基、仲丁基氧基、叔丁基氧基、正戊基氧基、異戊基氧基、仲戊基氧基、叔戊基氧基、正己基氧基、正庚基氧基、正辛基氧基、異辛基氧基、仲辛基氧基、叔辛基氧基、正壬基氧基、異壬基氧基、正癸基氧基、及異癸基氧基等。另外，Rc7 為烷氧基時，烷氧基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷氧基之例子，可舉出甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙基氧基乙氧基乙氧基、及甲氧基丙基氧基等。When R c7 is an alkoxy group, an alkoxy group having a carbon number of preferably 1 to 20, more preferably 1 to 6. When R c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R c7 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, and a sec-butyl group. Oxy, t-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, t-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, Isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. When R c7 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy Groups, propyloxyethoxyethoxy, and methoxypropyloxy.

Rc7 為環烷基或環烷氧基時，環烷基或環烷氧基的碳原子數較佳為3～10，更佳為3～6。作為Rc7 為環烷基時的具體例，可舉出環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。作為Rc7 為環烷氧基時的具體例，可舉出環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、及環辛基氧基等。When R c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples when R c7 is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R c7 is a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy Base etc.

Rc7 為飽和脂肪族醯基或飽和脂肪族醯基氧基時，飽和脂肪族醯基或飽和脂肪族醯基氧基的碳原子數較佳為2～21，更佳為2～7。作為Rc7 為飽和脂肪族醯基時的具體例，可舉出乙醯基、丙醯基、正丁醯基、2-甲基丙醯基、正戊醯基、2,2-二甲基丙醯基、正己醯基、正庚醯基、正辛醯基、正壬醯基、正癸醯基、正十一烷醯基、正十二烷醯基、正十三烷醯基、正十四烷醯基、正十五烷醯基、及正十六烷醯基等。作為Rc7 為飽和脂肪族醯基氧基時的具體例，可舉出乙醯基氧基、丙醯基氧基、正丁醯基氧基、2-甲基丙醯基氧基、正戊醯基氧基、2,2-二甲基丙醯基氧基、正己醯基氧基、正庚醯基氧基、正辛醯基氧基、正壬醯基氧基、正癸醯基氧基、正十一烷醯基氧基、正十二烷醯基氧基、正十三烷醯基氧基、正十四烷醯基氧基、正十五烷醯基氧基、及正十六烷醯基氧基等。When R c7 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the number of carbon atoms of the saturated aliphatic fluorenyl group or saturated aliphatic fluorenyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R c7 is a saturated aliphatic fluorenyl group include ethyl fluorenyl, propyl fluorenyl, n-butyl fluorenyl, 2-methylpropyl fluorenyl, n-pentyl fluorenyl, and 2,2-dimethylpropanyl N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecanyl N-pentadecanyl, and n-hexadecylfluorenyl. Specific examples when R c7 is a saturated aliphatic fluorenyloxy group include ethynyloxy, propionyloxy, n-butylfluorenyloxy, 2-methylpropylfluorenyloxy, and n-pentamyloxy. Oxy, 2,2-dimethylpropionyloxy, n-hexylfluorenyloxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonylfluorenyloxy, n-decylfluorenyloxy, n-decyl Monoalkylfluorenyloxy, n-dodecylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecanylfluorenyloxy, n-pentadecanylfluorenyloxy, and n-hexadecylfluorenyl Oxygen, etc.

Rc7 為烷氧基羰基時，烷氧基羰基之碳原子數較佳為2～20，更佳為2～7。作為Rc7 為烷氧基羰基時之具體例，可舉出甲氧基羰基、乙氧基羰基、正丙基氧基羰基、異丙基氧基羰基、正丁基氧基羰基、異丁基氧基羰基、仲丁基氧基羰基、叔丁基氧基羰基、正戊基氧基羰基、異戊基氧基羰基、仲戊基氧基羰基、叔戊基氧基羰基、正己基氧基羰基、正庚基氧基羰基、正辛基氧基羰基、異辛基氧基羰基、仲辛基氧基羰基、叔辛基氧基羰基、正壬基氧基羰基、異壬基氧基羰基、正癸基氧基羰基、及異癸基氧基羰基等。When R c7 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. Specific examples when R c7 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, and isobutyl Oxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxy Carbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl , N-decyloxycarbonyl, and isodecyloxycarbonyl.

Rc7 為苯基烷基時，苯基烷基之碳原子數較佳為7～20，更佳為7～10。另外，Rc7 為萘基烷基時，萘基烷基的碳原子數較佳為11～20，更佳為11～14。作為Rc7 為苯基烷基時的具體例，可舉出苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。作為Rc7 為萘基烷基時的具體例，可舉出α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。Rc7 為苯基烷基或萘基烷基時，Rc7 可在苯基或萘基上進一步具有取代基。When R c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. When R c7 is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, and more preferably 11 to 14. Specific examples when R c7 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples when R c7 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) Ethyl. When R c7 is phenylalkyl or naphthylalkyl, R c7 may further have a substituent on phenyl or naphthyl.

Rc7 為雜環基時，雜環基為包含1個以上之N、S、O的五元或六元的單環、或者為所述單環彼此縮合、或所述單環與苯環縮合而成的雜環基。雜環基為縮合環時，環數為3以下。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成所述雜環基的雜環，可舉出呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯并呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯并***、苯并噁唑、苯并噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、肉啉、喹喔啉、呱啶、呱嗪、嗎啉、呱啶、四氫吡喃、及四氫呋喃等。Rc7 為雜環基時，雜環基可進一步具有取代基。When R c7 is a heterocyclic group, a heterocyclic group containing one or more of N, five- or six-membered S, O, monocyclic, or condensed with each other to a monocyclic, or condensed with a benzene ring a monocyclic And formed into a heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, iso Quinoline, quinazoline, phthalazine, oxoline, quinoxaline, pyrimidine, verazine, morpholine, pyrimidine, tetrahydropyran, and tetrahydrofuran. When R c7 is a heterocyclic group, the heterocyclic group may further have a substituent.

Rc7 為雜環基羰基時，關於雜環基羰基中包含的雜環基，與Rc7 為雜環基的情況同樣。When R c7 is a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is the same as when R c7 is a heterocyclic group.

Rc7 為被1個或2個有機基取代的胺基時，關於有機基的較佳例，可舉出碳原子數1～20的烷基、碳原子數3～10的環烷基、碳原子數2～21的飽和脂肪族醯基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的碳原子數7～20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的碳原子數11～20的萘基烷基、及雜環基等。此等較佳的有機基的具體例與Rc7 同樣。作為被1個或2個有機基取代的胺基的具體例，可舉出甲基胺基、乙基胺基、二乙基胺基、正丙基胺基、二正丙基胺基、異丙基胺基、正丁基胺基、二正丁基胺基、正戊基胺基、正己基胺基、正庚基胺基、正辛基胺基、正壬基胺基、正癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯基胺基、正丁醯基胺基、正戊醯基胺基、正己醯基胺基、正庚醯基胺基、正辛醯基胺基、正癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。When R c7 is an amine group substituted with one or two organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon. A saturated aliphatic fluorenyl group having 2 to 21 atoms, a phenyl group which may have a substituent, a benzamidine group which may have a substituent, a phenylalkyl group which has 7 to 20 carbon atoms, which may have a substituent Naphthyl, naphthylmethyl which may have a substituent, naphthylalkyl having 11 to 20 carbon atoms which may have a substituent, heterocyclyl, and the like. Specific examples of these preferable organic groups are the same as those of R c7 . Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, iso Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, ethynylamino, propionylamino, n-butylfluorenylamino, n-pentamylamino, n-hexylfluorenylamino, n-heptanylamino, N-octylamidinylamino, n-decamidinylamino, benzamidineamino, α-naphthylmethylamino, β-naphthylmethylamino, and the like.

作為Rc7 中包含的苯基、萘基、及雜環基進一步具有取代基時的取代基，可舉出碳原子數1～6的烷基、碳原子數1～6的烷氧基、碳原子數2～7的飽和脂肪族醯基、碳原子數2～7的烷氧基羰基、碳原子數2～7的飽和脂肪族醯基氧基、具有碳原子數1～6的烷基的單烷基胺基、具有碳原子數1～6的烷基的二烷基胺基、嗎啉-1-基、呱嗪-1-基、鹵素、硝基、及氰基等。Rc7 中包含的苯基、萘基、及雜環基進一步具有取代基時，其取代基的個數在不妨礙本發明的目的的範圍內沒有限制，較佳為1～4。Rc7 中包含之苯基、萘基、及雜環基具有多個取代基時，多個取代基可相同亦可不同。 Examples of the substituent when the phenyl, naphthyl, and heterocyclic group contained in R c7 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon A saturated aliphatic fluorenyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms A monoalkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a pyrazin-1-yl group, a halogen group, a nitro group, and a cyano group. When the phenyl, naphthyl, and heterocyclic group contained in R c7 further has a substituent, the number of substituents is not limited as long as it does not prevent the object of the present invention, and is preferably 1 to 4. When the phenyl, naphthyl, and heterocyclic group contained in R c7 has a plurality of substituents, the plurality of substituents may be the same or different.

上文中說明的基中，作為Rc7 ，為硝基或Rc12 -CO-表示的基時，存在敏感度提高的傾向，為較佳的。Rc12 在不妨礙本發明的目的的範圍內沒有特別限制，可從各種有機基中選擇。關於作為Rc12 的較佳基的例子，可舉出碳原子數1～20的烷基、可具有取代基的苯基、可具有取代基的萘基、及可具有取代基的雜環基。作為Rc12 ，此等基中，特別較佳為2-甲基苯基、噻吩-2-基、及α-萘基。 　　另外，Rc7 為氫原子時，存在透明性變得良好的傾向，是較佳的。尚，Rc7 為氫原子並且Rc10 為後述的式(c4a)或(c4b)表示的基時，存在透明性變得更良好的傾向。Among the groups described above, when R c7 is a group represented by a nitro group or R c12 -CO-, the sensitivity tends to increase, which is preferable. R c12 is not particularly limited as long as it does not hinder the object of the present invention, and may be selected from various organic groups. Examples of preferred groups for R c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. Of these groups, as R c12 , 2-methylphenyl, thien-2-yl, and α-naphthyl are particularly preferred. When R c7 is a hydrogen atom, the transparency tends to be good, which is preferable. When R c7 is a hydrogen atom and R c10 is a group represented by formula (c4a) or (c4b) described later, the transparency tends to be better.

式(c4)中，Rc8 及Rc9 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基、或氫原子。Rc8 與Rc9 可相互鍵結而形成環。此等基中，作為Rc8 及Rc9 ，較佳為可具有取代基的鏈狀烷基。Rc8 及Rc9 為可具有取代基的鏈狀烷基時，鏈狀烷基可為直鏈烷基，亦可為支鏈烷基。In formula (c4), R c8 and R c9 are each a linear alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R c8 and R c9 may be bonded to each other to form a ring. Among these groups, R c8 and R c9 are preferably a linear alkyl group which may have a substituent. When R c8 and R c9 are a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.

Rc8 及Rc9 為不具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數較佳為1～20，更佳為1～10，特別較佳為1～6。作為Rc8 及Rc9 為鏈狀烷基時之具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、仲戊基、叔戊基、正己基、正庚基、正辛基、異辛基、仲辛基、叔辛基、正壬基、異壬基、正癸基、及異癸基等。另外，Rc8 及Rc9 為烷基時，烷基可在碳鏈中包含醚鍵(-O-)。作為在碳鏈中具有醚鍵的烷基的例子，可舉出甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。When R c8 and R c9 are chain alkyl groups having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples when R c8 and R c9 are linear alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-butyl. Pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, And isodecyl. When R c8 and R c9 are alkyl groups, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxy. Ethoxyethyl, and methoxypropyl.

Rc8 及Rc9 為具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數較佳為1～20，更佳為1～10，特別佳為1～6。這種情況下，鏈狀烷基的碳原子數不包含取代基的碳原子數。具有取代基的鏈狀烷基較佳為直鏈狀。 　　烷基可具有的取代基在不妨礙本發明的目的的範圍內沒有特別限制。作為取代基的較佳例，可舉出氰基、鹵素原子、環狀有機基、及烷氧基羰基。作為鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子。此等中，較佳氟原子、氯原子、溴原子。作為環狀有機基，可舉出環烷基、芳香族烴基、雜環基。作為環烷基的具體例，與Rc7 為環烷基時的較佳例同樣。作為芳香族烴基的具體例，可舉出苯基、萘基、聯苯基、蒽基、及菲基等。作為雜環基的具體例，與Rc7 為雜環基時的較佳例同樣。Rc7 為烷氧基羰基時，烷氧基羰基中包含的烷氧基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。烷氧基羰基中包含的烷氧基的碳原子數較佳為1～10，更佳為1～6。When R c8 and R c9 are a linear alkyl group having a substituent, the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the carbon number of the chain alkyl group does not include the carbon number of the substituent. The linear alkyl group having a substituent is preferably linear. The substituent which an alkyl group may have is not specifically limited in the range which does not prevent the objective of this invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the cycloalkyl group are the same as the preferred examples when R c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of the heterocyclic group are the same as the preferred examples when R c7 is a heterocyclic group. When R c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

鏈狀烷基具有取代基時，取代基的個數沒有特別限制。較佳的取代基之個數根據鏈狀烷基的碳原子數而改變。關於取代基的個數，典型地，為1～20，較佳為1～10，更佳為1～6。When the linear alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

Rc8 及Rc9 為環狀有機基時，環狀有機基可為脂環式基，亦可為芳香族基。作為環狀有機基，可舉出脂肪族環狀烴基、芳香族烴基、雜環基。Rc8 及Rc9 為環狀有機基時，環狀有機基可具有的取代基與Rc8 及Rc9 為鏈狀烷基的情況同樣。When R c8 and R c9 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. When R c8 and R c9 are cyclic organic groups, the substituents which the cyclic organic group may have are the same as when R c8 and R c9 are chain alkyl groups.

Rc8 及Rc9 為芳香族烴基時，芳香族烴基較佳為苯基、或多個苯環介由碳-碳鍵進行鍵結而形成的基、或多個苯環縮合而形成的基。芳香族烴基為苯基、或多個苯環鍵結或縮合而形成的基時，芳香族烴基中包含的苯環的環數沒有特別限制，較佳為3以下，更佳為2以下，特別佳為1。作為芳香族烴基的較佳的具體例，可舉出苯基、萘基、聯苯基、蒽基、及菲基等。When R c8 and R c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly Better to be 1. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

Rc8 及Rc9 為脂肪族環狀烴基時，脂肪族環狀烴基可為單環式亦可為多環式。脂肪族環狀烴基的碳原子數沒有特別限制，較佳為3～20，更佳為3～10。作為單環式的環狀烴基的例子，可舉出環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。When R c8 and R c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, and adamantyl.

Rc8 及Rc9 為雜環基時，雜環基為包含1個以上的N、S、O的五元或六元的單環、或者為所述單環彼此縮合、或所述單環與苯環縮合而成的雜環基。雜環基為縮合環時，環數為3以下。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。作為構成所述雜環基的雜環，可舉出呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯并呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯并咪唑、苯并***、苯并噁唑、苯并噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、肉啉、喹喔啉、呱啶、呱嗪、嗎啉、呱啶、四氫吡喃、及四氫呋喃等。When R c8 and R c9 are heterocyclic groups, the heterocyclic group is a five- or six-membered monocyclic ring containing one or more N, S, and O, or the monocyclic rings are condensed with each other, or the monocyclic ring and A heterocyclic group formed by condensing a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, iso Quinoline, quinazoline, phthalazine, oxoline, quinoxaline, pyrimidine, verazine, morpholine, pyrimidine, tetrahydropyran, and tetrahydrofuran.

Rc8 與Rc9 可相互鍵結而形成環。由Rc8 與Rc9 所形成的環所構成的基較佳為亞環烷基(cycloalkylidene)。Rc8 與Rc9 鍵結而形成亞環烷基時，構成亞環烷基的環較佳為五元環～六元環，更佳為五元環。R c8 and R c9 may be bonded to each other to form a ring. The group formed by the ring formed by R c8 and R c9 is preferably a cycloalkylidene. When R c8 and R c9 are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, and more preferably a five-membered ring.

Rc8 與Rc9 鍵結而形成的基為亞環烷基時，亞環烷基可與1個以上其他環縮合。作為可與亞環烷基縮合的環的例子，可舉出苯環、萘環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、呋喃環、噻吩環、吡咯環、吡啶環、吡嗪環、及嘧啶環等。When the group formed by bonding R c8 and R c9 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring condensable with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring.

上文中說明的Rc8 及Rc9 中，作為較佳的基的例子，可舉出式-A1 -A2 表示的基。式中，可舉出：A1 為直鏈亞烷基，A2 為烷氧基、氰基、鹵素原子、鹵代烷基、環狀有機基、或烷氧基羰基。 Among R c8 and R c9 described above, examples of preferred groups include a group represented by the formula -A 1 -A 2 . In the formula, A 1 is a linear alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

A1 的直鏈亞烷基的碳原子數較佳為1～10，更佳為1～6。A2 為烷氧基時，烷氧基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。烷氧基的碳原子數較佳為1～10，更佳為1～6。A2 為鹵素原子時，較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。A2 為鹵代烷基時，鹵代烷基中包含的鹵素原子較佳為氟原子、氯原子、溴原子、碘原子，更佳為氟原子、氯原子、溴原子。鹵代烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。A2 為環狀有機基時，環狀有機基的例子與Rc8 及Rc9 作為取代基而具有的環狀有機基同樣。A2 為烷氧基羰基時，烷氧基羰基的例子與Rc8 及Rc9 作為取代基而具有的烷氧基羰基同樣。The number of carbon atoms of the linear alkylene group of A 1 is preferably 1 to 10, and more preferably 1 to 6. When A 2 is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. When A 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A 2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. When A 2 is a cyclic organic group, examples of the cyclic organic group are the same as those of the cyclic organic group which R c8 and R c9 have as a substituent. When A 2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R c8 and R c9 have as a substituent.

作為Rc8 及Rc9 的較佳的具體例，可舉出乙基、正丙基、正丁基、正己基、正庚基、及正辛基等烷基；2-甲氧基乙基、3-甲氧基正丙基、4-甲氧基正丁基、5-甲氧基正戊基、6-甲氧基正己基、7-甲氧基正庚基、8-甲氧基正辛基、2-乙氧基乙基、3-乙氧基正丙基、4-乙氧基正丁基、5-乙氧基正戊基、6-乙氧基正己基、7-乙氧基正庚基、及8-乙氧基正辛基等烷氧基烷基；2-氰基乙基、3-氰基正丙基、4-氰基正丁基、5-氰基正戊基、6-氰基正己基、7-氰基正庚基、及8-氰基正辛基等氰基烷基；2-苯基乙基、3-苯基正丙基、4-苯基正丁基、5-苯基正戊基、6-苯基正己基、7-苯基正庚基、及8-苯基正辛基等苯基烷基；2-環己基乙基、3-環己基正丙基、4-環己基正丁基、5-環己基正戊基、6-環己基正己基、7-環己基正庚基、8-環己基正辛基、2-環戊基乙基、3-環戊基正丙基、4-環戊基正丁基、5-環戊基正戊基、6-環戊基正己基、7-環戊基正庚基、及8-環戊基正辛基等環烷基烷基；2-甲氧基羰基乙基、3-甲氧基羰基正丙基、4-甲氧基羰基正丁基、5-甲氧基羰基正戊基、6-甲氧基羰基正己基、7-甲氧基羰基正庚基、8-甲氧基羰基正辛基、2-乙氧基羰基乙基、3-乙氧基羰基正丙基、4-乙氧基羰基正丁基、5-乙氧基羰基正戊基、6-乙氧基羰基正己基、7-乙氧基羰基正庚基、及8-乙氧基羰基正辛基等烷氧基羰基烷基；2-氯乙基、3-氯正丙基、4-氯正丁基、5-氯正戊基、6-氯正己基、7-氯正庚基、8-氯正辛基、2-溴乙基、3-溴正丙基、4-溴正丁基、5-溴正戊基、6-溴正己基、7-溴正庚基、8-溴正辛基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基等鹵代烷基。Preferred specific examples of R c8 and R c9 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n- Octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy Alkoxyalkyl groups such as n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl Cyanoalkyl, such as 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl Phenylalkyl such as n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; 2-cyclohexylethyl, 3- Cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentyl Ethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl Cycloalkylalkyl such as 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl , 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonyl-ethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6 -Alkoxycarbonylalkyl groups such as ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4 -Chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n- Butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4, Haloalkyl such as 5,5,5-heptafluoro-n-pentyl.

作為Rc8 及Rc9 ，上述中較佳的基是乙基、正丙基、正丁基、正戊基、2-甲氧基乙基、2-氰基乙基、2-苯基乙基、2-環己基乙基、2-甲氧基羰基乙基、2-氯乙基、2-溴乙基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟正戊基。As R c8 and R c9 , preferred groups among the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl , 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5 , 5,5-heptafluoro-n-pentyl.

作為Rc10 的較佳的有機基的例子，與Rc7 同樣，可舉出烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯基氧基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環基羰基、被1個或2個有機基取代的胺基、嗎啉-1-基、及呱嗪-1-基等。此等基的具體例與針對Rc7 而進行的說明同樣。另外，作為Rc10 ，亦較佳為環烷基烷基、可在芳香環上具有取代基的苯氧基烷基、可在芳香環上具有取代基的苯基硫基烷基。關於苯氧基烷基、及苯基硫基烷基可具有的取代基，與Rc7 中所包含的苯基可具有的取代基同樣。Examples of preferable organic groups for R c10 include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic fluorenyl, alkoxycarbonyl, and saturated aliphatic, as in R c7 . Fluorenyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzamidine which may have a substituent, phenoxycarbonyl which may have a substituent, benzamidine which may have a substituent An oxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent Naphthylmethyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic group carbonyl which may have a substituent, 1 or 2 organic groups Substituted amino groups, morpholin-1-yl, and pyrazin-1-yl and the like. Specific examples of these groups are the same as those described for R c7 . R c10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituent which a phenyl group contained in R c7 may have.

有機基中，作為Rc10 ，較佳為烷基、環烷基、可具有取代基的苯基、或環烷基烷基、可在芳香環上具有取代基的苯基硫基烷基。作為烷基，較佳為碳原子數1～20的烷基，更佳為碳原子數1～8的烷基，特別較佳為碳原子數1～4的烷基，最佳為甲基。可具有取代基的苯基中，較佳為甲基苯基，更佳為2-甲基苯基。環烷基烷基中包含之環烷基的碳原子數較佳為5～10，更佳為5～8，特別佳為5或6。環烷基烷基中包含的亞烷基的碳原子數較佳為1～8，更佳為1～4，特別較佳為2。環烷基烷基中，較佳為環戊基乙基。可在芳香環上具有取代基的苯基硫基烷基中所包含的亞烷基之碳原子數較佳為1～8，更佳為1～4，特別較佳為2。可在芳香環上具有取代基的苯基硫基烷基中，較佳為2-(4-氯苯基硫基)乙基。 Among the organic groups, R c10 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably from 2. Of the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and even more preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferred.

另外，作為Rc10 ，亦較佳為-A3 -CO-O-A4 表示的基。A3 為2價的有機基，較佳為2價的烴基，較佳為亞烷基。A4 為1價的有機基，較佳為1價的烴基。In addition, as R c10 , a group represented by -A 3 -CO-OA 4 is also preferable. A 3 is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A 4 is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

A3 為亞烷基時，亞烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。A3 為亞烷基時，亞烷基之碳原子數較佳為1～10，更佳為1～6，特別較佳為1～4。When A 3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A 3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

作為A4 的較佳例，可舉出碳原子數1～10的烷基、碳原子數7～20的芳烷基、及碳原子數6～20的芳香族烴基。作為A4 的較佳的具體例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、正己基、苯基、萘基、苄基、苯乙基、α-萘基甲基、及β-萘基甲基等。Preferred examples of A 4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred specific examples of A 4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, Phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

作為-A3 -CO-O-A4 表示的基的較佳的具體例，可舉出2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-正丙基氧基羰基乙基、2-正丁基氧基羰基乙基、2-正戊基氧基羰基乙基、2-正己基氧基羰基乙基、2-苄基氧基羰基乙基、2-苯氧基羰基乙基、3-甲氧基羰基正丙基、3-乙氧基羰基正丙基、3-正丙基氧基羰基正丙基、3-正丁基氧基羰基正丙基、3-正戊基氧基羰基正丙基、3-正己基氧基羰基正丙基、3-苄基氧基羰基正丙基、及3-苯氧基羰基正丙基等。Preferred specific examples of the group represented by -A 3 -CO-OA 4 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, and 2-n-propyloxycarbonylethyl. , 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl Methyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyl Propyloxycarbonyl n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.

以上，對Rc10 進行了說明，但作為Rc10 ，較佳為下述式(c4a)或(c4b)表示的基。 　　[化21](式(c4a)及(c4b)中，Rc13 及Rc14 分別為有機基，n6為0～4的整數，Rc13 和R8 存在於苯環上的相鄰的位置時，Rc13 與Rc14 可相互鍵結而形成環，n7為1～8的整數，n8為1～5的整數，n9為0～(n8+3)的整數，Rc15 為有機基)。Above for R c10 has been described, but as R c10, preferred is a group represented by the following formula (C4A) or (C4b). [Chemical 21] (In the formulae (c4a) and (c4b), R c13 and R c14 are organic groups, n6 is an integer of 0 to 4, and when R c13 and R 8 exist at adjacent positions on the benzene ring, R c13 and R c14 may be bonded to each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, n9 is an integer of 0 to (n8 + 3), and R c15 is an organic group).

式(c4a)中的Rc13 及Rc14 的有機基的例子與Rc7 同樣。作為Rc13 ，較佳為烷基或苯基。Rc13 為烷基時，其碳原子數較佳為1～10，更佳為1～5，特別較佳為1～3，最佳為1。即，最佳Rc13 為甲基。Rc13 與Rc14 鍵結而形成環時，該環可為芳香族環，亦可為脂肪族環。作為Rc13 與Rc14 形成環的式(c4a)表示的基的較佳例，可舉出萘-1-基或1,2,3,4-四氫萘-5-基等。上述式(c4a)中，n6為0～4的整數，較佳為0或1，更佳為0。Examples of the organic groups of R c13 and R c14 in the formula (c4a) are the same as those of R c7 . R c13 is preferably an alkyl group or a phenyl group. When R c13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, the most preferable R c13 is a methyl group. When R c13 and R c14 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (c4a) in which R c13 and R c14 form a ring include naphthalen-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl. In the formula (c4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

上述式(c4b)中，Rc15 為有機基。作為有機基，可舉出與針對Rc7 而說明的有機基同樣的基。有機基中，較佳為烷基。烷基可為直鏈狀，亦可為支鏈狀。烷基的碳原子數較佳為1～10，更佳為1～5，特別佳為1～3。作為Rc15 ，可較佳例舉甲基、乙基、丙基、異丙基、丁基等，此等中，更佳為甲基。In the formula (c4b), R c15 is an organic group. Examples of the organic group include the same groups as those described for R c7 . Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of R c15 include methyl, ethyl, propyl, isopropyl, and butyl. Among these, methyl is more preferable.

上述式(c4b)中，n8為1～5的整數，較佳為1～3的整數，更佳為1或2。上述式(c4b)中，n9為0～(n8+3)，較佳為0～3的整數，更佳為0～2的整數，特別佳為0。上述式(c4b)中，n7為1～8的整數，較佳為1～5的整數，更佳為1～3的整數，特別佳為1或2。In the formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the formula (c4b), n9 is 0 to (n8 + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

式(c4)中，Rc11 為氫原子、可具有取代基的碳原子數1～11的烷基、或可具有取代基的芳基。作為Rc11 為烷基時可具有的取代基，可較佳例舉苯基、萘基等。另外，作為Rc7 為芳基時可具有的取代基，可較佳例舉碳原子數1～5的烷基、烷氧基、鹵素原子等。In formula (c4), R c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which R c11 may have when it is an alkyl group, a phenyl group, a naphthyl group, etc. are mentioned suitably. Moreover, as a substituent which R c7 may have when it is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are mentioned suitably.

式(c4)中，作為Rc11 ，可較佳例舉氫原子、甲基、乙基、正丙基、異丙基、正丁基、苯基、苄基、甲基苯基、萘基等，此等中，更佳為甲基或苯基。In formula (c4), as R c11 , a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl, and the like can be preferably exemplified. Among these, a methyl group or a phenyl group is more preferable.

式(c4)表示的化合物可經由包含將前述的式(c5)表示的化合物中所包含的肟基(＞C=N-OH)轉化為＞C=N-O-CORc11 表示的肟酯基的步驟的方法製造。Rc11 與式(c4)中的Rc11 同樣。The compound represented by the formula (c4) can be subjected to a step including converting an oxime group (> C = N-OH) contained in the compound represented by the aforementioned formula (c5) into an oxime ester group represented by> C = NO-COR c11 . Manufacturing method. The R c11 of formula (c4) R c11 same.

肟基(＞C=N-OH)向＞C=N-O-CORc11 表示的肟酯基的轉化可經由使前述的式(c5)表示的化合物與醯化劑反應而進行。 　　作為提供-CORc11 表示的醯基的醯化劑，可舉出(Rc11 CO)2 O表示的酸酐或Rc11 COHal(Hal為鹵素原子)表示的醯鹵。Conversion of an oxime group (> C = N-OH) to an oxime ester group represented by> C = NO-COR c11 can be performed by reacting a compound represented by the aforementioned formula (c5) with a halogenating agent. Examples of the halogenating agent that provides a fluorenyl group represented by -COR c11 include an acid anhydride represented by (R c11 CO) 2 O or a halogenated halide represented by R c11 COHal (Hal is a halogen atom).

作為式(c4)表示的化合物的較佳的具體例，可舉出以下的PI-43～PI-83。 　　[化22] Specific preferable examples of the compound represented by the formula (c4) include PI-43 to PI-83 below. [Chemical 22]

[化23] [Chemical 23]

關於光聚合引發劑(C)的含量，相對於樹脂組成物的固體成分整體之質量而言，較佳為0.5～30質量%，更佳為1～20質量%。經由使光聚合引發劑(C)的含量為上述的範圍，可得到不易發生圖案形狀不良的樹脂組成物。The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass, with respect to the mass of the entire solid content of the resin composition. By making content of a photoinitiator (C) into the said range, the resin composition which does not easily generate a pattern shape defect can be obtained.

另外，可在光聚合引發劑(C)中組合光引發助劑。作為光引發助劑，可舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲酸2-二甲基胺基乙酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮、9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、2-巰基苯并噻唑、2-巰基苯并噁唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯並噻唑、3-巰基丙酸、3-巰基丙酸甲酯、季戊四醇四巰基乙酸酯、3-巰基丙酸酯等硫醇化合物等。此等光引發助劑可單獨使用，或者可組合2種以上而使用。In addition, a photoinitiator can be combined with the photopolymerization initiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diamine. Isoamyl methylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl-p-toluidine, 4 , 4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy Anthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzo Thiol compounds such as thiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, and the like. These photoinitiation aids may be used alone or in combination of two or more kinds.

＜顏料(D)＞ 　　樹脂組成物包含顏料(D)。作為顏料(D)，沒有特別限制，例如可使用在染料索引(C.I.；The Society of Dyers and Colourists公司發行)中被分類為顏料(Pigment)的化合物，具體而言，可使用附有下述這樣的染料索引(C.I.)編號的顏料。<Pigment (D)> The fluorene resin composition contains a pigment (D). The pigment (D) is not particularly limited. For example, a compound classified as a pigment in the dye index (issued by The Society of Dyers and Colourists) can be used. Specifically, the following compounds can be used: Dye Index (CI) number of pigments.

作為可較佳使用的黃色顏料的例子，可舉出C.I.顏料黃1(以下，同樣也是「C.I.顏料黃」，僅記載編號)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、及185。Examples of yellow pigments that can be preferably used include CI Pigment Yellow 1 (hereinafter also referred to as "CI Pigment Yellow" and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185.

作為可較佳使用的橙色顏料的例子，可舉出C.I.顏料橙1(以下，同樣也是「C.I.顏料橙」，僅記載編號)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、及73。Examples of orange pigments that can be preferably used include CI Pigment Orange 1 (hereinafter also referred to as "CI Pigment Orange" and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

作為可較佳使用的紫色顏料的例子，可舉出C.I.顏料紫1(以下，同樣也是「C.I.顏料紫」，僅記載編號)、19、23、29、30、32、36、37、38、39、40、及50。Examples of purple pigments that can be preferably used include CI Pigment Violet 1 (hereinafter also referred to as "CI Pigment Violet", and only numbered), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

作為可較佳使用的紅色顏料的例子，可舉出C.I.顏料紅1(以下，同樣也是「C.I.顏料紅」，僅記載編號)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、及265。Examples of red pigments that can be preferably used include CI Pigment Red 1 (hereinafter also referred to as "CI Pigment Red", and only the number is described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

作為可較佳使用的藍色顏料的例子，可舉出C.I.顏料藍1(以下，同樣也是「C.I.顏料藍」，僅記載編號)、2、15、15：3、15：4、15：6、16、22、60、64、及66。Examples of blue pigments that can be preferably used include CI Pigment Blue 1 (hereinafter also referred to as "CI Pigment Blue", and only the number is described), 2, 15, 15: 3, 15: 4, 15: 6 , 16, 22, 60, 64, and 66.

作為可較佳使用的上述之外的色相的顏料的例子，可舉出C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37等綠色顏料，C.I.顏料棕23、C.I.顏料棕25、C.I.顏料棕26、C.I.顏料棕28等棕色顏料，C.I.顏料黑1、C.I.顏料黑7等黑色顏料。Examples of pigments that can be used in the hue other than the above include green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown. 26. Brown pigments such as CI Pigment Brown 28, black pigments such as CI Pigment Black 1, CI Pigment Black 7.

另外，樹脂組成物較佳為包含黑色顏料作為顏料(D)。藉由使用包含黑色顏料的樹脂組成物，從而可向所形成的硬化膜賦予遮光性。因此，包含黑色顏料的樹脂組成物可合適地用於液晶顯示面板中的黑色矩陣或黑色柱狀間隔物(black column spacer)的形成、隔堤(bank)(所述隔堤用於將有機EL元件中的發光層進行劃區)的形成。The resin composition preferably contains a black pigment as the pigment (D). By using a resin composition containing a black pigment, light-shielding properties can be imparted to the formed cured film. Therefore, a resin composition containing a black pigment can be suitably used for the formation of a black matrix or a black column spacer in a liquid crystal display panel, and a bank (the bank is used for organic EL The light-emitting layer in the element is formed by dividing a region).

作為黑色顏料的例子，可舉出碳黑、苝系顏料、內醯胺系顏料、鈦黑、銅、鐵、錳、鈷、鉻、鎳、鋅、鈣、銀等的金屬氧化物、複合氧化物、金屬硫化物、金屬硫酸鹽或金屬碳酸鹽等各種顏料(不論是有機物還是無機物均可)。此等黑色顏料中，從容易獲得、容易形成遮光性優異且電阻高的硬化膜方面考慮，較佳為碳黑。 　　尚，黑色顏料的色相不限於作為色彩學上的無彩色的黑色，亦可為發紫的黑色、發藍的黑色、發紅的黑色。Examples of the black pigment include carbon black, fluorene-based pigments, lactam-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, and composite oxides. Pigments such as metals, metal sulfides, metal sulfates, or metal carbonates (either organic or inorganic). Among these black pigments, carbon black is preferable in terms of easy availability, easy formation of a cured film having excellent light shielding properties and high electrical resistance. It is popular that the hue of black pigments is not limited to chromatic achromatic black, but it can also be purple black, blue black, and red black.

作為碳黑，可使用槽法碳黑(channel black)、爐法碳黑(furnace black)、熱裂碳黑(thermal black)、燈黑(lamp black)等已知的碳黑。另外，亦可使用經樹脂被覆的碳黑。As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, thermal black, and lamp black can be used. Alternatively, resin-coated carbon black may be used.

作為碳黑，實施了導入酸性基的處理的碳黑亦為較佳的。被導入至碳黑的酸性基為顯示基於布朗斯特的定義的酸性的官能基。作為酸性基的具體例，可舉出羧基、磺酸基、磷酸基等。被導入至碳黑的酸性基可形成鹽。與酸性基形成鹽的陽離子在不妨礙本發明的目的的範圍內沒有特別限制。作為陽離子的例子，可舉出各種金屬離子、含氮化合物的陽離子、銨離子等，較佳為鈉離子、鉀離子、鋰離子等鹼金屬離子、銨離子。As the carbon black, carbon black that has been treated with the introduction of an acidic group is also preferred. The acidic group introduced into carbon black is a functional group showing acidity based on the definition of Bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphate group. The acidic group introduced into the carbon black can form a salt. The cation which forms a salt with an acidic group is not specifically limited in the range which does not prevent the objective of this invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ion, potassium ion, and lithium ion, and ammonium ion are preferred.

上文中說明的實施了導入酸性基的處理的碳黑中，從達成使用樹脂組成物形成的遮光性的硬化膜的高電阻的觀點考慮，較佳為具有選自由羧酸基、羧酸鹽基、磺酸基、及磺酸鹽基所成之群中的1種以上的官能基的碳黑。From the viewpoint of achieving high resistance of the light-shielding cured film formed using the resin composition, the carbon black that has been treated with the introduction of an acidic group as described above is preferably selected from a carboxylic acid group and a carboxylate group. Carbon black of one or more functional groups in the group formed by sulfonic acid group, sulfonic acid group, and sulfonic acid salt group.

向碳黑中導入酸性基的方法沒有特別限制。作為導入酸性基的方法，例如可舉出以下的方法。 　　方法1)：經由直接取代法(其使用濃硫酸、發煙硫酸、氯磺酸等)、間接取代法(其使用亞硫酸鹽、亞硫酸氫鹽等)，向碳黑中導入磺酸基。 　　方法2)：使具有胺基與酸性基的有機化合物與碳黑進行重氮偶合。 　　方法3)：利用威廉森(Williamson)醚化法，使具有鹵素原子與酸性基的有機化合物、與具有羥基的碳黑進行反應。 　　方法4)：使具有鹵代羰基與被保護基保護的酸性基的有機化合物、與具有羥基的碳黑進行反應。 　　方法5)：使用具有鹵代羰基與被保護基保護的酸性基的有機化合物，針對碳黑進行弗瑞德－克來福特反應，然後進行脫保護。The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example. Method 1): A sulfonic acid group is introduced into carbon black via a direct substitution method (which uses concentrated sulfuric acid, oleum, chlorosulfonic acid, etc.) and an indirect substitution method (which uses sulfite, bisulfite, etc.). Method 2): Diazo coupling of an organic compound having an amine group and an acid group with carbon black. Method 3): Using a Williamson etherification method, an organic compound having a halogen atom and an acidic group is reacted with carbon black having a hydroxyl group. Method 4): An organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group is reacted with carbon black having a hydroxyl group. Method 5): Using an organic compound having a halogenated carbonyl group and an acid group protected by a protecting group, a Friedel-Crafts reaction is performed on carbon black, and then deprotection is performed.

上述方法中，從導入酸性基的處理容易進行並且安全的方面考慮，較佳為方法2)。作為方法2)中使用的具有胺基與酸性基的有機化合物，較佳在芳香族基上鍵結有胺基和酸性基的化合物。作為這樣的化合物的例子，可舉出對胺基苯磺酸這樣的胺基苯磺酸或4-胺基苯甲酸這樣的胺基苯甲酸。Among the methods described above, method 2) is preferred because the treatment for introducing an acidic group is easy and safe. As the organic compound having an amine group and an acidic group used in the method 2), a compound having an amine group and an acidic group bonded to an aromatic group is preferred. Examples of such a compound include an aminobenzoic acid such as p-aminobenzenesulfonic acid or an aminobenzoic acid such as 4-aminobenzoic acid.

被導入至碳黑的酸性基的莫耳數在不妨礙本發明的目的的範圍內沒有特別限制。相對於碳黑100g而言，被導入至碳黑的酸性基的莫耳數較佳為1～200 mmol，更佳為5～100mmol。The mole number of the acidic group introduced into carbon black is not particularly limited as long as it does not hinder the object of the present invention. The molar number of the acid group introduced into carbon black is preferably 1 to 200 mmol, and more preferably 5 to 100 mmol, with respect to 100 g of carbon black.

對於導入了酸性基的碳黑，可利用樹脂實施被覆處理。 　　在使用包含經樹脂被覆的碳黑的樹脂組成物時，容易形成遮光性及絕緣性優異、表面反射率低的遮光性硬化膜。尚，藉由利用樹脂進行的被覆處理，不會特別地對使用樹脂組成物形成的遮光性硬化膜的介電常數產生不良影響。作為可在碳黑的被覆中使用的樹脂的例子，可舉出酚醛樹脂、三聚氰胺樹脂、二甲苯樹脂、鄰苯二甲酸二烯丙酯樹脂、甘酞(glyptal)樹脂、環氧樹脂、烷基苯樹脂等熱固性樹脂；聚苯乙烯、聚碳酸酯、聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、改性聚苯醚、聚碸、聚對苯二甲醯對苯二胺、聚醯胺醯亞胺、聚醯亞胺、聚胺基雙馬來醯亞胺、聚醚碸聚亞苯基碸、聚芳酯、聚醚醚酮等熱塑性樹脂。相對于碳黑的質量與樹脂的質量的總計，樹脂對碳黑的被覆量較佳為1~30質量%。Carbon black to which an acidic group has been introduced may be coated with a resin.使用 When a resin composition containing carbon black coated with a resin is used, a light-shielding cured film having excellent light-shielding properties and insulation properties and low surface reflectance is easily formed. In addition, the coating treatment by the resin does not particularly adversely affect the dielectric constant of the light-shielding cured film formed using the resin composition. Examples of the resin that can be used for the coating of carbon black include phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkyl group. Thermosetting resins such as benzene resin; polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyfluorene, polyterephthalylene Thermoplastic resins such as phenylenediamine, polyamidofluorene imine, polyamidoimine, polyaminobismaleimide, polyetherpolyphenylenefluorene, polyarylate, and polyetheretherketone. The coating amount of the resin to the carbon black is preferably 1 to 30% by mass based on the total mass of the carbon black and the mass of the resin.

另外，作為黑色顏料，亦可較佳為使用苝系顏料。作為苝系顏料的具體例，可舉出下述式(d-1)表示的苝系顏料、下述式(d-2)表示的苝系顏料、及下述式(d-3)表示的苝系顏料。市售品中，可較佳為使用BASF公司製的製品名K0084、及K0086、或顏料黑21、30、31、32、33、及34等作為苝系顏料。In addition, as the black pigment, a fluorene-based pigment can also be preferably used. Specific examples of the fluorene-based pigment include a fluorene-based pigment represented by the following formula (d-1), a fluorene-based pigment represented by the following formula (d-2), and a fluorene-based pigment represented by the following formula (d-3) Actinide pigment. Among commercially available products, product names K0084 and K0086 manufactured by BASF, or pigment blacks 21, 30, 31, 32, 33, and 34 can be preferably used as the fluorene-based pigment.

[化24]式(d-1)中，Rd1 及Rd2 各自獨立地表示碳原子數1～3的亞烷基，Rd3 及Rd4 各自獨立地表示氫原子、羥基、甲氧基、或乙醯基。[Chemical 24] In formula (d-1), R d1 and R d2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R d3 and R d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetamyl group. .

[化25]式(d-2)中，Rd5 及Rd6 各自獨立地表示碳原子數1～7的亞烷基。[Chemical 25] In formula (d-2), R d5 and R d6 each independently represent an alkylene group having 1 to 7 carbon atoms.

[化26]式(d-3)中，Rd7 及Rd8 各自獨立地為氫原子、碳原子數1～22的烷基，可包含雜原子N、O、S或P。Rd7 和Rd8 為烷基時，該烷基可以為直鏈狀，亦可為支鏈狀。[Chemical 26] In formula (d-3), R d7 and R d8 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may include a hetero atom N, O, S, or P. When R d7 and R d8 are alkyl groups, the alkyl group may be linear or branched.

上述的式(d-1)表示的化合物、式(d-2)表示的化合物、及式(d-3)表示的化合物例如可利用日本特開昭62-1753號公報、日本特公昭63-26784號公報中記載的方法合成。即，將苝-3,5,9,10-四甲酸或其二酐與胺類作為原料，在水或有機溶劑中進行加熱反應。而後，將得到的粗製物在硫酸中進行再沉澱，或者在水、有機溶劑或它們的混合溶劑中進行重結晶，由此可得到目標物。The compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) can be exemplified by Japanese Patent Application Laid-Open No. 62-1753 and Japanese Patent Publication No. 63- Synthesized by the method described in Japanese Patent No. 26784. That is, hydrazone-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent thereof, thereby obtaining a target product.

為了使苝系顏料在樹脂組成物中良好地分散，苝系顏料的平均粒徑較佳為10～1000nm。In order to disperse the fluorene-based pigment in the resin composition, the average particle diameter of the fluorene-based pigment is preferably 10 to 1000 nm.

另外，作為遮光劑，還可包含內醯胺系顏料。作為內醯胺系顏料，可舉出例如下述式(d-4)表示的化合物。Moreover, as a light-shielding agent, a fluorenamine-type pigment can also be contained. Examples of the lactamamine pigments include compounds represented by the following formula (d-4).

[化27] [Chemical 27]

式(d-4)中，Xd 表示雙鍵，作為幾何異構物，各自獨立地為E體或Z體，Rd9 各自獨立地表示氫原子、甲基、硝基、甲氧基、溴原子、氯原子、氟原子、羧基、或磺基，Rd10 各自獨立地表示氫原子、甲基、或苯基，Rd11 各自獨立地表示氫原子、甲基、或氯原子。 　　式(d-4)表示的化合物可單獨使用或組合2種以上而使用。 　　從容易製造式(d-4)表示的化合物方面考慮，Rd9 較佳為鍵結於二氫吲哚酮環的6位，Rd11 較佳為鍵結於二氫吲哚酮環的4位。從同樣的觀點考慮，Rd9 、Rd10 、及Rd11 較佳為氫原子。 　　式(d-4)表示的化合物具有EE體、ZZ體、EZ體作為幾何異構物，但其可為它們中任一種的單一化合物，亦可為此等幾何異構物的混合物。 　　式(d-4)表示的化合物例如可利用國際公開第2000/24736號、及國際公開第2010/081624號中記載的方法製造。In the formula (d-4), X d represents a double bond, and as a geometric isomer, each is independently an E-form or a Z-form, and R d9 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, and a bromine group. Atom, chlorine atom, fluorine atom, carboxyl group, or sulfo group, R d10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R d11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (d-4) can be used alone or in combination of two or more kinds. From the viewpoint of easily producing a compound represented by formula (d-4), R d9 is preferably bonded to the 6-position of the indolinone ring, and R d11 is preferably bonded to the 4-position of the indolinone ring. . From the same viewpoint, R d9 , R d10 , and R d11 are preferably hydrogen atoms. The compound represented by the formula (d-4) has the EE form, the ZZ form, and the EZ form as geometric isomers, but it may be a single compound of any of them or a mixture of these geometric isomers. The compound represented by formula (d-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

為了使內醯胺系顏料在樹脂組成物中良好地分散，內醯胺系顏料的平均粒徑較佳為10～1000nm。In order to disperse the lactamamine pigment in the resin composition, the average particle diameter of the lactamamine pigment is preferably 10 to 1000 nm.

此外，以銀錫(AgSn)合金為主成分的微粒(以下，稱為「AgSn合金微粒」)亦較佳作為黑色顏料使用。對於該AgSn合金微粒而言，只要AgSn合金為主成分即可，亦可包含例如Ni、Pd、Au等作為其他金屬成分。 　　該AgSn合金微粒的平均粒徑較佳為1～300nm。In addition, microparticles containing silver tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy microparticles") are also preferably used as black pigments. The AgSn alloy particles need only be an AgSn alloy as a main component, and may include, for example, Ni, Pd, Au, or the like as other metal components. The average particle diameter of the AgSn alloy particles is preferably 1 to 300 nm.

AgSn合金由化學式AgxSn表示時，可得到化學穩定的AgSn合金的x的範圍為1≤x≤10，可同時得到化學穩定性和黑度的x的範圍為3≤x≤4。 　　於此，在上述x的範圍內，求出AgSn合金中的Ag的質量比，結果， 　　x=1時， Ag/AgSn=0.4762 　　x=3時， 3・Ag/Ag3Sn=0.7317 　　x=4時， 4・Ag/Ag4Sn=0.7843 　　x=10時， 10・Ag/Ag10Sn=0.9008 　　因此，對於該AgSn合金而言，含有47.6～90質量%的Ag時，化學穩定，含有73.17～78.43質量%的Ag時，可對應於Ag量而有效地得到化學穩定性與黑度。When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy can be obtained is 1≤x≤10, and the range of x in which chemical stability and blackness can be obtained simultaneously is 3≤x≤4. Here, the mass ratio of Ag in the AgSn alloy is obtained within the range of x. As a result, when x = 1, Ag / AgSn = 0.4762 x = 3, 3 · Ag / Ag3Sn = 0.7317 x = 4, 4 · Ag / Ag4Sn = 0.7843 x = 10, 10 · Ag / Ag10Sn = 0.9008 Therefore, when this AgSn alloy contains 47.6 to 90% by mass of Ag, it is chemically stable, and when it contains 73.17 to 78.43% by mass of Ag , Can effectively obtain chemical stability and blackness corresponding to the amount of Ag.

該AgSn合金微粒可使用通常的微粒合成法製作。作為微粒合成法，可舉出氣相反應法、噴霧熱解法、噴散法、液相反應法、冷凍乾燥法、水熱合成法等。The AgSn alloy particles can be produced by a general particle synthesis method. Examples of the microparticle synthesis method include a gas phase reaction method, a spray pyrolysis method, a spray method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

AgSn合金微粒雖然絕緣性高，但根據樹脂組成物的用途，為了進一步提高絕緣性，亦可用絕緣膜被覆表面。作為這樣的絕緣膜的材料，較佳為金屬氧化物或有機高分子化合物。 　　作為金屬氧化物，可合適地使用具有絕緣性的金屬氧化物，例如氧化矽(silica，二氧化矽)、氧化鋁(alumina，三氧化二鋁)、氧化鋯(zirconia，二氧化鋯)、氧化釔(yttria，三氧化二釔)、氧化鈦(titania，二氧化鈦)等。 　　另外，作為有機高分子化合物，可合適地使用具有絕緣性的樹脂，例如聚醯亞胺、聚醚、聚丙烯酸酯、聚胺化合物等。Although AgSn alloy particles have high insulation properties, depending on the use of the resin composition, in order to further improve the insulation properties, the surface may be covered with an insulating film. The material of such an insulating film is preferably a metal oxide or an organic polymer compound. As the metal oxide, a metal oxide having an insulating property can be suitably used, for example, silicon oxide (silica), alumina (alumina), zirconia (zirconia), or oxide Yttrium (yttria), titanium oxide (titania), and the like. In addition, as the organic polymer compound, a resin having insulation properties such as polyimide, polyether, polyacrylate, polyamine compound, or the like can be suitably used.

對於絕緣膜的膜厚而言，為了充分提高AgSn合金微粒的表面的絕緣性，較佳為1～100nm的厚度，更佳為5～50nm。 　　絕緣膜可利用表面改性技術或表面的塗覆技術而容易地形成。尤其是，若使用四乙氧基矽烷、三乙醇鋁等醇鹽，則可在較低溫度形成膜厚均勻的絕緣膜，因而較佳。The thickness of the insulating film is preferably 1 to 100 nm, and more preferably 5 to 50 nm in order to sufficiently improve the insulation of the surface of the AgSn alloy particles. The rhenium insulating film can be easily formed using a surface modification technique or a surface coating technique. In particular, if an alkoxide such as tetraethoxysilane or aluminum triethanolate is used, an insulating film having a uniform film thickness can be formed at a lower temperature, which is preferable.

作為黑色顏料，可單獨使用上述的苝系顏料、內醯胺系顏料、AgSn合金微粒，亦可將此等組合而使用。 　　此外，出於調整色調的目的等，黑色顏料可包含紅、藍、綠、黃等色相的色素。黑色顏料以外的色相的色素可從已知的色素中適當選擇。例如，作為黑色顏料以外的色相的色素，可使用上述的各種顏料。黑色顏料以外的色相的色素的使用量相對於黑色顏料的總質量而言較佳為15質量%以下，更佳為10質量%以下。As the black pigment, the above-mentioned fluorene-based pigment, lactam-based pigment, and AgSn alloy fine particles may be used alone, or these may be used in combination. In addition, for the purpose of adjusting hue and the like, the black pigment may include pigments of hue such as red, blue, green, and yellow. Pigments of a hue other than the black pigment can be appropriately selected from known pigments. For example, as the hue pigment other than the black pigment, various pigments described above can be used. The usage-amount of the pigment | dye of the hue other than a black pigment is 15 mass% or less with respect to the total mass of a black pigment, More preferably, it is 10 mass% or less.

為了使上文中說明的顏料(D)在樹脂組成物中均勻分散，可進一步使用分散劑。作為這樣的分散劑，較佳為使用聚乙烯亞胺系、聚胺酯樹脂系、丙烯酸樹脂系的高分子分散劑。尤其是，使用碳黑作為顏料(D)時，較佳為使用丙烯酸樹脂系的分散劑作為分散劑。 　　尚，有時亦從硬化膜中產生因分散劑而導致的腐蝕性的氣體。因此，在不使用分散劑的情況下對顏料(D)進行分散處理亦為較佳方式之一例。In order to uniformly disperse the pigment (D) described above in the resin composition, a dispersant may be further used. As such a dispersant, a polyethyleneimine-based, polyurethane resin-based, or acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the pigment (D), an acrylic resin-based dispersant is preferably used as the dispersant. In some cases, corrosive gases due to dispersants are also generated from the cured film. Therefore, it is also an example of a preferable method to disperse the pigment (D) without using a dispersant.

另外，對於無機顏料與有機顏料而言，可分別單獨使用，或者亦可併用2種以上，在併用的情況下，相對於無機顏料與有機顏料的總量100質量份而言，較佳以10～80質量份的範圍使用有機顏料，更佳以20～40質量份的範圍使用有機顏料。In addition, the inorganic pigment and the organic pigment may be used singly, or two or more kinds may be used in combination. In the case of using them in combination, it is preferably 10 to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. An organic pigment is used in a range of from 80 to 80 parts by mass, and an organic pigment is more preferably used in a range of from 20 to 40 parts by mass.

尚，樹脂組成物中，可組合使用顏料(D)與染料。該染料從已知的材料中適當選擇即可。 　　作為可應用於樹脂組成物的染料，可舉出例如偶氮染料、金屬絡鹽偶氮染料、蒽醌染料、三苯基甲烷染料、呫噸染料、花菁染料(cyanine dye)、萘醌染料、醌亞胺染料、甲川(methine)染料、酞菁(phthalocyanine)染料等。 　　另外，對於此等染料，可藉由進行色澱化(成鹽化)而使其分散於有機溶劑等中，從而將其作為(D)著色劑使用。 　　除了此等染料以外，例如，亦可較佳為使用日本特開2013-225132號公報、日本特開2014-178477號公報、日本特開2013-137543號公報、日本特開2011-38085號公報、日本特開2014-197206號公報等中記載的染料等。In the resin composition, a pigment (D) and a dye may be used in combination. The dye may be appropriately selected from known materials. Examples of the dyes applicable to the resin composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, and naphthoquinone dyes. Quinone imine dye, methine dye, phthalocyanine dye and the like. In addition, these dyes can be used as a (D) colorant by dispersing them in an organic solvent or the like by subjecting them to lake formation (salinization). In addition to these dyes, for example, Japanese Patent Application Laid-Open No. 2013-225132, Japanese Patent Application Laid-Open No. 2014-178477, Japanese Patent Application Laid-Open No. 2013-137543, Japanese Patent Application Laid-Open No. 2011-38085 may be preferably used, Dyes and the like described in Japanese Patent Application Laid-Open No. 2014-197206 and the like.

對於樹脂組成物中的顏料(D)的使用量而言，可在不妨礙本發明的目的的範圍內適當選擇，典型地，相對於樹脂組成物的固體成分整體的質量而言，較佳為2～75質量%，更佳為3～70質量%。The amount of the pigment (D) used in the resin composition can be appropriately selected within a range that does not hinder the object of the present invention. Typically, the amount of the pigment (D) is preferably more than the mass of the solid content of the resin composition. 2 to 75% by mass, more preferably 3 to 70% by mass.

對於顏料(D)而言，較佳在存在或不存在分散劑的情況下以適當的濃度使顏料(D)分散而製成分散液後，添加至樹脂組成物中。 　　尚，本說明書中，關於上述的顏料(D)的使用量，可定義為還包含上述存在的分散劑的值。The pigment (D) is preferably dispersed in a suitable concentration in the presence or absence of a dispersant to form a dispersion, and then added to the resin composition. In this specification, the amount of the pigment (D) used in the present specification can be defined as a value that further includes the dispersant present as described above.

＜矽烷偶合劑(E)＞ 　　樹脂組成物包含矽烷偶合劑(E)。 　　矽烷偶合劑(E)包含下述式(e1)表示的烷氧基矽烷化合物。 　　(Re1 O)a (Re2 )3-a Si-Re3 -NH-CO-Re4 -Re5 ……(e1) 　　(式(e1)中，Re1 及Re2 各自獨立地為碳原子數1～6之烴基，a為2或3，Re3 為碳原子數1～10之亞烷基，Re4 為2價之有機基，Re5 為布朗斯特酸性基、醇式羥基、胺基、或胺基甲醯基)。 　　經由在樹脂組成物中摻合包含上述式(e1)表示的化合物的矽烷偶合劑，由此，在使用樹脂組成物進行基於光刻法的圖案形成(patterning)時，可將形成的經圖案化的硬化膜良好地密著於基板，並且，可抑制在未曝光部產生顯影殘渣。<Silane coupling agent (E)> The resin composition contains a silane coupling agent (E). The silane coupling agent (E) contains an alkoxysilane compound represented by the following formula (e1). (R e1 O) a (R e2 ) 3-a Si-R e3 -NH-CO-R e4 -R e5 ... (e1) (In the formula (e1), R e1 and R e2 are each independently a carbon atom A hydrocarbon group of 1 to 6, a is 2 or 3, R e3 is an alkylene group having 1 to 10 carbon atoms, R e4 is a divalent organic group, and R e5 is a Bronsted acid group, an alcoholic hydroxyl group, and an amine Group, or aminoformyl). By blending the silane coupling agent containing the compound represented by the above formula (e1) in the resin composition, the patterning formed by the photolithography method using the resin composition can be patterned. The hardened film adheres well to the substrate, and can suppress development residues in unexposed areas.

式(e1)中，Re1 及Re2 各自獨立地為碳原子數1～6的烴基。 　　作為碳原子數1～6的烴基的較佳例，可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、正己基、環丙基、環丁基、環戊基、環己基、及苯基。 　　此等中，較佳為甲基、乙基、正丙基、異丙基、及苯基，更佳為甲基及乙基。In formula (e1), R e1 and R e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms. Preferred examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. , N-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl. Among these, methyl, ethyl, n-propyl, isopropyl, and phenyl are preferred, and methyl and ethyl are more preferred.

式(e1)中，Re3 為碳原子數1～10的亞烷基。作為Re3 的亞烷基可為直鏈狀，亦可為支鏈狀，較佳為直鏈狀。 　　作為Re3 的較佳的具體例，可舉出亞甲基、乙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基、及癸烷-1,10-二基。 　　此等中，從式(e1)表示的化合物容易獲得、容易合成，而且容易得到充分的圖案密著的效果與抑制顯影殘渣產生的效果方面考慮，較佳為乙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、及己烷-1,6-二基，更佳為乙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基，特別較佳為丙烷-1,3-二基。In the formula (e1), R e3 is an alkylene group having 1 to 10 carbon atoms. The alkylene group as R e3 may be linear or branched, and is preferably linear. Preferable specific examples of R e3 include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1. , 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane- 1,10-diyl. Among these, ethane-1,2-diyl is preferred from the viewpoints that the compound represented by the formula (e1) is easily available and easy to synthesize, and that it is easy to obtain a sufficient pattern adhesion effect and an effect of suppressing the development residue. , Propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl, more preferably ethane-1,2 -Diyl, propane-1,3-diyl, butane-1,4-diyl, particularly preferably propane-1,3-diyl.

式(e1)中，Re5 為布朗斯特酸性基、醇式羥基、胺基(-NH2 )、或胺基甲醯基(-CO-NH2 )。 　　由於此等基容易形成氫鍵，因此，在鍵結於基板表面的多個式(e1)表示的化合物的末端，-CO-Re4 -Re5 表示的基容易彼此經由氫鍵而進行封端化。 　　對於-CO-Re4 -Re5 表示的基彼此形成的封端部(block)而言，認為其防止在未曝光部顯影殘渣牢固地結合於基板表面，可抑制顯影殘渣的產生。 　　另外，-CO-Re4 -Re5 表示的基也容易在其與硬化膜之間形成氫鍵。因此認為，使用包含式(e1)表示的化合物的樹脂組成物形成的硬化膜良好地密著於基板表面。In the formula (e1), R e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amine group (-NH 2 ), or an aminoformyl group (-CO-NH 2 ). Since these groups easily form hydrogen bonds, the groups represented by -CO-R e4 -R e5 are easily terminated by hydrogen bonds at the ends of a plurality of compounds represented by formula (e1) bonded to the substrate surface. Into. It is considered that the blocked portions formed by the groups represented by -CO-R e4 -R e5 prevent the development residues from being firmly bonded to the substrate surface in the unexposed portion, and the generation of development residues can be suppressed. In addition, the group represented by -CO-R e4 -R e5 also easily forms a hydrogen bond between the group and the cured film. Therefore, it is considered that the cured film formed using the resin composition containing the compound represented by the formula (e1) adheres well to the substrate surface.

關於作為Re5 的布朗斯特酸性基的較佳的具體例，可舉出羧基、磺酸基、亞磺酸基、膦酸基、次膦酸基、及酚式羥基等。Desirable specific examples of Brønsted acidic group as R e5 can include a carboxyl group, a sulfonic acid group, sulfinic acid group, phosphonic acid group, phosphinic acid group, a phenolic hydroxyl group and the like.

Re5 中，從容易得到所期望的效果方面考慮，較佳為布朗斯特酸性基，更佳為羧基。From the viewpoint of easily obtaining a desired effect, R e5 is preferably a Bronsted acid group, and more preferably a carboxyl group.

作為Re4 的2價的有機基在不妨礙本發明的目的的範圍內沒有特別限制。作為Re4 的2價的有機基的碳原子數較佳為1以上50以下，更佳為1以上20以下，特別佳為1以上12以下。 　　關於作為Re4 的2價的有機基，可舉出2價的脂肪族烴基、2價的芳香族烴基、及2價的雜環基。 　　此等基均可具有取代基。The divalent organic group as R e4 is not particularly limited as long as it does not hinder the object of the present invention. The number of carbon atoms of the divalent organic group as R e4 is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less, and particularly preferably 1 or more and 12 or less. Examples of the divalent organic group as R e4 include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent heterocyclic group. Each of these groups may have a substituent.

作為Re4 的2價的脂肪族烴基、2價的芳香族烴基、及2價的雜環基具有取代基時，作為該取代基的較佳例，可舉出碳原子數1～6的烷基、碳原子數1～6的烷氧基、碳原子數2～7的飽和脂肪族醯基、碳原子數2～7的烷氧基羰基、碳原子數2～7的飽和脂肪族醯基氧基、具有碳原子數1～6的烷基的單烷基胺基、具有碳原子數1～6的烷基的二烷基胺基、鹵素、硝基、及氰基等。When the divalent aliphatic hydrocarbon group, the divalent aromatic hydrocarbon group, and the divalent heterocyclic group of R e4 have a substituent, examples of the substituent include alkane having 1 to 6 carbon atoms. Group, alkoxy group having 1 to 6 carbon atoms, saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, and saturated aliphatic fluorenyl group having 2 to 7 carbon atoms An oxygen group, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a halogen, a nitro group, a cyano group, and the like.

作為Re4 的2價的脂肪族烴基可為直鏈狀，亦可為支鏈狀，亦可為環狀，亦可為環狀，亦可組合地包含此等構造。 　　另外，作為Re4 的2價的脂肪族烴基可包含不飽和雙鍵。 　　關於作為Re4 的2價的脂肪族烴基為鏈狀基時的較佳例，可舉出亞甲基、乙烷-1,2-二基、乙烯-1,2-二基、丙烷-1,3-二基、丙烷-1,2-二基、丙烷-2,2-二基、及丁烷-1,4-二基等。The divalent aliphatic hydrocarbon group as R e4 may be linear or branched, or may be cyclic or cyclic, and these structures may be included in combination. Further, as a divalent aliphatic hydrocarbon group R e4 may contain an unsaturated double bond. Preferred examples when the divalent aliphatic hydrocarbon group as R e4 is a chain group include methylene, ethane-1,2-diyl, ethylene-1,2-diyl, and propane-1. , 3-diyl, propane-1,2-diyl, propane-2,2-diyl, and butane-1,4-diyl and the like.

作為Re4 之2價的脂肪族烴基為環狀時，作為較佳的基，可舉出從單環烷烴、雙環烷烴、三環烷烴、或四環烷烴等中除去2個氫原子而得到的基。 　　具體而言，可舉出從環戊烷、環己烷、環庚烷、環辛烷等單環烷烴、金剛烷、降冰片烷、異冰片烷、三環癸烷、及四環十二烷等中除去2個氫原子而得到的基。When the bivalent aliphatic hydrocarbon group of R e4 is cyclic, preferable groups include those obtained by removing two hydrogen atoms from a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. base. Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. A group obtained by removing two hydrogen atoms from the group.

關於作為Re4 的2價的芳香族烴基的較佳例，可舉出亞苯基、萘二基、菲二基、蒽二基、及芘二基等。Preferable examples of the divalent aromatic hydrocarbon group as R e4 include a phenylene group, a naphthalenediyl group, a phenanthryldiyl group, an anthracenyldiyl group, a perylenediyl group, and the like.

Re4 為2價之雜環基時，雜環基較佳為包含1個以上的N、S、O的五元或六元的單環，或者所述單環彼此、或所述單環與苯環縮合而成的基。 　　作為所述2價之雜環基，可舉出從呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚嗪、苯并咪唑、苯并***、苯并噁唑、苯并噻唑、哢唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、肉啉、及喹喔啉等中除去2個氫原子而得到的基。When R e4 is a divalent heterocyclic group, the heterocyclic group is preferably a five- or six-membered monocyclic ring containing one or more N, S, and O, or the monocyclic rings each other, or the monocyclic ring and Benzene ring condensation group. Examples of the divalent heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine , Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, oxazole, purine, quinoline, iso A group obtained by removing two hydrogen atoms from quinoline, quinazoline, phthalazine, oxoline, and quinoxaline.

作為Re4 ，從圖案密著的效果與抑制顯影殘渣產生的效果良好方面考慮，較佳為2價的芳香族烴基。As R e4 , a divalent aromatic hydrocarbon group is preferred in terms of the effect of pattern adhesion and the effect of suppressing the occurrence of development residues.

2價的芳香族烴基中，一方的化學鍵所鍵結的碳原子的位置與另一方的化學鍵所鍵結的碳原子的位置的關係較佳為鄰位(日文為“隣接位”)、或迫位(peri-position)。 　　作為Re5 的布朗斯特酸性基、醇式羥基、胺基、或胺基甲醯基為可與羰基之間產生氫鍵的官能團。 　　因此，2價的芳香族烴基中，一方的化學鍵所鍵結的碳原子的位置與另一方的化學鍵所鍵結的碳原子的位置的關係為鄰位或迫位時，多個式(e1)表示的化合物鍵結於基板上的鄰近位置時，式(e1)表示的化合物中的Re5 容易與其他的式(e1)表示的化合物中的羰基形成氫鍵。 　　另一方面，多個式(e1)表示的化合物鍵結於基板上的鄰近位置時，由於Re4 為2價的芳香族基，因而可在多個Re4 之間產生π-π堆疊(stacking)等。 　　基於上文中說明的理由，推測2價的芳香族烴基中的2個化學鍵的位置關係為鄰位或迫位的關係時，式(e1)表示的化合物的末端的-CO-Re4 -Re5 表示的基容易顯示出自組織化的行為，容易在基板表面形成封端部(其是由多個 -CO-Re4 -Re5 表示的基形成的)。 　　這種情況下，認為對於由-CO-Re4 -Re5 表示的基形成的封端部而言，在曝光部，由於與硬化膜之間的氫鍵、芳香環彼此的相互作用，使得硬化膜良好地密著於基板，在未曝光部，妨礙基板與顯影殘渣之間的直接的相互作用，可抑制顯影殘渣的產生。In a divalent aromatic hydrocarbon group, the relationship between the position of the carbon atom bonded by one chemical bond and the position of the carbon atom bonded by the other chemical bond is preferably an adjacent position ("adjacent position" in Japanese) or a forced position. Peri-position. As R e5 Bronsted acidic group, alcoholic hydroxyl, amino, methyl, or acyl group to produce a hydrogen bond between a functional group with a carbonyl group. Therefore, in a divalent aromatic hydrocarbon group, when the relationship between the position of the carbon atom bonded by one chemical bond and the position of the carbon atom bonded by the other chemical bond is adjacent or forced, multiple formulas (e1) When the compound represented is bonded to a nearby position on the substrate, R e5 in the compound represented by the formula (e1) easily forms a hydrogen bond with a carbonyl group in another compound represented by the formula (e1). On the other hand, when a plurality of compounds represented by the formula (e1) are bonded to adjacent positions on the substrate, since R e4 is a divalent aromatic group, π-π stacking can be generated between a plurality of R e4 )Wait. When the positional relationship between the two chemical bonds in the divalent aromatic hydrocarbon group is ortho or forced based on the reason explained above, -CO-R e4 -R e5 at the terminal of the compound represented by formula (e1) is estimated. The indicated group easily exhibits a self-organizing behavior, and it is easy to form an end-capping portion (which is formed by a plurality of groups represented by -CO-R e4 -R e5 ) on the substrate surface. In this case, it is considered that the end portion formed by the group represented by -CO-R e4 -R e5 is hardened in the exposed portion due to the interaction between the hydrogen bond with the cured film and the aromatic ring. The film adheres well to the substrate, prevents direct interaction between the substrate and the development residue in the unexposed portion, and suppresses the generation of the development residue.

關於作為Re4 的2價的芳香族烴基的較佳的具體例，可舉出鄰亞苯基、間亞苯基、對亞苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、及萘-2,7-二基。 　　此等基中，較佳為鄰亞苯基、萘-1,2-二基、萘-2,3-二基、或萘-1,8-二基。 　　這是因為，如上文所述，2價的芳香族烴基中，一方的化學鍵所鍵結的碳原子的位置與另一方的化學鍵所鍵結的碳原子的位置的關係較佳為鄰位或迫位。Preferred specific examples of the divalent aromatic hydrocarbon group of R e4 include o-phenylene, m-phenylene, p-phenylene, naphthalene-1,2-diyl, and naphthalene-1,3. -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene -2,3-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl. Among these groups, o-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, or naphthalene-1,8-diyl is preferred. This is because, as described above, in the divalent aromatic hydrocarbon group, the relationship between the position of the carbon atom bonded by one chemical bond and the position of the carbon atom bonded by the other chemical bond is preferably adjacent or forced. Bit.

作為式(e1)表示的化合物的較佳的具體例，可舉出以下的化合物。 　　[化28] Preferred specific examples of the compound represented by the formula (e1) include the following compounds. [Chemical 28]

上文中說明的式(e1)表示的化合物可與具有式(e1)表示的構造以外的構造的各種矽烷偶合劑組合使用。作為可與式(e1)表示的化合物一同使用的矽烷偶合劑，可從一直以來出於各種目的而使用的矽烷偶合劑中適當選擇。The compound represented by the formula (e1) described above can be used in combination with various silane coupling agents having a structure other than the structure represented by the formula (e1). As the silane coupling agent which can be used together with the compound represented by the formula (e1), a silane coupling agent which has been conventionally used for various purposes can be appropriately selected.

作為所述矽烷偶合劑的較佳例，可舉出甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丁基三甲氧基矽烷、正丁基三乙氧基矽烷等單烷基三烷氧基矽烷；二甲基二甲氧基矽烷、二甲基二乙氧基矽烷等二烷基二烷氧基矽烷；苯基三甲氧基矽烷、苯基三乙氧基矽烷等單苯基三烷氧基矽烷；二苯基二甲氧基矽烷、二苯基二乙氧基矽烷等二苯基二烷氧基矽烷；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等單乙烯基三烷氧基矽烷；3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷等(甲基)丙烯醯氧基烷基單烷基二烷氧基矽烷；3-丙烯醯氧基丙基三甲氧基矽烷等(甲基)丙烯醯氧基烷基三烷氧基矽烷；3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-三乙氧基甲矽烷基-N-(1,3-二甲基-丁叉基(butylidene))丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷等含有胺基的三(或二)烷氧基矽烷；及用醛等保護它們的胺基而得到的酮亞胺基矽烷；3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷等含有非脂環式環氧基亞芴基的烷基三(或二)烷氧基矽烷；3-環氧丙氧基丙基甲基二乙氧基矽烷等含有非脂環式環氧基的烷基單烷基二烷氧基矽烷；2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、2-(3,4-環氧環己基)甲基二甲氧基矽烷、2-(3,4-環氧環己基)甲基二乙氧基矽烷等含有脂環式環氧基的烷基三(或二)烷氧基矽烷；2-(3,4-環氧環己基)乙基甲基二乙氧基矽烷等含有脂環式環氧基的烷基單烷基二烷氧基矽烷；[(3-乙基-3-氧雜環丁基)甲氧基]丙基三甲氧基矽烷、[(3-乙基-3-氧雜環丁基)甲氧基]丙基三乙氧基矽烷等含有氧雜環丁基的烷基三烷氧基矽烷；3-巰基丙基三甲氧基矽烷等巰基烷基三烷氧基矽烷；3-巰基丙基甲基二甲氧基矽烷等巰基烷基單烷基二烷氧基矽烷；3-脲基丙基三乙氧基矽烷等脲基烷基三烷氧基矽烷；3-異氰酸酯丙基三乙氧基矽烷等異氰酸酯烷基三烷氧基矽烷；三-(三甲氧基甲矽烷基丙基)異氰脲酸酯、三-(三乙氧基甲矽烷基丙基)異氰脲酸酯等含有異氰脲酸酯的三烷氧基矽烷；3-三甲氧基甲矽烷基丙基琥珀酸酐、具有其他的酸酐基(例如，環己烷二甲酸酐基、4-甲基-環己烷二甲酸酐基、5-甲基-環己烷二甲酸酐基、雙環庚烷二甲酸酐基、7-氧雜-雙環庚烷二甲酸酐基、鄰苯二甲酸酐基等)的三烷氧基矽烷等含有酸酐基的烷基三烷氧基矽烷；作為羧基而具有琥珀酸基、或其半酯基、環己烷二甲酸基、或其半酯基、4-甲基-環己烷二甲酸基、或其半酯基、5-甲基-環己烷二甲酸基、或其半酯基、雙環庚烷二甲酸基、或其半酯基、7-氧雜-雙環庚烷二甲酸基、或其半酯基、鄰苯二甲酸基、或其半酯基的含有羧基的烷基三烷氧基矽烷；N-叔丁基-3-(3-三甲氧基甲矽烷基丙基)琥珀酸醯亞胺等含有醯亞胺基的烷基三烷氧基矽烷；(3-三甲氧基甲矽烷基丙基)-叔丁基胺基甲酸酯、(3-三乙氧基甲矽烷基丙基)-叔丁基胺基甲酸酯等含有胺基甲酸酯基的烷基三烷氧基矽烷；等等。Preferred examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n-propyltrimethoxy Monoalkyltrialkoxysilanes such as silane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane; dimethyldimethoxysilane, dimethyldimethoxysilane Dialkyldialkoxysilanes such as ethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldimethoxysilane and diphenyl Diphenyldialkoxysilane such as diethoxysilane; monovinyltrialkoxysilane such as vinyltrimethoxysilane, vinyltriethoxysilane; 3-methacryloxypropyltrimethyl Oxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyl (Meth) acryloxyalkyl monoalkyldialkoxysilanes such as diethoxysilane; (meth) acrylic acid such as 3-propenyloxypropyltrimethoxysilane; etc. Alkyltrialkoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethylsilane Oxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldisiloxane Ethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane , N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, etc. (Or di) alkoxysilanes; and ketimidosilanes obtained by protecting their amine groups with aldehydes, etc .; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Alkyl tri (or di) alkoxysilanes containing non-alicyclic epoxy fluorenylene groups, such as triethoxysilane, 3-glycidoxypropylmethyldimethoxysilane; 3-ring Oxypropoxypropylmethyldi Alkyl monoalkyldialkoxysilanes containing non-alicyclic epoxy groups, such as oxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxy Alkyltri (or di) alkoxysilanes containing alicyclic epoxy groups, etc .; cycloaliphatic rings containing 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, etc. Oxyalkyl monoalkyldialkoxysilane; [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxy Heterocyclobutyl) methoxy] propyltriethoxysilane and other alkylcycloalkoxysilanes containing oxetanyl; mercaptoalkyltrialkoxysilane such as 3-mercaptopropyltrimethoxysilane ; Mercaptoalkyl monoalkyldialkoxysilane such as 3-mercaptopropylmethyldimethoxysilane; Ureaalkyltrialkoxysilane such as 3-ureidopropyltriethoxysilane; 3- Isocyanate propyl triethoxy silane and other isocyanate alkyl trialkoxy silane; tri- (trimethoxysilyl propyl) isocyanurate, -Trialkoxysilanes containing isocyanurates such as (triethoxysilylpropyl) isocyanurate; 3-trimethoxysilylpropyl succinic anhydride, having other anhydride groups ( For example, cyclohexanedicarboxylic anhydride group, 4-methyl-cyclohexanedicarboxylic anhydride group, 5-methyl-cyclohexanedicarboxylic anhydride group, bicycloheptanedicarboxylic anhydride group, 7-oxa-bicyclo Heptanedicarboxylic acid anhydride group, phthalic anhydride group, etc.), trialkoxysilanes and other alkyltrialkoxysilanes containing acid anhydride groups; succinic acid groups, or half ester groups, Alkanedicarboxylic acid group, or its half ester group, 4-methyl-cyclohexanedicarboxylic acid group, or its half ester group, 5-methyl-cyclohexanedicarboxylic acid group, or its half ester group, or dicycloheptane Dicarboxylic acid group, or its half ester group, 7-oxa-bicycloheptane dicarboxylic acid group, or its half ester group, phthalic acid group, or its half ester group, and a carboxyl-containing alkyltrialkoxysilane ; N-tert-butyl-3- (3-trimethoxysilylpropyl) succinate fluorenimide-containing alkyltrialkoxysilane; (3-trimethoxysilyl group) (Propyl) -tert-butylcarbamate, (3 -Triethoxysilylpropyl) -alkyltrialkoxysilane containing a urethane group such as tert-butylcarbamate; and the like.

關於樹脂組成物中的矽烷偶合劑(E)的含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為0.01～10質量%，更佳為0.5～6質量%，特別較佳為1～5質量%。 　　經由使用上述範圍內的量的矽烷偶合劑(E)，從而容易將形成的圖案特別良好地密著於基板，另外，特別容易抑制在未曝光部產生顯影殘渣。The content of the silane coupling agent (E) in the resin composition is preferably 0.01 to 10% by mass, more preferably 0.5 to 6% by mass, and particularly preferably relative to the mass of the solid content of the resin composition as a whole. It is 1 to 5 mass%. By using the silane coupling agent (E) in an amount within the above range, it is easy to adhere the formed pattern to the substrate particularly well, and it is particularly easy to suppress development residues from occurring in the unexposed portion.

另外，式(e1)表示的化合物的質量在矽烷偶合劑(E)的總質量中所占的比率較佳為10質量%以上，更佳為15質量%以上，特別佳為30質量%以上。 　　另外，式(e1)表示的化合物的質量在矽烷偶合劑(E)的總質量中所占的比例的上限值沒有特別限制，例如，可為95質量%以下，可為90質量%以下，可為85質量%以下。 　　另外，亦可使式(e1)表示的化合物的質量在矽烷偶合劑(E)的總質量中所占的比例為100質量%。 　　藉由以上述的比例使用包含上述範圍內的量的式(e1)表示的化合物的矽烷偶合劑(E)，從而容易將形成的圖案良好地密著於基板，並且容易抑制在未曝光部產生顯影殘渣。The ratio of the mass of the compound represented by the formula (e1) to the total mass of the silane coupling agent (E) is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the proportion of the mass of the compound represented by the formula (e1) in the total mass of the silane coupling agent (E) is not particularly limited. For example, it may be 95% by mass or less, and may be 90% by mass or less. It may be 85% by mass or less. In addition, the proportion of the mass of the compound represented by the formula (e1) in the total mass of the silane coupling agent (E) may be 100% by mass. By using the silane coupling agent (E) containing the compound represented by the formula (e1) in an amount within the above range in the above ratio, it is easy to adhere the formed pattern to the substrate well, and it is easy to suppress generation in the unexposed portion. Development residue.

此外，樹脂組成物中，關於式(e1)表示的化合物的含量，相對於樹脂組成物的固體成分整體的質量而言，較佳為0.01～10質量%，更佳為0.5～6質量%，特別較佳為1～5質量%。 　　經由使用上述範圍內的量的式(e1)表示的化合物，從而容易將形成的圖案特別良好地密著於基板，另外，特別容易抑制在未曝光部產生顯影殘渣。In addition, the content of the compound represented by the formula (e1) in the resin composition is preferably 0.01 to 10% by mass, and more preferably 0.5 to 6% by mass, relative to the mass of the solid content of the resin composition as a whole. It is particularly preferably 1 to 5 mass%. By using a compound represented by formula (e1) in an amount within the above range, it is easy to adhere the formed pattern to the substrate particularly well, and it is particularly easy to suppress generation of development residue in the unexposed portion.

＜有機溶劑(S)＞ 　　對於樹脂組成物而言，為了改善塗佈性、調整黏度，較佳為包含有機溶劑(S)。<Organic solvent (S)> It is preferable that the resin composition contains an organic solvent (S) in order to improve coating properties and adjust viscosity.

作為有機溶劑(S)，具體而言，可舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單正丙基醚、二乙二醇單正丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚、丙二醇單正丁基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、二丙二醇單正丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚等(聚)亞烷基二醇單烷基醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯等(聚)亞烷基二醇單烷基醚乙酸酯類；二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷基酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、乙酸苄酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基異丁醯胺、N,N-二乙基乙醯胺、N,N-二乙基甲醯胺、N-甲基己內醯胺、1,3-二甲基-2-咪唑啉酮、吡啶、及N,N,N’,N’-四甲基脲等含氮極性有機溶劑；等。Specific examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl (Poly) alkylene glycol monoalkyl ethers such as ethers, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethyl ether Glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran And other ethers; Ketones such as ethyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2- Ethyl methyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl propionate 3-Methoxybutyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, benzyl acetate, propionic acid N-butyl ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl其他 Ethyl esters such as ethyl acetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramine, N, N-diethylacetamide, N, N-diethylformamide, N-methyl Lactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N, N, N ', N'- tetramethyluronium nitrogen-containing polar organic solvent; and the like.

此等中，較佳為亞烷基二醇單烷基醚類、亞烷基二醇單烷基醚乙酸酯類、上述的其他醚類、乳酸烷基酯類、上述的其他酯類，更佳為亞烷基二醇單烷基醚乙酸酯類、上述的其他醚類、乙酸苄酯等上述的其他酯類。 　　另外，從各成分的溶解性、顏料(D)的分散性等方面考慮，有機溶劑(S)亦較佳為包含含氮極性有機溶劑。作為含氮極性有機溶劑，可使用N,N,N’,N’-四甲基脲等。 　　此等溶劑可單獨使用，或者可以組合2種以上而使用。Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactates, other esters described above, and more Preferred are the above-mentioned other esters such as alkylene glycol monoalkyl ether acetates, the other ethers described above, and benzyl acetate. It is also preferable that the organic solvent (S) contains a nitrogen-containing polar organic solvent from the viewpoint of the solubility of each component, the dispersibility of the pigment (D), and the like. As the nitrogen-containing polar organic solvent, N, N, N ', N'-tetramethylurea and the like can be used. These solvents may be used alone or in combination of two or more.

有機溶劑(S)的含量沒有特別限制，可以可塗佈於基板等的濃度，根據塗佈膜厚進行適當設定。樹脂組成物的黏度較佳為5～500cp，更佳為10～50cp，進一步較佳為20～30cp。另外，固體成分濃度較佳為5～100質量%，更佳為15～50質量%。The content of the organic solvent (S) is not particularly limited, and the concentration of the organic solvent (S) can be applied to a substrate or the like, and is appropriately set depending on the thickness of the coating film. The viscosity of the resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid content concentration is preferably 5 to 100% by mass, and more preferably 15 to 50% by mass.

＜其他成分＞ 　　根據需要，可在樹脂組成物中含有界面活性劑、密著性提高劑、熱聚合抑制劑、消泡劑、環氧化合物等添加劑。所有的添加劑均可使用現有已知的物質。 　　作為界面活性劑，可舉出陰離子系、陽離子系、非離子系等的化合物，作為熱聚合抑制劑，可舉出對苯二酚、對苯二酚單乙基醚等，作為消泡劑，可舉出聚矽氧烷系、氟系化合物等。<Other components> If necessary, additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, a defoamer, and an epoxy compound may be contained in the resin composition. All additives can be made of known substances. Examples of the surfactant include anionic, cationic, and nonionic compounds. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples thereof include a polysiloxane-based compound and a fluorine-based compound.

＜樹脂組成物的調製方法＞ 　　上文中說明的樹脂組成物可經由在將分別為特定量的上述各成分混合後用攪拌機均勻混合而得到。尚，為了使得到的混合物變得更均勻，亦可使用濾波器進行過濾。<Preparation Method of Resin Composition> The resin composition described above can be obtained by mixing each of the above-mentioned respective components in a specific amount, and uniformly mixing them with a blender. However, in order to make the obtained mixture more homogeneous, a filter can also be used for filtering.

≪硬化膜的製造方法≫ 　　作為硬化膜的製造方法，可沒有特別限制地採用使用包含光聚合性化合物(B)的樹脂組成物的現有已知的硬化膜的製造方法。≪Method for producing cured film≪ As a method for producing a cured film, a conventionally known method for producing a cured film using a resin composition containing a photopolymerizable compound (B) can be used without particular limitation.

作為硬化膜的較佳的製造方法，可舉出包含下述步驟的方法： 　　藉由塗佈前述的樹脂組成物，從而形成塗佈膜的步驟， 　　位置選擇性地將塗佈膜曝光的步驟， 　　將經曝光的塗佈膜顯影，形成經圖案化的硬化膜的步驟，與 　　對經圖案化的硬化膜進行烘烤的步驟。As a preferable method for producing a cured film, a method including the following steps: a step of forming a coating film by applying the aforementioned resin composition, a step of selectively exposing the coating film at a position, A step of developing the exposed coating film to form a patterned cured film, and a step of baking the patterned cured film.

為了使用樹脂組成物形成硬化膜，首先，將樹脂組成物塗佈於對應於硬化膜的用途而選擇的基板上，形成塗佈膜。塗佈膜的形成方法沒有特別限制，例如可使用輥塗機、逆轉塗佈機(reverse coater)、棒塗機等接觸轉印型塗佈裝置、旋塗器(旋轉式塗佈裝置)、幕塗流動塗料器(curtain flow coater)等非接觸型塗佈裝置來進行。To form a cured film using a resin composition, first, the resin composition is applied to a substrate selected in accordance with the use of the cured film to form a coating film. The method for forming the coating film is not particularly limited, and for example, a roll coater, a reverse coater, a bar coater, or the like can be used as a contact transfer coating device, a spin coater (rotary coating device), or a curtain. It is performed by applying a non-contact coating device such as a curtain flow coater.

根據需要，將已塗佈的樹脂組成物乾燥，構成塗佈膜。乾燥方法沒有特別限制，可舉出例如下述方法：(1)用加熱板，於80～120℃、較佳為90～100℃的溫度，進行60～120秒乾燥的方法；(2)在室溫放置數小時～數天的方法；(3)放入至熱風加熱器或紅外線加熱器中數十分鐘～數小時而除去溶劑的方法；等。If necessary, the coated resin composition is dried to constitute a coating film. The drying method is not particularly limited, and examples thereof include the following: (1) a method of drying at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C using a hot plate for 60 to 120 seconds; (2) a A method of leaving at room temperature for several hours to several days; (3) a method of removing the solvent by putting it in a hot air heater or an infrared heater for several tens of minutes to several hours; and the like.

接下來，將塗佈膜曝光。曝光可介由照射紫外線、準分子雷射等活性能量射線來進行。曝光例如可介由隔著負型的掩模進行曝光的方法等位置選擇性地進行。照射的能量射線量隨著樹脂組成物組成的不同而相異，例如較佳為40～200mJ/cm2 左右。 　　尚，在對塗佈膜整面進行曝光的情況下，可形成具有與塗佈膜的形狀相對應的形狀的未經圖案化的硬化膜。Next, the coating film is exposed. Exposure can be performed by irradiating active energy rays such as ultraviolet rays and excimer lasers. The exposure can be selectively performed at a position such as a method of exposing through a negative mask. The amount of energy rays to be irradiated varies depending on the composition of the resin composition, and is preferably about 40 to 200 mJ / cm 2 , for example. When the entire surface of the coating film is exposed, an unpatterned cured film having a shape corresponding to the shape of the coating film can be formed.

在位置選擇性地將塗佈膜曝光的情況下，藉由利用顯影液將曝光後的膜顯影，從而將未曝光部溶解於顯影液中而將其除去，可形成經圖案化的硬化膜。顯影方法沒有特別限制，例如，可使用浸漬法、噴霧法等。顯影液可根據樹脂組成物的組成適當選擇。作為顯影液，可使用例如氫氧化鈉、氫氧化鉀、碳酸鈉、胺、季銨鹽等鹼性的水溶液。In the case where the coating film is selectively exposed by the position, the unexposed portion is dissolved in the developing solution and removed by developing the exposed film with a developing solution to form a patterned cured film. The developing method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. The developer can be appropriately selected according to the composition of the resin composition. As the developing solution, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, an amine, or a quaternary ammonium salt can be used.

接下來，對經圖案化的硬化膜進行烘烤(後烘烤)。烘烤溫度沒有特別限制，較佳為180～250℃，更佳為220～230℃。烘烤時間典型地為10～90分鐘，較佳為20～60分鐘。 　　經由如上所述地進行烘烤，可得到樹脂組成物的硬化膜。Next, the patterned cured film is baked (post-baking). The baking temperature is not particularly limited, but is preferably 180 to 250 ° C, and more preferably 220 to 230 ° C. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes.烘烤 Baking is performed as described above to obtain a cured film of the resin composition.

對於按照上述方式形成的包含顏料(D)的經著色的硬化膜而言，根據顏料(D)的色相，例如可作為色彩濾波器中的黑色矩陣、RGB等著色膜而合適地使用。 [實施例]The colored cured film containing the pigment (D) formed as described above can be suitably used as a colored film such as a black matrix and RGB in a color filter depending on the hue of the pigment (D). [Example]

以下，示出實施例進一步具體地說明本發明，但本發明的範圍不限於此等實施例。Hereinafter, the present invention will be described more specifically by showing examples, but the scope of the present invention is not limited to these examples.

[調製例1] 　　首先，在500ml四頸瓶中，裝入雙酚芴型環氧樹脂(環氧基當量235)235g、四甲基氯化銨110mg、2,6-二叔丁基-4-甲基苯酚100mg、及丙烯酸72.0g，一邊以25ml/分鐘的速度向其中吹入空氣，一邊於90～100℃進行加熱溶解。接下來，在溶液為白濁的狀態下，緩緩升溫，加熱至120℃，使其完全溶解。此時，溶液逐漸變得透明黏稠，保持該狀態繼續攪拌。期間測定酸值，持續加熱攪拌直至酸值變得低於1.0mgKOH/g。直至酸值達到目標值需要12小時。而後冷卻至室溫，得到無色透明且為固體狀的下述式表示的雙酚芴型環氧丙烯酸酯。 　　[化29] [Preparation Example 1] First, a 500 ml four-necked flask was charged with 235 g of a bisphenol fluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 2,6-di-tert-butyl-4 -100 mg of methylphenol and 72.0 g of acrylic acid were heated and dissolved at 90 to 100 ° C while blowing air into the solution at a rate of 25 ml / min. Next, in a state where the solution was cloudy, the temperature was gradually raised, and the solution was heated to 120 ° C. to completely dissolve it. At this time, the solution gradually became transparent and viscous, and the stirring was continued while maintaining the state. During the measurement of the acid value, heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It takes 12 hours until the acid value reaches the target value. Then, it cooled to room temperature, and obtained the colorless and transparent bisphenol fluorene type epoxy acrylate represented by the following formula. [Chemical 29]

接下來，向按照上述方式得到的上述的雙酚芴型環氧丙烯酸酯307.0g中添加乙酸3-甲氧基丁酯600g，將其溶解，然後混合二苯甲酮四甲酸二酐80.5g及四乙基溴化銨1g，緩緩升溫，於110～115℃進行4小時反應。確認了酸酐基消失後，混合1,2,3,6-四氫鄰苯二甲酸酐38.0g，於90℃進行6小時反應，得到樹脂A-1。經由IR光譜來確認酸酐基的消失。Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate obtained in the above manner, and dissolved, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide was gradually heated, and a reaction was performed at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain resin A-1. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[實施例1、實施例2、及比較例1～3] 　　實施例及比較例中，作為(A)鹼可溶性樹脂，使用卡多(Cardo)樹脂與酚醛清漆樹脂。 　　作為卡多(Cardo)樹脂，使用上述調製例1中得到的樹脂A-1。 　　作為酚醛清漆樹脂，使用Sumitomo Bakelite Co., Ltd.製的TO-547(商品名)。TO-547為向間甲酚90莫耳%與2,3,5-三甲基苯酚10莫耳%的混合物中添加草酸和濃度為37質量%的福馬林並利用常規方法進行縮合反應而得到的Mw30000的甲酚酚醛清漆樹脂。[Example 1, Example 2, and Comparative Examples 1 to 3] 中 In the examples and comparative examples, as the (A) alkali-soluble resin, Cardo resin and novolac resin were used. As the Cardo resin, the resin A-1 obtained in the above Preparation Example 1 was used. As the novolac resin, TO-547 (trade name) manufactured by Sumitomo Bakelite Co., Ltd. was used. TO-547 is obtained by adding oxalic acid and formalin at a concentration of 37% by mass to a mixture of 90 mol% of m-cresol and 10 mol% of 2,3,5-trimethylphenol and performing a condensation reaction by a conventional method. Mw30000 cresol novolac resin.

實施例及比較例中，作為光聚合性化合物(B)，使用DPHA(二季戊四醇六丙烯酸酯)。In Examples and Comparative Examples, as the photopolymerizable compound (B), DPHA (dipentaerythritol hexaacrylate) was used.

實施例及比較例中，作為光聚合引發劑(C)，使用OXE-02(商品名，BASF公司製，O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-哢唑-3-基]乙酮肟)。In the examples and comparative examples, as the photopolymerization initiator (C), OXE-02 (trade name, manufactured by BASF Corporation, O-ethylfluorenyl-1- [6- (2-methylbenzylfluorenyl)- 9-ethyl-9H-oxazol-3-yl] ethanone oxime).

實施例及比較例中，作為顏料(D)，使用碳黑。 　　作為碳黑，使用大同化成工業公司製的碳黑(顏料A(分散液))。 　　尚，本實施例項的表1中，關於該顏料及分散劑的固體成分的合計值，對於其數值進行了記載。In the examples and comparative examples, carbon black was used as the pigment (D). As carbon black, carbon black (Pigment A (dispersion)) manufactured by Daido Chemical Industries, Ltd. was used. It is said that in Table 1 of this example, the total value of the solid content of the pigment and the dispersant is described.

實施例及比較例中，作為矽烷偶合劑(E)，使用以下的E1～E3。 　　E1：下述式的化合物 　　[化30]E2：3-環氧丙氧基丙基三甲氧基矽烷 　　E3：3-苯基胺基丙基三甲氧基矽烷In Examples and Comparative Examples, the following E1 to E3 were used as the silane coupling agent (E). E1: a compound of the formula E2: 3-glycidoxypropyltrimethoxysilane E3: 3-phenylaminopropyltrimethoxysilane

將分別為表1中記載的量的鹼溶性樹脂(A)、光聚合性化合物(B)、光聚合引發劑(C)、顏料(D)、與表1中記載的種類及量的(E)環氧化合物溶解、分散於(S)有機溶劑中，使得固體成分濃度成為15質量%，得到各實施例、比較例的樹脂組成物。 　　作為(S)有機溶劑，使用乙酸3-甲氧基丁酯：丙二醇單甲基醚乙酸酯：環己酮=40：35：25(質量比)之混合溶劑。 　　使用得到的樹脂組成物，按照以下的方法，針對經圖案化的硬化膜對基板的密著性、和在未曝光部產生殘渣的情況進行評估。將它們的評估結果記載於表1。The amounts of the alkali-soluble resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), the pigment (D), and the types and amounts described in Table 1 (E ) The epoxy compound was dissolved and dispersed in the (S) organic solvent so that the solid content concentration became 15% by mass, and the resin compositions of the respective examples and comparative examples were obtained. As the (S) organic solvent, a mixed solvent of 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: cyclohexanone = 40: 35: 25 (mass ratio) was used. Using the obtained resin composition, the following methods were used to evaluate the adhesion of the patterned cured film to the substrate and the occurrence of residues in the unexposed portions. The evaluation results are shown in Table 1.

＜經圖案化的硬化膜對基板的密著性＞ 　　使用旋塗機將樹脂組成物塗佈於玻璃基板(100 mm×100mm)上，於80℃進行120秒預烘烤，形成膜厚2.0μm的塗佈膜。 　　接下來，使用鏡面投影對準曝光器(mirror projection aligner)(製品名：TME-150RTO，股份有限公司TOPCON CORPORATION製)，使曝光間隙為250μm，隔著具有下述寬度的線部的線圖案形成用的掩模向塗佈膜照射紫外線。使曝光量為40mJ/cm2 。 　　將曝光後的塗膜在25℃的0.04質量%KOH水溶液中浸漬60秒後，形成線的尺寸為2～100μm的線圖案，按照下述的基準評估所形成的線圖案的密著性。 　　◎：2μm以下的寬度的線圖案密著。 　　○：3～5μm寬度的線圖案密著。 　　△：6～10μm寬度的線圖案密著。 　　×：11μm以上的寬度的線圖案密著。<Adhesion of the patterned cured film to the substrate> The resin composition was applied to a glass substrate (100 mm × 100 mm) using a spin coater, and pre-baked at 80 ° C for 120 seconds to form a film thickness of 2.0 μm. Coating film. Next, using a mirror projection aligner (product name: TME-150RTO, manufactured by TOPCON CORPORATION), the exposure gap was 250 μm, and a line pattern was formed across a line portion having the following width The applied film was irradiated with ultraviolet rays. The exposure amount was set to 40 mJ / cm 2 . After the exposed coating film was immersed in a 0.04 mass% KOH aqueous solution at 25 ° C. for 60 seconds, a line pattern having a line size of 2 to 100 μm was formed, and the adhesion of the formed line pattern was evaluated according to the following criteria. ：: Line patterns with a width of 2 μm or less are in close contact. ：: A line pattern with a width of 3 to 5 μm is in close contact. Δ: A line pattern with a width of 6 to 10 μm is dense. X: A line pattern with a width of 11 μm or more is in close contact.

＜在未曝光部產生殘渣的情況＞ 　　使用旋塗機將樹脂組成物塗佈於玻璃基板(100mm×100mm)上，於80℃進行120秒預烘烤，形成膜厚2.0μm的塗佈膜。 　　接下來，使用鏡面投影對準曝光器(製品名：TME-150RTO，股份有限公司TOPCON CORPORATION製)，使曝光間隙為250μm，隔著可形成下述形狀的矩陣(matrix)的掩模，向塗佈膜照射紫外線。使曝光量為40mJ/cm2 。 　　將曝光後的塗膜浸漬於25℃的0.04質量%KOH水溶液中60秒後，形成尺寸為11μm的矩陣，對在矩陣中可確認到的殘渣個數進行計數。基於進行計數而得到的殘渣個數，按照以下基準，評估顯影後的殘渣的產生情況。 　　◎：有0～10個殘渣。 　　○：有11～20個殘渣。 　　△：有21～40個殘渣。 　　×：有41個以上的殘渣。<When a residue is generated in an unexposed part> A resin composition is coated on a glass substrate (100 mm × 100 mm) using a spin coater, and pre-baked at 80 ° C. for 120 seconds to form a coating film having a thickness of 2.0 μm. Next, a specular projection alignment exposure device (product name: TME-150RTO, manufactured by TOPCON CORPORATION) was used so that the exposure gap was 250 μm, and the coating was applied through a mask capable of forming a matrix of the following shape. The cloth film is irradiated with ultraviolet rays. The exposure amount was set to 40 mJ / cm 2 . The exposed coating film was immersed in a 0.04 mass% KOH aqueous solution at 25 ° C. for 60 seconds, and then a matrix having a size of 11 μm was formed, and the number of residues recognizable in the matrix was counted. Based on the number of residues obtained by counting, the occurrence of residues after development was evaluated in accordance with the following criteria. ：: There are 0 to 10 residues. ○: There are 11 to 20 residues. △: 21 to 40 residues. ×: There are 41 or more residues.

根據實施例可知，為包含(A)鹼可溶性樹脂、光聚合性化合物(B)、光聚合引發劑(C)、顏料(D)、與含有特定構造化合物的矽烷偶合劑(E)的樹脂組成物時，可形成對基板的密著性良好的圖案，並且可抑制在未曝光部產生顯影殘渣。 　　另一方面，根據比較例1～3可知，感光性樹脂組成物不包含矽烷偶合劑(E)、或矽烷偶合劑(E)不含有特定構造化合物時，難以同時實現下述效果：形成對基板的密著性良好的圖案；以及，抑制在未曝光部產生顯影殘渣。According to the examples, it can be seen that it is a resin composition containing (A) an alkali-soluble resin, a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D), and a silane coupling agent (E) containing a specific structural compound. In the case of an object, a pattern with good adhesion to the substrate can be formed, and development residues can be suppressed from occurring in the unexposed portion. On the other hand, from Comparative Examples 1 to 3, when the photosensitive resin composition does not include the silane coupling agent (E) or the silane coupling agent (E) does not contain a specific structural compound, it is difficult to achieve the following effects at the same time: formation of a counter substrate A pattern having good adhesion; and suppressing development residues in unexposed areas.

Claims (8)

一種樹脂組成物，其特徵為包含： 　　鹼可溶性樹脂(A)、 　　光聚合性化合物(B)、 　　光聚合引發劑(C)、 　　顏料(D)，與 　　矽烷偶合劑(E)； 　　前述矽烷偶合劑(E)包含下述式(e1)表示之烷氧基矽烷化合物， 　　(Re1 O)a (Re2 )3-a Si-Re3 -NH-CO-Re4 -Re5 ……(e1) 　　式(e1)中，Re1 及Re2 各自獨立地為碳原子數1～6之烴基，a為2或3，Re3 為碳原子數1～10之亞烷基，Re4 為2價之有機基，Re5 為布朗斯特酸性基、醇性羥基、胺基或胺基甲醯基。A resin composition, comprising: an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a pigment (D), and a silane coupling agent (E); the aforementioned silane coupling agent (E) contains an alkoxysilane compound represented by the following formula (e1), (R e1 O) a (R e2 ) 3-a Si-R e3 -NH-CO-R e4 -R e5 ... (e1) In formula (e1), R e1 and R e2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is 2 or 3, R e3 is an alkylene group having 1 to 10 carbon atoms, and R e4 is a bivalent An organic group, R e5 is a Bronsted acid group, an alcoholic hydroxyl group, an amino group, or an aminoformyl group. 如請求項1之樹脂組成物，其中，前述Re4 為2價之芳香族烴基。The resin composition according to claim 1, wherein the R e4 is a divalent aromatic hydrocarbon group. 如請求項2之樹脂組成物，其中，前述2價之芳香族烴基中之一方的鍵結處所鍵結的碳原子的位置與另一方之鍵結處所鍵結之碳原子的位置的關係為鄰位或迫位。The resin composition according to claim 2, wherein the relationship between the position of the carbon atom bonded to one of the aforementioned divalent aromatic hydrocarbon groups and the position of the carbon atom bonded to the other bonded position is adjacent Bit or force. 如請求項3之樹脂組成物，其中，前述2價之芳香族烴基為鄰亞苯基、萘-1,2-二基、萘-2,3-二基、或萘-1,8-二基。The resin composition according to claim 3, wherein the divalent aromatic hydrocarbon group is o-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, or naphthalene-1,8-di base. 如請求項1～4中任一項之樹脂組成物，其中，Re5 為羧基。The resin composition according to any one of claims 1 to 4, wherein R e5 is a carboxyl group. 一種硬化膜，其特徵為將如請求項1～5中任一項之樹脂組成物進行硬化而形成的。A cured film formed by curing the resin composition according to any one of claims 1 to 5. 一種色彩濾波器，其特徵為具備如請求項6之硬化膜。A color filter comprising a hardened film as claimed in claim 6. 一種硬化膜之製造方法，所述製造方法包含下述步驟： 　　藉由塗佈如請求項1～5中任一項之樹脂組成物，從而形成塗佈膜之步驟， 　　位置選擇性地將前述塗佈膜曝光之步驟， 　　將經曝光的前述塗佈膜顯影，形成經圖案化的硬化膜之步驟，與 　　對前述經圖案化的硬化膜進行烘烤之步驟。A method for manufacturing a cured film, the method includes the following steps: 步骤 a step of forming a coating film by coating the resin composition according to any one of claims 1 to 5, selectively applying the aforementioned coating at a position The step of exposing the cloth film includes the steps of developing the exposed coating film to form a patterned hardened film, and baking the patterned hardened film.
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